Pe-249 598 SULFURIC ACID PLANT EMISSIONS DURING START-UP. SHUTOOKN, AND MALFUNCTION E. L. Calvin, et 2 Catalytic, Incorporated Prepered for: Industrial Environmental Research Laboratory January 1976 DISTRIBUTED BY: National Technical Information Service U.S. DEPARTMENT OF COMMERCEEPA-600/2-76-019 ; January 1976 Environmental Protection Technology SeriesTECHNICAL REPORT DATA (Met rad Vator fot: Rene comeing) Fear i Br EEN RECTION WS: Sulfuric Acid Plant Emissions During Start-up. January 1976 ‘Shutdown, and Malfunction ‘PERFORM ONG »NTEATION ESOE E.L. Calvin and FD. Kodras SRR ETERNT HO Catalytic, Inc. IABOI3; ROAP 21BAV-014 PO, Bex 1402 [Fr cowrakcriceanr we Charlotte, North Carolina 28202 68-02-1322, Task 6 EPA, Office of Research and Development Final Industrial Environmental Research Laboratory Research Triangle Park, NC 27711 SARITA The report gives results of a study of dual-absorption contact sulfuric acid plants, as well as single-absorption plants equipped with vent gas cleaning systems for removal of SO2, to determine the relationship between process parameters and air emissions. Processes studied were dual-absorption acid plants and single- absorption acid plants equipped with sodium scrubbers, ammonia scrubbers. and molecular sieve adsorbers. Emissions considered were SO2 and acid mist emis- sions and vent gas opacity. Relationships were developed for normal operations and compared to off-normal operations such as shutdown, start-up, malfunction, and misoperation. Process parameters and emission relationships are presented in statistical, tabular, and graphic form. Converter bed operating temperature ranges were established and causes of SO2 and acid mist emissions are illustrated from plant operating data, Air Pollution Scrubbers Air Pollution Control. [13B OTA Industrial Plants Sodium Stationary Sources Sulfuric Acid. Ammonia Molecular Sieves om Mist ‘Absorbers Sulfur Dioxide (Materials) NG Opacity PRICES SUBJECT TO CHANGE) SORTRGTOT EATEN ee PO Unlimited os 0-50-95 |EPA-600/2-76-010 SULFURIC ACID PLANT EMISSIONS DURING START-UP, SHUTDOWN, AND MALFUNCTION by EL. Calvin and F.D, Kodras Catalytic, Ine. P.O, Box 11402 Charlotte, NC 28209 Contract No. 68-02-1322, Task 4 ROAP No. 21BAV-014 Program Element No. 1ABOI3 EPA Task Officer: R.V. Hendriks Industrial Environmental Research Laboratory Office of Energy, Minerals, an¢ Industry Research Triaigle Park, NC 2711 Prepared for U.S, ENVIRONMENTAL PROTECTION AGENCY Office of Research and Development Washington, DC 20460 January 1976RESEARCH REPORTING SERIES Research reports of the Office of Research and Development, U.S. Environmental Protection Agency, have been grouped into five series. These five broad catzgories ere established to facilitate further development and application of environmental technology. Elimination of traditional grouping was consciously Planned to foster technology transfer and a maximum interface in related fields. The five series are: 1. Environmental stealth Effects Research 2. Environmental Protection Technolony 3. Ecological Research 4. Environmental Monitoring 5. Socioeconomic Environmental Studies This report has been assigned to the ENVIRONMENTAL PRCTECTION TECHNOLOGY series. This scries describes research performed to develop and demonstrate instrumentation, equipment and methodology to repair or prevent environmental degradatios. from point and non-point sources of pollution. This work provides the new or improved technology required for the control and treatment of pollution sources to meet environmental quality standards. EPA REVIEW NOTICE ‘This report has been reviewed by the U.S. Environmental Protection Agency, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the Agency, nor does mention of trade names or commercial products constitute endorse- ment or recommendation for use. This document is available to the public through the National Technical Information Service, Springficld, Virginia 22161.TABLE oF Page STOP RIGUReS ve LIST OF TABLES... 2 ee ee ee EE ACKNOWLEDGEME Foe bd oe doo egos SECTIONS I. SUMMARY AND CONCLUSIONS 26 ee eee ee 1 Gre terete IIT, STUDY OBJECTIVE AND APPROACH. © 2... 2-6 QU) emcees Descuipmion Contact Sulfuric Acid Process: 2 . 13 Single Absorption Process... +--+... - 14 Dual nbso! Sodium Scrubber System... 2-2... 0 22 Ammonia Scrubber systeu. - - -. 4-24 Molecular Sieve Adcorption instr: Beicuancontrol: 0 | Gn V. 0 SURVEY © ACIP PLANT ENISSIONS AND CONTROLS . 17 ants for Field Surveys... . 37 of tnisaion Contrei systems... 2... 45 Foussion Dat sotained. 2.2 ae VI, ANALYSIS OF PROCESS VARIABLES 3 + 50 : tan, “ecrations 6... ee ee 80 converter Tanperacsre Control... 2. . 51 rmile Absorption Plants... 2. 59vir. Single Absorption Slants Cleaning Systems . . - Dual Absorption Plants . Shutdown Operations . 2. . - Start-v p Operations... . - Single Absorption Plants Single Absorption Plants Cleaning Systems . . . . Dual Absorption Plants - Malfunction Conditions. . . . Single Absorption Plants Single Absorption Plants Cleening. 2... ee ee Dual Absorption Plants . DISCUSSION. 2-2 ee eee with Gas with vent Emissions During Normal Operation . Steady State Emissions and Equipment Limits. ee Feedstock Changes. . . - EPA Performance Parameters. . Shutdown Emissions... . Planned Shutiowns. . - Unplanned Shutdown and Equipment Malfunctions... . + Emissions from Misoperation of Plant Start-Up Procedures... . ~ New Plant and New Catalyst Start-up. Cold Plant Start-Up - Dual Absorption. Vv 64 6s n 79 79 84 as 94 94 98 107 us naPage Warm Plant Start-Up = Dual Abscrption. . . 139 Vent Gas Cleaning systems - Single Abecrocioniee ree fest 1 129 Witt, fereerices te cose APPENDICES Appendix A Process Descriptions. ..... +. +. 158 Appendix B Plant Start-up pata... 2... 197 Appendix C Statistical Analysis... --.. ~~. . 216No. Le 10. al. 22. 3. 4a. LIST. OF PIGURES Single Absorption Sulfur Burning Contact sulfuric Acid Plant Process Flow Diagram... .- +. ++ - Dual Absorption Sulfur Burning Contact Sulfuric Acid Plant Process Flow Diagram... +--+ +--+ Sodium Scrubber Tail Gas Cleaning System Process plow (Diagrams@) eee eee Ammonia Scrubber Tail Gas Cleaning System Process Flow Diagram. - ee eee et tt ee Molecular Sleve Tail Gas Cleaning System Process Flow Diagram. ee ee et ee Dual Absorption Sulfur Burning Contact Sulfuric Acid Plant P. and I. Diagram...) ee eee E.P.A. Sulfur Dioxide Emission Standard for New Contact Moidiplante wcuctem semast cs ee E.P.A. Acid Mist Emission Standard for New Contact Acid Plants. ee ee ee ee Normal Range of Operation of Single Absorption and Dual Absorption Avid Plants as Found in this Study Monthly Variations in Acid Mist Emission Over the Past Six Years (Plant U,, Bright Sulfur Burned in a Single Absorption Contact Acid Plant)... . ~~ Normal Operating Range for Dual Absorption and Single Absorption Acid Plants... - . +e eee Dual Absorption Average Emissions After Start-Up . Example of S?, Emissions During Start-Up of Single Absorption Acid Plant vs. Single Absorption Acid Plant with Cominco-Type Ammonia Scrubber Plant U)- An Example of a Single Absorption Plant "U2" Entering and Leaving Malfunction Operating (Cond itlonats scene, Stgeeses eee | Cold Start-Up of Typical Dual Absorption Acid lente vt Page as as 22 25 30 33 a7 48 37 62 n 76 a3 9016. 17. 1s. 19. 20. 21. 22. 23. 24a. Page An Example of a Dual Absorption Plant ("Q") Entering und Leaving Malfunction Operating Conditions - During Stare Ope ee 8 8 Acid Mist Emission Average Operating Levels for Both Dual (Plant "Q") and Single (Plant Uy ¢ U,) Contact acid Plants. 2. . ee ee ee te ee ee 96 Normal Range of Operation for Acid Mist Emissions of New Dual Absorption and Single Absorption Acid Plents Burning Bright and Dark Sulfur... .: +. + 97 Computer Plot of Acid Mist vs. Time... ..- +. . 99 Malfunction of Single Absorption Acid Plant "K" with Ammonia Scrubber... ee yee eee ee ee 100 Malfunction of Single Absorption Acid Plant "K” with Ammonia Scrubber... ee ee eee ee ee lL Malfunction of Single Absorption Acid Plant "x" with Ammonia Scrubbers. yee ete eee ee ee e102 Malfunction of Single Absorption Plant “Y" with Sodium Scrubber... - eee ee ee et ee + 0106 ‘Transient Process Conditions During Dual Absorption Plant Malfunctions... ee eet ee ee ee ee ehO7 vir4a. an. ac. lo. ul. 12. 13. LIST OF TABLES A List of Candidate Companies for the Su’ furic Acid Plant Malfunctions Emissions Survey... « Summary of Emissions from Various Types of, Contact Sulfuric Acid Plants Surveyed During Normal; Operations) 2) 2) eee E.P.A. New Source Performance Standards Test Data Dual Absorption Contact Acid Plant (Plant “Q") Normal Steady State Operating Temperatures and Conversions in Each Converter Stage of Contact Reid Plants... eee ee ee et Converter Temperature and $0, Outlet Concen- tration Plant "J"--Upset Conditions. ..-. ++ Converter Temperature and SO, outlet Concen- tration Plant "J"--Normal Operation... 1 +. + + Plant °N" Test Data, oe ee eee ee eee Reid ise Mose Acid Mist Observations... +e eee ee eee E.P.A. Performance Test Results for $0, and Acid Mist Emission Control Effectiveness frdm Sodium Scrubber (Plant "Y") sete tte tee ee ee Effect of Primary Absorber in the Dual Absorption Process: (Plant (Gaye sss ces ee Summary of Test Results from Dual Absorption Plant OO ‘The Effect of Downtime Shutdown Durations Upon Et‘luent S02 Concentrations (pn) During Start-Up (for Plant #3"). Summary of Start-Up Data on Dual (DAP) and Single (SAP) Absorption Acad Plants for Figures 25 through Tee eas oe Start-Up Temperatures for Plant "U," Single Absorp- tion Acid Plant with Ammonia Scrubber... . ~~. VIII an 46 51 58 56 38 61 63 66 eo 69 4 7 aL1s. 16. Page Start-Up Plant "U,"-Ammonia Scrubber Start-Up Conditions and Emissions » + eee ee eee ee ee 82 Start-Up Temperature Contac: Acid Plant "U," Single Absorption Plant with Ammonia Scrubber. . . . 86 Anmonia Scrubber Start-Up Conditions and Emissions on Plant "U," (with Mist Eliminator) . .. ++ ++ + 87 IxACKNOWLEDGEMENTS The assistance of the BPA Task Officer, Mr. Robert V. llendriks, is acknowleiyel with sincere appreciation. Mr. Donald Carey, Divi- sion of Stuticnary Enforcement, EPA, Washington, D. C., also provide! saluable information and guidanc The personnel of the Technical Library, Continuous Monitoring Branch, and Enforcement Branch, EPA, Research Triangle Park, North Carolina furnished useful data during the preparation of this report. This support is appreciated. ‘The EPA Reaion 1Y personnel, Atlanta, Georgia and the Florida Department ot Pollution Control personnel, Winter Haven, Florida, supported the project through use of their experience and knowledge in performance testing. Special assistance in obtaining useful operating data and operating experience was provided by members of the Manufac- turing Chemists Association, the Florida Phosphate Council, and other v< converter design. There is @ lower limit to the concentration of SO, in the vent gas imposed by equilibrium conditions within the catalytic con- verter and the amount of catalyst that can be installed eco- nomically in the plant. Because of thse limitations the single absorption sulfuric plant must be equipped with sulfur dioxide recovery processes to reduce the SO, concentration in the vent gas to the accestable level. Many processes have been proposed to perform this operation but only three have been applicd commercially. These are 20the sodium scrubber process, the ammonia scrubber process, and the molecular sieve adsorption process. These three pro- cesses will be described in the following paragraphs. Sodium Scrubber system The sodium scrubber process for removing sulfur dioxide that was included in this study is a wet regenerative system based on a sodium sulfite/bisulfite cycle. This process, currently being marketed by Davy Powergas Inc. under the Wellman-Lord trademark, is represented by Figure 3 that depicts the absorber and chemica! regencration areas. The reactions that take place in the process can be simplified to the following: Absorption - $0, + NaS0, + H,0 ---» 2 Naliso, Regeneration - 2 NaHSO, ---P Na,S0, + SO, + #0 Sodium sulfate (Na,S0,), which is non-regenerable in the nor- mal process, is formed in the absorber as a result of the reaction between the sulfite ion and oxygen or sulfur trioxide ‘as follow: Na,80, + 1/20) > NayS0, 2 Na,SO, + SO, + 11,0 ---P Na,SO, + NaHSO, ‘The sodium sulfate formed is controlled at a level of approx- imately five to ten percent by weight in the absorber feed stream by maintaining a continuous purge from the system. Caustic addition is required to replace the sodium lost in the sodium sulfate purge. This caustic make-up solution 2RSE ERRreacts with the sodium bisulfite in the absorber to form additional sodium sulfite solution: NaOH + NaHSO, ---» NaS0, + 1,0 ‘The caustic can also react with the SO, to form bisulfite as follows: NaOH + SO, NaHso, ‘The S0,-rich gas is contacted counter-currently in the absorber by the sodium sulfite solution and passes out the top stripped of S0,. An absorber with inlet concentration of 1560 parts per million $0, and 95 percent scrubber efficiency can achieve an emission of 86 parts per million $0. The absorber bleed stream, rich in sodium bisulfite, (NaHS0,), is discharged to a holding tank. From the holding tank the solution flows to the chemical regeneration area for recovery of the S0, gas. The sodium bisulfite solution flows to the evaporator erys- tallizer in the chemical regeneration area where it is boiled by indirect heating with steam, resulting in the decomposition of the sodium bisulfite solution into S0,, water vapor, and a precipitate of sodium sulfite crystals. ‘The overhead gas from the evaporator-crystallizer passes through a condenser to remove most of the water vapor. Con- densate is recycled to the dissolving tank to dissolve the sodium su} fite crystals and the product 50, gas is recycled to the sulfuric acid plant or Claus elemental sulfur plant. Precipitate from the evaporator-crystallizer is processed 23through a centrifuge where sodium sulfite solids are discharged to a dissolving tank for recycle to the absorber. The bulk of the mother liquor from the centrifuge is recycled to the evaporator-crystallizer for solids density control. A small portion of the mother liquor is purged from the process to control the level of sodium sulfate as previously stated. The sodium ions lost in the purge stream are replaced by addition of sodium hydroxide (50 percent NaOH) solution directly to the absorber. Ammonia Scrubber Process Ammonia has been used for removing sulfur dioxide from vent gases in the sulfuric acid and smelter industries for many years. Several commercial ammonia scrubber processes are available for application to sulfuric acid plants. All of iiese processes are based upon the same chemical reactions. A flowsheet of this process is shown in Figure 4. Ammonia provides one of the most vigorous reactions with sul- fur dioxide of all the alkaline materials and produces soluble by-products. ‘The primary reaction in the ammonia scrubber is the conversion of ammonium sulfite to ammonium bisulfite by the reaction with sulfur dioxide. The ammonium bisulfite is regenerated by reaction with ammonia to again form ammonium sulfite. The equations for the two reactions are as follows: So, + (NH,),S0, + 11,0 2NH,HSO,, NH, + NHjHSO, ---» (NiI,), SO 24In applying the anmonia scrubbing system to a sulfuric acid plant exhaust gas, the gas is first treated by spraying water into the exhaust duct tc humidify and cool the gases leaving the absorber. The cool cases are then passed through an ab- sorber counter current to the flow of the ammonia brine and the $0, removed by reaction with ammonium sulfite. The con- centration of ammonia sulfite is controlled by the addition ‘of ammonia on the basis of pl. Operation with a large concen- tration of ammonium sulfite promotes the reaction with SO, but increases the usage of ammonia since a large amount of ammonium sulfite is withdrawn with the spent scrubber liquor. Operation with a large concentration of ammonium bisulfite reduces the absorption capability of the brine and increases the concentration of S0, leaving the absorber. Careful con- trol of the pH of scrubbing liquor is required for efficient operation of the system. A secondary reaction taking place in the absorber is the oxi- dation of the anmonium sulfite to ammonium sulfate by reaction with excess oxygen in the exhaust gas stream. The chemical equation for this oxidation process is as follows: (Hy) 980, + 1/2 0, ~ (Ht) 280,- ‘The oxidation of ammonium sulfite to sulfate is undesirable since ammonium sulfate is unreactive in the scrubbing mech- anism and removes ammonia from the system in the largest ratio to the sulfur content. 26‘The top of the absorber is equipped with a mist entrainment separator to prevent the carry over of ammonia brine in the gas stream. This separator is usually of the wire mesh type. ‘he primary disadvantage of removing SO, by absorption with ammonia brine is the generation of particulate matter by gas phase reaction between S0, and ammonia to form ammonium sul- fite. The ammonium bisulfite particulate is very finely divided and passes through the absorber and is “isible in the vent gas as a blue haze. The quantity of haze produced depends upon the partial pressures of the various gases in the vapor phase and cannot be completety eliminated using pH control in a single stage absorption. ‘here the particulate haze is not permissible in the exhaust gas from sulfuric acid plants, it has been standard practice to equip the plant with a venturi scrubber or a fiber pad demister operating at very high efficiencies to remove the submicron particulate. Al- though these high efficiency filters are satsifactory for removal of the particulates, the high pressure drop across the filters requires a large investment in additional blower capacity and energy consumption. Similar costs are encountered using a high energy venturi scrubber for removal of the par- ticulate. Various processes have been developed for reclaiming the sul- fur velues from the ammoniacal brine withdrewn from the absorber 27processes. ‘These include acidulation with sulfuric acid, thermal decomposition of the annonium bisulfite to sulfite and S0,, and mixing of the ammonium sulfite-bisulfite Liquor into fertilizer solutions. The thermal decomposition process is still in pilot plant development by TVA and was not applied commercially in any of the plants studied. In the acidulation process, the ammoniacal brine from the absorber is mixed with sulfuric acid before being admitted to a packed column. In this column the reaction of sulfuric acid with ammonium sulfite-bisulfite takes place, liberating gaseous 50, and generating ammoninm su)fate. The primary reactions in the acidulation process are shown in the follow- ing equations. (i,) 80, + 50, ---P (NH,) SO, + H,0 + SO, > (NH,) 280, + 2H,0 + 2 So, 2 NHAHSO, + H,SO, ‘The packed column disengages the gaseous SO, from the ammon- ium sulfate sclution so the SO, can be recycled back to the stilfuric acid plant while the anvonium sulfate solution is collected for further processing. ‘The ammonium sulfate solu- tion is either concentrated and crystallized to produce solid ammonium sulfete or is included in mixed fertilizers. when the acid plant is a part of a fertilizer complex, the anmonium sulfate or ammonium sulfite-bisulfite brine can be used in ‘the diammonium phosphate production process as was the case in Plant "U" included in the study. The brine can also be used in other fertilizer concentrates using standard processes 28for manufacturing solid or fluid products. Molecular Sieve Adsorption Process one of the newest 0, recovery processes to be applied com- mercially to sulfuric acid plant vent gas is the PuraSiv S Process development by Union Carbide. This process uses a ary bed molecular sieve material for removing so, from the vent gas. ‘The primary features incorporated in this system are the high removal efficiency for $0, especially at low 80, concentrations, freedom from liquid chemical handling problems, absence of waste products, and simple operation. Evaluation tests on production models of this system have been run very recently and data could not be fully evaluated in this study. However, general process descriptions are included because of the prospects of future applications. A process flow diagram for the molecular sieve sulfur dioxide covery system is shown in Figure 5. The tailgas from the sulfuric acid plant at approximately 170F is cooled to 100F by pausing through a water cooler. Any sulfuric acid en- trained from the absorption tower is collected from this cooler in an acid circulation pot. Acid from the circulation pot is continuously recycled to the cooler to aid in conden- sation and collection of the sulfuric acid mist. since it is undesirable for liquid sulfuric acid to enter the molecu- Jar siev? adsorption tower, the gas is passed thzough a filter containing packed fiber elements to remove entrained sulfuric acid. The sulfuric acid collected in this filter is also 29returned to the acid circulation pot. This feed preparation system for the PuraSiv operation is similar to that included in many sulfuric acid plants to reduce the amount of sulfuric acid entrainment from the absorber system. After removal of all excess sulfuric acid mist from the gas stream the gases axe passed through 2 tower packed with gran- ular PuraSiv S. In this tower the SO, is removed from the vent gas to a level of 15 to 20 parts per million. The molec- ular sieve adsorption system consists of two adsorber towers to permit regeneration of one tower while the second is being When the molecular sieve in one adsorption tower nears satu- ration, as indicated by an increase in the sulfur dioxide con- centration in the vent gas the towers are switched and the saturated tower is put on the regeneration cycle. Regenera~ tion of the PuraSiv § is accomplished by passing a hot, dry air stream through the bed in reverse direction to strip out the adsorbed s0,. Regeneration air is brought into the plant through an air filter and a weter cooled indirect cooler to remove as much of the water vapor as possible. The air is then passed through a desiccant bed dryer to remove the renaining moisture before being preheated to 200F in indirect fired air heaters. The air is then used for stripping the SO, in the regeneration cycle. Stripping air leaving the regencrating adsorber flows 31to the acid plant for mixing with dilution air in the sulfur furnace. This air contains from four to 0.3 percent SO, depending upon the point in.the regeneration cycle. Ia this manner the recovered S0, is returned to the sulfuric acid plant converter for recovery as sulfuric acid. To provide an uninterrupted flow of regeneration aiz two des- iccant towers are used for air drying. As in the SO, adsorp- tion towers, one tower is on adsorption cycle while the second is being regenerated. Regeneration is accomplished by passing the dried hot air from the fired air preheaters through the desiccant hed in reverse direction to strip out the adsorbed water which is then vented to atmosphere. A control system is provided to determine the point when re- generaticn of both the $0, adsorber and the dryer is required and to eutomatically cycle the units to place a newly regener- ated tower into operation. In this manner there is no inter~ ruption of cither process or regenerating air flow. The regeneration air flow required in the $0, absorber is approx- imately 20 percent of the design process flow. Since about the same percentage of the total air flow is required for re- generation of the air dryers, the air drying units are small compared to the SO, adsorbers. ‘The SO, content of the recycled stripping air varies from four to 0.3 ercent $0, throughout the regeneration cycle. The addition of this So, to the SO, contentration leaving 32the furnace will vary the $0, concentration entering the converter also. During novmal operation this variation of 80, entering the converter dors not adversely affect the operation of the sulfuric acid process. Also, since the ad- sorption efficiency of the PuraSiv $ is not highly dependent upon flow rate or concentration of $0, normal upsets in acid plant operation do not affect the concentration of SO, in the vent gas from the PuraSiv $ system. It has also been found that the presence of CO, and No, in the vent gas as a result of burning acid sludges or dirty sulfur do not affect the adsorption efficiency of the PuraSiv S system. Instrumentation and Control Pach manufacturer of sulfuric acid plants includes variations in the instrumentation control systems as well as variations in equipment and equipment arrangements. Although different instruments and controls are included, certain process para- meters are either controlled automatically or recorded to permit manual control in all acid plants. The most important instruments and controls are shown in the process and instrument diagram of Figure 6. This diagram shows a typical dual absorption acid plant as previously de- scribed. The most important process parameters are those affecting the temperatures and sulfur dioxide concentrations in the converter, and the sulfur trioxide concentrations and temperature of acid in the absorbers. All of these process parameters directly affect the emissions of $0, and acid mist 33from the unit. The sulfuric acid production rate is controlled by regulating the flow of molten sulfur and air to the sulfur furnace. These flows are properly raticed and controlled by the temperature of the gas leaving the furnace. The SO, concentration in this gas is hiyher than required for the converter feed, so the gas is diluted by addition of dry air controlled by a temperature controller on tie feed to the converter. This re- duces the So, concentration in the feed gas to the first stage of the catalytic converter. The inlet temperature to the converter must be precisely controlled for optimum conversion of SO, to SO,. Additional temperature control 1s obtained 2 3 in the feed stream by regulating the amount of cold cases from the primary absorber flowing to the No. 1 heat exchanger. Since the waste heat boiler must be operate? to provide suf- ficient steam for driving the turbine on the primary blower, the balance in heat transfer between the No. 1 and No. 2 exchanger must be adjusted manually with by-pass valves to Properly set the range of heat transfer in the No. 1 heat exchanger ard heat recovery boiler. These by-pass valves and others around heat exchanger No. 2, also are uscd to adjust the temperature distribution in the various stages of the catalytic converter. For proper con- version of So. to S03, inlet and outlet temperatures of each 2 3" stage must be carefully controlled within a narrow range. Control and adjustment of the converter temperatures is provided by a multi-point temperature recorder recording the 34inlet and outlet temperatures on each catalyst section. Ob- servation of the temperature profile across the converter will permit quick analysis of the status of the conversion efficiency of the unit. This multi-point temperature recorder is the heart of the control system for the sulfuric acid plant. Critical parameters around the primary absorber are the temp- erature, flow, and concentration of the acid feed to the ab- sorber. If these parameters are outside the acceptable range, acid mist is generated in the absorber and is discharged from the plant vent. Temperature of the absorbing acid is controlled by adjusting the water flow on the inlet acid cooler while the concentration of acid is adjusted by a concentration analyzer controlling the amount of water make-up to the strong acid exiting the absorber. The same process parameters are as im- portant on the secondar: absorber as on the primary unit, and must be controlled as well. Since the dual absorption plant was designed for the purpose of redueing the $0, and acid mist emissions from the plant, as well as increasing the efficiency of acid manufacturing, the important measurenent of the success of operation of the plant is the $0, analyzer installed in the vent gas stack. mis automatic analytical instrument continuously monitors the 50, concentration in the vent gas, indicating when one of the process variables exceeds optimum range of operation. ven an excessive concentration of $0, in the stack exists, the instrumentation including the multi-point recorder on the 35converter, is used to diagnose the problem and correct the emissions. Many other instrument and control systems are required for proper operation of a sulfuric acid plant. These include instruments on such auxiliaries as the waste heat boiler, economizer, concentrated acid sumps, boiler feedwater for economizers and boiler, the air drying tower, and storace units. Although these instruments are important to operation of the plant, their effect on the emissions of the plant are not as direct as those previonsly discussed. Most of the data collected in our plant survey and presented in the next section include the important process parameters discussed in the first portion of this section and are analyzed in the succeeding section. 36SECTION V SURVEY OF ACID PLANT EMISSIONS AND CONTROLS SELECTION OF PLANTS FOR FIELD SURVEYS ‘The primary, purpose of this study was to obtain information showing the relationship between acid plant process variables and emissions. The study was concerned with those plants that could meet the air pollution control standards under normal operation. Reporting only those plants that will meet air pollution control standards limits the study primarily to dual absorption acid plants and those single absorption plants equipped with vent gas cleaning systems. Three vent gas cleaning systems were selected as being properly proven in commercial installations. These were the sodium scrubbing system, the ammonia scrubbing system, and the Univn Carbide PuraSiy system. The application of the dual absorption process is relatively new in this country and only a limited number of these plants are in operation. Ven€ gas cleaning systems are also rela~ tively new in commercial application, limiting the number of plants available from which information could be obtained. Because of the limited number of dual absorption plants avail- able for study, comparative information from several single absorption plants was included in the study to support informa~ tion obtained from dual absorption plants. Many process variables can be correlated between the two plants since pro- cess variables have similar effect on emissions in both. 37‘The newest gas cleaning system applied commercially is the Union Carbide PuraSiv system. Only one plant is operating conmercially with sufficient experience to provide operating data. ‘This plant was not available for a visit because of the proprietary nature of the process but data was obtained from the performance test performed by EPA. (3) After a review of the industry a list of tentative plants was prepared (See Table 1) including all the known dual absorption plants and examples of the three major gas cleaning processes. A list of acid plant design companies was also compiled as a possible alternate source of acid plant operating information. ‘Visits to several of the major plant design firms produced very Little useful data because they considered theiz plant designs as proprietary to themselves and performance test data from plants that they installed as proprietary to the clients. After this initial effort attention was turned to obtaining data from operating plants. All of the candidate sulfuric acid plants were investigated and five companies were selected for visits. ‘The selection was based upon the appropriateness of plant type and willing- ness to provide the required information on the operation of the plants. The EPA task officer approved the list of selected Plants to be visited. During the field visits to the selected locations, contractor Personne} examined a total of 12 contact acid plants. 386c ‘TABLE 1 ‘ALLIST OF CANUIDATE COMPANIES FOR THE SULFURIC ACID PLANT MALFUNCTIONS EMISSIONS SURVEY Single W/NHy Scrubbing Single W/Na Scrubbing Dual Absorption on Line New Dual Absorption Start-Up No. of No. of No. of No. of : Plants Company. Plants Company 2 Company Plants Company. @) C.F. Industries (1) Olin, Ines Q) American Cyanania Q) Freeport chem. (1) Conserve, Inc. (1)_—Olimy Tne (1) Miss. Chemical 1) Agricultural Prod. 2) olin, tne. (1) Allted Chemical Q) ON, L, Industries ()— Texasgulé @Q) Collier Carbon & Chemical Company Q) Stauffer Chemteal Q) NL. Indusertes (1) Allied Chenteal Co. (1) Standard 041 of cal. (1) Allied Chemical GQ) WR. Grace 1) _ American Seelting @) 6. F. Industries * ~ ‘and Refining Co. @) Texas Guilt Q) Miss. Chemteat (2) Agrico @) omeThe location and type of plants visited are listed below: No. of Plants ‘Type of Contact Acid Surveyed Plant, Location 2 Single Absorption without North Carolina ‘Tail Gas Cleanup 4 Single Absorption with Florida ‘Anmonia Scrubber 3 Single Absorption with Maryland Sodium Scrubber 3 Dual Absorption (1) Florida (2) North Carolina Q) Texas 12 ~ Total nunber of plants surveyed at the five (5) TYPE OF EMISSION CONTROL SYSTEMS The acid plants visited are listed in Table 2 using letter codes to protect the confidentiality of the plant data. This table indicates the types of emission control systems found at each plant. The information on plants "A" and "x" was furnished from EPA records as these two plants were not available for inspection. The data furnished on these two plants are helpful in this study even though the plants could not be visited. The two (2) single absorption plants (%,,M,) located in North Carolina have no tail gas cleaning systens. The single ab- sorption plants (K, T, Uj, U2) visited in Florida had ammonia Scrubbing systerts for tail gas cleanup. Plant "U,", also uses a mist eliminator on the downstream side of the ammonia scrubber. 40w ‘TABLE 2 ‘SUROUARY OF EMISSIONS FROM VARIOUS TYPES OF CONTACT SULFURIG ACID PLANTS SURVEYED DURING NORMAL OPERATIONS Code Letters @ ‘Type of Sulfur Bright Sulfur ‘type of Plant Dual H,80, (100%) Pro- 1600-1650 Guction Rate, tons/day Conversion Effictency Percent 99.7-99.9 StackyGas Rate, scfm x 10) 96-106.6 80, Entering Converter va. x 8.6-8.9 $0, Renoval Eff. % 99.7 502 Exiteed, 9 09 Von. 301-136 tbs per Ten _ 1.17-2.08 1b /sef x 10 160-2248 $0, Enitted, mgs0,/act Vo. % 80. 0.00009 pom (vol. } su, 0.9 ppm Mise Hy80, Scheced Yo./toh Abid 0.037-0.955 50, Mist. Renoval :fhetency 99.54 ng/sef 0.15-06-.03 Average $0, mg/scf 0.88, Average $03, ag/scf 0.65 Opacity % ° Local Standard N, Carolina 80, (new) 20it a Bright Sulfur Single 1565 97.44 0,56-6.15. +0004~,0059 4-59 98.3 5-10 N. Carolina 20/t M Dark Sulfur Single 1565 95.6% 7.0-8.0 98.0 1300-3300 17.4-44.2 1,0-30.55, 0:17-0.30 1700-3600 0,03-0.06 99.9 20-80 N. Carolina 270/T 8 Dark Sulfur Dual 1500-1800 99.75-99.85 85-105, 9.0 99.7 40-300 1,0-4.0 1,0-3.0 97.7 ° Florida 108/tey TABLE 2 (continued) SUMAiy OF Bt1$stovs FROM VARIOUS TYPES OF CONTACT SULFURIC ACID PLANTS SURVEYED DURING NORMAL CONDITONS Code Letters A Type of Sulfur Bright Sulfur Type of Plant Dual H,50,(100%) Produc- 1500-1510 Sot Rate, tons/day Conversion’ Eitiefency 99,00-89.9 Percent StackyGas Rate, scat x10 Entering Converter 9.39.4 1. 80, Resoval Eff. % 99.7 Sof Enttted, ppa by 170-400 van. tb. per ton Ib./sce x 10 S0,Eaitved, mgS0,/scf vob. 2 0 ppm (vol.} 50 wee is, bedecea 1b./ten Acta 480, Mist Removal Bettetency % mg/ecf Averaye 50, ng/act ‘Average 503° mg/act Opacity % 1 Local Standard Misotssippt 80, (new) 500 ppa (a) 2000 ppm (a) Dpap feed from snelter. x Bright & Dark Single 1100-1150 97.6-98.0 74.3 8.0 97.9 1600 34.96 99.5+ 3.10 Florida ict Y Sludge Acid & Sulfur Single with sodium serubbing 1000 98.0 8.0 90-92 30-200 +200-.224 +068-.087 99.5 Maryland 2000 ppm 30) Copper Ore Roaster $0, Dual 500 92.7-99.9 100.0 2-19 99.7 0.03-3110.2 Texas 250/Tey TABLE 2 (Continued) SUWMARY OF EMISSICNS FROM VARIOUS TYPES OF CONTACT SULFURIC ACID PLANTS SURVEYED DURING NORMAL OPERATIONS code Lettere 4 ‘type of Sulfur Dark Sulfur Type of Plant Single with ammonia scrubber & mar elim. H,$0, (1002) Produe~ Gof Rate, tons/itay 1000 Converaion Efficiency Percent 98.6-98.3 Stack Gas Razey ccf tt 31.6 50, Entering Converter van. 8.4 $0, Removal Eff. % 98.3 502 Eaitted, ppa by foi. 482-509 bs! per tong 16.6 1b. /acf x 10 50, Enieted vol. % $0. pp (vol.} $0. Mise #50, Enfeeed ib. /ton head 4,80, Mist Removal 98.0 Bettctency ag/act ‘Average 80>, ng/act ‘Average $03, ng/scf Opacity % o-Brink Local Standard Ploride $0, (nev) 10/t y Dark Sulfur Single with Ammonia serubbing, No mist eliminator, 1000 98.0 86.4 5.45-8.80 98.3 910-1900 12,2-25.4 1.43-3.00 Florida 20/8 kK Bright Sulfur Single with ammonia scrubbing 1300 98.99 83.4 8.0 98.0 500-1000 2.554 99.54 5-20 Florida 10/# t Sulfur Single with Aumsox Single with Amonia scrubbing 1000 63.0 63 7.5, 98.0 2100-2200 10-33 5-10 2.0 99.5 o-Brink Florida 10/8The single absorption plants located in Maryland ("Y") use sodium scrubbing systems. The process descriptions of the ammonia scrubbing system and the sodium scrubbing system are found in Section Iv, “Process Description". In the dual absorption plants (A,H,Q,J) the SO, emission con- trol is inherent in the process itself. Control of acid emissions is a complished through mist elimination devices incorporated in plant design. Section IV has further infor- mation on the emission control system found in the dual absorp- tion plants. EMISSIONS DATA OBTAINED ‘The emissions and operating data obtained during this study were supplied by most of the major sulfuric acid manufacturers that are locate in the United States. Emissions data was received from more than 65 percent of the new dual absorp- tion plants that were started up during 1974, ‘ablé 2 shows operating data and emissions asta from ail plants visited by the contractor plus datz on two plants (A,X) not visited by the contractor. Production rates are shown for each plant and the SO, emitted is shown in pounds of SO, per ton of 100 percent #50, produced. The acid miat enitted is Listed in terms of pounds of (100 percent) H,S0, mist per ton of 100 percent #,50, produced. The data in Table 2 were recorded during steady-state operations and serves as a basis for comparison to data obtained during upsets. 4aTable 3 lists data that were recorded at a dual absorption acia plant during a new source performance standards test conducted in 1974. This test was observed by EPA personnel and all emissions were well below the EPA standard. Figure 7 shows the relationship between the EPA standard emis- sion limit for SO, expressed as “pound per ton of 100 percent acid prodicea" and “parts per million by volume" in the stack gas for various 80, concentration inlet to the converter. The standard of “four pounds per ton" is marked. A similar rela~ tionship for acid mist is presented in Figure 8 comparing pound per ton" and "ng per scf*. This basic format witl be used to present much of the date from operating plants col- lected in the study. ‘The steady state data in Table 2 can be used for comparison to information obtained during plant malfunctions. A variety of malfunctions were observed and appropriate data concerning ‘these malfunctions are presented in Section VI - "Analysis of Process Variables and missions". Malfunction data ob- tained included many start-up conditions for single absorp- tion acid plants equipped with either ammonia scrubbers or sodium scrubbers, and for dual absorption acid plants. pata were obtained on a dual absorption acid plant (plant Q) show- ing the effect on $0, emissions of catalyst ageing, bu-ning bright and dark sulfur, loss of absorber acid concentration, and loss of sulfur feedstock. Data from plant "J" shows the effect of inlet $0, variations on $0, emissions, and converter 45TABLE 3 EPA NEW SOURCE PERFORMANCE STANDARDS TEST DATA DUAL ABSORPTION CONTACT ACID PLANT ‘@LANT "Q") a H,$0, (Acid Hist) 50 scfm ‘Wet ie/fon Acid = Wb/ef____tb/ ton Acid Sample #1 106,593 5.59 x 1077 0.055 1.65 x 10> 1.66 Sample #2 99,472 4.25 x10? 0.037 Lorx o> 1.42 Sample #3 96,262 5.€0 x 10-7 0.046 2.48 x10 2.06 46uw 80, Exit Gas Concentration ~ ppa by Voluse Sulfur Conversion - Percent of Feedstock Sulfur ani vii 10,000 1—! —. >, L vA, / : ttl 1.0 2.0 3.0 5.0 10.0 15 20 30 $0 200» 200 300 $00 1000 50, Entsstons ~ Lb Per Ton of 100% H,S0, Produced Figure 7av Acid Mist Concentration - MC HyS0, Per SCF 10. +01 EPA ACID MIST EMZSSTONSTANDARD FOR NEW CONIACT ACID PLANTS PERFORMANCE STANDARD ae PH SULFURIC ACID PLANT VOLUMEERLC AND 1 iaSs BUSSIONS OF ACID AUST A aOUS INLET $02 CONCENTRATIONS BY VOLUME if Tt tT PT 102.93 05 10 25,20 30 80202 Acid Miet Eniesions - Lb H,S0, Per Ton of 100% #,S0, Produced Figure 8malfunctions, on a dual absorption plant. Data were obtained from a single absorption plant equipped with an ammonia scrub- ber (plants K and U) showing the effecc on $0 emissions of PH control, specific gravity variations, effluent concentra tion variation from the ammonia scrubber, and deterioration of the scrubber packing. A single absorption acid plant with a sodium scrubber (plant ¥) was studied during a loss of pi control in the sodium svrubber, specific gravity variations, and evaporator plugging in the reclaiming system. The effect of these malfunctions on SO emissions is illustrated by the aata. An extensive study was made of the effect of downtime duration on SO, emissions during subsequent start-up. These data will be further analyzed in the next section to establish a criterion for converter reheat requirements with various shutdown periods.SECTION VI ANALYSIS OF PROCESS VARIABLES AND EMISSIONS NORMAL PLANT OPERATIONS The primary emphasis of this study is the relationship be- tween process variables and emissions from contact sulfuric acid plants operating in upset conditions. ‘The upset condi- tions have been classified as start-ups, shutdown, and mal- function or misoperation. In order to understand completely the nature of plant upset conditions and how the process variables effect emissions, it is necessary to review data obtained from plants in normal operation. The normal operating Gata were used to establish a basis for comparison with para~ meters during upset conditions. Converter Temperature Control ‘The most important parameter for controlling sulfuric acid converter efficiency are temperatures in the catalyst bed. In normal operation the temperature of each bed is controlled by adjusting the heat transfer in the heat exchangers between converter stages. In normal operation a range of temperatures of one to three percent is permitted for the inlet temperature to each bed. Deviation from this range of temperatures will reduce the conversion efficiency of the catalyst. when temp- eratures are controlled within this range a specific converter efficiency is expected for each stage. The summation of the efficiencies of each stage represents the overall conversion for the plant. ‘Typical converter temperature setpoints and 50Seandard Single Absorption Operating Conditions teste ty aed 0) Single Absorption ith Ate Quenching rature Conver Range of Temp. al x Dual Absorption Test Runa(4) wan ee -} 4 c aid "Fon, Pointe Range sion, 1 2 7 4 a. no aiss2s 77797425797 20° 170-830 795-797 800036 mus fo uu a: uu 00-109 tom oh ana se ie ta Tow. Bs m0 ets eID Ya 720 sma 35s mo ak ae taectog te Mowe meas ono too" sno-0 mews ss sete : te aetna soo am nossa som, 200 2k set a ve te Teme 47.38 soto sone ot toe gaan Slate Gane 5 cocierrerias ee 435-440 815-824 439822 800° 800-830 29832822 G BL ses taming 8) 880 sso __ au ws soto aw os Sint “2 SP eo = =e a oe Mice tn Temps UL 20 tg tots aT oak soo soe 8 8 4 Gamatattve Conversion oh sects vem eu tteing 27,0. 0 42400 nos asm 2 aoe or mw moms oan ewig 800 06 soos oes o ane w me ‘eet at = = alae 18 Zep. cae Ao 8 son stat non os Somacive os oh Ts sibs (rie Nigh value te based on « Reich ‘alue for actual plant operstion abould be 98.5%. it with an expected error of #12, eherefore theranges are given in Table 4A, This table also presents the expected conversion for each stage. Three major types of plants are included: single absorption, single absorption with air quenching, and dual absorption plants. As shown in Table 4A an overall conversion efficiency of 98 percent is anticipated from a single absorption plant. The addition of air quench to a single absorption plant will in~ crease the conversion efficiency to 99.5 percent. A dual absorption plant can obtain between 99.7 and 99.9 percent overall conversion efficiency. A series of five test runs on the dual absorption plant described in Table 4A shows the effect of catalyst bed inlet temperatures on the temperature rise across each bed and upon the conversion efficiency for each stage. This series of runs illustrates the need for close temperature control on catalyst bed inlet temperatures. The data presented in this table were obtained from previous zpA test. (4) A study was made to determine a quantitative relationship be- tween converter temperatures and SO, emissions in a dual ab- sorption acid plant. A multiple linear regression analysis Program was run using temperature and emission data from plant "J" during upset conditions to provide a wider range of temperature variations. An analysis was also performed on data taken from normal plant operations. ‘The relationships developed in the analysis will be presented in a later section. 52Several models were used in the regression analysis, with SO, as the dependent variable and converter temperatures as in- depent variables. Complete computer results of this analysis is contained in Appendix C. The analysis of normal operating conditions was run on 30 datz points selected at random from the plant "J" operating data. Six different regression models were used in an effort to establish correlation between SO, and temperatures. None of the correlations was significant. Tt is believed that the lack of significant correlation resulted from: (1) interdependency between temperatures, and (2) process parameters affecting S0, emissions that were not considered in the regression study. These variables include inlet 50, concentrations, sulfur furnace temperatures, and catalyst ageing. Because plant "J" is fed from a copper smelter and therefore has a highly variable imput concentra~ tion and flow rate, an additional regression analysis was per- formed on 31 random data points selected from normal operations from plant "Q". It was thought the more stable conditions of inlet concentration of S02 and other process variables might improve the correlation from the regression analysis. The correlations from this analysis were also included. after performing these two analysis it was concluded that a regres- Sion model of S02 emissions in terms of converter temperatures cannot be developed without additional data and study. 2 base case was established for operation of double absorption acid plants by running standard statistical analysis on 64 33random data points selected from normal operation of plant "J", This study was performed in an effort to confirm the information presented in Table 4A derived from a variety of sources of data. The results of the study on plant "J" ii dicates that if the eight converter temperatures are controlled within a specified range, the S0, emissions will be between zero and 307 ppm. The results of this study were highly significant and compared favorably to data presented in Table 4A, The results of this study are presented in Table 4B. To further confirm the converter temperature ranges for nor- mal SO, emissions 13 data points were selected from the data for plant "J" during times of high $0, emissions. Standard statistical analysis was performed on these data points and the mean temperatures calculated. Table 4C compares the mean temperatures from the normal run analysis and those from the off-normal analysis. ‘he converter temperatures during up- sets were consistently below the mean operating temperature for normal operations and generally fell outside of the acceptable range. The statistical analysis comparing converter temperatures and SO, emissions confirms the data presented in Table 4A and clearly establishes the important relationships between these Parameters. Some variation in acceptable temperature range will occur between plants because of variation in catalyst activity and types of catalysts. ‘These data should be a gcod indication, however, of the acceptable ranges for modern dual 54ss TARLE 4B CONVERTER TEMPERATURE AND SO, OUTLET CONCENTRATION PLANT "5" ~ UPSET CONDITIONS vartabze "oy batestone (pes) ¥ (ppm) $0, Exhaust Stack a7 1678 Mean Temperature (°F) X, (°F) Inlet ~ Ist Converter Bed 824.0 315.0 X, (F) Outlet ~ et Converter Bed 1040.9 1006.5 % (F) Inlet - 2nd Converter Bed 837.0 aii.s X, @F) outlet! tnd converter ted 892.0 a41.0 X, (i Inlet ~ 3rd Converter Bed 786.0 72.5 Xe (OF) Outiee ~ 3rd Converter Bed 791.0 79.0 X, CF) talet ~ 4th Converter Bed 762.0 702.0 Xq (°F) Outlet - 4th Converter Bed 762.0 707.09s TABLE 4¢ CONVERTER TEMPERATURES AND $0, OUTLET CONCENTRATION PLANT "J" NORMAL OPERATION Range Vartable 50, Emtsetons (pp) (v1) pe 80, Extaust Stack 427 0-307 Temperatures °F) (1) Temp (°F) Inlet - 1st Converter Bed 824 810-838 (2) Teap (°F) Outlet ~ 1st Converter B 1041 948-1133 (3) Temp (°F) Inlet - 2nd Converter Red 837 891-855, (X4) Teap (°F) Outlet - 2nd Converter Bed 892 611-973, (45) Teap (°F) Inlet - 3rd Converter Bed 786 734-838 (X6) Temp (°F) Outlet - 3rd Converter Bed 7 737-845 (X7) Temp (°F) Inlet ~ 4th Converter Bed 762 704-820 (8) Teap (°F) Outlet - 4th Converter Bed 762 702-822$0, tate cae oncantcaton pe by Yoke 10,009 3,00 00 388 8 NORMAL RANGE OF CPERATION OF SINGLE ABSORPTION AND DUAL ABSORPTION ACID PLANTS AS FOUND IN THIS STUDY Single Absorption Acidt Plant Operating Range PERFORMANCE STAYDARD. i New Dual Absorption: Operating Range cttr tre cot Figure 9 87TABLE 5 PLANT "Xx" TEST DATA Conversion Tons Average We. 2 S02 We. 250, Ef fictency Per Day Opacity Inlet ppm) Outlet (pfs) Percent Production Percent 1 9.8 0.20 97.6 1025 ° 2 9.8 0.20 97.6 1048 2.0 3 95 0.26 98.9 1049 9.5 4 9.2 0.20 97.6 1039 os 5 10.0 0.17 97.9 1049 5.0 6 9.8 0.18 97.8 1028 25 7 10.0 0.38 97.8 2078 25 58absorption plants equipped with the newer types of catalyst. Single Absorption Plants ‘The basic sulfuric acid producing plant for many years has been the single absorption type. This type plant has a long history of operation in contrast to the dual absorption plant and consequently a large amount of data are available. Even though the single absorption plant will not meet EPA standards (see Figure 9) it is importaat as a basis for studying the application of tailgas cleaning systems to single absorption plants and for supplementing data obtained from dual absorp tion plants. Plant X shown in Table 2 of Section VI was selected as a typ- ical single absorption plant to illustrate the 80, emissions and converter efficiency for this type of plant. The 50, con- version data, daily production rate, and opacity of the vent gas for plant X is shown in Table 5. This 1,000 ton per day acid plant was operating far in excess of allowable SO, emis- sion standards and at times in violation of opacity standards. ‘The SO, emissions from plant X as shown in Table 5 fall within the range of SO, emissions for all single absorption plants studicd. The S0, emissions ranged from 30 to 60 pounds per ton of 100 percent sulfuric acid produced. Acid mist emissions originate from three separate sources. Because of the different form of the acid mist from these three sources, special provisions must be made for measuring 59the quantity of each type of mist emitted. Table 6 illustrates the amount of acid mist occurring in each of these types as measured by three separate analytical procedures. In the series of five tests shown, the EPA standard measurement method measures only the entrained acid carried over from the absorber. The results from this method are lower than those obtained using the special Monsanto method that measures, in addition to absorber carry-over the fine particulate acid mist formed in the absorber and $0, passing throtgh the ab- sorber. A comparison of the standard and special methods will show the standard method will always yield a result that is lower than the special method. In this particular single absorption acid plant located in the Northeastern United States, the acid mist standards were not violated, even when applying the special analysis method. These data were furnished from an EPA performance test. (5) Though the single absorption acid plant shown in Table 6 could meet the acid mist standard, data from plant "U" covered in this study indicate that this plant cannot meet the acid mist standard. Data plotted in Figure 10 shows monthly averages of acid mist emissions over a period of six years. None of the points plotted fallwithin the performance standard. This @ata illustrates the need for special equipment to control acid mist emissions regardless of the type of plant considered. As a contrast to data shown in Figure 9, Table 7 shows a sum- 60~ TABLE 6 AcIp MIST TEST (5) (DATA FURNISHED BY EPA) Eatesion Stack Gas 1b 1,50, Production tbs 1504 Ton of Acid Flownace per ef 2s 1,50, "Tono/bey Retsoton Standhed® " Specter Test scfm x 10-7 per cf (,80,) Ibs H,S0,/Day Method Method 1A 20,737 5.37 0.226 185 0.087 iB 229 0.096 16 0.12 2A 20,386 4.60 0.208 us 0.077 2 0:30 0.061 2 ais 0.055, oat ak 20,958 4.40 0,200 15 0.076 3B 0:78 0.036 36 0:96 0.043 out 4a 20,506 ahs 0.202 193 0.068 ry 0.82 0.037 rr 0:97 0.044 0.10 sk 20,549 4.57 0.207 193 0.070 33 0:96 0.043 5c 0:90 0.041 0.102° Acid Mist Concentration - MG HyS0, Per SCF +01 Monthly Variations in Acid Mist Emission Over th Past Six Yea (Plant Uj, Bright Sulfur Burned in a Single adsorption Contact Acid Plant) PERFORMANCE STANDARD SULFURIC ACID PLANT VOLUMETRIC AND MASS EMISSIONS OF ACID MIST AT VARLOUS| INLET $07 CONCENTRATIONS BY VOLUME 02 03 05° 20.25.20 30 501.0 203 AciA Mist Ta sions ~ Lb H,S0, Per Ton of 100% H,S0, Produced Figure 108 aatative Acid viet, Opactty, guy. Maidity, Sty heptane Toph MGM: tte coments - © SO Matar Place Lindesy WJ. mertean Dark $ pri o on Grom followed ono ee 8 (Corporation aioe ooo 860 Pealebere, RJ. Olin Corp. Siagte Ae. + = ry setae 7 = ok 0, Scrubber = = =f = ow oes 8 = bo = 0 8 = 0 8 Widuaberh, HJ. Allied Ghenteal peat Sina oy = © OSS «N/A Chews alee Corporation AEG, s Mietrpeton Byte! 09 Ce 6 ne osecn 8 Se art zs Cd ea eT tae ela Be age ae oa ss ‘Tinden, WT. boFaat, Craanel 1. ighe 8 Single Woe "Fea Ta bad = oor TaNBeER TT ones tapas bark SH A eee = 3s a Beepatar, WS. —buteot, Chaabere task 8 Siagia abe; ——foralos = Ta as Sorts Seasies Tea ‘Ailted Chestead Single Ti Mi series =e eT WTO Wein sears ‘Corporation followed oy ey be leaking. Z We eter plas.mary of acid plants tested by EPA that will generally meet the acid mist performance standards. All these plants were burning spent acid or dark sulfur, contributing to an increased acid mist evolution. A review of the acid mist emissions and opacity for these plants shows that the application of a packed fiber filter (Brink) will eliminate all acid mist carry-over contributing to opacity. In two cases, plants equipped with filters packed with pebbles or Intalox saddles had a vent gas stream with opacity of 30 to 40 percent. ‘This type of packed bea has a low removal efficiency for the very small particle size of the acid mist. ‘The Newell, Pennsylvania plant was equipped with a Brink filter and had an opacity reading of 10 to 20 percent. The high opacity reading in the vent gas probably indicated the Brink filter was leaking. An important conclusion that can be drawn from the data of Table 7 is that a single absorption acid plant equipped with a vent gas clean- ing system must also be equipped with an efficient filter for eliminating acid mist and high opacity in the vent gas. Single Absorption Plants with Gas Cleaning Systems ‘The need for acid mist filters on a single absorption plant equipped with a vent gas cleaning system was indicated in the previous paragraph and in Table 7. It has also been pre~ viously indicated that the single absorption plant cannot reach the 50, emissions standards without provisions for re- moving So, from the vent gas. When a single absorption plant, however, is equipped with 64proper acid mist filters and an efficient vent gas cleaning system, both the SO, and acid mist performance standards can be met. Data obtained in our study from plant "Y" is shown in Table 8. Plant "Y" is a single absorption acid plant equipped with a sodium scrubber system and acid mist entrain- ment filters. As indicated in Table 8 this plant in normal operation can reach an SO, emission level of 2.59 pounds per ton and an acid mist emission level of .043 pounds per ton. In a series of three tests, Test 1 was discarded because of possible sampling equipment failure. Test 3 was run at a higher gas flow rate than Test 2 and produced acid mist emis- sions equal to the performance standard of .05 pounds per ton. Although the tendency toward increased acid mist emissions at higher gas rates is expected, the cause and effect relation- ship of this data cannot be substantiated. Dual Absorption Plants The primary difference between the single absorption acid plant and the dual absorption plant is the installation of a primary absorber following the third catalyst bed. A primary absorber in this location reduces the S0, concentration of the gas entering the fourth catalyst stage. Removing sO, from this gas permits a higher driving force in the fourth converter stage to shift the conversion equilibrium in the direction of more SO, formation, The effect of the primary absorber on overall conversion efficiency is illustrated in Table 9. 6599 ‘TABLE 8 EPA PERFORMANCE TEST RESULTS FOR SO) AND ACID MIST EMISSION CONTROL EFFECTIVENESS FROM SODIUM SCRUBBER (PLant "y") 3 + Acta Mist Production (Outlet) Gas Flow Rate 50, (Outlet) #80, 80, 1,50, Test Nos (scrH) (fons/Dey) PPM” tb/Ton ont abso) = 48/TEn) 2 35,261 730 250 2.59 2.26 0.279 0.063 3 36,292 730 227 2.85 7.79 0,965 0.162wg Converter Feed Cas Vol. % 50, 97% Conversion a To First Absorber Vol. % $0, TARLE 9 EFFECT OF PRIMARY ABSORBER IN THE DUAL ABSORPTION PROCESS PLANT "Q") 18 100 mols Feed Gas at 9.0% $0, and 12% 0,) ~O.aT 635 :73 79.0 Overall Conversion Efficiency 99.91% 9.00 12.00 0 79.0 200.00 73-4365 48.73 Oa 65 5 0 0-873 0 =8.730 to'Fourth Catalyst Vol. % $0, 0.270 7.635 079.0 86.905 97% Conversion 20.262 -0.131_+0.262 O=0.131 To Final Absosber Wil. % 80, 0-008 7-504 0-262 19.0 86.774 0 00.262 o__ ~0.262 ToPExtt Stack 9.008 7.504 079.0 86.512 Volume, % $0, 0081 Volume, ppn’so, a1 2700 2700 a a1As indicated in Table 9, the S0, to SO, conversion in the first three sections of the catalyst converter reaches a total of 97 percent. If this gas were sent directly to the fourth catalyst bed an additional conversion of 1.3 percent could be expected as indicated in the review of the single absorption plant presented in Table 4Aof Sectivr VI. This will give an overall conversion efficiency for a single absorption plant of 98.3 percent. ‘The addition of the primary absorber after the third catalyst stage, however, will reduce the $0, concentration in the gas entering the fourth catalyst bed to essentially zero. The renaining 80, can now be converted in the fourth catalyst stage =o an additional extent of 3.8 percent (based on origi- nal $0, present) providing an overall conversion efficiency 99.91 percent. This high overall conversion efficiency reduces the $0, concentration in the vent gas to less than 100 ppm. The result of this increased S0, conversion efficiency can be seen in test data obtained from plant "Q". These data presented in Table 10 show results of three performance test runs mea- suring 50, and acid mist emissions. During these tests the plant was operating somewhat higher than design capacity, as indicated by the omission results based upon actual production rates and design production rates. Comparison to the perfor- Pance standards indicates the plant was operating well below the standards at all times. 68‘TABLE 10 SUMMARY OF TEST RESULTS FROM DUAL ABSORPTION ysed on actual production Based on design rate Based on actual production adjusted for higher in- stack monitor readings Acid Mist Emissions, 1b/ton Based on actual production Based on design rate 27 2.056 0.057 69 1.43 1.52 1.86 0.037 0.039 2.06 2.28 2.85 0.046 0.081 NsPs 4.0 4.0 ous 0.15Plant "Q" was typical of all dual absorption plants in normal operation. The range of SO, emissions from all plants studied was presented in Figure 9 (Page 57) in the preceding section on single absorption plants. This figure also shows the range of emissions from dual absorption plants. Plant "Q" falls approximately mid-way in this range. This figure also illu- strates that essentielly all the data obtained from dual absorp~ tion plants for SO, emissicas fall below the performance stand- ard limit. Figure 1) further illustrates the $0, emissions from single and douole absorption plants operating under normal conditions. In addition to showing the minimum, maximum, and average emis- sions for the single absorption and double absorption plants, Figure 11 also indicates the range of emissions experienced during initial operaticn of new plants. During the initial operation of a new plant in good operating order, the SO, emis-, sions will fall between 1.5 and two pounds per ton of 106 per- cent sulfuric acid produced. Another important fact illuctrated ty Figure 11 is the effect of higher concentration cf $0, entering the converter of the Gouble absorption plant (eight to ten percent). For a single absorption plant the maximum S0, concentration in the feed gas to the converter was eight percent. High 0, feed concen- trations and higher conversion efficiencies both promote in creased production from the dual absorption acid plant and more efficient and economical overall operation. 70‘Sulfur Conversion - Percent of Feedatock Sulfur E ! 6.0 92.! 99.92 99,7 9.0 98.0 92.9 10,000 5,000 3,000 | START-UP DAP.1.0 -~ 2.0 Lus/T™ 2,000 4,500 PERFORMANCT. STANDARD 1,000 | NEW PLANT CONDITION AFTER 500 NORMAL OPERATING RANGE FOR DUAL ABSORPTION AND SINGLE 300 ABSORPTION ACTD PLANTS Aaseaians 209 rade an 150 wu 50, Exit Gas Concentration ~ ppa by Volune 200 o 2.0 3.0) 5.0 10.0 15 20 30 50, 100 © 200 300 S00 1000 80, Balasions - Lb Per Ten of 109% H,S0, Produced ‘THE NORMAL OPERATING RANGE FOR DUAL ABSORPTION PLANT Figure 11 ‘THE HORMAL OPERATING RANGE FOR SINGLE ABSORPTION PLANTSHUTDOWN OPERATION The operation of shutting down a contact sulfuric acid plant does not necessarily produce $0, cr acid mist emissions in ex- cess of performunce standards. If the proper shutdown procedure is followed, nost emissions associated with the shutdown ori- ginate froma malfunction or upset that is algo the cause of shutdown. The most important aspect of the stutdown procedure ie preparation of the plant for subsequent start-up to minamize start-up emissions. In this section we discuss shutdown operations as they affect emissions on the start-up of a dual absorption acid plant. Our primary attention is applied to the length of the shutdown period compared to emissions on restarting the plant. The data obtained frou most of the plants studied did not con- tain a sufficient number of shutdoim operations to provide a basis for statistical analysis of shutdowm duration compared to start-up emissions. Data from plant "J", however, was collecied over a long pericd of time including many shutdown and start-up operations. The monitoring program fer plant "3" froa which the data was extrected covered a pericd of 5,038 hours or 212 days.'7) puring this period of time the acid plant vas in operation for a total of 190 days or 90 percent of the time period. After accounting for periods of inoperation of the plant and emission monitoring instrumentation, data vere collected during 86 percent of the period of the monitoring Program. The monitoring instrumentation recorded one reading Rfor each process parameter every three minutes. At the end of each 15 minute interval the average of the previous five readings was computed. These fifteen minute averages were used as the basic data points for analyzing the performance of the plant. During this period of operation, data for 23 start-ups were obtained after plant shutdowns ranging from 30 minutes to five days. To simplify the analysis for the plant shutdowns, shutdown periods were divided according to duration of the shutdown in categories of less than one hour, one to two hours, two to six hours, six to ten hour, 10 to 15 hours and over 15 hours. The sulfur dioxide emissions from the plant during start-up from the beginning of the start-up operation through the sixth hour after start-up operations began, were plotted against time using a linear regression analysis program on a computer. The sulfur dioxide emissions were used as the dependent variable and operation time as the independent variable. Regression curves were plotted by the computer averaging all the data points in each category on each hour of operation during the start-up period. A summary of these regression plots is presented in Table 11. A review of Table1l shows that data from two to six start- up operations were included in each of the six categories. In the “less than ore hour", category where only two start-ups were obse-ved, the confidence level of the results is quite low. For those categories containing larger numbers of 3be TABLE 11 ‘THE EFFECT OF DOWNTIME SHUTDOWN DURATIONS UPON EFFLUENT $0, CONCENTRATIONS (VOL. ppm) DURING START-UP wy (FOR PLANT Shutdown Duration Peak 50,3 ppm ours to reach —Nunber of Reading at Sth Hours During Stareup 300 ppm $0, Startup Cases _‘Hour_(50,-ppm) <1 1s ~ 2 64 1-2 520 ~ 5 123 2-6 1,920 os 3 350 6-10 31,600 3.50 3 25 19-15 2,250 4.80 4 400 1s 2,970 5.70 6 19start-ups a greater confidence level can be assigned. Con- sidered as a total analysis the results have high significance. Comparison of the "hours to reach 300 ppm” for each category indicates the operation time to compliance with the standards increases with increased duration of shutdown. This time curve flattens, however, at approvimately six hours, indicating that with normal start-up operations all plants should be able to come within compliance within six hours. Tt is also apparent that the longer the shutdown period, the higher the peak SC, emissions during the start-up operation, This analysis shows that most of the start-up operations approached 300 ppm at the fourth hour, indicating that most plants can be started up within four hours with S0, concentration reduced to the performance standards regardless of the length of the shut- down duration. The start-up analysis provided hece must be evaluated in terms of the type of plant providing the operational data. Plant "g" is a sulfuric acid plant using the dual absorption design with So, feed from a copper smelter. Because of the nature of the S0, feed, concentration of S0, entering the converter varies from 1.6 to 19 peccent. Also, the start-up of the acid plant is dependent upon start-up problems within the smelter, giving a much wider variation in start-up conditions than wouid be expected from the same type of plant operating with elemental sulfur feed. ‘The peak SO, concentration reached during start- up is probably the parameter most affected by the variation in start-up conditions of the smelter. 78' CO"IQUAL ABSORPTION AVERAGE EMISSIONS AFTER START-UP - 1 Ieoo 1700 l6co 1500: 1400] 13004 N 3 6 110. RRM. EXIT STACK 8 6 SO s 3 6 READING HOURS AFTER START-UP Figure 12 16ue Fig. No. 25 26 27 8 29 30 31 2 33 34 35 38 37 38 39 40 aL Type of Plant SRRERESE ‘TABLE 12 SUMMARY OF START-UP OPERATIONAL DATA ON DUAL (DAP) AND SINGLE (SAP) ABSORPTION ACID PLANTS FOR FIGURES 25 THROUGH 41 Downtime Duration (ours: x Incomplete Data 1.0 160-0 Tine Roguired Tine TerReach $0, Enlesions ‘Normal “exceeded Peak Operating EPA Standard $0, ievel ‘of 300 pom Entsdions 6.5 3.0 1800 25 20 3500 55 us 1600 io 510 1200 50 wo 1590 eo 20 700 3.0 20 2000 : 7 4000 Scrubber Down for 28 houra = Plant not in Compliance at Anytine 1.0 2900 15.0 2300 33 2400 70 3100 60 3100 3.0 3500 20 350 Ls 2200 512 3000To provide a more realistic presentation of the start-up data for the 23 cases presented in Table 11, arithmetic averages of 80, concentration tor each hour of start-up within each cate- gory of downtime were plotted on Figure 12. ‘The use of arith- metic averages and time plots show the cyclic nature of most plant start-up operations and the increase in maximum SO, con- centration with increased shutdown duration period. This plot also shows that most shutdown and start-up cycles will provide SO, emissions below EPA standards within six hours. With Ue amception of very lang shutdowns, exceeding ten house, the plant can be brought to compliance within about four hours. ‘The four hour shutdown-period-breakpoint for heat conservation and restart without reheating the plant is also illustrated by this curve. The EPA standard of 360 ppm for a 10 percent inlet S0, concentration is shown. This is typical for dual absorption acid plants but may be high for a plant fed from @ copper smelter. Concentrations of S0, during start-up were obtained for most of the dual absorption plants studied, providing data from a variety of plants in a variety of shutdown end start-up conditions. 80, concentration was plotted against time at the beginning of the start-up operation for each of these data sets. This information is presented of Figures 25 throagh 41 included in Appendix 8. These figures are summarized in Table 12. ‘The data, taken from plants burning elemental sulfur and using the dual absoxption process, generally confirm the in- formation obtained from the regression analysis on plant 18A general sunmation of all of the plant start-up data indi- cates most plants can reach compliance within four hours regardless of the shutdown period, and essentially all plants can be below 300 ppm after ix hours of start-up operations. Also verified is the four-hour maximum shutdown duretion be- fore reheat of the converter is required to insure SO, emis~ sions of less than 300 ppm during the start-up operations. These data and conclusions apply to typical sulfuric acid plants in normal operation with no special precautions for minimizing SO, emissions (such as maintaining low production rates during initial operation periods or using heat and hot concentrated acid from associated plants to assist in the start-up operation). This data also include the occurrence of normal upsets and equipment failures during the start-up operation resulting in higher $0, emissions during some opera~ tions. START-UP OPERATIONS Single Absorption Plants During the course of this study data were not collected on single absorption contac. acid plants unless they were equipped with a vent gas cleaning system permitting them to meet emis- sions standards. Understanding of the start-up procedure on a single absorption plant, however, is inportant to the evalua~ tion of the operation of the vent gas cleaning systems. Start- up data from two identical single absorption acid plants (Plants Wy and U2) is shown in Tables 13 and 14, and 15 and 16 respec- tively in the next_section (page 61). cz)A review of converter temperatures tabulated for these plants indicates that all temperatures were controlled acceptably during the entire start-up opera’ fons. One variation in temp eratures, however, occurred that might be considered a cause of higk SO, emissiors. As shown in Tables 15 and 16, the peak emissions of S0, from plant U, occurred at a point where the inlet temperature of the catalyst mass B was also at a peak. ‘The outlet temperature for macs B in the preceding reading was also hich indicating thiv temperature was some- what out of control. Since insufficient data were available from these plants to run a statistical analysis, conclusive relationships between catalyst bed temperatures and SO, emis- sions cannot be established. A general evaluation of this plant operation, however, indicates that the peak So, occurred approximately two hours after start-up, which is normal for a single absorption plant of this type. A review of furnace temperatures for plant U, presented in Table 13 indicates full sulfur feed to the furnace was not established until approximately five hours into the start-up operation: A reduction of $0, entering the converter contri buted to the relatively low concentration of S0, emissions fron this plant during this start-up. If full sulfur feed had been applied to the furnace at the beginning of the start- up operation, 0, concentration exit the ahsorber tower would have reached approximately 4,000 ppm rather than the 3,000 ppm experienced. 80w suaxt-oe TmeEMATURES FoR FLU “U," SINGLE ABSORPTION ACID PLANT WITH AREWTA BoRUBBER etd Temperature Pocaege Mosler A= Mans A= Haas Do tace c= Nase C= ene DNase D- nase 7:7 Act ete Absorption Hioe_teme "Bett Eater Eat’ _Socemee_° bate c_” bele tater te Toe. 43 mo az rrr ne ae Stoo nip ona 2 eS DR stk a 200 ose ta mae 20 ino ae a io. De ae a 200 ie am Ho ue & a0 az ie oe Bb ae og a ua ene is a sD in OD ia 4 ie in oe ite ine oe He oe ne ae he v0 ao oe Hy in) 8s a ams a som 0 206 a 3 1100 30 ioe Be oo Lio aS aos Bi co 1036 a ioe Bt yorts A11 Temperstures are 8 °F.zs TABLE 14 START-UP PLANT "U,' AMMONTA SCHUSSLR CONDITIONS AND E x 50, Entrancé to Converter MH TONS. x so2 Absorbing Towerce 50, Extt Gas Concentration ~ pya by Volune Sulfur Conversion - Percent Feedstock Sulfur 99.7 99.0 98.0 10,000 5,000 3,000 2,000 1,500 11,000 500 300 200 150 109 96.0 92.9 ve t ia} = HH tit iH + { i 4—4 + { eo i 4 4 [EXAMPLE OF 0, EMISSIONS DURING START-UP OF SINGLE ABSORPTION ACID PLANT VS. SINGLE ABSORPTION ‘ACID PLANT WITH COMILICOMTYPE (| ‘AYMONTA SCRUBBER PLANT Up 2.0 3.0 5.0 10,0 15 20 30 50 100-200 300 500-1000 $0, Eatesions ~ Lb Per Ton of 100% 1,50, Produced Figure 13The only operating parameter for plant U, that seems to be abnormal is the temperature of the acid in the absorber. This temperature is somewhat higher than normal, possibly in- dicating a shortage of cooling water for the acid coolers in the absorption system. This high temperature possibly con- tributed to an increase in acid mist emissions although con- firmation of this fact is not available in the data. Single Absorption Plant with Vent Gas Cleaning Systems Plants U, and U, described in the previous section are equipped with ammonia scrubber vent gas cleaning systems. Extensive data were obtained from these two plants in various modes of operation. ‘The temperature profile across plant U, is pre- sented in Table 13 while absorber operating conditions are presented in Table 14. The performance of the ammonia scrubber applied to plant U, is illustrated in Figure 13. A significant feature of Figure 13 is the illustration of con- stant SO concentration from the ammonia scrubber in terms of parts per million by volume over a range of scrubber inlet 0, concentration of 1,900 ppm to 3,350 ppm. This comparison illustrates the lack of precision in defining S0, emissions on the basis of ppm in the vent gas. When calculated in terms of pounds of S0, per ton of acid produced the output from the ammonia scrubber varied from 3.5 to 10 pounds per ton. SO, emissions presented in mass units much more clearly illustrate the effect of variable input concentrations of SO, to the ammonia scrubber. Although plant U, showed a performance of 845.5 to 10 pounds of SO, per ton of acid produced, this plant is capable of producing vent gas containing less than four pounds per ton during periods of careful operation and no malfuaction. Start-up data for plant U, is presented in Table 15 and 16, with ammonia scrubber performance in Figure 14. Plant U, is identi- cal to plant Uj, and comparison of temperature profile across the plant and the $0, concentration differential across the converter indicates the two acid plants were opercting in very similar manner. Comparison of the SO, emissions from the ammonia scrubber, however, indicates a great difference in operation between the scrubbers on plants, and plant U2. During the start-up operation of plant Uz the vent gas booster blower used in conjunction with the Brink fiiter in the scrub- ber outlet was not in operation. This blower was shutdown because of lack of steam for driving the turbine. with the blower shutdown and the Brink filter bypassed, a very dense plume of particulate matter was being emitted from the ammonia scrubber. Since all process parameters for the two scrubber systems are similar except for the SO, emitted, the only explanation for the difference in SO, emissions is error in the S0, analysis, The SO, was analyzed in this start-up using the Reich test. If the gas sample collected for the $0, analysis were insufficiently filtered it would contain quantities of ammonium bisulfite and ammonium sulfite parti- culate, that interferes with the $0, analysis producing a 8s98 TABLE 15 ‘START-UP TEMPERATURE CONTACT ACID PLANT U, SINGLE ABSORPTION PLANT WITH AMMONIA SCRUSEER tass mass mass mass otler 2 c D Inlet held Intec Tine Exit’ Entrance Exie Entrance Exit Entrance Exit Enrrance Exit To Scrubber Temperature 6:00 503629, 810.60 73K— 738 BK_C( (HID ers 58064078 HGCC( LST 733 6H 139 G00 ey ss eset 159 6:45 HOt aso 7s a7 ess lt, tee ce 1864 7:00 57607292 OBB 93182 186 71s $90 -760.«= 080.733.1000 900 878 «8K6 (80 197 7:30 602 78L_= 983762 87B_SBKS LDS 888 202 7:65 606 021080 822_—«BUS. 79S 88S 808 82H 208 8:00 609 14-95 69906 SLB 92h 200 22 8:15 612 «8H NG BKB BK 80S 88H 203 2s 8:30 615 819,32 8569868908 BLL BH 206 as aus 615 ste 982 8839266204 208 Oe 203 G7* TERBEPATURES ARE TH °Fry TABLE 16 AMMONIA SCRUBBER CONDITIONS AND EMISSIONS DURING ACID PLANT START-UP ON PLANT (COMINCO SCURBBER WITH MIST ELIMINATOR) Entrance to Absorbing Re fiuent Converter Tower Exit outlet 250, 450, 118 6.45 = 15 aa 8.8 190 8.3 152 8.55 : 128 0.55 128 8.65 128 85 sn10 9.0 +103 096 snoAn Example of a Single Absorption Plant "U2" Entering and Leaving : Malfunction Operating Coniitions SULFUR CONVERSTO! - PERCENT OF FEEDSTOCK SULFUR 99.7 99.0 98.0 97.0 96.0 95.9 9 9 —* SULFURIC ACT) PLANT FEEDSTOCK SULFUR.. ‘CONVERSION VS, VOLUMETRIC AND MASS S02 EMISSIONS AT VARIOUS INLET $0, CONCENTRATIONS BY VOLUME Input to Cominec Output of Coninco Enissio NCE_STASDARD Soy EXIT GAS CONCENTRATION — PP BY VOLUME PERF 1 2 3 4 5 6 7 8 a ee ees EEE) Tsao as boc 50 G70 80 90100 802 EMISSIONS LB. PER TON OF 100% 1,50, PRODUCED Figure 14 Not Numbers represent clock time sequence. 88higher result. ‘This explanation for the high So, emissions cannot be verified at this point, but appears to be the most logical explanation. 1n addicion the SO, emissions from the scrubber from plant U, do not show the same degree of varia~ tions with changes in scrubber input S0, concentrations as seen in data from plant U,. This fact may be an indication the particulate matter is masking the true S0, concentration in the vent gas. Dual Absorption Plants It has been previously stated that the dual absorption plants can be started up without exceeding $0, emissions by careful attention to procedures and process control, and if malfunc- tions of equipment and control instruments do not occur. This type of start-up, however, requires up to five days of prepara~ tion time, and process equipment and instrumentation do not always perform properly after a shutdown period. A preheat syle for a dual absorption acid plant not equipped with auxiliary heaters is shown in Figure 15. During this preheat cycle all of the heat for preheating the converter is obtained by firing fuel in the sulfur furnace. Since the maximum temp- erature of the sulfur furnace is 1,500F, fuel must be burned in the furnace in a cyclic manner to prevent overheating the furnace. The off-on control of heating in the furnace permits adjustment of the heating rate of each catalyst bed. Because of the thermal lag throughout the converter, the first catalyst bed is heated in a cyclic manner reflecting the off-on cycles 89COLD START-UP OF TYPICAL DUAL ABSORPTION ACID SLAiT 72" LEGEND 4TH 820 a FURNACE TEMP ‘F ; CONVERTER TEMP. °F | 5 i 4 time iN pays? 7 Figure 15in the furnace, while the fcurth catalyst bed heats at a slow rate continuing for a period up to five days. If sulfur feed to the furnace is started before the fourth catalyst bed reaches operating temperature, incomplete conversion will take place in this bed causing high emissions of S0, from the absorber. Because of lost production resulting from the slow preheating procedure, preheat is often reduced and sulfur feed begun before proper temperature is obtained in the fourth bed. ‘This is the primary cause of high SO, emissions from a sulfuric acid plant during the initial one to two hours of start-up operations. Once $0, is admitted to the converter the exothermic oxidation in the converter will quickly bring the catalyst bed to operating temperature, reducing the $0, emissions to a more normal level. Another cause of high SO, emissions during stert-up operations is operation of the sulfur furnace at full sulfur feed rates from the beginning of the start-up procedures and before catalyst bed temperatures have stabilized. These emissions on start-up can be reduced by initiating sulfur flow at re~ duced rates until proper operating temperatures in all catalyst beds have been obt: ned. A typical dual absorption plant start-up will produce $0, enis- sions with a peak value of up to 3,000 ppm at one to two hours after start-up. Emissions will normally be in excess of per- formance standards for a period of two to four hours after the beginning of sulfur feed. This range and duration of 2emissions will normally occur during start-up operations fol- lowing a shutdown period of more than four hours. This is primarily due to the lack of adequate preheating time when converter temperatures have fallen below permissible limits. ‘These start-up relationships are shown in Figure 12, discussed in the previous section. ‘The complete history of SO, emissions for a dual absorption plant (Plant "Q") cons:dered typical during start-vp opera- eSef€ns is shown in Figure 16. This curve indicates that the Plant was started up w:th maximum sO, concentration feed to the absorber, with a peak $0, emission reached in approxi~ mately two hours after start-up began. At this point the sul- fur feed concentration was reduced, causing the S0, emission to fall from 1,500 ppm to 600 ppm. The $0, feed concentration was again slowly increased as the converter stabilized, and emissions continued to drop to 200 ppm at normal S02 concen tration in the feed. At this point the unit was operating at a total emission of 2.4 pounds per ton of FH, 70, produced. An attempt was made to establish a statistical model for start- up emissions in terms of converter temperatures using data from plant "J" start-ups. A standard statistical analysis Of these same thirteen data points was presented in Table 5B as compared to normal data. The regression analysis gcve Correlations that could not be considered significant, for the same reason discussed in the section on normal operating data, In addition, the inability of the catalyst masses to 92ae i Be 8 eeaed $0 EXE GAS CONCENTRATION = PP BY VOLUME & eee 50, pussiats - ». g8.0_ sre SWLAVRIC ACID naz FEEDSTOCK. SULFUR ORERSION WS. VOLIMETEIC ano ta58 Sty BnUssions a7 vaRIOUS TMUET 80; ‘OnicEereATIonS Br YOUN - x TO OF 100% #04, PRODLCED 56.0 95.0. 92.9follow sudden changes in SO, inlet concentrations causes a displacement in the temperature--30, emissions relationship during the transient conditions of start-up. An acceptable model of the catalyst operation during start-up must include factors involving this lag in conversion efficiency that could not ke determined from the data avaiable. ‘The 13 data points considered in the regression analysis were also analyzed statistically for 0, emissions in terms of time after the beginning of start-up operations until 300 ppm SO, emissions is reached. It was calculated that the average period was 6.34 hours, with 95 percent of all start- up periods falling between 3.14 and 9.54 hours. These results were in agreement with the graphical data presented previously in this section. Details of the statistical analysis are in- eluded in Appendix “c’ MALFUNCTION CONDITIONS Single Absorption Plants Single absorption acid plants cannot meet performance stand- ards for SO, emissions without the addition of vent gas clean- ing systems. Acid mist emissions from single absorption plants are also frequently above the performance standards unless the plant is equippe? with special means for eliminating this mist. Although single absorption plants are not specifically included in this stuly, data were obtained from two single absorption acid plants (Plant 0; and U2) for acid mist emissions when using both dark and bright sulfur. These data serve to illu- 94strate the problems encountered when burning dark sulfur in a single absorption plant that is not equipped with appropriate filters to remove the acid mist. As illustrated on Figure 17, the emission of acid mist for dark sulfur feedstock is approximately three times that encountered with bright sulfur. The emissions from dual absorption acid plants equipped with norm1 mist eliminators is plotted on the same curve for com- parison. The burning of dark sulfur in the modern dual ab- sorption acid plant does not normally affect the acid mist emissions significantly, since these plants are equipped with efficient mist removal systems. The single absorption acia plants plotted on this figure are equipped with high efficiency Brink filters, and when these are in operation acid mist emis~ sions are below performance standards. The range for acid mist emissions for all plants studied, burning dark sulfur and bright sulfur, are shown in Figure 18. ‘The plants described in Figure 17 fall within the rarye of all the plants studied. A statistical study was made of Plants U, and U, in an effort to show the effect of catalyst aging on SO) emissions and acid mist. The results of the study for SO, emissions were in- conclusive, since factors other then catalyst aging mask the change of SO, with time. One of the major causes of SO, variation in time was the introduction of dark sulfur into the unit during some periods of operation. The specific effect of dark sulfur on S0, emissions was not clear, however, since 9596 Acid Mist Concentration - mg H,S0, Per scf Acid Mist Eatssion Average Operating Levels for Both Dual (Plant Q) and Single Absorption (Plant U, & U2) Contact Acid Plants 99.92 99.7 99.0 98.0 96.092." _ eee “Plane Uy-U, ) Dark sulfur 25.0 mg/ScF Plant 1-1 Bright Sulfur Af" ty SULFURIC ACID PLANT VOLUMETRIC AND MASS EMISSIONS OF ACID NIST AT VARIOUS INLET $0, CONCENTRATIONS BY VOLUME TT OL 02.03.0510 -28.20 20 50 Acid Miot Eoteaione - Lb H,80, Per Ton of 100% H,50, Produced Figure 17sere nest comeersrion ne My60, ren 7 ‘000 NOSMAL RANE OF OPERATION FOR ACID MIST EMISSIONS ‘OF NEW DUAL ABSORPTION AND SINGLE ABSORPTION ‘ACID PLANTS BURNING BRIGHT AND DARK SULFUR LEGEND sar New Dual Absorption Plants tumumes- Single Absorption Acid Plants Burning Bright Sulfur qm Single Absorption Acid Plants Burning Dark sulfur ty PERFORMANCE STAN Le lz Acro mist istions, Us m50, FEL TOW OF 100 Hs PRED Figure 18 97other factors were also involved. The effect on SO, emissions of catalyst aging probably cannot be determined using this type of evaluation, since the addition of new catalyst during each cleaning cycle will tend to replace the aged catalyst over a period of approximately 10 to 12 years, thus maintaining the overall activity of the catalyst bed at a point slightly below that of a new plant. Correlation of operating time with acid mist for these plants however show a very significant change during the period when dark sulfur was being burned, When bright sulfur was burned a very constant acid mist emission rate was experienced. When ark sulfur was introduced to the plant the acid mist emi sions increased (approximately 20 times) until the dark sulfur feed was discontinued and bright sulfur was again fed to the furnace. With the introduction of bright sulfur, acia mist immediately dropped to the normal level. A plot of the acid mist emissions with respect to time is shown in Figure 19. Single Absorption Piants with Tail Gas Cleaning Operating data were obtained froman extended period of opera~ tion from a single absorption acid plant burning bright sul~ fur and equipped with an ammonia scrubber. Three operating periods for this plant (Plant "K"), containing a series of malfunctions is shown in Figures 20, 21, and 22, A study of the total operating data from this plant indicates that the important operating parameters are scrubber gas flow, ammonia concentra- tion in scrubber liquid, and scrubber liquid pH. in the opera~ 98COMPUTER PLOT OF ACID MIST VS. TIME Plant My FIGS e& Trom coy. Reproduced [BEES 99oot men 4% NH, CONTROL summa fennel n= FRM. SO, OUT ————NH, CONCENTRATION FUNCTION OF SINGLE ABSORPTION. ACID PLANT “kK” WITH AMMONIA SCRUBSE POINT a a a a Y TET ETRE TAT ETE Ta ETE Ea TIME "IN HOURS Figure 20Tot MALFUNCTION OF SINGLE ABSORPTION ACID PLANT WITH AMMONIA SCRUBBER 2M. SO> GUT NH, CONCENTRATION Gaon eene Om Mignon een On ie butaj sara uiel a On coat ens dee gel TIME IN HOURS Figure 21MALFUNCTION OF SINGLE ABSORPTION ACID PLANT ‘kK’ WITH AMMONIA SCRUBBER zor NH, CONCENTRATION LN [= me femmes 4% NH, mr CONTROL PSINT PTET TN ETT ETE TOM ETT TET ETT ET TIME IN“ HOURS Figure 22tion of the plant observed, the last two parameters were gener- ally related. Ammonia concentration was selected for plotting against sulfur dioxide emissions, with periods of abnormal gas flow noted on the graphs. Figure 20 contains one period of 24 hours when $0, emissions were below 300 ppm. During this period of time the ammonia concentration was steady at six percent. Prior to this opera- tion the ammonia concentration was out of control, generally running lower then six percent, causing the $0, emissions to maintain a constant 800 ppm. At the end of the stable oper- ating period the flow through the scrubber was increased beyond the scrubber capacity for a short period, causing the 50, emissions to increase drastically from 300 ppm to approx- imately 1,000 ppm. During this time the ammonia concentration remained generally high but was unable to control the emission of S0, because of high gas flows resulting from hignacia pro- @uction. A reduction of gas flow for a stort period again reduced the emissions to below 300 ppm, followed by another period of high gas flow with 1,000 ppm emissions. This curve shows the effect of exceeding the scrubber capacity for gas flow, resulting in a large increase in $0, emissions. Simply maintaining high concentrations of ammonia in the solution during these high gas flow periods will not maintain SO, emissions at the appropriate level. Figure 21 further illustrates the effect of ammonia concen- tration on SO, emissions. During the initial part of this 2 103operating period the gas flow through the scrubber was below the normal level, permitting control of $0, at 250 ppm with an ammonia concentration of only five percent. When the ammo- nia concentration ws lost because of ammonia evaporator prob- lens, SO, momentarily increased to 1,000 ppm before the ammonia concentration was raised reducing the $0, emissions. Continued upset in the control of ammonia concentration eventually re- sulted in the shutdown of the unit. In Figure 22 the ammonia scrubber was operating at a gas flow above its normal rates during the initial part of this period. During this 12 hour period the SO, emission was 500 ppm with an ammonia concentration of seven percent. Significant in- creases in the gas flow through the scrubber resulted in loss of ammonia concentration control, with the ammonia concentra- tion dropping to the set point of four percent. During this period of time the SO, emissions increased to 800 ppm. This portion of the curve illustrates the inability of the scrubber to maintain $0, emissions at the 390 ppm level with an ammonia concentration equal to the four percent setpoint. After con~ tinuing upsets in flow rates and ammonia concentrations during the remainder of the two and a half day period shown on this curve, the ammonia concentration was again established at approxi- mately seven percent,and with gas flow returned to normal, SO, emissions dropped below 300 ppm. ‘These three figures show the need for careful anmonia concen- tration control at a level of approximately seven percent 104and gas flow rates within the proper limits of scrubber design if 80, is to be maintained below the 300 ppm standard. Con- trolling the ammonia at a concentration of four percent will reduce the amount of ammonia consumed in the scrubber, but will always result in an emission level of approximately 800 ppm when gas flow rates are within design limits. Data were collected on one single absorption acid plant equipped with a sodium scrubber. This plant is designated as Plant "Y". Figure 23 shows the response of the sodium scrubber to a sud- den drop in gas flow rates through the scrubber. The desiga flow of this scrubber is 5,000 scfm but normal operation is set at 6,300 scfm. During the period of operation shown on the graph the gas flow through the scrubber was dropped to 3,200 scfm causing the SO, emissions to drop from 940 ppm to 50 ppm. During this same interval the scrubbing solution temperature increased and the pl dropped slightly. These other parameter changes were primarily results of the drop in flow rates. The sodium process is capable of reducir~ SO in the vent gas to 250 ppm in normal operation, as deno.r: rated by BPA performance test. The data from plant "Y" indicates the high sensitivity of the process to flow rates, and the need to restrict jas flows to within design limits. 105| MALPLNCTION OF SINGLE ABSORPTEON PLANT "Y" ITH SOOTY SCRUBSER took osx i es, er LE a 4 900 i a 2 = 30 ¢ ° Bae ew ee ae BeBe TIME IN: HOURS Figure 23 106Dual Absorption Plants A series of operating data for plant "Q" covering a five hour operating period is presented in Figure 24. Plant "0" is a dual absorption acid piant burning bright sulfur, with a capacity of 1650 tons per day of 100 percent sulfuric acid. At the time the datawere taken the plant was still in its shake down period after its initial start-up and all the initial construction problems had not been eliminated. the five hour period shown contains a series of malfunctions affecting a variety of process parameters and causing excess enissions of $0, and acid mist. ‘The basic malfunctions that occurred were the loss of tempera~ ture control in the fourth bed of the converter, loss of dilution water to the acid tanks feeding the absorbers, and loss of sulfur flow to the sulfur furnace. The result of the combination of these malfunctions was an increase in SO, con- centration from less than 100 ppm to a peak of 1,300 ppm and an increase in opacity from zero to 40 percent. The sequence of events during the five hours of operation can be followed by referring to the large numbers of Figure 24, and is described in the legend on the second page of the figure. During the first hour of operation the plant was operating with normal emissions and with all parameters in normal range. At the one hour point vemperature of the fourth bed of the converter began to show loss of control. This decrease in catalyst bed temperature began to change the SO) concentration 1072 contnan, nem PReUry 8 a Re Tt oF co Concentration contane —d p— wo win EXCESSIVE Sap Euro ‘$70 wm ts w 59 corm TIME IN HOURS FIG.24Point No. 1 10 u 2 1B “ 35 16 uv 18 FIGURE 24 (CONTINUED) DESCRIPTION OF SIGNIFICANT OPERATING POINTS Dilution water off vith resulting rapid rise in W,S0, concentration and $0, Emissions Beginning of excessive $0, Emission du: to loss of converter temperature control Sulfur gun plugged Loss of 50% sulfur flow Loss of 75% sulfur flow 25% sulfur flow SOX sulfur flow 75 sulfur flow 100 sulfur flow Tenperature recovery point - start of conversion inprovenent Stab{lized converter bed teaperatures $0, Emissions back within EPA standard compliance due to stable converter temperature levels 98.5% H,50, concentration point at vhich high (30%-402) opacity’plime disappears Dilution water maifunction 96.5% acid in Final absorber - poor 50, absorption into high opacity plane Opacity due to loss of H,S0, concentration control Subcooling of converter tenperature Lost 4th bed conversion because of interpass absorber failure 208in the vent. The SO, concentration increased slowly at first, crossing the 300 ppm line at point 2. A short time after this point, dilution water flow to the acié pump tanks feeding tie absorbers became inadequate causing the concentration of acid in the absorbers to increase. The concentration of acid to the primary absorber crossed the control point of 98.5 percent. acid concentration at point 1, The increased acia concentra- tion was seen in the final absorber at point 14. The reduction in dilution water flow resulted from a makeup water line of Ansufficient size to provide the required water. When the insufficient water flow became apparent from the control charts water hoses were added to the pump tanks to dilute the acid and restore concentration control. As the concentration of acid in the primary absorber began to increase the amount of 0, absorbed in the acid was reduced, increasing concentration of SO, in the fourth bed of the con- verter. This increased S0, reduced the efficiency of the fourth bed causing an increase of SO emissions from the vent. ‘The result of this reduced conversion efficiency in the fourth bed is seen in the converter temperatures at point 18. As the So, emitted from the stack began to increase, the opacity a) readings began to climb at about the third hour. While the SO, emissions were increasing and the opacity was ing, the operators attempting to re-establish dilution water flow failed to notice the sulfur furnace temperatures were dropping. Low sulfur furnace temperatures resulted from 209the failure of one sulfur gun at point 3, reducing the flow by 25 percent, and the loss of a second sulfur gun at point 4, re- ducing the sulfur flow to 50 percent of normal. A third sul- fur gun filed at point 5,leaving only 25 percent of normal sulfur flow at point 6 on the furnace temperature curve. During this period of loss of sulfur flow, two actions were occurring that partially counter-acted each other. The loss of $0, flow to the converter reduced the temperatures in the converter, which in turn reduced conversion efficiencies. During the same period the reduced so, concentration in the feed reduced the need for conversion, permitting the excess 80, and unabsorbed SO, to be purged from the primary absorber and fourth catalyst bed. As the SO, was removed from the fourth catalyst bed the efficiency of this bed increased, reducing the amount of S0, emissions from the stack. The $0, emissions reduction begin at about 3.5 hours. When the dilution water flow was re-established at point 15, opacity began to fall at point 16, reaching zero at point 13. After it was determined that the three sulfur guns had failed, they were immediately restarted (at points 7, 8, and 9), re~ storing the flow of So, to the converter and starting reheat of the catalyst beds. After re-establishing the sulfur flow the catalyst beds reached stable temperature at point 11, one half hour after starting the last sulfur gun. The short time re~ quired for recovery of normal converter temperatures illustrates the large hedt input fron the $0,-S0, reaction compared to the alosmall heat loss (illustrated by the slow cooling of the con- verters when the flow of SO, to the converter was reduced). ‘The SO, concentration from the stack reach 300 ppm at point 12, 4.5 hours into the operating period. A very interesting sequence of events is presented in Figure 24, pointing up one of the major differences in operation between single absorption and gual absorption acid plants. In a single absorption plant, loss of dilution water to the absorber increases the S0, .mission, causing acid mist, but does not appreciably change the SO, concentration in the vent stack. In a dual absorption plant however, loss of @ilution water to the primary absorber reduces the absorption of S03, increasing the concentration in the fourth cazalyst bed reducing its conversion efficiency. This will result in an SO, emission increase. Continued loss of dilution water, causing an increase in concentration of acid in the final absorber, results in high $0, emissions and increased opacity. In the case of the plant "Q" experience, an acid concentration of 108 percent is reached in the primary absorber and about 100 percent in the final absorber. It is also interesting that in the case of the operation of plant "Q" the SO, emis~ sions from the plant decreased as the sulfur feed to the fur- nace was being lost and catalyst temperatures were falling. This sequence indicates the SO, emissions under the operating circumstances encountered in this event are more sensitive to 80, inlet concentrations than to catalyst temperatures. The qncurves also show the slow decrease in catalyst temperatures when sulfur is lost, and the very rapid increase in catalyst temperatures when sulfur flow is reinstated. It appears from this sequence of events that if loss of sulfur guns is detected sufficiently early to re-establish flows within a reasonable time, the converter temperatures can be re-established in a short period without causing excessive SO, emissions from the plant. Considering the size of Plant "Q", the transient conditions oxhibited during this sequence of operations are surprisingly fast. This illustrates the need for close temp- erature and flow control of all the major process parameters. azSECTION vir DISCUSSION EMISSIONS DURING NORMAL OPERATION The normal emissions for steady state operation of sulfuric acid plans consist of sulfur dioxide (s0,), acid mist and opacity. Acid mist and opacity are related and under certain conditions, are different methods of measuring the same pol- dutant. The SO, emission from a sulfuric acid plant results from a Single cause. This cause is the inability of the catalyst in the converter to convert 100 percent of the 50, generated in the sulfur furnace into 60, for eventual absorption in the absorber. The effect of conversion efficiency is illustrated in Table 2, Page 41 of Secticn VI. Unconverted So, is un- affected by passing through the absorber and is emitted with the vent gas. The acid mist, on the other hand, can result fron three aif- ferent sources, all of which generate sulfuric acid, the lltinate form of the acid nist emitted. The nost direct source of acid nist is curry-over of Liquid particles of sul- farie acid from the top of the absorber. These particles ange in size above three microns. A second source of acid mist emission is the formation of fine particles of sulfuric acid in the sysien by the reaction of 50, fron the converter with water vapor contained in the gas. This water vapor is Present because of insufficient drying of combustion gas or 113the generation of water vapor by the combustion of organic material contained in the sulfur. The effect of dark sulfur on emissions can be seen in Figure 17, Page 96 of Section VI. This source also produces sulfuric acid particles in the range of three microns and larger. The third source of acid mist emissions is the failure of the absorber to fully absorb all. $0, fed to the bottom of the tower. Any 50, leaving the top of the absorption tower will immediately react with moisture inthe ambient air to form very fine particles of sulfuric acid. These particles range in size below one micron. Measurement of the opaéity of the vent gas stream from a sul- furic acid plant is to a large extent the measure of the amount of sulfuric acid emitted from the process. Because of the fine particle nature of the acid mist and the effect of atmos- pheric conditions on the emissions, the measurement of opacity may be greater in one situation for the: same amount of acid mist emitted than in another. Atmospheric effects on opacity may be seen in Table 7, Page 63 of Section VI. Acid mist resulting from acid carry-over from the absorber or reaction between 50, and water vapor in the absorber produces a dense white cloud in a cool, moist atmosphere, while the reaction of $0, gas and atmospheric moisture produces a blue sloud of @ less dense nature. In addition to acid nist, the oxides of nitrogen (NO,) may alsv contribute to opacity. The pre- sence of NO, and SO, in the ges stream produces acid mist by formation of a NO,-S0, complex sinilar to tie reaction in a4the chamber process. Nitrogen oxides are generated by com- bustion in the sulfur furnace or by the release of nitrogen oxides from combustion of organic material contained in the sulfur. Steady State Pmissions and Equipment Limits As shown in Table 2, Page 41 of Section III a typical single absorption sulfuric acid plant emits SO, in a concentration between 1,500 and 4,000 ppm. This SO concentration results from operation at normal design capacities depending upon the efficiencies of the converter to oxidize $0, to S0,. The major variables influencing converter efficiency are the amount and condition of the catalyst contained in the converter. ‘The catalyst becomes dirty with use and loses efficiency. EY- ficiency can be increased by cleaning. The cleaned and par- tially replaced catalyst will again perform at higher effi- ciencies: with proper cleaning and operation a catalyst bed will serve for a period of 15 to 20 years. During the cleaning process, six to ten percent of the catalyst is lost due to screening of the material in the first bed and must be replaced by new catalyst. The new catalyst is generally Placed in the last bed and the catalyst from succeeding beds is used to replenish the material in the first bed. Misopera~ tion of the converter or the use of sulfur containing large Quantities of organic material can increase the deterioration rate of the catalyst. The effect of burning dark sulfur on catalyst activity is shown on Figure 19, Page 99 of Section VI. us‘Te use of dirty sulfur feedstock will increase the frequency of cleaning of the catalyst as well as hasten the tine of re- placement. Overheating of catalyst to the range of 1200F will reduce useful life of the catalyst to three or four years. Careful operation and maintenance of the converter will assure SO, emissions in the range specified in the design of the plant. The most important operational parameters effecting SO, emis- sions from a single absorption acid plant are the temperatures of the converter beds. Converter temperature ranges are shown in Table 4A, Page 51 of Section VI. Operation within a re~ latively narrow range of temperature for each bed is required to achieve optimum conversion. These temperatures are con- trolled by sdjustment of by-pass dampers on the heat exchangers, by careful regulation of the $0, concentration in the feed gas to the converter, and the temperature of the sulfur fur- nace. The allowable range of converter temperatures is shown in Table 4C on page 56 of Section VI, Analysis of Process Variables and Emissions. Mean operating temperatures for the plant observed are also shown. Each constructor of sulfuric acid plants employs individual details of design for the converter. These variations in converter design cause smell variations in the efficiency of the catalyst and require different amounts of catalyst to obtain the appropriate conversion efficiencies. Some of the important design details in catalytic converters are the 116features reducing the wall effect or channeling of jas along the vessel wall, where contact with catalyst is reduced. A very significant reduction in the $0, emission of sulfuric acid plants was achieved by the introduction of the dual ab- sorp: m process in Europe approximately ten years ago. A dual absorption process is capable of reducing S0, emissions to a range between 100 and 300 parts per million. The process descriptions presented in Section Iv detail the design of the ual absorption plant and the use of the primary absorber for increasing $0, conversion. Improved efficiency is also ob- tained by more careful control of temperatures in the con- verter and the use of higher catalysts loadings. Most of the process parameters in the dual absorption plant affect $2, emissions in the same manner as for the single absorption plant. ‘The use of vent gas cleaning systems in conjunction with single absorption sulfuric acid plants provides an alternate to the dual absorption sulfuric acid plants for reducing SO) emis- sions. Under normal steady-state operations a concentration of 250 parts per million of SO, is ‘obtainable using the sodium Scrubber system (Table 8, Page 66). Concentrations as low as 200 parts per million have bean demonstrated by the ammonia scrubber system (Table 16, Page 93). The most efficient vent gas cleaning system studied is the molecular sieve system. ‘This system will produce normal operating SO, concentration of less than 10 parts per million. 17With any vent gas cleaning system, the concentration of SO, in the gas leaving the single absorption plant absorber in- fluences the concentration of SO, in the vent gas from the cleaning system. However, this influence is not felt to the same extent as with a single absorption plant operating with- out a cleaning system. The buffering effece of the vent gas cleaning system somewhat reduces the effect of temperature control and the catalyst condition in the acid plant. with a vent gas cleaning system of sufficient capacity the single absorption plant can be operated up to 100 percent of the original capacity without excessiv: SO, emissions. Operating parameters in the cleaning system, however, often strongly influence the concentration of $0, in the vent gas and become the primary parameters that must be controlled to maintain the concentrations within standards. In the sodium and armonia alkali scrubbers, the most improtant pro- cess parameters are concentration and pl of the scrubbing fluid, temperature, and the liguid/gas ratio’ flowing through the absorber. These control points must be established for @ specific scrubber design and must be maintained within narrow limits to insure proper S0, absorption. The molecular sieve systen is less sensitive to both $0, con- centration in the input and other operating parameters. Suf- ficient detail is not available on the operating conditions of the system for a full analysis of the effect of process Paraneters. Because of the simplicity of the system the pri aemary control of adsorption efficiency is the condition of the.molecular sieve packing in the adsorption tower. acid mist resulting from carry-over of sulfuric acid from adsorption towers is controlled primarily by the installation of demisters in the outlet section of the absorber. In the case of the double absorption plant a demister is installed in the top of the primary absorber to reduce the carry-over of sulfuric acid into the converter bed and to protect the heat exhangers following the absorber. When properly equipped with demisters and operated to minimize generation of acid nis in the unit, the normal dual absorption acid plant will emit between three and 15 milligrams of sulfuric acid per standard cubic foot of vent gas. These concentration levels apply when burning clean elemental sulfur as feedstock. If dirty sulfur containing organics or acid sludges are burned, additional acid mist is generated within the process, seen in Figure 18, Page 97 of Section VI. Part of the acid mist will carry through the demisters, increasing the concentration of acid mist emitted. Most sulfuric acid plants constructed during the last ten years are equipped with appropriate de~ misters for controlling acid mist emissions. However some Older single absorption plants still in operation cannot meet the standards because of lack of appropriate mist eliminator installation. The Liquid alkali vent gas cleaning systems cannot of them- Selves remove sufficient quantities of acid mist to permit usdards to be met. When sodium or ammonia scrubbing systens are installed, demisters capable of reducinc the acid mist carry over to within standards, mist be installed before or after the scrubbers. In sone cases a high energy venturi scrubber is operated in conjunction with the So, vent gas ab- sorber to eliminate the acid mist emissions. Adsorption of acid mist as well as SO, gas is inherent in the nature of the molecular sieve vent gas cleaning system. with this system it is claimed no additional mist elimination equip- nent is required; however, data on the one plant evaluated to date indicate that the acid mist concentration before the molecular sieve adsorber will mest the standards without further cleanup and thus ‘the claim cannot be verified as yet. Since opacity in sulfuric acid plant vent stacks results pri- marily from acid mist, any of the previously discussed remedies for reducing acid mist will also reduce opacity. In addition to acid mist, NO, is also a contributor to opacity. The pre- sence of NO, in the absorber feed will not only add a yellow color to the vent plume but will generate acid mist by forma- tion of a complex between NO, and.$0, as in the chamber pro- cess. Proper operation of the furnace can reduce the NO, generated from this source. However, if sulfur containing organics must be burned, more efficient filters are needed to remove the small sized partictlate formed by reaction of water vapor and SO. Addition of high efficiency filters after the absorber of a single absorption plant will permit burning 120less expensive dark sulfur without excessive opacity. stock Changes The effect of sulfur containing organic material has previously been discussed. In plants burning sludge acid a large variety of contaminants are encountered in the feedstock, making con- trol of emissions from the plant difficult. sulfur dioxide enissions vary with such feedstock because of the variability in the concentration of 80, fed to the converter. sudden increases in the inlet 50, concentration increases the outlet 50). Because the operation of the sulfur furnace is rore difficult, burning sludge acids can cause upset in the tenp- eratures in the furnace, resulting in sublimation of sulfur and eventual deposition on the catalyst. s return to normal operating conditions will then oxidize the deposited sulfur greatly increasing the SO, load in the converter. This resvits in large concentrations of 50, over a short period of time in the plant vent stack. With fresh catalyst in a dual absorption plant the design sul- fur feed rate should not cause the SO, concentration in the stack to exceed the design limits. However as catalyst deteriorates or becomes dirty, feed rates must be reduced to maintain the acceptable concentration of SO, in the vent. Some modern plants are designed with sufficient catalyst to Permit feed rates in excess of the design quantity when the catalyst is new and has maximum activity. ‘The intention of the excess catalyst in such a plant is to provide for some a2.deterioration of catalyst activity without exceeding emission standards at designed operating rates. Every effort must be made to control the feed rate ani composition of the burner exit gas and conditions in the sulfur furnace as consistently az rossible to reduce the possibility of So, emissions. Except in the case of dirty sulfur or sulfur containing or- ganics the molten sulfur feed rate or sulfur furnace condi- tions do not appreciably effect the acid mist emissions from a plant adequately equipped with mist control equipment. EPA PERFORMANCE TEST PARAMETERS Federal regulations require that a performance test be run on a new or modified acia plant within a specified time after plant start-up and that periodic information be provided on operation cf the plant after acceptance. These reports will include the stack emissions for S0,, acid mist, and opacity. Certain process parameters are basic to determination of the emission rates and must be determined with sufficient accuracy to justify the reported figures. Table 3 in Section V is a summation of production plant data obtained in an EPA perfor- mance test. Since emission rates are based upon tons of production of 100 Percent acid per day, an acceptable method of meacuring pro- duction rate must be provided. Either flow meters or storage tank levels are acceptable for measuring flow rate when properly confirmed by overall process material balances. If 122tank levels are used, arrangonents must be made to isolate the tank from other product inputs or products outputs during the period of the test. If storage capacity is limited this isolation requirement may be a visadvantage in using this method of production measurement. If a flow meter is avail- able for continuously measuring the flow of product, the read- ings from this meter can be used for establishing daily pro- duction rate. Appropriate calibration procedures must be followed to assure accuracy of the meter, and periodic test must be run to prove this accuracy. With either production rate measurement method, analysis of the product must be per- formed on a periodic basis to permit calculation of production on the 100 percen'. sulfuric acid basis. During the initial performance test of a new acid plant, stack yo> analysis is normally rua using the stan¢-rd EPA impinge- ment train methods to establish the gas ‘«:.sity, gas velocity, and concentration of $0, and acid mist. In order for this test to be performed, proper sampze poi in the stack in compliance with the regulation. plant designs have provided stacks of insufficient neight to obtain the necessary lengths of straight run before and after the sample points to permit compliance with this test proce dure. Full Liance with sample point configuration must be assured for the performance test or any follow up testing that mast be done using tne standard EPA methods. ‘The regulations also reguire a continuous SO, monitor installed 123fon the vent stack. The instrument most commonly applicd at this time is the DuPont model 460 analyzer. Data obtained from plants using this instrument indicate that the so, con- centration readings are reliable if the instrument is proper- ly maintained. Improper installation and maintenance of this instrument. however, can cause erroneous results, generally in the direction of low concentration measurements. If main- tenance records are kept on this instrument a better evalua- tion of its performance can be obtained. A variety of instruments using the principle of light trans mission have been used for measurement of opacity in sulfuric acid vent stacks. These instruments generally appear to have difficulty in maintaining reliable operation, and visual com- parison of the opacity of the vent gases is normally relied upon. Since visual opacity estimates include water vapor contained in the stack gases, complete analysis of the gases including sulfuric acid mist must be available before corrected opacity measurements can be obtained. ‘he only reliable methods available for obtaining acid mist concentration in the vent stacks are the impinger analysis methods. Since these test are difficult and time consuming, requixing two hours to run, they are not normally run in rou- tine operation. Most plant operators will use visual measure- ment of opacity as anindicator of possible problems with acid mist emissions. When visual opacity estimates indicate the Possibility of the presence of excess acid mist the impinger 124tests are run on the stack to provide information necessary for correcting the problem. Impinger tests must also be run during any period of special performance test and evaluation required by EPA. SHUTDOWN EMISSIONS Most plant shutdowns can be classified as either planned or unplanned shutdowns. ‘The shutdowns resulting from catastrophic failure are beyond our concern ‘in this study. Shutdowns can further be classified by short term or long term depending upon the length of time the plant is expected to be shut down. For purposes of our discussions a short term shutdown can be considered as one lasting less than four hours and a long term shutdown as one lasting more than four hours. When a planned shutdown is properly handled no excess emissions shuld be ex perienced from the sulfuric acid plant. The primary impoctance of shutdown method used is the effect of the shutdown on the Subsequent start-up emissions. A properly prepared plant, shutdown for four hours or less, can be restarted without re~ heating the plant equipment. Figure 12, Page 76 of Section VII shows Sc, emissions from a dual absorption plant during 2 start-up after shutdown of various durations. If the shut- down extends for more than four hours, reheat of plant equip- ment is required to minimize emissions on start-up. Plannea_shutdown The most important feature of a planned shutdown is prepara~ tion of the plant for eventual start-up to minimize start-up 125emissions. The first action in preparing for a planned shut- down is to have available a supply of strong acid for a transfer to the absorber and the drying tower. This increase in acid strength will help to offset the effect of moisture leakage into the plant and the accumulation of excess moisture result- ing in dilution of the acid during the start-up operation. Stronger acid in the absorber and drying tower during start- up will reduce the acid mist emissions from the plant. After the plant is prepared for shutdown by increasing the concentration of the acid, the sulfur feed to the furnace is simply shut off and the generation of sulfur dioxide stopped. After a very few minutes of continued air flow to remove ex- cess $0, from the furnace and move SO, from the converter to the absorber the air supply is shutoff and the dampers iso- lating the heat exchangers and converter are closed. The closed dampers will help to reduce the influx of humid air and conserve heat contained in the equipment. with normal heat losses from the plant, four hours downtime should not reduce the temperature below the point for start-up without preheat. If the plant shutdown will extend for a prolonged period and maintenance must be performed on the process equipment, the unit must be cooled sufficiently to permit entrance. with this type of shutdown, air flow through the system is continued until all S0, is transported from the furnace to the converter and all SO, is removed from the converter to the absorber to 3 126make sulfuric acid. After most of the SO, has been stripped from the catalyst and transported to the absorber, the drying tower is bypassed to prevent dilution of the drying acid that would make start-up more difficult. The undried air contain- ing very small quantities of $0, is vented to the atmosphere until the converter temperatures approach a dew point of ap- proximately 100C. At this temperature dry air is again in- troduced to the system to prevent condensation of moisture and formation of sulfuric acid in the equipment, causing ex- cess corrosion. The dried air containing the residual amounts of $0, is again vented to the atmosphere until the converter has reached the desired temperature. If only the furnace and the waste heat boiler must be cooled, undried air can be used for cooling if it is vented before entering the converter. Unplanned shutdown and Equipment Malfunctions Many problems can arise in a contact sulfuric acid plant that cause emissions in excess of standards arid often require an unplanned shutdown. Only a few of the major causes of shut- down are discussed here. Related shutdown causes can be grouped together in the fcllowing sections: 1. Sulfur feed system (Figure 24) 2. Combustion air (Figure 24) 3. Heat exchanger and converter temperature control (Figure 24) 4. Absorber and strong acid systems (Figure 24) 5. Vent gas cleanup systems (Figures 20, 21, 22, and 23) 127one of the most frequent causes for unplanned shutdown is failure of the molten sulfur pumps and burners. When sulfur pumps or burners are lost and the SO, to the converter is reduced, excess emissions froa the absorber do not necessarily occur. If the flow of sulfur can be reinstated before the converter temperatuzes have dropped below the acceptable range, the $0, converter efficiency can be maintained and S0, emis- sions controlled within limits. However if the converter temperature drops below 750F, the converter efficiencies decrease as the temperatures decrease and emissions increase when flow of molten sulfur is reinstated. A complete sequence of plant operation following loss of sulfur feed is shown in Figure 24, Page 108 of Section VI. The combustion air blower in a sulfuric acid plant is one of the most critical items in the plant. This blower is normally driven by a steam turbine supplied with steam from the waste heat boiler. ‘The speed of the air blower is controlled to provide sufficient air for com-lete combustion of the sulfur to sulfur dioxide and dilution air for subsequent catalytic oxidation of the sulfur dioxide to sulfur trioxide. If in- sufficient air is provided by the blower because of malfunc~ tions of the blower control system or operation below the normal operating speed, incomplete conversion of 50, to 50, Wi] take place in the converter. Failure to supply sufficient air to the systen is probably the most freqient cause of ex- cessive $0, omissions in sulfuric acid.plants. When the air supply is dropped further, insufficient air is available for 128the combustion of sulfur to SO). In this situation the high temperatures in the sulfur furnace cause sublimation of sul- fur and subsequent redepositing of sulfur in the catalytic converter. Since the deposition of sulfur in the converter takes place éuring periods of low temperatures, resulting from insuffi- cient sulfur combustion, a return to normal operating tempera- tures will oxidize the sulfur providing a large increuse in the concentration of sulfur dioxide in the converter. This situation results in 2 large increase in $0, emissions from the plant. An added danger of subliming sulfur in the fur- nace is the deposition of the sulfur on boiler tubes causing failure of the tubes. Failure is caused by the burning bf silfur on the tube surface, resulting in localized melting of the tubes. If the combustion air blower shuts down suddenly removing the flow of air to the furnace, no transfer medium will be available for sweeping the excess $0, and SO, from the system. In these situations higher levels of emissions will occur during the subsequent start-up operation. The control of acid mist emissions depends upon feeding dry air to the sulfuric acid system to prevent reaction of SO, and water vapor to form the acid mist. If the concentration of acia in the drying toner drops below the operating limits, or if the quantity is reduced below that required by the air 129passing through the tower, excessive acid mist emissions will occur. This situation is usually detected first by the appear- ance of a heavy white plume from the vent stack. Heat exchangers in sulfuric acid plants are subject to excess- sive corrosion because of the presence of sulfuric acid and high temperatures. I£ a leak occurs in a water cooled heat exchanger the addition of water to the S0,-S0, system results in a dense white plume of steam and sulfuric acid emerging from the vent stack. This situation will require a plant shutdown and excessive acid mist emissions will occur during the period of operation while the plant is being shutdown. In a dual absorption plant using gas-to-gas heat exchangers, a leak in a heat exchanger can result in gas with a high con- centration of $0, by-passing a portion of the converter catalyst beds. When this occurs the third or fourth catalyst bed can be overloaded with 0, and the concentration of 50, from the vent stack will increase. With this type of failure the plant must be shut down for repairs and excessive SO, will occur until the plant is completely purged of SO, Failure of temperature control systems for the converter is one of the most minor malfunctions in terms of hardware but can be a major cause of excessive $0, emissions. Many of the older plants relied heavily on manually adjusted dampers bypassing the heat exchangers to regulate the inlet and outlet temperatures of the catalyst beds. Most modern acid plants 130depend more heavily on automatic control, introducing the pos- sibility of temperature control failure. In most cases the significant temperatures in the converter are vecorded on a multipoint recorder that gives a profile of the temperatures across the converter beds, providing a powerful tool for trouble shooting temperature control problems. If such a failure occurs manual control can usually be assumed to return the temperatures to proper operating points. Emissions resulting from this type of failure should not last long since the cause is easily corrected. Plant shutdowns resulting from failures in the absorber system generally will arise from failure of the concentrated acid pumps supplying scrubbing acid to the absorber. If the son- centration of the strong acid flowing to the absorber is re- duced below operating requirements, SO, gas will be emitted from the absorber because of the inability of the lower con- centration acid to absorb the S0,. This reduced absorption results from the increase in surface tension of the low con- centration acid, reducing the transfer of 50, into the absorber liquid. r£ the concentration of the absorber acid becones too high the emissions of S03 will also increase because the Feduced solubility of S03 in acid with concentration above 99.2 percent will increase the amount of SO, emitted. The effect of absorbez acid concentration on S0, emissions is shown very graphically in Figure 24 of Section vir for both the primary and secondary absorber. Temperature of the ab- 131sorbing acid must be maintained between 185F and 212F to maintain the vapor pressure of the sulfuric acid sufficently Jow to permit absorption of the S03. Efficient absorption of 50, and sulfuric acid in the absorp- tion tower requires good distribution of the acid flow down the tower and intimate contact with the S0, gases flowing up the column. If the volume of acid fed to the colunn is reduced, distribution of liguid in the column will be uneven and incomplete absorption results. Also, there is a risk of increasing the acid concentration in the tower beyond the 99.2 percent, thus producing $0, emissions. Complete failure of the concentrated acid pump feeding the absorber will result in immediate shutdown of the plant and large concen- trations of SO, emissions for a short period of time until the S0, content of the plant has been vented. Al1 modern sulfuric acid plant absorption towers are equipped with a knitted wire mesh demister in the top of the absorption tower. In normal operation this denister collects most of the entrained acid particulates and prevents them from being carried into the vent gas stream. If this demister becomes Partially plugged for any reason, the velocity of gas through the remaining portion of the demister will be too high to permit collection of the acid mist in the demister. This acid mist will be carried through the demister and emitted from the vent stack as entrained ‘acid mist. 132vent gas cleaning systems are subject to many of the sane problens affecting acid absorbers. the proper liquid/gas ratio in the absorber mist be maintained to assure high ab- sorption efficiency. If the flow of liquid is reduced or the flow of gas is increased beyond normal operating ranges, poor absorption of $0, will take place and S0, emissions will in~ crease. ‘The alkali scrubber systems operate with close pH control on the absorbing solution flowing down the column. If the con- trol system fails and the pt is allowed to deviate from the established range, poor absorption of the SO, from the tail- gas will result. in the case of the anmonia scrubber an excessive amount of sub-nicron particulates of ammonium sul- fite will be generated, possibly overloading the packed bed filter (Brink) normally installed to eliminate particulate emissions from the ammonia scrubber. Plants have been observed in operation where the Brink separators were plugged or the booster blowers for transporting the gases through the Brink separators were inoperative. When the filter system was by- passed a large cloud of particulate matter was emitted from the ammonia scrubber. The emission is not classified as acid Mist but is objectionable none the less and mist be controlled to meet opacity standards. Cooling water is used in a sulfuric acid plant for cooling | Product and recirculating acid streams. Failure or cooling 133water in these systems will permit the acid temperatures to rise beyond the range of satisfactory operation resulting in various amoutns of acid vapors being emitted from the pro- cess. ‘These emissions may occur from storage tanks or other areas where the hot acid is accumulated rather than from the vent gas stack. The failure or impropoer operation of many other small pieces of equipment will cause similar problems in operation of the plant increasing emissions. Most of these, however, will fall into the same categories as those discussed and result in the same type of situations occurring. Enissions from Misoperation of Plant Frequently, high emissions from the acid plants result from misoperation of the plant. One of the major reasons for emissions is an attempt to operate the plant at a production rate higher than permitted by the amount or condition of the catalyst. Full recognition of the condition of the catalyst and its reduced capacity due to ageing must regulate the amount of production expected from the plant. If more production is demanded than is permitted by catalyst condition, excessive 80, emissions will occur. In some cases it is necessary to burn sulfur containing quantities of organic matter. Burning this sulfur will cause emissions above the established limite, that may not be con- trollable with the existing plant equipment under any oper~ ating conditions. The only solution for eliminating these 134emissions is to prefilter the sulfur to remove the organic material or to obtain a supply of pure sulfur. Improper attention to control of catalyst temperatures is one of the most common causes of excessive 50, emissions, but also one of the easiest problens to solve. Careful and constant operator attention to this control area will yreatly reduce the probability of SO, emissions. Both laboratory and process instrumentation information is lable to assist in controlling the acid concentzation and temperature in the absorber and drying towers. These process parameters are normally easy to tontrol with proper attention and must be kept within proper range if acid mist standards are to be maintained. Improper attention to or misadjustment of many of the process Parameters in acid plants or vent gas cleaning systems will cause oneor more of the plant pollutants to exceed standards. Careful and skillful control of the process at all times is Yequired to comply with regulations. START-UP PROCEDURES Contact sulfuric acid plant start-up can be classified into. three categories. These are initial plant or new catalyst, short term shutdown, and cold start-up hot start-up afts after long term shutdown. Each type of start-up will require @ particular start-up procedure to compensate for the condi-~ tions existing in the plant. The start-up procedure 135applied to the plant will also depend upon the availability of start-up heaters in the equipment and upon the availability of an associated sulfuric acid plant to provide the required heat and concentrated acid. New Plant and New Catalyst Start-up When a new sulfuric acid plant is constructed the catalyst is received packed in polyethylene bags to prevent adsorption of excessive atmsopheric moisture. During installation of cata~ lyst in the converter, however, considerable atmospheric moisture is adsorbed in the catalyst, requiring predrying of the catalyst bed before introduction of sulfur dioxide into the converter. During the start-up procedure the catalyst must also be activated to complete the reaction of the cate~ lyst and sulfur to provide maximum activity. ‘The initial operation in the start-up procedure ‘10 is to pass hot air at approximately 250F through the catalyst bed at such a rate to permit inczease in catalyst temperature at a rate of 50°F per hour. This air is dried by passing through the air drying tower. The flow of ary air through the cata- lyst is continued until the temperature has been increased in the catalyst beds to approximately 357F and the inlet and outlet bed temperatures are approximately equal, indicating the catalyst is now dry, After the catalyst is dry, heating is continued until the first catalyst bed inlet temperature reaches 825F. At this temperature the catalyst is capable of converting SO, to $0,. Sulfur feed to the furnace is started 136at a low rate to provide low concentrations of $0, flowing through the converter. A low concentration of 60, is required to limit the maxinum temperature in the catalyst bed to below 1,000F. Temperatures not exczeding 1150F mst be maintained to prevent damage to the catalyst. Control of these maximum tomperatures in the first catalyst stage will provide lover temperatures in the succeeding stages. The 80, concentration should be gradually increased, maintain- ing these maximum temperatures, until full sulfur input rates are achieved. The total activation period for new catalyst will range between two and three weeks. ‘The SO, emissions during catalyst activation should remain below the permissible concentrations if the inlet S0, is controlled at the appropriate low concentrations relative to the increasing activity of the catalyst. Once completed this procedure is not repeated un- jess the converter is opened for catalyst cleaning or addition of new catalyst, permitting the adsorption of water vapor. Gold Plant Start-Up ~ Dual Absorption ‘The single absorption acid plant cannot obtain erassions within the permissible limits cf the standards in normal operations without the addition of a vent gas cleaning system. The dual absorption acid plant, however, can achieve standard emissions Limits. Discussion with plant engineers during plant surveys ‘®) indicated dual absorption plants can be started from a cold condition without exceeding standard $0, emissions. To accom- plish a start-up without exceeding standards, the start-up 137procedure must be performed very carefully maintaining close control on all process parameters. It is also necessary to provide a complete preheat of the converter to obtain maximum conversion efficiency before S0, is emitted to the systom. Wot concentrated sulfuric acid is required in the drying tower and absorption tower to Limit the amount of acid mist genera- tion in the system. Although a clean start-up of a cold plant is possible, it is seldom feasible because of time and production constraints. ‘This type of start-up is best accomplished in a plant assoc: ated with another sulfuric acid plant that can provide hot concentrated acid for charging the air dryer and absorber. Although this type of start-up is ideal and has been demon- strated, a short period of $0, emissions exceeding standards is more frequently experienced. Routine difficulties in establishing temperature control around the catalyst beds, will generally cause the emission of S0, to exceed the standards for several hours. Difficulties in controlling sulfur feed at a satisfactory rate to control temperatures of the sulfur furnace and concentrations of $0, in the converters will also cause $0, emissions. A plant that is not equipped with preheaters rust depend upon the reaction of the $0, in the converter to heat the converter to final reaction temperatures. With this arrangement hich concentrations of 0, will be encountered during the rather long period of time required to heat the converter to peak 138efficiency. This procedure will usually produce emissions in excess of standards for two or more days. A cold start-up procedure for a dual absorption plant is show in Figure 15, Page 90 of Section VI. Most new sulfuric acid plants being designed today are equipped with adequate preheaters. Table 12, Page 77 of Seccion V7 summarizes start-up data for plants of all types with various pericds of downtime prior to restarting. These figures clearly illustrate the difficulty in obtaining low SO, emissions after a shutdown of four hours or more, requiring reheating of the converter. wm Plant Start-Ups - Dual Absorption Process If a plant shutdown has not extended beyond a four hour period and proper heat conservation has been practiced in the plant catalyst temperatures should be sufficiently high to permit restarting of plant without reheating. In these situations restarting the sulfur flow to the furnace and careful read- justment of dampers to maintain temperatures in the catalyst converter beds will permit restarting the plants without exceeding 50, or acid mist standard emissions. The SO, emis~ sions during hot start-ups are summarized in Table 12. Vent Gas Cleaning systems - Single Absorption The star:-up of vent gas cleaning systens applied to a single absorption acid plant requires very simple operating procedures. The emissions from the vent gas cleaning system will depend largely upon the start-up procedures used in the single ab- 139sorption plant, since the outlet SO, is dependent upon the concentration cf SO, in the incoming gas to the clean-up system. Figures 13 and 14, Pages 83 and 88 of Section VII show this relationship with an ammonia scrubber. As previously stated, the vent gas cleaning systems provide a buffer between the single absorption plant and the vent gas that will reduce the intensity of concentration swings in S0, emitted from the single absorption plant. In general terms it appears the sodium and anmonia scrubbing systems can be started up with peak $0, emissions one half of those normally encountered in a single absorption plant (Figure 13, Page 83 of Section vn). Start-up of the ammonia and sodium scrubbing systems requires only the establishment of proper sodium or anmonium concen- trations and liguid flow rates through the scrubbers and appropriate pl of the circulating solutions. These condi- tions are established before starting the sulfur flow to the furnace. The primary operating precautions required to pre- vent excessive $0, emissions from the scrubbers are careful control of temperature, the pH, and concentration of the cir- culating solutions during the period of increase in $0, con- rentrations om the single absorption plant absorber. Emis- sions from an ammonia scrubber system during typical start-up are shown in Figure 14 of Section VI. 140In an ammonia scrubber system, opacity is most likely to occur in excess of standards during start-up. The quantity of the ammonium sulfite particulate generated in an ammonia scrubber of the types now in use is very sensitive to control of pil and relative concentrations of NH, and S0,. It is pos- sible that the equipment installed to remove this particulate will be overloaded by the excessive amounts of particulate formed during the upset condition experienced during the start-up. In some situations sufficient steam is not avail- able from waste heat boilers during start-up to operate both the air blower and the booster blower required to overcome the pressure drop in the ammonia scrubber particulate filter. Inthis situation it is routine practice to bypass the parti- culate filter so the steam driven booster blower is not required. When the filter is bypassed large quantities of particulate matter are emitted from the ammonia scrubber causing a heavy blue plume far in exicess of the opacity standards. These emissions can largely be eliminated if arrangements are made to place the particulate filter in operation before $0, is introduced to the system. No data were available on start-up conditions for the Union Carbide molecular sieve system, but according to literature Previously published) this system is very tolerant to large surges in SO, and acid mist concentrations from the absorber and should emit very low levels of these pollutants during a normal start-up of the single absorption plant equipped with the PuraSiv system. 142.4 56 SECTION VIII REFERENCES Environmental Protection Agency, Standards of Performance for New Stationary Sources. (40-CFR - Part 60, Sub Part H) Federal Register Vol. 36, No. 245, December 23, 1971. Environmental Protection Agency, Standards of Performance for New Stationary Sources Emissions During start-up, Shutdown, and Malfunction, (40-CFR - Part 60) Federal Register, Volume 39, No. 39 872, Nov. 12, 1974. Evaluation of H,804 Plant Emissions at the Coulton Chemical Corporation which is Controlled by the PuraSiv s Process, York Pasearch Corp. for Control Systems Laboratory, Office of Research and Development, EPA Research Triangle Park, Report No. Y-8479-2, Contract No. 68-02-1401. May 6, 1975. NSPS Compliance Test Report, Feb. 19-20, 1974, EPA Region IV file D-10.9.3. EPA Continuous Source Monitoring Program Test Results, Files of Performance Standards Branch, Standards Develop- ment and Implimentation Division, EPA Research Triangle Park. Continuous Monitoring of a Copper Smelter Double Contact Process Acid Plant, Scott Research Laboratories Inc. for EPA Research Triangle Park Report No. SRL 2113 15 0574, Contract No. 68-02-0233, May 31, 1974. Towse, C. F. Private Communications with F. D. Kodras, Catalytic, Inc., November 11, 1974. uaz10. collins, J. J., L. L. Fornoff, K. D. Manchanda, W. C. Miller, D. C. Lovell. ‘The PuraSiv S Process for Renoving 80, from Sulfuric Acid Plant Tail Gas, Union Carbide corp. (Presented at the 66th Annual AICHE Meeting, Philadelphia, November 15, 1973). Private Communication from R. 5. Twichill of the Volunteer Army Anmunition Plant, Chattanooga, Tennessee with F. D. Kodras 143SECTION Ix GLOSSARY OF TERMS, ABBREVIATIONS, AND SYMBOLS ‘The following listing is a glossary of terms and abbre- viations that are used in this report. Also included is a list of chemical symbols that are found in the report. GLOSSARY OF TERMS Absorber A device utilized to extract selectively one or nore elements of a gas stream from others by absorption in a Liguid medium. Usually the process is performed in cylindri- cal towers packed with an inert material thus providing a large surface area for intimate contact between the rising gas and the falling liquid. (The process may also be carried out in a tower containing perforated trays in which the rising gas bubbles through the layer of liquid on the trays.) Absorption ‘A process in which one or more constituents are removed from a gas stream by dissolving them in a selective liquid solvent. This may or may not involve a chemical change. Acid, New Sulfuric acid made from elemental sulfur or other sul- fur-bearing materials, but not from spent acid strengthened by addition of sulfur trioxide. 14aAcid, Regenerated High-purity sulfuric acid made from decomposition or regeneration of spent acid from petroleum refineries or other chemical processes. acia Sludge The residue left after treating petroleum oil with sul- furic acid for the removal of impurities. It is a black, viscous substance containing the spent acid and impurities which have been separated from the oil. Adsorption A reaction in which one or more constituents (adsorbates) are renoved from a gas stream by contacting and adhering to the surface of a solid (adsorbent). Periodically the adsor- bent must be regenerated to renove the adsorbate. Aerosol A colloidal system ia which particles of solid or Liquid are suspended in a gas. There is no clear-cut upper limit to the particle size of the dispersed phase in an aerosol, but as in all other collodial systems, it is commonly set at 1 micro-meter. waze, most snoke, and some fogs and clouds nay be regarded as aerosols. Agglomeration Groups of fine particles clinging together te fora a larger particle. Amb nt Air ‘That portion of the atmosphere, external to buildings, to which the general public has access. 14sboiler A closed pressure vessel in which the liquid, usally water, is vaporized by the application of heat. British Thermal Unit (Btu) The mean British thermal unit is 1/180 of the heat required to raise the temperature of one pound of water from 32°F to 212°F at a constant atmospheric pressure. It is about equal to the quantity of heat required to raise one pound of water °F, A Btu is essentially 252 calories. Burner A device for the introduction of fuel and air into a fur- hace at the desired velocities, turbulence, and concentration to establish and maintain proper ignition and combustion of the fuel. Carryove: ‘The chemical solids and liquid entrained in the steam from a boiler or effluent fron a fractionating column, absorber, or reaction vessel. Catalyst A substance capable of changing the rate of a reaction Without itself undergoing any net change. ‘The catalyst in a chamber plant is gaseous nitrogen oxides. In the contact process the catalyst is a solid, consisting of vanadium pentoxide and various promotors deposited on a highly Porous siliceous carrier. Claus Elemental Sulfur Plant A process for converting SO, to elemental sulfur by catalytic reaction with HS. 146condensed Funes Minute solid particles generated by the condensation of vapors from solid matter after volatilization from the molten state, or generated by sublimation, distillation, calcination, or chenical reaction when these processes create airborne par- ticles. converter ‘The vessel that houses the solid vanadium catalyst. The catalyst is placed in several horizontal trays or stages located in series, with means for gas cooling between the various stages. Denister (Collector) 2, A mechanical device used to eliminate finely dividea liguia particles from process streams by impaction and agglon- eration. 2. Apparatus made of wire mesh or glass fiber and used to eliminate acid mist as in the manufacture of sulfuric acid. Economizer "a heat recovery device designed to transfer heat from the products of combustion to a fluid, usually feedwater for a steam boiler. The water flows through a bank of tubes placed across the flue gases and is heated by these gases prior to entering the boiler. BEfluent Any waste material (solid, liquid, gas) emitted by a pro- cess. 147paission ‘The total amount of a solid, liguid, or gaseous pollutant emitted into the atmosphere from a given source in a given time, and indicated in grams per cubic meter of gas, pounds per hour, or other quantitative measurement. Entrainment ‘The process of particulates or other materials being carried along by a gas stream. mxeess Ai Aix supplied for combustion in excess of that theoretically required for complete combustion, usually expresses as a per- centage of theoretical air, such as "130 percent excess air." Exothermic Reaction A-reaction which produces heat. Feedstock Starting material used in a process. This may be raw material or an intermediate product that will undergo additional Processing. Flue Any duct, passage, or conduit through which the products of combustion are carried to a stack or chimney (see also breeching) . Flue Gas ‘The gaseous products of combustion passing from the fur nace into the stack. Fuel Any form of combustible matter--solid, Liquid, vapor, o= 9a8, excluding combustible refuse. 148Fume Fine solid particles predominately less than 1 micro-meter in diameter suspended in a gas. Usually formed from high- temperature votilization of metals, or by chemical reaction. Inpingement In air sampling, impingement refers to a process for the collection of particulate matter in which the gas being sampled is directed forcibly against a surface. 1. Dry impingement: the process of impingement in the gas stream where particulate matter is retained upon the surface against which the stream is directed. The collecting surface may be treated with a film of adhesive. 2. Wet impingement: the process of im- pingement in a liquid which retains the particulate matter. Inpingemeat Separators Devices using the principle that when a gas stream carry- ing particulate matter impinges on a body, the gas is deflected around the body, while the particles, because of their greater inertia, tend to strike the body and be co!lected on its sur- face. The bodies may be in the form of plates, cylinders, ribbons, or spheres. Material Balance An accourting of the weights of material entering and leaving a process. 149‘The number of holes per linear unit in a sieve or gauze, or the space between the wires of the sieve expressed in inches or millimeters. tric Ton 2204.6 pounds or 1000 kilograms. Mis A suspension of any finely divided liquid in a gas. Mist, Sulfuric acid Extremely small acid particles that are true aerosols. No exact range cf particle size is available. Net Ton 2000 pounds (sometimes known as a “short ton"). Nitrogel A general term pertaining to a mixture of nitric oxide oxides (No) and nitrogen dioxide (N02). Qleun (Fuming Sulfuric Acid) A heavy, oily, strongly corrosive Liquid that consists of a solution of sulfur trioxide in anhydrous sulfuric acid. Tt fumes in moist air and reacts violently with water. Onstrean Tine ‘The length of time a unit is in actual production. opacity The degree to which emissions reduce the transmission of light and obscure the view of a distant object. 1s0An apparatus used for analyzing flue gases volumetrically. oxidation ‘The act or process of combining oxygen with a substance, with or without the production of a flame. oxides, Sulfur As used in this report, sulfur oxides include sulfur diox- ide and sulfur trioxide, and/or sulfuric acid mist or spray. Packed Column (Packed Scrubber or Packed Tower) A vertical column used for distillation, absorption, and extraction, containing packing; e.g., Raschig rings, Berl saddles, or crushed rock, which provide a large contacting surface arca between phases. Normally, gas flow is counter current to liquid flow. Particulate Matter . Any dispersed matter, solid or liguid, in which the indi~ vidual aggregates are larger than single small molecules (0.0002 nicro-meters) but smaller than 500 micro-neters. Performance Test Measurements of emissions used for the purpose of determin- ing compliance with a standard of performance. Plume ‘the path taken by the continuous discharges of products from a chimney or stack. ‘The shape of the path and the con- centration distribution of gas plumes is dependent on turbu- lence of the atmosphere. 1stprimary Air In incineration, air which is introduced with the refuse into the primary chanber. Primary Standard The national primary ambient air quality standard which defines levels of air quality which are necessary to protect public health. ‘Ringelmann Chart A standardized chart giving shades of gray by which the densities of columns of smoke rising from stack may be com pared. Scrubber A device used to remove entrained liquids and solids from a gas stream by pa.sing the gas through wetted "packing" or spray (see absorber). Secondary Air Air introduced into a combustion chamber beyond the point of fuel and primary air introduction for the purpose of achieving more complete oxidation. Snelting Any metallurgical operation in which metal is separated by fusion from impurities with which it may be chemically com- bined or physically mixed, such as in ores. 802 Gas or $03 “as A gas in which $0, or S03 is present with other constituents Such as oxygen or nitrogen. 152spray, Sulfuric Acid Large acid particles introduced into the gas by mechanical entrainment. If emitted to atmosphere, they are invisible and fall rapidly to the ground. stack or Chimne; : Any flue, conduit, or duct arranged to conduct an effluent to the open air. sulfur, Crode A lov-sulfur-content raw material consisting of a mixture of elemental sulfur and inert material. Sulfur, Elemental Any sulfur in elemental form, regardless of source. Sulfur, Recovered An extremely high-purity sulfur containing no organic matter, less than 0.005 percent ash, and no free acid or water unless exposed to the atmosphere. (If shipped molten, it may also contain traces of hydrogen sulfide.) Surge Tank A storage reservoir at the downstream end of a feeder pipe to absorb sudden rises of pressure and to furnish liquid quickly during a drop in pressure. fail cas ‘The exhaust or waste gas from a process. 153Vapor The gaseous phage of a substance that generally exists as a liquid or solid at room temperature. Vapor Plume The stack effluent consisting of flue gas made visible by condenseé water droplets or mist. Venturi Scrubber A type of high energy scrubber in which the waste gases pass through a tapered restriction (venturi) and impact with low-pressure water. Gas velocities at the restriction are from 15,000 to 20,000 fpn and pressure drops from 10 to 70 inches water gage. Visible Emission An emission of air pollutants greater than 5 percent opacity of 1/4 Ringelmann. Waste Heat Boilers Boilers which utilize the heat of exhaust gas or process gas to generate steam or to heat water. 154ABBREVIATIONS °c ft. tt £e?, ef oF Mscfm psig PSIA scfm SCFH sp. gr. temperature, degrees Celsius feet * square feet cubic feet temperature, degree Fahrenheit pounds thousands of standard cubic feet per minute parts per million by volume pounds per square inch gauge pounds per square inch absolute cubic feet per minute measured at standard conditions: (70°F and 760 mm (29.92") Bg standard cubic feet per hour specific gravity--compared to water at 60°F 155ICAL SYMBOLS 8,80, Naz603 Naiis0, NazS0, (01) 980, NHgis0, (nH) 2595 carbon dioxide water ammonia nitrogen total nitrogen oxides in a mixture oxygen sulfur sulfur dioxide Sulfur trioxide sulfuric acid sodium sulfite sodium bisulfite sodium sulfate ammonium sulfate ammonium bisulfite ammonium sulfite 156UNITS OF MEASURE Conversion Table pegrees Fahrenheit (°F) 9/5 Degrees Celsius (°C) + 32 inches (in) = 215 Centimeters {cm) Feet (ft) = 30 Centerneters (cm) square Inches (in?) = 6.5 Square Centimeters (em?) cubic Feet (ft?) (cf) = .03 Cubic Meters (n°) Pounds (1b) = 45 Kilograms (kg) ‘ton (short) = .9 Tonnes (t) Gallons (gal) = 3.8 Liters (1) Pounds Per Square Inch (psi) = .06 Kilograms Per Square Centi- meter (kg/om2) 4s?APPENDIX A PROCESS DESCRIPTIONS SULFURIC ACID PRODUCTION AND ‘ATL GAS CLEANING PROCESSES Table of Contents ‘Theroretical Operating Data for Sulfuric Acid Plants . . 159 Single Absorption Process for Sulfuric Acid Production... eee ee eet ee ee ee 162 Dual Absorption Process for Sulfuric Acid Production . . 169 Sodium Scrubbing Process for Sulfuric Acid Tail Gas Cloaniigy soc ee 178 Ammonia Scrubbing Process fo.: Sulfuric Acid Tail Gas (Cleantrigisecse screen eg sae ates as, 8d Molecular Sieve Process for Sulfuric Tail Gas = Cleanings. eee te et ee te tee 1586st OPERATING DATA FOR THE SULFURIC ACID PLANT (THEORETICAL) TABLE 17 Pressure, in. 1,0 ‘Temperature, °C uocation in acid plant 316 tons/day 150_tons/day 316 tons/day 150 tons/day Enter blower =5 3/4 =. 0 (32°F) 14-57°F Enter dry tower 95 172 282 29.0-(85) Leave dry tower =. 60- (35) - Enter sulfur burner 89 1/2 26 1/2 Leave sulfur burner 24 1/4 25 3/4 972- (1782) 948- (1738) Leave boiler #1 78 24 374 424- (795) 293- (559) Enter filter 16 24 174 434- (813) 427~ (801) Leave filter 67 3/4 22.174 nn Enter pass #1 66 3/4 22 426- (799) 405- (761) 60 374 19 3/4 476- (889) 476- (889) Leaw pass #1 60 1/4 17 374 = ~ 56 1/4 (1134) 603- (1117) Air enter pass #2 46 1/2 1s 3/4 450- (842) (824) Leave pags #2 37 1/4 12174 510- (750) 491- (916) Air entef pass #3 26 1/4 2 439 (822) 434- (813) Leave pass #3 29 9 3/4 447- (837) 439- (822) Enter pass #4 28 1/4 91/2 422- (792) 401-(754) Leave pass #4 19 3/4 4 426- (799) 400- (152) Enter economizer 16 3/4 31/4 = - Leave economizer 7 ii 259- (498) 198-(398) Enter 98 absorber 6 1/2 ~ 240~ (464) - Leave 98 absorber 4374 we Pressure drop (knock out) 1 Pressure drop demister 3 3/8 - Leave burner 971- (1780) 948- (1738) Leave boiler 423- (793) 294- (561) Enter hot gas filter 434- (813) 430- (806) Enter "A" layer #1 425- (797) 405-(761)* Leave “A” layer #1 476- (889) 476-(889)* "see Table 5oot TABLE 17 (Continued) Pressure, in. 11,0 ‘Temperature, °C Location in acid plant 316 tons/day 150 tons/day 316_tons/da 150 tons/day Leave "B" layer #1 612-(1134) 603-(1117)* Enter layer #2 438- (820) 440- (825) Leave layer #2 500- (932) 491-(916) Enter layer #3 439- (822) 434~ (813) Leave layer #3 448- (838) 439- (822) Entor layer #4 423- (793) 401- (754) Leave layer #4 427- (801) 400-(752) Leave economizer gas 259-(498) 198- (388) *See Table 5. Parameter 316 tons/day 150 tons/day ower pm % So, after boiler #1 #803 into reactor 4 S03 ont stack & Cofversion Stack appearance Boiler #1 bypass valve Boiler #2 bypass valve Superheater #1 valve Superheater #2 valve Saturated steam bypass Sulfur consumption Production rate @ 100% 250, 4225 10.3 9.5 0.25 : 97:55 -gooa 28° open closed full open 1/2 open closea 212,550 1b/day 632,250 Ib/aay 2400 10.3 8.5 0:19 98.0 good 32° open 3/4 open full open 1/2 open closed 2 Ib/he19t TABLE 17 (Continued) Parameter 316 tons/day 150 tons/day Temperature of sulfur in pit, °c 140°- (284) 140°- (284) Temperature of sulfur entering burner, °C aoe- (284) Qn) Saturated steam, psig 338 Superheated steam, psig 322 Superheated steam, °C 307° (585) (599) 110 psig steam to plant, ° 254° (489) (545) Rate of flow to plant, ibs/hr 32,800 Feed water entering economizer 105°~ (221) (219) Feed water leaving economizer 208°- (406) 213°- (415) Temperature of acid entering acid absorber, °C 82- (180) 80- (116) ‘Temperature of acid leaving acid absorber, °C 120- (248) 91- (298) Strength leaving acid absorber 99.178 99.18 Acid level tank-o-meter, in. 814 8.2 ‘Temperature of acid entering dry tower, °C 68- (154) 60 (140) ‘Temperature of acid leaving dry tower, °C 66- (151) - Acid level tank-o-meter, in. 7-45) 7-(75) Temperature of acid leaving pumps, °C (66°Be") 110- (230°F) 98- (208)PART 1. SINGLE ABSORPTION PROCESS FOR SULFURIC ACID PRODUCTION 162MAJOR EQUIPMENT LIST Figure A-201 SINGLE ABSORPTION SULFURIC ACID PLANT Equipment Number Description e101 Sulfuric Furnace F-102 Air Filter c-103 Main Air Blower v-104 Drying Tower B-105 Waste Heat Boiler No. 1 X-106 Economizer After Fourth Bed v-208 Converter with Four Catalyst Beds v-109 Secondary Absorber Tower v-110 Secondary Absorber Acid Cooler Be111 Waste Heat Boiler No. 2 v-112 Secondary Absorber Acid Pump znd Tank X-113 Product and Storage Tank X-114 Product Acid Cooler MoUs Drying Tower Acid Cooler x-119 Product Acid Cooler 163¥9T Figure A-201 MATERIAL BALANCE SINGLE ABSORPTION PLANT Stream No. a 2) (3) Description* Sulfur Air to Air to Feed Drying sulfur ‘Tower Burner sulfur, § 0,332 Sulfur Dioxide, $0, Sulfur Trioxide, 505 air 2.988 2.988 Sulfuric Acid, #50, : Sulfuric Acid Mist Water 0.030 Total (tons per day) 0,331 3.018 2.988 Temp (°C) 135 50 50 Pressure (inches water) 85 80 Corzosition 10.20 Conversion Total (scrM) 51.9 514 Total (gal/min) *Flow Basi: one ton per day 100 percent H,S0, production. CO) Gas Leaving Sulfur Burner 0.663 2.656 3.319 850 18 $0 (Volume) 509, is) cas Entering Converter 0.663 2.656 3.319 410 60(Continibea) Streas Ne. “) m @ «3 ao) Deseription® cae Gas mitoring olewn Product: cas Leaving Gan Entering tanving Sleun Tower Leaving Oleun over Oleun Tower Absorption Tower converter (wo! Oleun Production) sutur, 5 Sulfur Dioxide, 30, 0.010 0.010 Sulfur Teioxite, 50, o.a6 a o.a16 Me 2.483 2.493 Lalfurte Acka, 1,504 Sulfurte Acta Mist Total (tons per day) sans 3319, ‘reap. (20) “ws 10 Depends on £05 absorbed 1s aso Pressure (inches water) 20 10 3 10 Composition 10.6 05 (volume) 256 oleun conversion 90.50 of so, te 505 ‘otal (sera) ° a0 «0 ‘total (gal/ain) sriow taster one ton per day 1008 1,50, production.oot Strean to. pp Description’ noid Product sulfur, 5 Sulfur Dloxige, 50, Sulfur Trioxide, 505 Ae Sulfurte Resa, 1,504 1,000 Sulfurte Acta Mist Water 020 Total (tous per day? 1.020 ‘temp. (*0) 7” Presmare (inches water} composition conversion Torah (serm) Total (ga1/ain) 091 an Gas Leaving ‘Rororption "Tower 2493 2.503 8 3 3995 Ppa 80, 43.06 ‘rio pasta: one ton per day 1008 1,504 production. cexetneth wo se Lie ae aes an 25 x an 04 for su Tower 10 as y$04 Clrcuiation 20 nbaorption 10.000 as 50, circufatton Drying Tower 9.054 so a2PART 2 DUAL ABSORPTION PROCESS FOR SULFURIC ACID PRODUCTION 168MAJOR EQUIPMENT LIST Figure a-202 DUAL ABSORPTION SULFURIC ACID PLANT Equipment Number Description +201 Sulfur Furnace P+202 Air Filter ¢-203 Main Air Blower v-204 Drying Tower 3-205 Waste Heat Boiler -206 Economizer After Fourth Bed X-207 Economizer After Third Bed v-205 Converter With Four Catalyst Beds v-209 Secondary Absorption Tower X-210 Secondary Absorber Acid Coolor x-211 No. 1 Heat Exchanger ve2.2 Primary Ahsorber Acid Pump and Tank v-213 Product Acid Storage Tank X-214 Product Acid Cooler X-215 Drying Tower Acad Cooler v-216 Drying Tower and Secondary Absorber Acid Pumps X-217 No. 2 Heat Exchanger X-218 Steam Superheater X-219 Product and Cooler X-220 Primary Absorber Acid Cooler e221 Primary Absorber Tower 169out Pigure A-202 MATERIAL BALANCE DUAL ABSORPTION PLANT Stream No. a Description* sulfur Feed sulfur, $ 2327 Sulfur Dioxide, $0, Sulfur Trioxide, S03 air Sulfuric Acid, #,S0, Sulfuric Acid Mist Water Total (tons por day) 2327 Temp. (°C) 135 Pressure (inches water) Composition Conversion Total (SCFM) Total (gal/min) ‘Flow Basis: @ Air to Drying Tower 2.945 0.030 2,945 50 78 52.2 one ton per day 1008 #0, production. a) Air to sulfur Burner 2.945 2.945 50 76 51.2 4) Gas Leaving sulfur Burner +653 2.618 3.271 850 78 10.1 $0, (Volume) 50.2ut ‘Stress No. Deseriptian* sulfur, § Sulfur Dioxide, 50, Sultur Trioxide, £05 Mr Sulfurte Acta, 604 Sulfuric Acie Mist Mater ‘otal (tons per day) ‘temp. ("0) Pree 1e (inches water) Composition ‘conversion Total (scrH) ‘Total (gel/atn) *mlow Basis: one ton per “s) cae Entering Convertor 653 2.618 aan a0 0 10, 50.2 yy 1008 1,80, production. (Contineed) Gas taaving Sra stage of Converter on 790 2.460 aan us ss -44 805 (Voluse) 96.78 conversion Of" 80, to 805 as o cae oleun Tover 150 “ @ oteun Product Teaving oteun Tower Depends on $0, absorbed 250 oteunut ‘Seroan to. Descriptions sulfur, 5 Sulfur Dioxide, 50, Sulfur trioxide, 50, ry Sulfurte Rela, 1,804 sulfurte Acta Mint Water ‘Total (tne per day) ‘esp. -(*0) Pressure (inches vater} ‘cospost tion conversion ota (scr) ‘Total (gal/min) ‘Plow Bante: one ton per ry ° ay 1008 #50, production. (Continued) ao) cag notering Primary ‘absorption Tover’ (qo Sleus Producten son, 190 2.460 aan 150 “ ane an neta Product 1,000 1.000 ga ae teaving Peinary Absorpeion Tover 2.460 1 “0 0700 PPB 50strana to. Description? sulfur, 5 Sulfur Dioxide, 50, Sulfur Trioxide, 505 Me Suifurie Acid, 1,50, Sulfuric Acid Mit ‘otal (tons per day) Teap. (*c) Pressure (inches water) cosposition Conversion ‘otal (scrm) ‘otal (gal/ain) sriow Bass (Continued) sore te weit coc es Absorption fort Ofeuh Tower Abeorption rovers se ae as 0 0.030 one ton per day 1008 3804 production, g5y Shecntats 2 acinaey aprorpelon fever 10.953 20.953 0 ase y$04 Circulation to secendary Absorption Tovar 0.592 8.532 ” ors(Continued) Bescriptiont aity ag Eatortng circulation to ‘deh stage’ eying Tover of Converter surtar, § Selfur Dioxide, £0, 021 sulfur tehoride, 805 ae 2.460 Sulfurte Acta, 1,50, Sulfuric Acid Mist ‘Sater ‘Total (tons per day? emp. (") 24m so as Prassure (inches water) “o Componttion conversion otal (scr) ans ‘potal (gal/atn) 0.022 eriow baste: ‘one ton per day 1000 8,60, production, ane as) as Entering ‘econsary’ Absorption Tower +0005: 1026 2.455, ao ean Gas frou ‘Secondary ‘Abeorber 2.455 7 228: pra Sy 22PART 3 SODIUM SCRUBBING PROCESS FOR SULFURIC ACID TAIL GAS CLEANING 176MAJOR EQUIPMENT LIST Figure A-203 SODIUM SCRUBBING PROCESS ‘Bquipment Number Description B-301 Booster Fan v-302 Prescrubber P-303 Prescrubber Circulation Pump D-304 Denister > v-305 80, Scrubber p-306 $0, Scrubber Denister Pad P-307 $0, Scrubber Circulation Pump v-308 Brine Holding Tank 2-209 Brine Holding Tank Agitator P-310 Brine Feed Tump to Evaporator - Crystallizer vou Evaporator - Crystallizer x-312 Heat Exchanger for Evaporator - crystallizer P-313 Evaporator-Crystallizer Pecizculation Pump Pos Evaporator-Crystallizer Discharge Pump 5-315 centrifuge v-316 Mother Liquor Tank A317 Mothex Liquor Tank Agitator P-318 Mother Liquor Discharge Pump c-319 Conveyor for NayS0, Crystals to Dissolving Tan! v-320 Dirsolving Tank 477Equipment Number an321 +322 x-323 v-324 P3275 v-326 327 v-328 p-329 Description Dissolving Tank Agitator Dissolving Tank Pump Condenser Separator Tank Separator Tank Condensate Pump 50 Percent NaOH Storage Tank 5G Percent NaOH Pump Alkali Make-Up Tank Alkali Make-Up Tank Discharge Pump 178ser Figure A-203, MATERIAL BALANCE SODIUM ScRUBETHG PEOCERS ‘Scrubber soitur, 8 Sulfur Dioxide, $0, 0.00996 Sulfur Trioxide, 50, ae Sulfuric Acie Sulfurie Acid Mis water Sodium Bisulfite, NaHsO, Sodium Sulfite, Na,s0, Sodium Sulfate, Na,504 Sodium Hydroxide, Naot ‘Total (tone per day) aes9e ‘Total (scrH) S130 ‘cotal (Gallons per minute) ‘Temp. (*C) 1% Pressure (laches of water composition 1860 2pm 80, conversion *riow nents: one ton per day 1008 1,604 production, Leaving Tackes tower Gas Serubber 0.00080 2.025 51.30 1s 86 pom 50, 958 Scrubber Bfttotency o doduun Hydroxide Packed car Servbber 001216 001316 ‘oozes? 900322 20ost (Continued) ‘Stream Wo. w wy co) a Description’ scrubber Brine Scrubber Brine Brine Feed fron Gas exiting Bleed to Holding Recirculation to Holding Tank to the Evaporator "Tank Packed Gas Serubber Evaporator-crystallizer Crystaliizer sulfur, § Sulfur Dioxide, $0 0.00381 Sulfur Trioxide, 50, 5 Mr Sulfurte Acta Suifurie Acta Mist water 0.3882 5.6054 0.3882 0.03010 Sodium Bisuifite, waHs0, 0.01238 1.9534 o.01238 . Sodium Suifive, Ne,505 0.00323 0.5096 0.00323 Sodium Sulfate, Na,60, 0.00269 0.4246 0.00268 Sodium mydroxtde, Naot ‘Total (tons per day) 0.08382 0.08382 0.04191 ‘otal (scrH) Aonsy, ‘otal (Gallons per minute) 00096 0.00896 Lises, ‘Temp. (*c) Presuure (inches of water) composition Conversion *rlow nasie: one ton par day 100% 1,804 production,wt Stream No. 1} Descriptions Gas Entering ‘the Separator ‘rank solfur, 5 fur Dioxide, 50, Sulfur Trioxide, 55 air Sulfuric Acid Sulfuric Actd Mist 0381 water 0.03810 Sodium Biauitite, waHso, Sodium sulfite, Naps05 Sodium Sulfate, maj50y odie Hydronide, Hoh Total (tons per day) a,oansn ‘oval (scr) 1.9851 ‘otal (Sallons per ainuted tasp. ("e) Praswure (inches of water) Composition conversion ‘low Besta: one ton per day 1000 #50, producto (Contsnudd 0) a0) Recycle Condensate from eee Separator tank Acid Plant. Racyeied to Dissolving Tank 0.00301 0.02010 0.00381 0.03010 0.02968, 0.00634 ay concentrated Liquor Peed e> centrifuge 0.00182 0.03099 0.00465 o.o1si6(Continued) ser00e Hoe oo wa Ben £0, {2 ya, 20, Bescriptiont 1a950, Crystals in,80, Slur: ta,$09 and Na, : to biosdivin Becdeie tor sider} to mother* Packed Gas Scrubber Liquor Tank ae, Haz 604 Purge sulfur, Sulfur Dioxide, 50, Sulfur-trioxide, $05 Mr Sulturte Acta Sulfuric Acid Mise Water 000745, 01024 Sotium Blaulfive, Naltso, Sodium Sulfite, 3505 00546 00846 -09353 00353 00177 Sodium Sulfate, 1a,50, 0.00465 0.00465 100223 Sodium Hydroxide, Naolt ‘Total (tons per ay) 1906205 0237 00096 00055 00449 Total (scrH) Total (Gallons per minute) ‘Temp. (*c) Pressure (inché 000775, 900388 tH of water) Composition Conversion Orie ton per day 1000 #60, production.PART 4 AMMONIA SCRUBBING PROCESS FOR SULFURIC ACID TAIL GAS CLEANING 184MAJOR EQUIPMENT LIST Figure a-204 AMMONIA SCRUBBING PROCESS Equipment Number Description v-400 Packed Tower Gas Scrubber - 1 P-401 Ammonia Scrubber Brine Circulation Pump v-402 Packed Tower Gas Scrubber - 2 v-503 Ammonia Scrubber Brine Circulation "ump v-504 1.D. Exhaust Fan v-405, Holding Tank v-406 Holding Tank Mixer v-407 Ammonia Brine Preparation Tank Mixer F-408 Brink Filter P-409 Ammonis Brink Preparation Tank Pump x-410 Ammonia Vaporizer van Ammonia Brine Preparation Tank 185oer Figure A-204 MATERIAL BALANCE AMMONIA SCRUBBING PROCESS Stream No. a a Descriptions rain Ges Entering Cleaned cas Leaving Packed Tower Gee ‘Packed Tover Cas ‘Serubbere ‘Serubbere suifur, 6 Sulfur Dioxide, 50, + 0.00896 0.00080 Sulfur Trioxide, 505 . ar 2.022 2.022 Bulferic Acta, 1,50, Sulfurie Acid Mist Ammonium Bisulfite, NiKSO, ‘Ammonium Sultite, (1) 60, Ammonium Sulfate, (Hy) 504 Ammonia (Anhydrous) ‘total (tons par day) ‘Total (ScPM) 51.38 31.30 ‘otal (gal/ain) ene. (*C) 6 8 Pressure (inches vater) Composition 1860 ppm 50, 86 ppa 50, Conversion 954 scrubber Eefiote slow basis: one ton per day 1000 1,504. production. o, Ammonda Maka to" Packed Tower Coa ‘Sorubber 0.00189 o.o0189 0.05544ut ‘Stream Ho. Dascription* suttur, 6 Sulfur Dioxide, so, Sulfur Trioxide, 505 Mr Sulfurte Acta, 1,504 Aulfurie Acid Mist water Ammonios Bisulfite, N,H50, ‘Ammonium Sulfite, (iy) 7503 Ammonium Sulfate, (W250, Ansonia (Anhydrous) ‘Total (tone per day) otal (scr) ‘otal (gel/ain) Teap. (°C) Presmure (inches water} composition Conversion snes (Conesived) w (sa Scrubber Brine Serubber Brine Bleed to folding Tank Recirculation o,026e. 5 2.693 0.01039 0.9595, 0.00377 o.aoss 0.00204 0.2505 0.04261 2465 0.00720 0.707 81 One ton per day 100% #50, production, (30) Sequbber Brine ‘Circulation 2.633 0.9595 0.4038 0.2505 4.2485 0.707 sr Brine Feed to Regeneration Colum c.02601 0.01039 0.00377 0.00204 0.04261 0.00720oer Streas No. Description? suitor Sulfur Dioxide, 50, Sulfur Trioxide, 505 ar Sulfurie Aeld, 4,604 Sulfurte Acid Hiat water Aasoniun Biaulfite, MHyHSO, Ammonium Sulfite, (sy) 7603 Ammonium Sulfate, (Wy) 750, Amwonta (Anhydrous) ‘otal (tone per day) ‘otal (scr) ‘otal (gal/atn) Tenp. (*c) Presmure (inches water) composition Conversion sriow bass 1 One ton per day om as Baiting the Regeneration Column 0.003355, 0.000945, 0.004300 0.0523 1000 13,80, production. (Continued) Gas Entering the Separator yank 0.003355 000845 0.004200, 0.823 0, Recyel Ban co seid Plant 0.003355, 0.003355, 0.0261, a0) reed fo Vertical ‘Ribe Evaporator o,ens25, 0.03966 an Annoniisn sulfate Solution Feed t> enerifuge 0.00129 0.01325 o.oreseon Stream No. Description’ seifur, 5 Sulfur Dioxide, 50, Sulfur Trioxide, 505 ate Sulfurte rela, 1,50, Sulfurte Acta Mat Ammonium Bisulfite, NigKEO, Anmoniun Sulfite, (Hi) 50, Ammontun Sulfate, (My) 250, Ammonia (Anhydrous) ‘Total (tons per day) seal (ScrH) ‘otal (gal/atn) emp. (°C) Pressure (inches water) Composition conversion slow Bastar one ton per day 1000 H,50, production. aa ‘Ammonium Sulfate Peed to Oryer 0.00036 0.00265 9.0030 (Continued) 0.01060 01159 ao amoniun sulfate Exiting ‘the Dryer 0.00003 0.00265 0.00260 as Ammonia sulfate e> ‘storage 0.00003 0.00265 0.00268PART 5 MOLECULAR STEVE PROCESS FOR SULFURIC ACID TAIL GAS CLEANING 392MAJOR EQUIPMENT LIST Figure A-205 MOLECULAR SIEVE PROCESS Equipment Number Description X-500 ‘Tail Gases Cooler X-501 Tail Gases Demister v-s02 Acid Circulation Pot P-503" Acid Circulation Pot Pump v-504 80, Absorbers P-505 1.D. Fan for Tail Gases F-506 Air Filter X-507 Condenser v-508 Air Dryers X-509 Furnaces P-510 I.D. Pan for Air Osi Drier Regeneration Fan 2512 80, Gas Cooler 192e6t Stream No. Description* sulfur, $ Sulfur Dioxide Sulfur Trioxide, so, Sulfuric Acid Mist Water Air Total (tons per day) Total (SCFM) ‘Temperature (or) Pressure (inches of #0) Composition Removal Efficiency *Plow Basis: ne ton per Figure A-205 MATERIAL BALANCE - MOLECULAR SIEVE PROCESS a Q Tail Gases Entering Demisted Gases Demister Entering $0, Adsorbers 0.00994 0.00994 0.00082 0.000082 2.822 2.822 2.833 2.832 51.38 51.38 170 170 35 in, #20 28 in. H,0 1560 ppm 0. 1560 ppm SO. day 100% #260, production. Dy Collected Mist Flow from Demister To Acid Circulation Pot 0.000738 90% Acid Mist Removalvet (Continued) Stream No. (ay Description* Clean Gases out from Adsorbers to Stack sulfur, $ Sulfur Dioxide, 50, 0.0000994 Sulfur Trioxide, so, Sulfuric Acid Mist Water Air 2.8220 Total (tons per day) 2.8221 Total (SCFM) 51.38 ‘Temperature (°F) 100 Pressure (inches of #,0) 18 in. H,0 Composition 15-25 ppm $0, Removal Efficiency 998 So, ‘Flow Basis: One ton per day 100% H,S0, production. (5) Containing Deforbed Gases Recycled to Acid Plant 0.00994 0.5648 0.56434 10.5 200 6000 ppm SO, (6) Air Plow to Air Dryers 0.0115 0.5650 0.5765 10.5 60set Stream No. Description* Sulfur, § Sulfur Dioxide, 80, Sulfur Trioxide, So, Sulfuric Acid Mist Water air Total (tons per day) Total (SCFM) Temperature (°F) Pressure (inches of #,0) Composition Removal Efficiency (Continued) (2) Dry Air Flow From Air Dryers ‘To Furnaces 0.565 0.565 10.5 60 *Flow Basis: One ton per day 1008 production. (3) Dry Heated Air Flow From Furnaces To Adsorbers 0.365 0.565 10.5 200erase wesAPPENDIX B PLANT START-UP DATA 197No. 25 26 27 28 29 30 2 32 33 36 35 36 37 38 39 40 a LIST OF FIGURES Appendix B Dual Absorption Plant Start-Up 8 June 1974 Three Hours to Compliance , Dual Absorption Plant Start-Up of 29 June 1973 - A Series of Two Malfunctions With Each Start-Up Requiring Less Than One Hour to Reach EPA Standard Single Absorption Plant Start-Up 20 August 1973 Unstable Start-Up of Less Than wo Hours After Two Hour Shutdown Dual Absorption Plant 6 September 1973 shutdewn Dual Absorption Plant 7 September shutdown Dual Absorption Plant 11 September 1973 start-up Dual Absorption Plant 16 September 1973 start-up Single Absorption Plant 17 Septenber 1973 start-up Dual Absorption Plant 2 October 1973 Szart-Up Dual Absorption Plant 23-24 October 1973 Start-Up Dual Absorption Plant 31 October 1973 Start-Up Dual Absorption Plant 20 November 1973 Start-Up Dual Absorption Plant 27 Novenber 1973 Start-Up Dual Absorption Plant 29 November 1973 Start-Up Dual Absorption Plant 1 December 1973 Start-Up Dual Absorption Plant 30 April 1974 start-up Dual Absorption Plant 20 October 1974 Start-Up 198DUAL ABSORPTION PLANT START-UP 8 JUNE 1973 3 HOURS TO EPA CONPLTANCE oo Figure 25 Percent Efficiency (exit stadk) ‘802 Conversion ' a O° EPA Standard 3000 = go Percent Efficiency f— 98 — 97 — 96 — 95 — 4 66t — 3 — 2 2 — 9 EPA Stendard 300 ppa Tame HoursDUAL ABSORPTION PLANT SUAT-UP OF 29 JUNE 1973 A SERTES 07 TWO MALFUNCTIONS WITH EACH STAKT-UP REQUIRING LESS THAN ONE I1OUR TO REACH EPA STANDARD ppm 80, Figure 26 Percent nefteteney (exit St oe 802 Conversion | prichtanbabaiib i 5 +i 100 gpa standard Pen ay Percent 2000 — A 98 beticlency 98 7 96 95 4 93 92 on 20 A stand 0 ppm ‘Tine Hours‘SINGLE’ ABSORPTION PLANT START-UP 20 aUcUST 1973 ae: UNSTABLE START-UP OF LESS THAN e 43 7 ‘TWO HOURS APTER TWO HOUR SHUTDOWN Ng Percent Efficiency (exit stage) Figure 27 ee , 802 Conversion + - Fj— 100 PA Standard 7 Percent 3900 99 Efficiency 98 97 2500 96 98 . 2000 9% 2 93 92 1soc — ot 90 1000 —! 500 =} EPA Standard 300 ppm b ! ° 1 2 3 4 5 Tine HoursDUAL, ABSORPTION PLANT © 6 SEPTEMBER 1973 SHUT-DOWN — ee Percent Efficiency Ppm SO, et Ett (Exit stazk) “ 802 Conversion 100 EPA, Standard Porcent Efficiency 99 — 98 — 97 — % — 95 2000 — 9% zoz — 9 —2 — a — 9% 2A Standard 20 ppm ‘Time Hours ;DUAL ABSORPTION PLANT 7 SEPTEMBER 1973 Figure 29 0, oe Percent Efficiency taek) er 802 Conversion i a — 100 PA standard Percent 99 Efficiency 98 7 Ppa (exit Si 3000 2500 96 95 94 coz 3 92 Ey 30 500 EPA Standards 300 ppm ‘ine HoursDUAL ABSORPTION PLANT 11 SEPTEMBER 1973 — ‘START-UP so, (exit state) wii Percent Efficiency 802 Conversion [— 100 EPA standard Percent 99 Effictency 3000 —| 38 ” 96 9s 9% voz” 93 92 on 90 EPA Sy 300 pe ‘Tine HoursDUAL: ABSORPTION ‘PLANT 16 SEPTEMBER 1973 ‘START-UP ; Figure 31 : Percent Efficiency ry " | 802 Conversion Z 100 EPA standard : Percent om EE 99 Ef fictency pa 80). (exit seazk) 98 97 96 95 34 soz 33 92 2 90 EPA Standard 300 ppm b 1 ° 1 2 3 4 5 6 ’ ‘Tine Houre :oz pom 80, (Bett Stack) 4000 3500 3000 2500 2000 150% 200% SINGLE ABSORPTION PLANT : ‘START-UP 5 ¥ 17 SEPTEMBER 1973 oe aay Figure 32 ie ey ee % ‘WELLMAN-LORD SODIUM “SCRUBBING SYSTEM DOWN ee 0 hee 30) 36) 60 ak na a2 ‘Time (Houre) Etfictency 100 90 80 70 60 50. 40 30 20 10DUAL ABSORPTION PLANT ‘START-UP 2 OCTOBER 1973, pen $0, Figure 33 Percent Efficiency (exit stage) 802 Conversion 100 EPA standard Percent t= 99 Erictency — 98 3900 —: t i— 97 iL 96 | 95 — 4 Loz — 9 — 2 Ee 90 EPA Stan; 300 ppm Tine Houreppm $0, (Exit Stack) gor EPA Standard, 300 ppm 4000 3500 3000 2500 2000 1500 1000 500 DUAL ABSORPTION PLANT 23-24 OCTOBER 1973 START-UP Figure 34 yp ou Tine (Kours) 16 18 20 2 26 26 Percent Effictency $0, Conversion 100 90 80 70 60 30 40 30 20 10 EPA StandardDUAL ABSORPTION PLANT START-UP 31 OCTORER 1973 Figure 35 em 50, Percent Effictency (exit Stade) 809 Conversion i —* 100 3o00 —E 99 Efticiency i— 97 i— 96 I— 95 60z — 90 ERA St 300 ppm Tine HoursDUAL ABSORPTION PLANT ‘START-UP 20 NOVEXBER 1973 Pigure 36 pom $0, Percent Effietency (exit stage) 802 Conversion 1—_100 5 mi soo =F Eh — 8 7 2500 — % — 8 2000 — 4 soe 500 —: EPA Sed. 300 pom Tine HoursPpa SO, (Exit stagk) 3000 DUAL ABSORPTION PLANT staRT-UP 27 NOVEMBER 1973 Pagure 37 Percent Efficiency $0, Conversion ,— 100 99 aia | uz EPA Standard 300 ppm 5 6 Tine Hours og 7 96 — 95 — 9 — 9 — 2 9 — 90 EPA Standard Porcent EfficiencyDUAL ABSORPTION PLANT START-UP 29 NOVEMBER 1973 Figure 38 pn $0, Percent Efficiency (exit staék) S02 Conversion FELT 200° ea standard Percent Conversion % 98 ” 96 95 6 zz 93 92 2 90 EPA Standard 300 ppe | Poor tT seas see ine HoursDUAL ABSORPTION PLANT START-UP 1 DECEMBER 1973 Figure 39 ppm 80, Percent Efficiency (exit stagk) 802 Conversion, = 100 EPA standard Percent 3000 —| — 99 Conversion i — 98 ” 2500 96 95 2000 4 ez 33 92 2 90 EPA Standard 300 pps b ‘Time Hourspte pa $0, (Exit Stack) 3000 DUAL ABSORPTION PLANT START-UP OF 30 APRIL AFTER ONE HOUR , SHUTDOWN WITH ONE HALF HOUR TO EPA STANDARD ure 40 ‘Tine Rours Percent BEfictency 100 9 38 7 96 8 i— 9% 2 92 — 91 — 90START-UP 20 OCTOBER 1974 Figure 41 ppm.S0, Percent Efficiency (exit stabk) $0, Conversion y— 100 EPA Standard Percent [— 99 Efficiency 3000 = — 98 7 — 96 ~ 95 — 4 st — 3 —2 — 91 90 EPA Standard 300 ppm et ent | l 3 4 ‘Tine Hours -APPENDIX C STATISTICAL ANALYSIS OF PROCESS PARAMETERS AND EMISSIONS Table of Contents Regression Analysis Model of Dual Conversion Acid Plants - Mehta... ee ee ee et ee ee ee OWT Statistical Analysis of Dual Conversion Acid Plants - Mixon, see et ee et ee ee eee 286 216REGRESSION ANALYSIS MODEL ov DUAL CONVERSION ACID PLANTS catalytic, Inc. Project 42466 EPA Contract 68-02-1322 27An attempt was made to explain SO, emission in terms ot process control parameters in #SO, plant, particularly temperatures of the four catalyst beds in which SO, to 50, conversion 1s carried out. Data were collected from two, dual absorption sulfuric acid plants: 1) Sulfuric acid plant of ASARCO at ElPaso, Texas, and 11) TexasGuif sulfuric acid plant. ach data point constituted 9 observations. They are: 1) parts per million (ppm) of SO, - exit stack and 11to ix (X) Inlet and outlet temperature in °F of four catalyst beds. For easy interpretation data are divided in two parts. 1) start-up and shutdown of plant and 11) normal plant run. Several models were tried using multiple regression with ppm of SO, as the dependent variable and process parameters and their different transforms selected as Andependent variubles. In the following pages each model is described ir brief, Complete computer results are attached. ASARCO ta set (ASAR1) consist of 30 data Normal run points selected randomly from normal plant run, Different statistical models were tnen tried on this set. 218Run 1 SO, emission as a function of inlet temperature of the four cat*tyst beds. Y= RH LH Od + Ky KE KY HF The regression was not significant at the 5 per cent level. Run 2 80, emission as a function of inlet and outlet tempera- tures of the four catalyst beds. Ms Ky # Oya + M32 + ged + Ma + oa + KK + oxen ‘The regression was not significant at the 5 per cent level. Run 3 80, emission as a function of inlet temperature of the four beds and temperature rise across each bed. YL = ody # My KL MKS EMS AS HOM, RTH Xe (2x1) # RM _ (EAB) + My (26-25) + OX (x8-x7) ‘The regression was not significant at the 5 percent level. Run 4 80, emission as a function of temperature increase across the four catalyst beds and temperature drop across inter coolers. V1 = ap + % (xQex1) + Xp (xed) + My (x6-x5) +My (XBERT) # OMe X32) + OM CS—alt) + oy (x7-x6) ‘The regression was not significant at the 5 per cent level. 219Run 5 = SO, emission as a function of inlet temperature at the four catalyst beds and temperature drop across the three inter coolers. YL = yt Ry xD + 0K, 13 + OG x5 + OXY HT $M Lx5oK2) + Xo (x5exH) + My x76) ‘The regression was not significant at the 5 per cent level. Run 6 80, emission as a function of tenperature rise across the four catalyst beds and equilibrium constants at the inlet temperature of each bed. YL = Mo t ALTO KBH ORS XE IKI og (x2-x1) + OX (HB) # 06x45) Hoag (8-7) where C= EXP (8929/(460 4x1) ~ 1.678) F = EXP (8929/(N60 4x3) ~'4.678) I= EXP (8929/(460 4x5) ~ 4.678) L = EXP (8929/(460 4x7) ~ 4.678) ‘The regression was not significant at the 5 per cent level. For this data none of the models satisfactorily e:plain $0, emissions in terms of the process parameters, from point of view of 6 significant regressions. Several explanations for lack of fit are: 1) variables on the right-hand side are not independent of each other and are highly correlated, 41) there are other process parameters (measured and not measured) which affect the SO, emission which were not taken into account; e.g-, concentration of ll,S0, used in absorption tower, initial concentration of S0,, furnace temperature and catalyst coins. 220Tt 4s known that S0, to SO, conversion 1s favored by lowering the temperature at which reaction takes place and it 1s also known that reaction rate 1s favored by higher reaction temperature. This sets a definite range on the temperature of Catalytic oxidation zones. Thus, to have 80, emission below certain set level, the eight temperatures should be controlled within a certain range. To find out this range, 64 data points were randomly selected from the normal plant run (ASAR 3) and standard statistics were cal- culated. Summary of the calculations is as follows: Variable Mean 95% range for xi Rt Rit 26 PPM SC, Exist Stack 127 0-307 Temp. (°F) Inlet 1st 824 810-838 converter Bed Temp. (°F) Outlet 1st 2041 9B - 1133 Converter Bea Temp. (°F) Inlet 2nd 837 819 - 855 converter Bea Temp. (OF) Outlet 2nd 892 811 - 973 converter Bea Temp. (°F) Inlet 3rd 786 734 ~ 838 ‘Converter Bed Temp. (°F) Cutlet 3rd 191 737 - 845 Converter Bed Temp. (CF) Inlet 4th 162 Tou ~ 820 Converter Bed Temp. (°F) outlet Wth 762 To2 - 822 Converter Bed 22aTe has been found that in this ASARCO plant, SO, emission 4s below EPA limits, if the 8 temperatures stay within above ranges. There are not enough data on the upset condition in order to define the effect of deviation from above tempera- ture range on SO, emission from stack. Start up of ASARCO acid plant: ASARCO plant is not able to control the $0, emission during start-up. SO, emission appears dependent on length of shutdown time to a certain extent. It was observed that if shutdown time of the plant is less than two hours, £0, emission will not exceed the EPA Limit. Above two hours of shutdown time, SO, emission is above the EPA limit during start-up, There are 13 data points (STAl) for start-up time and shutdown time. Start-up time 1s defined as the time in hours which a plant will take to come under the EPA compliance. An attempt was made to find a Lincar relation between start-up time and shutdown time. Start-up time = , + OX; (shutdonn tine) ‘The regression was not significant at the 5 percent level. Mean and standard deviation were calculated based on this 13 data points. It is calculated that average start-up time is 6.34 hours. For 95 per cent of the time the start-up time should be between 3.14 and 9.54 hours. Not a single data point was more than nine hours, Details of above two runs can be found at the end of this report. 222‘Thirteen dita points were sélected (ASAR2) having high emission and standard statistics were calculated from ‘these and are compared with one of normal run. Variable Mean Normal Run Start Up v1 (ppm) a27 1678 x1 (R) 824.0 815.0 x2 (RP) 1040.9 1006.5 x3 (°F) 837.0 811.5 xh (PR) 897.9 a.9 x5 (PR) 786.7 732.5 x6 (°F) 792.9 729.0 x7 (RF) 162.9 702.0 x8 = (°P) 162.9 707.0 Above table clearly shows that four converter beds were not hot enough for proper SO, and SO, conversion. TexasGulf Sulfuric heid Plant Data set (Tax2Jeonsists of 31 data points selected randomly from large set of normal plant run. Different statistical models were then tried on this set. Run 2 80, emission as a function of inlet temperature of the four catalyst beds. YL = Xpt Kp xl + oxy x3 HM y 1H + MY XT The regression was significant at the five per cent level. Hypothesis that, and of are zero cannot be rejected at five per cent level. This reduces the usefulness of the regression model. 223Bun 2 S02 emission as a function of inlet and outlet temperatures of the four catalyst beds. Wreg, HEL HME 2 teeg KS tM RH Hg 5 eK 6 tm eT 0x 9 The repression yas LALLA a8 Eyve percent Level, Hypothesis that 15 3, 3» 5+ g and 7 are zero, can nat be rejected at five percent level. This reduces the usefulness of the regression model. Run 3 SO, emission as a function of log tranform of inlet and outlet temperatures of the four catalyst beds. YL = %q + % logel 4% 1oRx2 +Xzlogx3 + OX,logxl + OGlogKS + OK LogXS + oyyloneT +OXg Logx8 ‘The regression is significa at the five percent level. Regression model suffers from same drawbacks as in Run 2. For this data none of the models satsifactorily explains SO, emission in terms of the process parameters, from point of view of three significant regression. Same reasons can be sited here as before (for ASARCO Data) for not getting a useful model from a predictive stand point of view. Due to lack of model, an attempt was made to define a temperature range for each of the eight temperatures such that 8% emission will be below the EPA limits. ‘Thirty data points were selected randomly (T6qx4) from normal plant run and standard statistics were calculated. Summary of results is as follows.s 95% Range x for xi Variable Mean Mean + 26 PPH SO, Exit Stack 128 56 ~ 200 Temp. (°F) Inlet 1st 802 702 - 814 Converter Bed Temp. (°F) Outlet Ist 27 1095 ~ 1139 Converter Bed Temp. (°F) Inlet 2nd Ba 817 - 865 Converter Bed Temp. (°F) Outlet 2nd 17 903 - 1051 Converter Bed Temp. (°F) Inlet 3rd 812 784 - 840 Converter Bed Temp. (°F) outlet 3rd 848 797 - 899 Converter Bed Temp. (°F) Inlet 4th 816 788 - 844 Converter Bed Temp. (°F) Outlet 4th aun, 809 - 873 Converter Bed Té-has been found that SO, emission will be below the EPA limita tions 4f the eight process temperatures remain within the respective ranges. ‘The plant has a capability of heating the catalyst beds to a proper temperature before passing SO, through catalyst; because of this they are able to control the emission during start up. RECOMMENDATION FOR FUTURE DATA COLLECTION AND ANALYSIS: At every point of analysis it was felt that there is a lack of total number of complete data points. Large number of data points were incomsete, meaning one or more process variableswere not recorded. There were no data to compare 225the two plants of the same design. To make any conclusive statements data should be collected from at least three plants of same design. Record of each higher SO, emission should be kept. This record of upset conditions will help us narrow the temperature range for eight variables (x1, X2-X8) and define the exact variable with its magnitude which caused the higher emission. It will be easier for the regulatory agency to pin- point whether a particular upset condition was legitimate cr not. Reliability of SO, analyzer should be checked very often to ensure us of correct data. Nomenclature Used_in Regression Analysis Yi = PPM $0, Exit Stack Xl = Temp (°F) Inlet 1st Converter Bed X2 = Temp (°F) Outlet 1st Converter Bed X3 = Temp (°F) Inlet 2né Converter Bed X4 = Temp (°F) Outlet 2nd Converter Bed X5 = Temp (°F) Inlet 3rd Converter Bed X6 = Temp (°F) Outlet 3rd Converter Bed X7 = Temp (°F) Inlet “th Converter Bed X8 = Temp (°F) Outiet 4th Converter Bed 225MULTIPLE REGRESSION ANALYSTS ASARCO PLANT NORMAL OPERATION 227ASARCO Data set 1 ASARL KEADY LIST Asari ASARL Ns07EST 1725/74 100 101 102 103, 104 105, 106 108 109 10 m 12 113, 114 415 116 47 116 ng 120 rt 122 123 124 125 126 ter 128 129 YL xt 2 AS Mh AS xe 49 XP 19 1 25s 1100, 850, 975, 835, 860 825, 795, 145, 810+ 1030, B30, 890, 785, £00 765» 760 228, 818» 1058, 842, 934, 826, 810+ 798+ 182 1562830» 1100, 8307 900+ 760+ 7180+ 755. 780 701s 825, 955s 820, 845+ 730+ 1257 105+ 710 95+ 830, 1000, 830, 860, 795, 780, 740.730 138, 830+ 1070, 845,930, ROS» 840+ 785,775, 2394 825s 1120, 8.40, 9.40, 600, 835, 795.810 145,820» 1075, 845, 9.25, 895, 640, 625,815, 1122.815s 1100, 850+ 955, 820, 650, 825.620 129» 830+ 1000s 850, 900+ 790s 790s 7455750 1492 825», 1080, 845,950, 835,840, 820, 825, 2225 825, 1070» 830, 955, 825+ 790+ 770+ 755 2592820, 1055; 835, 915, 780» 780, 760.755 17328152 1075, 835, 895, 775+ 800+ 765+ 770, 3317830r 1060830, 910, 770» 790, 770+ 780 3@7+ 830+ 1010, 35,870» 765» 785+ 750+ 765 388+ B30, 1110+ 850,930, 300» 815, 765s 770 2294810» 1000, 840+ 890, 825+ $40» 815+800 255,825, 1080, 820, 855, 720» 690, 675+ 685 257-835» 10354840, 865s 780» 790» 770» 760 2232 82S, 1090s 40, 895. 785+ 80S» 770» 760 2972820, 10102 835, 9.407 770» 780» 765.750 9741815, 1065. 835, 910s 780» 790s 760+ 770 953s 14s 960s 834) G3, 796» BOA» 78H 770 18176 12s 11187 894936, TBO» 800 782, 754 182, 824s 1114, 834, 922, 76Bs775+ 758s 764 1022 624+ 1136, 840, 942, 800+ 830, 782,782 228RUN 1 MULTIPLE REGRESSION PKEGRAM XMEAN 8. 22a828F+02 1-061241E+03 8-373793E+02 9+ 1489 66F+02 7.91551 7E+02 8.022069E+02 7. 7320698 +02 TeT17931E+02 OBSERVED 1.9100000F "2 1. 4500000E+02 2374000008 +02 8 00000E+02 1. 5600000F+02 7.010CN00E+02 925000000F+01 1. 38000008 +02 223900000F+02 1+ 4$00000F+02 1. 1200000F+02 19 00000E+ 02 11.4900000E+02 2.2200000F+02 2: 5909000F+02 1.7300000F+ 02 323100000F +02 3.?70C000F+02 3: 16800000F+02 2. P900co0F+02 SOUCOCF +0? 225700. COF+0? 2: 2300600F+02 2.9700000F+02 3: 740U000E+02 3+$300000E+02 1.8100000F +02 1.8200000+02 10200000F+02 YMEAN 2.363793F+02 CALCULATED 1.4541 1SBE+02 2. 6274889E+02 2:1089986F+02 1.6604196F+02 32 1621091E+02 3. 6632825E+02 21 2058276F +02 1.9546666E+02 21306394aE+0P 1.6267472E+02 1.7914977E+02 1.7519773E+02 11594921 4E+02 1.8181375E+02 21 5662385E+02 2. 7112709F+02 3:0795300E+02 BigazZ071E+02 1.7173433E+02 18a 7A31F COD 3 6020267E+02 2295173516 +02 31 a062902F +02 26.4059 68E +02 228501 194F+02 2. A848 755E +02 214954 62E+02 2-6 €3.4020E +02 2. 1785139F+02 229 EST vak 1.9074241E+03 223663184F+03 221.4500S6E+03 1.53831 48F+03 224381770F+03 2.9301549E+03 ‘4,0136465E+03 1.9826847F +03 110300517F+03 1.59028276+03 2: 7250538E+03 5.5225457E+03 11874441 4E+03 6241854106403 625617222E+02 1.4858 165F +03 3: 19.45885F+03, 123731419F +03 3:5124348F+03, 2.2762290F +03 452575563F+03 2. AT09R9OF +03 7.3540339F+02 152105110F #03 113776373F+03 1,3649071F +02 21 4a64908E+03 9-61375S6F+02 '523500893F+02RUN 1 (Continued) kroresston CPSKE OF PREF. SUM OF SUUARES. VARIANCE ESTIMATE SeoRF stow’ a + 9.782241Fs0a 2. AgaO6OFSOM Reman : 4 + 9:155564F+05 5 1.314R1BF+OR : 28 + 4113076BE+05 > MULTIPLE COWKRELATION COFFFICIENT = 4.858875F. 91 CONSTANT TEKMCINTFKCEPT) = 2. 6R0666F+03 F ORATION 4, 24 DEGKEES @F FREEDOM)= 1.654294F+00 UPPEK RT HAND PORTION OF MATRICES ONLY INVEKSE ADJ DATA MOMENT MATRIX OKC 1) -966541F-04 -4.60B1F-04 9+ 7809E-07 1,3341F-04 Fae 2) 114839F-03 -1.5673F-04 ~1.5615E-04 Howe 3) 2.2331F-04 -1.40a5E-04 HOw 4) 116742F-04 EST COEFFICIENT VAR-COVAK MATRIX FOKC 1) 162699E+01 -6.058BF=00 1-2660F-02 1+ 7541E+00 FaWC 2) 1.9S03EF01 -7-0608F+00 ~2-0530E+00 ROWE 3) B.9361E00 -1.8467F+00 Fue 4 2.20126+00 ADJ DATA CORKELATION MATRIX FOC 13. 1-0000F+00 -9.850BF-01 2-1066E-03 9-3184F-O1 Faue 2) 1s0000F+00 -2.7233F-O1 ~3.1334E-Ol Rowe 99 1,0000F+00 -7.2642F-01 FRC 4) 110000F+00 230RUN 2 MULTIPLE KFGRFSSION PROGRAM XMF AN YMEAN 2.363793F+02 8. 224826E+02 1061241F+03 6.973793F: 02 9: 148966F+02 7.91551 7E+02 8. 022069F+02 7. 732069E+02 TLT17931F +02 NUMBER» INDICES OF YARIATES DFSIKED?6: 142+ 3+ 4s Se 6s 768 WANT TO SFF PREDICTFD VALUES, YFS Ok NA?YFS ORSFRVFD CALCLATFD FST VAK 1-9100000F+02 1. 340SKHRF+02 5. 1931016F +03. 1a500G00F+02 2.5402067F+0? —3.1793207F +03, 2+7400000F+02 1.8126159F+02 2.2841035F+03 222800000F+0? —1.8290439F+02 3.739 7948F +03 1+S600000F+02 2. 7816R02F+02 3. K3822SRF +03 T.0100000F+02 4. a28021SF+02 4. 2BOSRTKF +03 9+S000000E+01 2.1989134F+02 —5.9655442F +03 1,3800000F+02 —1.8402139F+0? 4. 12 705a9F +03, 2.3900000F+02 1.8897909F+02 2.7757 4K7F +03 1eaS00000F+02 1. 7634925F+0? 2. 3800124F +03, 1:1200000F+02 1. 7RSSBLAF+OR 2.996531 4F +03 152900000F+02 2: 6600859F #02 7. R33SK9SF +O 1+4900000F+02 1. 8S42841F+02 4.269202KE+03 22 2200000F+02 1. 74KASISE+02 © 7.353KKS7F +03 2+ S9C0000F+02 2. 64219S7E+02 1 1255771F +03. 157300000F+02 © 2:3084653F402 2.19 727SHF +03, 9+3100000F+02 3. 2133RS9F +07 3. AARAABSF+03 3:2700000F+02 —3.2950727F +07 2. 9K0R.A52F +03 BsBBOOO0OF+02 —1.395KarFeOR —_3.78271R5F+09 Bie90G000F+07 —7.2S23RSSF+O? 4.041 AP9OF +03 2.8500000F+02 3. 1a75504F+02 —./S7ANLTF +03 BiSTOOOQE+OR —F-SPPTIONF+O? —KLOTSLARIF+OS 2.2300000F+02 —1.9552913F+07 7-011 1004F +03, B59700000F+02 3. 79976AKF+O7 —6.6555059F +03 3+7400000F+02 2.$134933F+02 P0307 PRRF +O BlS300000F+0% © 3.374705RF+N? —-3.S187125F +03 1-B1OOO0OF+02 1. 7319439F#0? —4.3945007F +03 1R200000E+02 2.397 1095F4G2 7. SRAKPOAF +03 1s0200000F+02 1. 5A01144F#02 3-07 70284F +03 231TUECKER OF SES "OF SOARES! “VARIANCE ESTIMATE 1.9693a5F+0a a 11277656E+08 : RECKFSSION. 5 2 LeS78a7KF +05, REMAINDER 20 I pisssai2r+0s TATAL 7 oe 130788F+05 MULTIPLE CORRELATION COFFFICIENT = 6175746F-01 CONSTANT TFKMCINTFFCFPT) = 2.5121¢2F+C3 COFFFICIFNIS FST OF SD .19aSa39F-01 3. FIT 16RIF+OO 19% 25-7901 760+ 750 160 164,838, 104546407 49Qs 7400775, 7406745, Nel 122s835;1098¢A80r945¢41 5.154 7406755, 142: He 690s 1OKO, 40» 900-7907 15» TRO, 760. 165. 2995820, 1045. 495s 690, 265, 2504715, 710 164 69. 825, 1050, 450+ 920-810. AOD, 7436775, 16S BEBLAPL. Ton SER Abe D1Oe 1RSe P78, 7804750 166 140,822, 1000, 645.875. THO. 7hS, 725. 725, 162 294, 895s 109064P5¢ AKOs 1550 790, 750. 740 V6B 9246354955, HA0, W652 TROr 775, 7306725 244coterie ataruarien f SegeeesetestasoRs: beesdy! eesennee 245 ~~‘fevusTED coneLaseoy vantasce, URTOSIS « suncencl=xEni ears ceneuvnen esasee tiny init 246 cv4ton w evanrsinveratnwny startitteaoa DESCRIPTIVE STATISTICS FOR X2 NUMBER OF OBSERVATIONS ... MEAN ~ XBR = SUM(X(I))/N ... MEDIAN .eeeeeeeeeeee RANGE UNADJUSTED (BIASED) VARIANCE SUM ((X(T)-XBR)**2)N = UVR + UNADJUSTED STANDARD DEVIATION = SORT(WR) = $ .--+2+eseee ‘ADJUSTED (UNBIASED) VARIANCE ~ UVRN/(N-1) = AVR -eeseeeseeesseeeee ‘ADJUSTED STANDARD DEVIATION — SORT(AVR) ON STANOARD DEVIATION CONFIDENCE LOWER UPPER LOWER UPPER LEVEL, uit LIMIT uit Limit 90.0% 031.4 1050.4 41.3 55.9 95.05 1029.5 1052.3 40.4 57.62 99.0% 1025.9 1055.9 38.35 617 FOR A NORMAL DISTRIBUTION 247 1040.9 1082.5 206.1 2077.2 45.57 2143.7 46.31NUIBEK OF OBSERVATIONS ++ DESCRIPTIVE STATISTICS FOR x3 + 64 MEAN = XBR = SUNCXCIDIZN 836.75 weDtan cece + 849-00 RANGE soe — + 40.000 UNADJUSTED CRIASED) VARIANCE = 2 SUNCCRCES“ROAI#EEIN © UVR e+ 78.875 WADJUSTED STANDARD DEVIATION = SCRTCUVED = S + s.ee12 fOJUSTED CLNBIASED? VARIANCE = UVREN/GN=12 = AVE« 80.127 fOJUSTED STANDARD DEVIATION = SORTCAVRY s+eeeee s.9514 SKEWNESS = SUNCCXCL)-XBRD##99/ cMUUR##L 5) -0.67846 KURTOSIS — SUNCCKCT2=KBRD#EAD/0N" URED? os ae77 2-SIDED CONFIDENCE INTERVALS ON MEAY & STANDARD DEVIATION ro “Sranbako DEVIATION GonFipence . LOWER Tener urreR LEVEL tint Uiatt Unter 90.0% 834.88 838-62 7.8209 10505 35.02 b30.51 838-99 Tees to.eat 55:02 839078 839-72 Teeat 112380 FOR A NORMAL DISTRIBUTION JAHRE OEE OK Ene renee x3 7 INPUT ORDERED CUILATIVE CUMULATIVE beta pata PRLCENTICE NSMAL DIFFERENCE Bas 530 27.692 22-540 =5.152, Bop 835 432077 427250 0-827 335 840 73-385 64172 9 ~11.212 640 B40 752365, 6ai72 | =11.212 Be0 gas 87.692 62.164 3.528 850 850 OR. 262 93.089 = Ta02 0.2042 = KOLMOGOKAV-SMIFNOV STATISTIC 248DESCRIPTIVE STATISTICS FOR xa MUABER OF OBSERVATIONS «eeeeeee ee MEAN = XBR = SUM CKCIDIZN sees oe 891.91 MEDIAN . * 896.00 BRACE | 220.00 WADJUSTED (BIASED? VARIANCE SUNCCXCDD“XBRD ORIN = UVR + steseeee 1689.2 WADJUSTED STANDAKD DEVIATION = SGRTCUVR) = 5 * antoo ADJUSTED CUNBIASED? VERIANLE = UVREN/(NO1) = AVR 1716.1 AOJUSTED STANDARD DEVIATION = SORTCAVED anaes SEWESS © SIMCCXCID=XBRI#€)/(VeUVEHH LS -129778 MURTOSIS = SUMCCKCID-XBRI¥8-A)/¢NOUVKAH2) 6.9809 B-SIDED CONFIDENCE INTERVALS CN MEAN & STANDARD DEVIATION MEAN STANDARO DEVIATION CONFIDENCE LOWER UPFER LOWER UPPER LEVEL Limit LIMIT ciwir . | LIMIT 90.0% 883.26 900-55 36.194 48.616. 95.02 881-56 =, 902.25, 35.286 50-171 99.0% 878.15 905-66 33.620 53.453, FOR A NORMAL DISTRIBUTION Brrr rere ceenerEneeceee eee xa INPUT RDF RED. CUMLLATIVE — CLECLATIVE ete DATA FEACE\IAGE NORMAL OLFFELFACE 930 R60. Po.cce 22.089 52 37s 32.508 34.159 895 890 36.769 48.165 890 900 612504 37.745, =3.793 955 926 16.923 75.17 =11308 920 94s 92.308, 90. 0u2 306 0.1090 = KoLYnERsAy=SHLitY STATISTIC 249DESCRIPTIVE STATISTICS FOR X? MUIBER OF CBSERVATIONS +40 se 6a MEAN = XBR = SUWCKEDDIZN sees 105.95 MEDIAN sseeeeeeees 790.00 MANGE sseeseeesees 118-00 WWADJUSTED CRIASFOD VARIANCE SUNCCKEDD “ABAD HEADS UVR > 699.11 WADJUSTED STAVDARD DEVIATION = SLETCLYRD = 5 260aat fOJUSTED CLNGLASED) VARIANCE = UVRAV/(N=1) = AVRe 710.20 (OJUSTED STANDAKD DEVLATION = SORTCAVID +++ 26.650 SKEWNESS = SUMCCXCT)-XBRI##32/ (NU K#F165S) ceeeeee Lo.a6017 MURTOSES = SUICCKCI=XBRD#RAD/CUAUUEAEDD ee eeee oe 2.7862 2cSIDED CONFIDENCE INTFRVALS @N MEAN & STANDARD DEVIATION MEAN STANDARD OFVIATION CeNFIDFNCE LOWER UPPEK, LOVER UPPER LEVEL Limit Limtt Cimit Limit 90.02 780.39 791.51 23.284 31.276 95.02 779.30 792.61 22.700 32.276 99.07 qe 194.85 21.628 34.387 FOR A NORMAL DISTRIBUTION JOS CHEE RHO EHH aud Ceneer anni PRDERED. CoeLLATIVE CUMULATIVE DATA PERCENTAGE NORMAL DIFFFEENGE to 160 16.929 16-506 0.417 20 770 Ba. 769, 27.aTt 31258 30 ms 48.573, 2.420 40 798 63.287 al210 50 aps. 810 53.077 81.656 eet 60 B10 225 95.523 922857 741066 STATISTICDESCRIPTIVE STATISTICS FOR x6 MUMEER OF OBSERVATIONS - + 6a MEAN © XBR = SUNCKCIDIZN aoe : 191636 MEDIAN «++ : 790.00 ‘RANGE : . 128-00 INADJUSTED (BIASED) VARIANCE = SUNCCKCID-XBRD*#2)N = UVR + 727.82 UADJUSTED STANDARD DEVIATION SCRTCUUR) = S seeeeceeeees 26.978 ADJUSTED CUNBIASED? VARIANCE = UVRANZ(NG1) = AVR. 739.98 ADJUSTED STANDARD DEVIATION = SCRTCAVR) seeeeseeeereeeeeee ‘e7. wt SKEWNESS = SUMC(XCT)-XBRD443)/ (N#UVA#ET 5) in63 KURTOSIS = SUMCCXCLD-XBRI#HAD/CNEUUE EHD) 6 3.0185 @-SIDFD CONFIDENCE INTERVALS CN MEAN 2 STANDARD DEVIATION MEAN STANDARD DEVIATION NF IDENCE LOWER UPPER LOWER UPPER LeveL Limit Limit Limit Liat 90.07 785.69 797-03 23.787 31-912 95.02 784.57 798-15, 23.162 32-932 99.07 782.33, g0c.39 22.068 35.086 FOR A NORMAL DISTRIBUTION RUHR UEn Oren err REeeis x6 INPUT OROFR CUMLATIVE — CLYULATIVE DATA | DATA PERCENTAGE NOFMAL DIFFERENCE 19 830 770 20-000, 21.608, 1.608 20 122 720 BR. 462, 3. ROK 740655 30 800 790 52.806 22.006 7-5-8240 “0 330 soc 622.467 76.768 2c 525 BIS 50-769 731846 66 800 835 92.208 94.875 2.267 ' 09-0785 — KALMRCOROV- iTV STATISTIC 2s1DESCRIPTIVE STATISTICS FOR x7 NUMBER OF OBSERVATIONS « 6a MEAN = XBR - SUMCXCIDI/N T6194 MEDIAN 765.00 RANGE + pe 141.00 UNADJUSTED (BIASED? VARIANCE SUMCCKCL)“XBRIFS2IN = LVR ee UNADJUSTED STANDARD DEVIATION = SCRTCUVRD 29.258 ADJUSTED (UNBIASED? VARIANCE = UVREN/(NS1) 869.62 ADJUSTED STANDARD DEVIATION = S¢RTCAVR? 29.489 SKESNESS = SUMCCXC1)=XBR2##39/ (N#UVROR TS) -O.12111 KURTOSIS = SUMC(XCI)-XER)##4)/(N#UVR##2), 31832 2x SIDED CONFIDENCE INTERVALS GN MEAN 2 STANDARD DEVIATION MEAN. STANDARD DEVIATION CONFIDENCE Lower UPPER LovER LEVEL, Liat LIMIT Cait 90.02 755-78 168-09, 25-765 * 34. 608, 95.0% 754.57 769-30 35.715 99.02 752.15, 771273 3s.051 FOR A NORMAL DISTRIBUTION Pererreretertrecrtertccentetrregtetietegs x7 INPUT DDEKED CUMILATINS CUMULATIVE DATA ATA PERCENTAGE NORMAL DIFFERENCE 10 820 730 15.385 13.940 -1.485 20 654 750 36.923 34.281 21642 30 765 760 47.692 47.381 -0.312 40 790 770 6a. 615, 60-773 =3.842 50 785 Tas, 31.538 78.291 -3.287 ao 785 310 92.308 94.843 2.535 0.0832 = KOLMOGOROV-SMIRNDV STATISTIC \ 252MUMEEN OF OBSERVATIONS +eseseeeeee DESCRIPTIVE STATISTICS FOR x8 we 6a MEAN = XBR = SUNCKCLDOUN re1.92 MEDIAN seeee : 162.59 FONGE 2+ 142.00 WADJUSTED (BIASED) VARIANCE ‘SUM CXCT)-XBRI#420N = GVR aoe 920.51 WADJUSTED STANDARD DEVIATICN = SCRTCUVA) = S see 30-340 ADJUSTED (UNBIASED? VARIANCE = UVRENZEN=1) = AVES 935-12 AOJUSTED STANDARD DEVIATION = SORTCAVRY se eeeeeee 30-580 SKEXNESS = SUNCCX(12-XBRD6#99/(NAUUREEI.5) + *o.27600 KURTOSES = |SUMCCXCLD=KBRIS#AD/UEUURERDD vee 2.8667 caNE IDENCE, LeveL 90-02 95.0% 99.02 Me 2-SIDED CONFIDENCE INTERVALS @N MEAN £ STANDARD DEVIATION MEAN STANDARD DEVIATION LOWER PER Limit Limit LIMIT 755-54 168-30 26-718 35-888 734.28 769-56 26.048 37-036 751.77 172,07 24.818 39.458 FOR A NORMAL DISTRIBUTION DERE EERE EO EEE REE x8 INPUT ciDERED CUMULATIVE CUMULATIVE DATA DATA PERCENTAGE NORMAL DIFFERENCE eis 730 20-000 14.827 =32173, 678 750 92.504 34.892 B.5za 770 760 a5.P2t 47.494 =1.736 785 770 63.077 60.417 2.660 115 13s 7a. 462 17.478 0.983 775 B10 93.Kee 94.205 > 0.359 0-0827 ~ KOLMIC9ROV-SMIRNOV STATISTIC 253MULTIPLE REGRESSION ANALYSIS ASARCO PLANT - START-UP DATA 254100 5.0, 12, 101 6.0451 ASARCO Data Set STA 1 8 3s 102 5.0.6.5 103 7.0516. 104 5.0.9.0 10S 9.0.5.5, 106 8-0,37 107 6+5.160 “108 920.16 » 109 420,13. 110 740,16, B11 6604 40. H2 $:0,9.0 MULTIPLE REGRES: XMEAN 2-800000E+61 OBSERVED '5+0000C00E+00 £5.0000000E+00 '8+0000000E+00 7..0000000E+00 5-000G000E+00 92.0000000E+00 8-0000000E+00 6: 500G000E+00 9-000C000E+00 4.0000000E+00 7.0000000F+20 6: 0000000E+00 5 0G0G000E+00 5 8 3 5 SIAN PROGRAM YHEAN 6+34615aE+00 CALCULATED 6-3005722E+00 654182616E+00 382927 6E+00 623123352E+00 62902795E+00 622799869E+00 6+3726206E+00 62 7343335E+CO 6. 31086a8E+00 6230351296 +00 34239526 +00 6:29.46907E+00 6-2902795E+00 255 EST YAK 2.45232008-01 2LB661375E-01 2.746767 1E-01 213090740E-01 2.6124755E-01 21B0S1240F-O1 2-2a11012E-01 2152437625 +00 2+3246602E-01 214125303E-01 2-3090760F-Ot 2. 5358SE6F-01 2.612¢7SSE-01: TT DEGREE @F FREE: SU "OF SOUARES. VARIANCE ESTIMATE + REGRESSION. 1 + 1+808564E-01 + 1+808S64E-01 I OREMAINCER + " 2 alosiiase+or 2:773768E+00 12 3-069231F+01 : MULTIPLE CORRELATION COEFFICIENT = 7-676304E-02 CONSTANT TERMCINTERCEPT? — 6.263813E+00 CREFFICIENTS EST GF SD 2.9407546F-03, 1516670E~02 FUATIOC 1 11 LEGKEES OF FREEDOWI= 4. S20242E-07 efi n1 HESL FDETIAN OF MATRICES ONLY IMGEESE ELS DATA MOMENT MATRIX C1) ke 7B17F=08 FST CREFFICIENT VAn-COVAK MATRIX ave 1) 1.3263F=94 : ADJ DATA CGRAELATION MATAIX ate 1) 1+0000F+00 DESCRIPTIVE STATISTICS FOR YI MOBER 9F OBSERVATIONS «4.4 13 MEAN = XBR = SUMCXCIDIZN 6.34062 MEDIAN coessseeerseeeeeeeneree 6.0000 RANGE on : +0000 ADJUSTED (BIASED) VARIANCE = SUNCCKCT“ABRIHR2IN = UWA cerceee 2.9608 WWADJUSTED STANDARD DEVIATION SLATCUVAD = S : 1es36s POJUSTED CUNBIASED) VARIANCE = UURAN/(N=1D = AURecteeeee 2.5577 ADJUSTED STANDARD DEVIATION - SCATCAVED .eeee - 1.5999 SKEWNESS = SIMCCXCT-XBRINHSIZONEIVREETOS? 6 41800 MURTOSIS = SUICCKCED“XBRIERAD/OMLUEAHDD ceseeeeeeee 20771 \ 2562-SIDED CONFIDENCE INTERVALS ON MEAN & STANDARD DEVIATION MEAN STANDARD DEVIATION CONFIDENCE Lever UPPER Lewer UPPER LEVEL, Limit Limit tisit LIMIT 90-02 545556 721367 1.2082 2.4234 95.0% 523797 T3126 121463 216400 99-02 A.9913) 7.7010 leoara 3.1599 FOR A NORWAL DISTRIBUTION HOO RESO HEE EEO E roo oie eeaan es a ; INPUT ORDERED CUMULATIVE CUMULATIVE DATA DaTA PERCENTAGE © -NARMAL = DIFFERENCE 1 5.0000 4.0000 76143 Teas ~0.028 2 6.0000 5.0000, 19-997 18-717 a 5.0000 | 5.0000 192997 2182717 4 7.0060, 5.0000, 19.997 15.717 5 5-000 5.0000 192997 -15.717 6 93-0000 6-0000, 41.432 82568 7 830060 60000, ala3e 78.568 8 6+5009 65000 33.832 -3.311 9 920000 72.0000 65-867 352561 10 4.0000 7.0000 65.867 756561 mn 7.0000 820000 8419.46 6.375, 12 60000 9-0c00 92.857 95.148 2.291 13, 5-000 920000 92.857 956148 291 0-18.46 = KOLMAGOROV-SHIRNAV STATISI DESCRIPTIVE STATISTICS FOR x1 MOIBER OF OBSFRVATIONS see 13 MEAN = KER = SUMCKCIDIZN + 28.000 MeD1an : peer 13.500 BANGE ‘sree . sees Peete eee eeeeeeee 154.50 wuADJUSTED CELASED) VARIANCE SUNCCKCL“RERDORZIN. UVR ceeeeeeeeeeseeene 1608.7 WADJUSTED STANDARD DEVIATION = SURTCUVRD =. 5 +++ 40.109 POISTED (UNBIASED) VARIANCE = UVRAN/EN=1) = AUReee : 1742.7 ADJUSTED STANDARD DEVIATION = SCRTCAVR) «+++ — alsTa6 SKEEESS = SUC CKCTD-KBRI##39 /(N#IVEEPLESD vee 2.6968 KURTOSIS = SUNCCXCID=XERI#EAD/ENHUUR#E2) oe 9.0626 ‘\ 287CaFIDENCE LEVEL 90.0% 95-02 99-02 10 12 13 2-SIDED CONFIDENCE INTERVALS ON MEAN £ STANDARD DEVIATION STANDARD DEVIATION MEAN LOWER UPPER Lever Liat Limit cit 73641 + 48.636 31.538 2.7730 93.227 29.936 77.3665 63.366 27.184 “FOR A SEH EHH rE or rene eerie x INPUT ORDERED. CUNULATIVE CUMULATIVE Data DATA PERCENTAGE NORMAL 124500 5.5000 Teas 29.495, 514500 645000 142256 30-327 €.5000 9.0000 es.s71 32.451 16.500 920000 2H.ST71 32451 93-0000 19-560 35.714 33-754 5.5000 12500 222357 35-521 37.060 13.500 50-030 3e.a17 160-00 16-006 87.123 38.688 16.000 16.500 71.429, 39-148 132500 162500 Tass 391148 16.500 37-600 78.571 38.535, 10.500 512500 aS. 714 712326 90000 160.09 92.857 99.922 069778 = KOLMIGORGV-SMIFNDV STATISTIC 258 UPPER Uiwit 63.259 68-912 82.284, DRMAL, DISTRIBUTION DIFFECENCE 22.353, 16.041 36779 31379 2961 =72336 13.563, m18.455, -32.281 -32:2R1 -20.037 7141389 7.065‘ASARCO Data Set ASAR2 lest. 11727778 100 8591620 1120, 850, 950, 835, 660, 600, 780 101 2463+ 835, 1010, 830+ 870, 790s, 780» 760+ 765 11 12 21452816» 8244 770+ 772+ 104s 7110+ 674. 664 103 1863+ 6667 822, 720, 754, 68.4, 692, 638,640 . 104 1695+ 825, 1030+ 830.875» 765+ 175+ 7452 740 : 105 13115830. 1075, 825,870, 745, 740+ 7007695 : 106 ‘11774830, 1030, 845+ 920, 790-165. 735- 725, . . 107 10122840, 1055s 7904 750, 615. 625+ 700, 820 * 108 3107-810, 1030, 730s 785, 635. 640+ 640, 645 109 3092s 825, 990, 800; 820, 700, 690+ 650+” *0 MO 9952835» 1065, 8.a0+ 890, 765, 755s 71» + 10+ 111 1086+860s 1090, 8304345, 725, 7152 690. 685. 1, 2 10098105955, 6.40, 860.770, 730» 685» 680 ‘ v DESCFIPTIVE STATISTICS FOR YI NUMBER @F OBSERVATIONS «+ 13, MEAN © XBR = SUMCKCIDI/N “1678-2 MEDIAN 1311.0 RANGE ++ . 2248-0 UNADJUSTED (BIASED) VARIANCE SUMCCKCL)=ABKD #290 = UVR oe + 0.59019F+06 7 168-24 UVADJUSTED STANDARD DEVIATION = SORTCUVK? = S ADJUSTED (UNBIASED? VARIANCE = UVREN/(N1) = AVReseeeeeees 0+ 63997E+06 ADJUSTED STANDARD DEVIATION — SORTCAVR) +++ 7 199.61 on 0.76180 SKEMVESS - SUM CCKCI=XPRI HES) /(NSUVREATS) KURTOSIS — SUMC(KCII“XBRI##4)/(NSUVRIHZ) eo eee os Bel TIS 259CONFIDENCE LEVEL 90.0% 95.02 99.0% 2=SIDED CONFIDENCE INTE: nts ON MEAN & STANDARD CFVIATICN STANDARD DEVIATION ' Lower UPPEK Lower UPPER CIMT Limit Limit LiMit 1282.9 2073-4 604.07 1241.7 1195.0 2161.4. $73.39 1319.9 1003-7 2355-6 520.69 1579.9 FOR A NORMAL DISTRIBUTION, HER Or OHHH ooo Une renee rete v1 ANPUT @RDERED CUMULATIVE CUMULATIVE DATA DAA PERCENTAGE NORMAL DIFFERENCE B59 859 eras 15.281 8-138 2263 99S 14,286 192645 5.359 2145 1009 , 21.029 20.134 21.295 1862 1012, 28.571 20.239 -8.232 1695 1088 35.714 23.024 712.690 1311 177, 42.857 26.5at 160316 4177 i3ny 56.000 32.306 == 17.694 1012 1695) 575143, 50.840 =6 +302, 3107 1663 64.286 59. 1al 52145, 3092 2145 71.429 721034 0-605 995 2463 83.684 Sette 1088 3092 96.148, 10.434 1009 3107 ~ 0.2154 = KOLMBGORGV-SMIRNOV STATISTIC 260 96.303DFLCRIFIISE STATISTICS FOR x1 HUMBES 9F PESFRVATIONS «+ MEAN = XBR = SIMCXCIDI/N soeee Hee RIS.54 MEDIAN Boece cco eee ee 825.00 nawce Sacnee ee eeedcu Sep 194,00 UJADJUSTEL CBIASED) UAKIANCE SUICEKCLI“ABRIEH?IN UK + 2028.7 ADJUSTED STANDALD DEVIATION = SURTCUVRD =f sereeeee 45.041 ADJUSTED CUNGIASED) VPLIANCE = UIVREN/ «N= 1D 197.8 AUJUISTED STANDARD DEVIATION = SUATCAVKD «++ 46.880 SKEWNESS = SUMC (XCD) =XERIR#DD/(NAUVRAEL AS) see eeeeees 2.7100 KURTOSIS = SUNCCKCLI=XBKDAEAD /ENMLIVRERED « enor 9.431 2-SIDED CONFIDENCE INTFhVALS ON MEAN & STANDARD DFVIATION MEA STANDARD DEVIATION CONFIDENCE OFFER LeKFR UPPER LEVEL LIMIT, Lisit LIMIT 90.03 ‘ 792.36 498.71 Beare | 71.039 95.02 787-21 843247 33.617 772387 99.07 175.62 55.25, 30.528 92.628 FOL A NORMAL DISTRIBUTION UE UCU EE HG ceria rere ieee x . INPUT PLDERFO CUMULATIVE CIMULATIVE eta BAMA PERCENTAGE NORMAL DIFFFRENCF 1 zo eee Ties 0.071 27.072 2 kas, K10 elapse 45.298 2R.R69 3 ne io. Pies, 45.298 23.869 a 66 Ble 26.571 90.393 21.821 5 aes, LkeO ass71a 53.791 192077 ‘ 820 ees. 50.ce0 $7,997 72997 7 30 925, 5e2900 37:997 71997 « a0. 830 Fan DwE eae 2.172 9 10 830 (an2b6 ea 22.178 1G x5, 535, Tee571 KEL09K 1.74 n Ba R35, TRISTI 662098 a iplara a KEO a0 KeThe £92909 215-805, 13 10 EO. 97.887 ap 1RSa =102003 STAisti¢ 0.9761 ~ KOLMAGT HOW Sot ANE) \ 261DESCRIPTIVE STATISTICS FOR x? NUMBER OF OBSERVATIONS eeeeeeeeee MEAN XBR = SUNCXCLD9/N oe MEDIAN veeee KANCE UWADJUSTED CRIASED) VARIANCE SUMCOKCI“XERIES2IN = UVE ADJUSTED STANDAKD DEVIATION = SUKTCLVKD = S .+ ADJUSTED CUNBIASED) VARIANCE = UVREN/EN=1) = AVRece ees ADJUSTED STANDAKD DEVIATION = SOKTCAVKD +++ SKEWNESS = SUICCXCLD=XFR2##39/ (NFUVK@HIS) se eeeee KURTOSIS = SUMCEXCII“XBID## 4) /(NFUVKHE2) oe 1006.6 1030.0 298-00 1899.9 88.878 587.6 92.507 1.0771 3.1248 SIDED CONFIDENCE INTFRVALS @N MEAN £ STANDARD DEVIATION MEAN STANDAKD DEVIATION CONFIDENCE LOweh UPPER LOWFK UPPER LEVEL Cia Limit cimtt Limit 90.02 960.89 1082.3 69.886 149.18 98.02 950.71 1oK2-5, 66-336 152.70 99.0% 928225, 1085-0 60.239 182.78 Fok @ NORMAL DISTRIBUTION Pree ter eee enceccreresrenesy xe INPUT ORDERED. CUMULATIVE CUMULATIVE pata DAA PERCENTAGE NORMAL 1 1120 a2 Tray 2 1010 wea 1aspge 3 Bea 995 1.429, a 822 9K0 26871 3 1030 1010 35.714 6 1075 1030 Sus 1aa 7 1020 1030 970143 & 1085, 1030 570143 9 +030 1058 6a. 2KE 10 960 1065 7h 4.029 W 1065 1075 78-571 12 1090 1090 65.714 13 955 1120 97 .BST 09-2152 = KALMAcanaU: IRNOV STATISTIC DIFFFRENCE 74.848 11.867 als, 10-107 15.745 2.835, 2.835, 21838 5.667 P.1ta 712560 741083 =3:873DESCRIPTIVE STATISTICS FOR X3 NUMBER OF OFSERVATISNS se eeee +13 MEAN XBR = SUMCXCIDI/N eee : Bina MEDIAN see panne) aren : 830-00 HANGE scsccsesseoee a. = 130.00 WWANJUSTED CRIPSED) VARIANCE = SUICOXCDD=XBIDS#2IN = UK vow ees ee oc 1316.9 IWALUUSTFD STANDARD DEVIATION — SORTCWHD = S oe 5 36.289 ADJUSTED CUNPIASED) VATANCF = UVNENZ(NG1) — AVRee eee eres rare. e ADJUSTED STANDARD DEVIATION = SURTCAVA) seeeeeee . 27.770 SKEWNESS = SUMCCXCI=XBAI##3) /ENSUVEREL SSD : 71.1587 KURTOSIS = SUMCCKCII=KPRIREAD/ENEUURERPD oe 7 34 50R6 PeS1DFD CONF IDENCF INTFAVALS ON MFAN 2 STANDARD DFVIATION MEAN STANDARD DFVIATION COVE TENCE Laver UPrEh LOwFk UPPER LEVEL ciat uimit cimit Limit 90.07 192647 30.21 28.534 587.224 9507 TKRL71 34,36 27.085, 622349 99.07 119.54 Raa. a 24.595, 10, 62R FOR ®-NGKMAL DISTHIPITION RUE HER HI ET creeeeen renee ne x3 Weer ORDERED CUMULATIVE CIMULATIVE para pala PERCENTAGE NORMOL | DIFFFRENCF ao Te1an 6.374 ' 770 1as2ue 20.714 3 0 B1.ap9 r1ie23, ” 790 eu.sT1 PRL APG 0.146 5 500 ASiT1a 382000 2LPRS ‘ KES or857 aa.923 21.066 7 x30, 8,750 An aes . 430 685750 pers 3 R20 682750 20465 10. a0 Tana a 12128 uw a0, Waan s1lipR ? Kay 1.217 4497 13 Rot Bal57S. Rte Ra KOLMAGARMUHEMEL NS STATISTIC \ 263DESCKIFIIVE STATISTICS FOK Xa NUMBER OF OBSERVATIONS «+ oo 13 MEAN = XBR ~ SUMCKCIDI/N seceeeeeeeeeneeeeenenes 840.85 MEDIAN eee ee cae 860.00 hANGE Se eee nen oodo os oe 200.00 IWADJUSTED (BIASFO> VARIANCE SUNCCKCD=RbKI«S 200 = UVR 4014.3 WADJUSTED STANDARD DEVIATION - SURTCLVKD 63.358 ADJUSTED UNBIASED) VARIANCE = UVKEN/(N=19 = AVRe ++ 4346.6 ADJUSTED STANDAKD UEVIATIAN 2 SCKTCAVRD seeee 65.945 SKEWNESS © SUMCCXCL)-XPRI#HSI/(NEUROHL SD oo eeeee 0. 10921 KURTOSIS = SU*CEXCII=XBEI#EAD/ CNHUVRES2? 8710 SIDED CONFIDENCE INTERVALS @N MFAN & STANDARD DFVIATION MEAN STANDARD DFVIATION CONFIDENCE LOuFR UPPEK Lourk UPPER LEVEL Lrart Limit Limit LIMIT 90.07 808.25, 873.44 49.819 99.929 95.07 601.00 480.70 47-289 108.86 99:07 784.98 896.71 42.942 130-30 FOK & NORMAL DISTRIBUTION HOU CE EERE OEE EES CURE R SEE xa INPUT ORDERED CUMULATIVE CUMULATIVE baa DATA PERCENTAGE © -NOKMAL=—DIFFFRENCF 1 930 730 Te1ag 8.416 Leora ze 870 184 14,286 91399 41893 3 1? 755 21.229 92650 =1e779, a 134 12 28.571 1acKes 130747 5 875, Bec 35.714 374596 1.882 6 870 Bas, 222857 5assil 91584 7 920, 660 30-000, 61.426 11426 8 730 870 6a eRe 67,079 21793 9 155 70 64286 61.079 2.793 10 B20 RTS 711429 69.774 12655, " 890 390 78.571 77.198 =1374 12 B45 220 as.714 88.499 2.784 13 860 950 92.857 95.106 2.209 0+159.4 = KOLMAGAKAV-SMIANGV STATISTIC 264SCHIFIIVE STATISTICS FOR x5 NUMEFK OF @HSEKVATIONS eeeeeeee MEAN = XR = SUMCXCIDOZN MEDIAN LANGE + UNADJUSTED CBIASELD GARTANCE > SUMCOXCD ABI EEN VE: INALJUSTFL STANDARD FFVIATION = SUKTCHVE? ADJUSTED CUNFIASFL) VARIANCE = UVRANZON@1D = ADJUSTED STANDARD DEVIATION = SORTCAVID + SKEWNESS = SUMCCXCI I= AGA ##3) 7 (NEUVKEEISS) cee KURTHSTS = SUM COXCL KER EE AIZONEUURORED eee Ps CONFIDENCE Lover UWP Level LEVEL cma Len Last 90.07 ores 7ea. 474970 95.07 69a01T T0091 452533 99.07 1818 THEA At. gai Fok A NMBMAL DISTHT TEE EEOC HOBIE CEU EE or trees eid cH Ivett OL bE LED: CeULATIVE CUMULATIVE bate DATA PERCENTAGE 0 ACeMAL eas Tag 20% ee Alpe blepe aa Praeo pes 700. paisty gos ai7 Toa a7 rear a8 287 aneTs Tas Secone, cnn a Caoee aiseo MS Caeee ry 840 770 Tears 190 SMTLa 795 go714 KSS, BERET KOLMO CARAMELL NOU STATISTIC 265 DED CONFIDENCE IVTFIVALS GN MFAY £ STANDARD DFVIATIAN STANDARD DEVIATION 13 np 54 105.00 20.00 a1 1k «1.006 4031.9 62.498 =0.38832 2.3599 nEPri, LIMIT 96.719 104.82 125.4e T10N DIFFERENCE 295, tore, lR02 nae 089) rats 7.179 51258 Sips, oeRit S989 21989 sieDESCRIPTIVE STATISTICS FOR x6 NUMEE OF CBSFLLVATIONS «+ MEPN XBR = SUMCKCIDIZN MEDIAN s eee HANGE seers UNADJUSTED (BIASED) VARIANCE SUMCCXCLDXERIEAPIN NVA vee eee ee IWADJUSTEL STANDARD DEVIATION = SCKTCUVK) = S seeeeseeeeee AUJUSTED CUNRIASFD) VARIANCE UIVRANZ(N= 19 - AVKe ADJUSTFU STANDARD DEVIATION = SCRTCAVR? KEY F SE SU CCX C12 =XBKI4439/ (NATURE 165) KURTOSIS © SIMCCXCLI=XERI#EADZENAIVTAE2) peeve ee PaSIDED CONFIDENCE INTFAVALS ON STANDARD DFVIATION 729.00 730-00 235-00 3550.5 59.586 anae.3 er.ois 0.21607 3.0022 MFAN 2 STANDAKN DFVIATION UPPER Limit 93.978 102438 172.54 Fok A NOMAL DISTRIBUTION CONFIDENCE Lovrk LEVEL Limit 90.02 46.853 95.07 4a. ATS. 99.07 40.385, HHL ler Rees ener ee rece enne ee eeneey ve INFUT onorKED, CUMULATIVE CLOLLATIVE DATA bate PELLCENTAGE NOK 1 REO eos, Tian A678 z 150 640. 1alaKe T5460 3 no «90, 21.a09, P6.a73, a «92 692 euESTI 272899 5 775 110 35.714 37.967 é 740 mS 422857 415070 7 165 730 50.606 50.643 4 625 740 572143, 57.039 9 640 755 64.266 66.248 10 90 165, 112429 71.920 W 735 15 7H.571 77.087 12 m5 780 5.714 79.456 13 730 860. 97.857 98.767 Os 12HS = KALMAGOKOV-EMIKNOW STATISTIC 266 DIFFFLENCE 22.265, tel TPP 5.044 -T0a? 2.252 -12787 6.683 0.104 1.962 01492 16285, 761259 52410DFSCKIPTIVF STATISTICS FAH x7 NUMRFh OF OBSFRVATIONS ~ MEAN = KBR = SUMCXCIDD/N MEDIW oes NOE ceeeeeeee UADJUSTFD (BIASED? VARIANCE SUNCOKCL=KBRIE#2IN ~ UVR weer ee UNADJUSTED STANDARD DEVIATION SORT CLV? ADJUSTED CUNBIASED) VAKIANCF = UVIAN. (NOT) = ADJUSTED STANDARD DFVIATION = SUKTCAVAD seeeeeee SKEWNESS = SUMCCXCTD-XBRD#439/ (WAUUKE#I 5) KURT@SIS = SUCCKCI=KERDERAD/(NSUVRERDD 2-SIDFD CONFIDFNCF INTFEVALS ON MFAN MAN (CONF 1DFNCE LOWER UPPFR ue LEVEL, Limit Limit u 90.07 678.27 725.89 95.02 672.97 731.16 99.07 661.27 702.88 Fa THERE HOO rere eco ener x7 INPUT ORDERED CUM LATIVE pata pata PFRCENTAGE ' 800 66 7183 2 160 620 1alpRe a ea #50 21.a79 “ aK Ta PASTE 5 745 685 ALTA ‘ 700 £90 22.887 7 735 700 572143, 200 700 9 ean, 710 10 £50 735 n no 75, a eon. 140. Hs, 400 1RPE & KOLMOEALAVH EMT STATISTIC \ \ 267 13 702.08 700.00 162.00 erates pees 46.276 2319.5 48.565 o.aares 2.4753 2 STANDARD DEVIATION STANDARD DEVIATION UPPFR LOWER MIT Limit 36.387 72.986 34.539 19.508 31.364 95.167 A NORMAL DISTRIPUTION preeaed CUMULATIVE NORMAL RIFFEKENCF 9.170 2.027 9.878 -alai3 13980 =TaaR 27.997 01s7a 342146 01.437 20.101 27.756 aR. 2K0, TRIBES aK. PHO tRLRES 96.532 272783 15.747 32858 1.388 poTR6 BRISA, BoRe9 97.49% SloatNUIKER OF OBSERVATIONS «~ DESCRIPTIVE STATISTICS FORK. x6 13 MEAN XBR SUM CXCIDIVN 7 706.85 MEDIAN : 695-00 ONCE ee a 180.00 INADJUSTFD CBIASED) VARIANCE = SUMCCKCI-XBROAEDIN = UIC + 7 993.2 AWADJUSTED STANDARD DEVIATION = SOKTCUVKD = S 5 54.710 ADJUSTED CLNBIASED) VARIANCE = UVKEN/(N=1) = AVKs on 3202.6 ADJUSTED STANDARD DEVIATION = SOKTCAVED eeseeeee 5 56.944 SKEUNESS = SUNCCKCID=XBRD##S)/(NEUVER#ILS) coon + 0.saa32 KURTOSIS = SUCCXCLD=XBRD#RAD/CNEUUKEE + Sore 2.2669 OONFIvENCE LEVEL 90.02 95.07 99.0% 2-SIDED CONFIDFNCF INTERVALS ON MFAN % STANDARD DEVIATION MEAN STANDARD DEVIATION Lover UPPFE LOWFR UPPEK UIMit Limit Limit Limit 678.70 734.99 43.019 36.289 67z.4a 741.26 40.838 94.000 658.60 755.09 372081 112.51 Fok A NOKMAL DISTRIRUTION HEC ERE Or Eonar aenanein ek x6 INPUT ORDERED CUMULATIVE CUMULATIVE DATA DATA PEKCENTAGE NORMAL = DIFFERENCF 140 640 14.286 12.022 =2.264 165 640 142286 122022 =2.264 664 645 21.429 13.872 27.556 640 664 28.571 2.590 75.982 740 680 38.714 312866 3.848 695 685 42.857 352062 27.795, 8 695, 30.000 . 416760 8.240 820 710 572143, 522208 241938 645, 725, 6.286, 62.506 =1.780 640 740 712409 11.979 02850 no 165, 78.571 84.643 6.072 6RS, 780 5.714 90.054 4,340 660 820 92.857 972654 4.797 0-1209 KOLMOGOKOV-SMIKNOV STATISTIC 268MULTIPLE RFGKESSION ANALYSIS TEXAS GULF PLANT NORMAL OPERATION 269Texas Gulf Data set ‘TCx2 Tox iase7esT 11718774 100 135, 806s 11184845, 99148214 B69 6214846, 101 120,805) 1115+ 846, 992, 822, B63, 822, 8.46 102 134, B06, 1118, 845,992, 821,263, 4214846 303. 132,800, 1118, 843,994, 822, B65, B20, 847 104 1407803, 1113+ 845, 98H 81 6.859, 815,842 105. 135, 803-1117, 640,991,616, 660, 818.842 106 2224 797+ 1104, 630+ 1001, 632, 686,834» 866 107 188, 795+ 1096, 828, 1001, 829, 844, 892+863 108 200, 795, 1097, 826, 1000, 826, 883+ 830, 862 109 120,606, 1125, 8495 98.4, 811,849, 823856 110 127,803» 1117, 843, 982, 808, 848, 820, 849 M11 130,805, 11204845, 961, 808, 645,818, 848 112 140, 808» 1128, 648, 960, 800, 830, 810+ 838, 113 14148114 1134, 855, 963, 808, 842, 821,847 114 127,809» 1130, 853, 986, 613,851,827 851 N15 100, 799+ 1121, 6424979, 616,852, 826,849 116 425, 805s 1110s 840s 920, 730s 730+ 735 755, 1171252 7999 1120+ 040s 950s 763s 762s 169» 786, 118 132,801, 1126, 840, 968, 790, 608, 795, 22 119 120, 803, 1125, 640, 969, 600, 830, 601-630 120 110 +808, 1130, 841,970+ 800, 830, 803,631 121 70,802, 1105, 842,977,811, 8469801, 828 122 80s 800s 1091, 83949754811 8455808, 827 123 604778, 1103, 828,960, 604, 834+ 406,815 124 118,805, 1109+£46, 999, 826, 869,821,649 125. 11046065 1113+ 849,999, 826, 868, B21, 846, 126 11046094 1117, 850+ 999s 826. B67, 8215 B46, 127 200, 793s 11264 79 1, 79 1 600» 812s 793, 821 128 130,800» 1120, 843, 980. 803, 8: 55616, 837 129 95+ 798» 1118, 847, 983, 617, 645» 633,650 130 100,803, 1126, 634,972» 61 4» 850+ 830» B55, 270RUN 1 MULTIPLE REGRESSION PROGKAM XMEAN 8.01967 7E+02 12116581F+03 1B. 409032E+02 94.753871E+02 8.09419 .4E+02 8. 438064E+ 02 8B. 13225BE+02 8.385161E+02 OBSERVED 1.35000008+02 1,2000000F +02 1,3400000F +02 1.32000008+02 1. a000000F+02 1.35000008+02 2.2200000+02 1.800000E+02 2.000000 +02 1-2000000F+02 1.2700000E+02 1. 3000000+02 1, a000000F+02 1,.4100000E+02 1.2700000€ +02 1. 0000000E+02 4,2500000E+02 2500000E+02 1.3200000F +02 2000000F - 02 1, 10000008 +02 7, 000C000E+01 %.0000000E+01 6-0000000F+01 1. 18000008+02 121000000 +02 1, 10000008 +02 + 00000008 +02 130000008 +02 9250000008 +01 1200000008 +02 YMEAN 1.97995SE+02 CALCULATED 1420789008 +02 1.1261185E+02 120789008 +62 1.0160772F+02 1.1758125E+02 1. 2855834E+02 1. 1ts0aa8e+02 1.1500999E+02 122596205E+02 1.3082470E+02 14.41381186+02 1..4250045E+02 1.586a5aae+02 1.3809330E+02 1.28261698+02 1. 1518727E+02 2: 8460406F+02 1.797S210E+02 1,6967646E+02 1.5894531E+02 3.75523718+02 1.2717273E+02 1,2959251E+02 973025 634F+01 1204062966 +02 929424274E+01 1.07805326+02 2: 5528C1SE+02 1.25741 57E+02 9.811731 7E+01 1.57965S8E+02 an EST VAR 1.7629593E+02 1.72161 12E+0e 1.7629593E+02 2.143033aE+02 1.593839aE+02 1.25a22616+02 2.8636440E+02 3+ 1667466E+02 343377359E+02 2. 25832a2F+02 2.0372619F +02 1.659a186F+02 2.2959603E+02 3+7$31740E+02 3-$310062E+02 2.0482986F +02 1.5403200E +03 7.7619038E+02 1,7183168E+02 1,3067693F+02 22.407960E+02 4.595479 1E+02 2.682428 1F +02 1.65589 76F +03 3..0912896F+02 325614376402 4.1230886E+02 1.9507907£+03. 3 4419073E+02 4.7251964E+02 3:5681231E+027 SDEGKFE OF FREF- + REGRESSION. fOREMAINDER + 2 ToTaL : MULTIPLE COKRELATION COEFFICIENT = CONSTANT TERMCINTERCEPT? COFFFICIENTS FST OF SD 3. 7227268F +00 — 1.9.468376E+00 +2.7871378E+00 —1.091.4522E+00 =2.0432343E+00 —143717363E+00 3+ 759S600E-01 —1-3798760E+00 F RATIO’ & RUN 1 (Continued) SUM OF SQUARES. 5-330958F+04 - 6.949829E+04 « 1:228079F+0S + 26 DEGKFES @F FKEED@M)= VARIANCE ESTIMATE 1,3327a0F+0a 226730115403 6-5885a5F-01 8. 4a2381E+02 4.98591 1E+00 UPPEK RT HAND PORTION OF MATRICES ONLY INVERSE ADJ DATA MOMENT MATRIX FOWC 1) 1-4179F-03 -4-9918E-04 -9.6133E-05 1.0495E+04 ROWE 2) 4.AS67E-04 1. 6484F-04 -1.7670F-04 RBkC 3) 7.0395SE-04 -6.6529E-04 FOwe 4) 721233E-04 EST COEFFICIENT VAR-COVAR MATRIX HOWE 1) 9+7902E+00 -140343E+00 ~2-5697E-01 2-80S2F-01 , HOC 2) 11913400, 4.4061F-01 4. 7233E-01 HOWE 3) 1.8217E+00 =1.7783E+00 owe 4) 1.90a1F+00 ADJ DATA COKRELATION MATKIX HOWE 1) 1-0000E+00 -6.2795E-01 -9.6222F-02 1.0442E-01 HOWE 2) 1-0000F+00 2.9429F-01 ~3.1362F-01 FOWC 3) 1-0000E+00 -9.39S0F-01 ° Fowe 4) 1.0000E+00 272RUN 2 MULTIPLE KESRESSION PROGRAM MEAN 8-019677E+02 1.11658 1F+03 8. 409032E +02 9275387 1E+02 3.0941948+02 + 498064E+ 02 8. 13225KE+02 8.385161E+02 OBSERVED 1.3500000E+ 02 1, 20000002+ 02 1..3400000E+02 1..3200000E+02 1, 4000000E+02 1. 3500090F +02 2. 22000008 +02 1. 8800000F +02 2. 00000002+02 1. 2000000F+02 1. 2700000E+02 1. 3000000E+02 1. aG00000E+02 1, 4100000F+G2 1. 27000008 +72 1ooooouce sz 4. 2500000F +02 1. 2500000802 1. 3200000F +0@ 1: 200v9008 +02 1. 10000008 +02 7.00000008*01 8. 00000008 +01 6-00¢0000F+01 1. 1g0SG0F=02 ¥. 1090000802 1. 1n9a000F+07 2. 0v000U0E+ 02 1. 2000000F +0z 9:500000cE+01 1. 0000000E+ 02 YMEAN 1.9799550+02 CALCULATED EST _VAK 1.2065665E*02 1. 9785551F+02 1, 1030036€+02 1. 2104080E+¢2 8.251399 6E+0) 1.2426820E+02 1,3865016F+02 1.4953898E+ 02 1.7398691z+02 2.01858248+02 1.2962520E +02 1, 66467642+02 1.51102396+02 1.5a1018aF+02 1.2018286€+02 1e2seeaze+ce 1,0040894F+02 9. 5849 109z+u2 1.477741 36+02 1. 36€904aE +02 1.420728 -02 1.676029%E+02 1.27369 58E+02 1.631882 16+02 7.8306632E+01 1.0081eutE+02 8. 6a69852Ec01 9. 1HaH912F+O1 LeG252a7E+02 7. 6800663E+01 4. 9803340E+U1 272A 1.7232858E+02 2.03524a96+02 3-1108.493E+02 © +2289 126E+02 3287371596 +02 9-8340641F +92 4. 19981 75E+02 6. °076563E+02 219235762F+02 230898E+02 3. a323903E+02 2.0027279F+02 3-83030S1E+02 350876623E+02 1.67865308+62 1,.4281389E+03, 6.1707298F+02 6.S819022E+02 3.93194946402 3-98929.46E+02 4: 2868723502 1. 1a13875E+ue 129482220403 2.6827986E+02 2.621S510E+0e 3 S800741F +02 1:7648602E+03 1.1139225E+03 5. 626€279E+02 6-9730915F+02RUN 2 (Continued) : DEGREE OF FREE. SUM OF SQUARES. VARIANCE ESTIMATE . + REGRESSION. 8 + 8.392108F+0a - 1-0a151aF+0a + REMAINDER « 22 + -36948679E+04 + 1.794854E+03 + TOTAL . 30 + 14228079F+05 . MULTIPLE COKKELATION COEFFICIENT — 8.226911E-01 CONSTANT TERMCINTERCEPT) = 3-377379E+03, COEFFICIENTS EST OF SD 6+9265897F+00 2+962275BE+00 7129615544E+00° 1-3438454E+00 =4:9321602E+00 2.6892745E+00 3.8414426E-01 7-8205S21E-O1 =B+0901479E+00 — 2-8653007E+00 2.6723307F+00 —1.96603478+00 3+3243019E*00 3.6216309E+00 7124300937E+00 —3-.4853787E+00 273OESERVED 1.3500C00E+02 1, 2000000E+02 1..3400000E+02 1. 3200000E+02 1. 4000000E+02 1.3500000E+02 2. 22000008 +02 1..8800000F +02 2..c000000E +02 1, 2000000E+02 1,27000G0E+02 1, 30000098 +02 1, 4000000E+02 1..4100000F+02 2700000F+ 02 10000000 +02 4. 2500000E+ 02 1,2500000E+02 1..3200000E+02 200G000E+02 1000000E+02 7. 00000008 +01 6. 0000000E+01 60000000 +01 1. 1800000E+02 1, 1000000E+02 1. 10000008 +02 2..0000000E+02 1. 3000000F +02 9.000000E+01 1..0000000E+02 RUN 3 CALCULATED 1.2020103E+02 1.1019730F+02 1.20635338+02 8.26859 16E+01 1.2360301F+02 1.39 a5266F+02 125329643E+02 1.76549 7BE+02 1,.9066319E+02 1. 2883658E+02 1.6709222E+02 1.810191 7E+02 1.5933083E+02 1..1790353e+02 1.209788 7F+U2 1.018210SE+02 3.6049421E+02 1..4720163E+02 1.3748979E+02 1.4178868E+02 1.6679512E+02 1.2717058€+02 1.65608868+02 7.6136909E+01 1,.0048923E+02 8.S780494E+01 920594877401 1.838764BE+02 8. 1264360F+01 8. 1622675E+91 126996275402 274 EST VAR 1.96000226+02 1. 72265136402 2.0134636F +02 2.823881 7F+02 2.157639SE+02 3+9.460361E+02 3.80500386+02 B585695E+02 52 6866451E+02 2.8990100F+02 3. 7909062E+02 3.5555361E+02 2.0519385F+02 3.6860193E+02 1769836 +02 1.7098269E+02 1,.4479093F+03 6.158450 7E+02 6. 42524386+02 3429263376 +02 3.94163a2E+02 4.2381 024E+02 6.954361 7E+02 1.387471 6E+03 134381402 2.6150071E+02 3+5628143E+02 1.75409 74F+03 1. 1008696E+U3 5279538568402 6.95521876+02RUN 3 (Continued) ‘DEGREE OF FREE. SUM OF SQUAKFS. VARIANCE FSTIMATF « REGKESSIAN. 8 2 8.366912E+0a . 1-045789E+04 7 REMAINDER - 22 3:914a75E+04 | 1.779307E+03 TOTAL : 30 1.228079E+0S + MULTIPLE COKKFLATION COFFFICIENT = 6-259800F-01 CONSTANT TEHMCINTERCEPT? = 3.690478E+04 COFFFICIENTS EST OF SD + Be6S9S9S4FAUS — 3-$086377E403 =3441853336E+03 2.093961 4E+03 ~6.7058524F+03 —3.4049073F+03 619034928F+02 1.044612 7E+03 =1ozegaaaesoa 3. 7574227F +03 312799901403 2. $669906E+03 4. 4362479F+03 4, 6816896E+03 : -149235075E+03 4.6394966E+03 F KATIO€ 6 22 DEGREES OF FREEDOM 5+877508E+00 UPPER KT HAND PORTION OF MATKICES @NLY INVERSE ADJ DATA MOMENT MATKIX FOWC 1) 6.918 7E+03 -6.6065F+02 -5.0060F+03 1.0083E+03 “B.3B59E+02 6.0114E+03 ~5.6340E+03 WOW 2) 2.4649E403 -1.2062E403 5.0306E+02 1-0187E+02 6. 90RBE+02 6-1970E+*01 -1-a519F+03 HOWE 3) 6.5157F+03 -1.7610F+03 -1;3366E+03 1.1855F+03 -4.9090F+03 ‘5+ 4034F+09) OWE A 6. 1B2HESOZ 9.339 7EF02 -6.61KEF+O2 6.S211F+02 -9.7282F+02 JOE 5) 7.9347F+03 ~4.7959E+03 -3.9622+03 2-6049F +03 HOWE 6) 3.7034F+03 2.0485F+0R -2.2883F+03, fOWe 7) 1.231848 ~1.1230F+04 fowe 8) 1.209 7E+04 = 6869F+02 EST COFFFICICNT VAk-COVAK MATRIX HQC 1) 1.231 1F#07 ~141755E+06 -8-9079E+06 1-7941F+06 8.3995F+05 1.492 1E+06 _1-0696F407 ~1.0025F+07 WOUC 2) 4.38A7F+06 -2-14G61E406 B+9SIOF*OS 1-R125F40S 1.2299F+06 1, 1026E+05 2. 5833F+06 WOUC 3) 141593E407 =3.1984E+06 -2.3786E406 2-1094E+06 ~8.7239E+06 9.6 1a3E+06 WWE 4) 1.091PE+06 1-6618E+06 -1-1777F406 1. 1603F+06 - SOUC 9) 1.411BE#07 -B+S334F+06 ~7.0501E+06 4.6349F+06 HOWE 6) 6.SB9AEF06 4.6451E+06 - 4.0715E+06 HOWE 7) 2.191KF+07 -1.9961E+07 Foue $) 2.1525F+07 + 7309E+06 275RUN 3 (Continued) ADJ DATA CORRELATION MATRIX FOWC 1) 1,0000E+00 ~1.6C90E-01 -7..4559E-01 1.6567E-O1 645116E-01 ~6.1583E=01 ROWC 2) 1.0000E+00 =3-0101E-01 4.0921E~01 i+ 1248E-02 ~2.6591E-01 f@NC 9) 1.0000E+00 ~8.8097E-01 -1.8592E-01 6-0861E-01 ORC 4) 1-0000F+00 4.2339F-01 -4.3918E-01 FQWC 5) 1.9000E+00 -8-8472E-01 -4.0077E-01 FOC 6) 1,0000F+00 3-0331E-01 -3.4187E~01 FC 7) 1.0000F+00 -9. 1990-01 Fore 8) 1.000cE+00 EADY 2STOP USED 14.78 UNITS. YE 0014.89 CkU 0000-37 TCH 0009 FF AT 14:20EST 11721774 276 4.8950E-01 6.3257E-02 2.3037E-02 - 2-2870E-01 2.a134F-01 2.3725E-0 2. 6588E-01 ~5.4727E-01 +3. S716E-01Texas Gulf Data set Toxd T6Ke lOranFSi 12709774 too 10) 102 103 104 108 106 107 108. 109 0 m ne n3 a us 16 17 ne. ang. 120 11 qe 13 va 2s 126 127 128 129 130 1BbsOF + 1118 845,991, 8214 REI EP 1 BE 1200805) 11) $4 6469 992s HEP, HEBs BPE, BAG 134, 806, 1118, 845,992, HPI, RE KOLA Hae 132s 8UCs 111s 443, 99 as 822, R655 B20» HAT 1409 403s 1213+ R45, 9B WI Ge BSYs 1S, KAP 135» 803s 111748405 99 1, 81K, 460s 818, BAe 222s 7974 1104, R305 1001, 632s ABE, B34, HEE 186,795, 1096, BPH. 1001629 HR Ae H326 ES POC» 1955 1097s BPs 1000s BF Fs KB, K30, BE? 120s 4OFs 11254 8.495 984, 811, 449s R23, 650 1272803, 1117, 643, 982, BOK, Bak, BPO, 829 130s KOS) 1120, 6455 981, BOK, RASs KIB. BAK 1403 808) 1128, Hams 9RO, BOO, 630 B10, 438 141s 8115 1134) 8555 983s BOK, 842+ 87 15 BAT 1272 809, 1130, 853, 986. #13, 8514827651 100s 7994 11214 8424979» 816, 8529 WP 6s B49 125s 7994 1120s 850» 980» 163+ 763s 769+ 786 132+ BO1s 1128, 840, 9b, 790, GOB, 795, BEE 120s 603, 1125, 540s 969, 00, 630, 601, R30 110. 5 £085 1130+ 6414970, ROU, 830. 8034831 10+ OP» 1103, 8422977481 1+ HAF» RO1s HOR 80+ 800, 109146395975, 611,845, 805, 827 60 778» 4 1034828, 960, B04, B24, BOK, 819 116s 805s 1109. 86, 9995 826, 869s 62 16 809 1102 606s 111378494 9994 K26, BAK B21 5.46 1105 409s 1117, 8505 999, 826, 667, 821, 846 200+ 7935 1126s 79 14 791, 800, 612+ 793, 621 130, 400s 1120, 848s 980» 803, 6155 & 1B 837 955 798s 11 16s BAT 943, 17s 54K 633% B50 100+ 603» 1124, 634,972,614, 650» 8305855, 277NUMFER OF OFSERYATIONS. MEAN = STANDARD STATISTICS DFSChIPTIVF STATISTICS FOK YI sees 30 KEK = SUNCKELDOZN oe 120.97 MEDIAN eeseeeeesseeeeseeene 127.00 hance : 1462.00 UWADJUSTED CEIASED) VARIANCE = SUMCCKCLD“XBKDO#2)N = UVE — 1255.2 WADJUSTFD STANDARD DFVIATION = SCRTCUUKD = S 25.408 ADJUSTED CUNBIASFD) VARIANCE = UVKEN/EN=1) ~ AUK + e984 ADJUSTED STANDARD DEVIATION = SOKTCAVRY «sees 36.038 SKFRNESS 2 SUMCCK(1D=XBKI4029/ (NADVREELES) coe o. 77892 KURTOSIS = SUICCKCLD=xBKDNAD /cWeLUKHH2? 3.0945 2rSIDED CONFIDENCE INTERVALS ON MEAN 4 STANDAKD DFULATION Fan STANDARD DEVIATION CONF LDENCE Laver UPPER LaveR CUPP LEVEL crert Limit Limit Cini 3Scez asst iitee Bato aeiaat 99:02 10229 146.50 26.823 $3:570 FOR A NORMAL NISTRIPUTION 278va INPUT DATA 135 120 134 132 120 135, 222 138 200 120 127 130 140 yay 127 100 125 132 120 Ho 10 80 60 118 no 110 200 130 95 100 0.2296 ORDFRFD. DATA 60 70 80 95 100 100 110 10 no 1B 120 120 120 125 127 127 130 130 132 132 13a 135 135 120 140 1a 188 200 200 eee = KALNAGOKOV-SMIANAV ClmULATIVE PEKCENTAGE 279 3.226 6.452 92677 12.903 192355 19-355 29.032 29.032 292032 3? 258 41.935 21.935, 41.935, 45.161 31.613 31.613 38.065, 38-065, 64.516 64.516 67.742 83.871 57-097 93.548 93.548 96.774 STATISTIC CUMULATIVE NORMAL, 24890 5.264 8.976 176723 21.558 21.558 302513, 30.512 307513, 38.479 40-820 40.820 20-620 26.278, 45.487 48.467 51.808 51.808 Sa.016 54.016 56.212 87-303 $7:303 62.659 2.659 3.705, 95.103 97.659, 976659 99.592 DIFFERENCE -0.336 = 12188, =0. 702 4.820 22203, 2.203, 1481 1.481 12481 61421 e1eae w1ette ae way 730126 =36126 762257 =6.257 =10.500 =10-500 =112530 =16.891 =16.891 =17. 986 s17L986 =20. 166 L008 att anny PL 75KDFSCKIPTIVE STATISTICS F@h xt AWHREK OF OFSERYATIONS +o eeeee 30 HAN ~ XBR = SUMEXCIDIZN veae 801-87 MEDIAN sereeeee 803-00 UNG seseeee ee 33.000 WADJUSTED (BIASED) VAKIANCE = SUMCCKCII@ABHI#OIN = UVA eeeeeseeceeeeeee 39-116 WADJUSTED STANDARD DEVIATION = “SORTCUVK? = S - wee + 622542 WJUSTED (UNBIASED) VARIANCE = UVREN/(N-1) = AVRseeeeeeeee 40.464 MGQJUSTED STANDARD DFVIATION - SGRTCAVR? 663612 SERNFSS = SUMCCKC1)=XBK)#439/(NAUIVREET «5? -1.7507 WURIOSIS > SUNCCXCTD=XBKD## 497 CNAUVK#HED cd 7.6792 2-SIDED CONFIDENCE INTFKVALS ON MEAN £ STANDARD DFVIATION MEAN STANDARD DEVIATION (CONFIDENCE Lowek UPPEK LOWER. UPPER LEVEL, Limit Limtt Limit Limit 90-02 199.69 503.84 8.2511 8.1404 95.07 199.49 woa.ea 5.0661 8.5514 99.02 198.67 805.07 4.7352 9.4569 FOR A NORMAL DISTRIBUTION 280wruausun- xt ‘NpuT RDFAED. CUMULATIVE CUMULATIVE DATA DATA PERCENTAGE NORMAL, 806 778 3-226 0.009 80s, 793 6.452 8.168 B06 795, 122903 142019 800 795 12.903 14.019, 603 797 16.129 22.212 803 198 196355 197 799 25.806 795, 799 25-806 798 00 35.484 806 800 35-484 38.459 803 00 35.484 38.459, 805, gor 38-710 44.581 808 802 41.935 50.836 air 803 58.065, 57.070, B09 803 38.065, 37-070, 199 603 38-065 37.070, 799 803 58-065 57-070 801 803 38-065 37-070 803 BOS 672742 68-884 B08 80s 676742 68-884 B02 80S 67.742 68.884 ‘800 806 80.645 74.208 78 806 80-645 742208 80S 806 80.645 74.208 606 806 80-645 742208 809 808 87.097 83.252 793, 808 87.097 83.252 800 sco 93.548 86.894 198 809 93-548 86.894 803 sir 96.774 92.407 0+1374 = KOLM@OGAROV-SMIRN@V STATISTIC 281 DIFFERENCE -3.217 1716 116 rine 62083 1.809 628C6 C2896 21975 2.975 21975 5.872 8.901 -0.994 70.994 70.994 20.994 -0.994 1142 1etae irae 6.437 762437 = 6.437 262437 =3.844 31844 -6.655 =62655 327DESCKIPTIVE STATISTICS FOR x2 NUMBER @F OBSERVATIONS - MEAN = XBh ~ SUMCXCIDI/N « MEDIAN «. wANGE INADJUSTED (BIASED) VAKIANCE = SUMCCKCE=XBKI##29N = OVE UNADJUSTED STANDARD DEVIATION = SORTCUVR) = S ++ ADJUSTED CUNBIASED) VAKIANCF = UVR#N/(N-1) = AVR. ADJUSTED STANDARD DEVIATION SORTCAVKD « SKEWNESS © SUMCCXCID=XBh#43)/(NSUUK#E1 659 ee KUKTOSIS © SUMCCXCID=XBRI##A)/(NAUVRHA2) oe eee 30 1116.8 1118-0 43-000 1it.4a 106556 115.27 10.736 =0..66769 2.7854 2-SIDFD CONFIDENCE INTFRVALS @N MEAN Z% STANDARD DFVIATION (CONFIDENCE Lovrr. Loven LEVEL Limit Linit 90.07 1113.5 112061 8.8628 1128 1120-8 825505 nae 1122.2 7.9920 STANDAKD DFVIATION UPPFK Limit 13.739 142433 15.981 FOR A iORMAL DISTRIBUTION 282RERLSSHIADTOBIS oaseusen- S3gse xe INPUT DATA 1118 Wis Mis mie 1113 m7 1104 1098 1097 1125 ny 1120 1128 1134 1130 1121 1120 1128 nes 1130 1103 1091 1103 1109 Ha, vay 1126 1120 1116 1126 O.17a1 OnDEKED DATA 1091 1097 1098, 1103, 1103, oa 1109 113, 113 15, way M17 WaT KOLMACOROV-SMIRNOV STATISTIC 283 cuMLATIVE PERCENTAGE 34226 6.452 92677 16.129 162129 192355 22.581 29.032 29.032 32.258 412935, 41,935 412935, 54,839 54,639 54.839 34.839 64.516 64.516 6a. 516 67.742, TA 194 Tas 194 qTa19, 87.097 87.097 87.097 93.548 93.548, 96.774 cumcaTiVve NORMAL 0.813 3.288 31997 9.933 91933 11.659 23.376 96.169 36.169 43.343 50-743 30.743, 30-743, 34.450 34.250 34.450 54.450 61.717 61.717 61.717 65.217 77.750 17.750 80.425 85.157 85.157 85.187 89.055, 89.055, 94.543, DIFF! 2, -3. 25. -6 76 7 9. 7, 7 1 8. 8. 8 +0, +0! -0) +0) 2. -2 +2) 2. 3, 3. 3, a “1 ERENCE 2413 194 1681 2196 19e 2696 796 6137 137 2085 +808, +808, 2808 +389 2389 389 2389 2799 2799) +799 1525, 7556 556 2008 19.40 2940 i920DESCRIPTIVE STATISTICS Fok x3 MEIBER OF OBSERVATIONS «eee oo MEANY = XBR | SUMCKCIDIIN caseseesees 840.93 WEDIAN 6 oe . Beacon WANGE + tees oo seeee : 64.000 WADJUSTED CBIASED) VAKIANCE = SUMCERCI@XEKIEAOIN = UK = + 137660 WNADJUSTED STANDAKD DEVIATION = SOKTCUVKD = + e790 A0JUSTED (UNBIASED) VARIANCE —UVKEN/@N=1) ~ AVKe + 12.4 fOJUSTFD STANDARD DEVIATION = SORTCAVRD sees 1.901 SKEWNESS = “SUMCCXCL)=XBKD4#2)/(NHLIVRRAT 65> . se67 MURTOSIS © SUMCEKCLD=XBKDSNAD/(NAUVROGRD eeseeeseeserseens 114921 2-SIDED CONFIDENCE INTERVALS ON MEAN & STANDARD DFVIATION MEAN STANDARD DFVIATION (ConF LDENCE LOWER. UPPER LOVER UPPER LFVEL Limit LIMIT Limit Limit 90.02 824.63 9.8487 15-268 95:07 845.39 925016 165039 99.07 46.94 8.8810 17.737 Fok A NORMAL DISTRIRUTION 284“x3 TpUuT ARDERED CUMULATIVE — CUMULATIVE DATA DATA PERCENTAGE © NORMAL = DIFFERENCE eas 91 3-726 0.008 -3-224 846 826 6.452 10.534 4.083 Bas eee 12.903 131917 aoa Bag BOR 12.903 13.917 ioe B45 830 162129 172973 gaa 840 834 19-355 28.087 8.703 830 639 22.561 432563, 20.983 828 840 32-258, 46.882 14.624 826 840 32.258 46.882 1ar624 849 840 92.258 46.882 14.624 Baa sat 35.484 30.223, 14.739 Bas Bae 41.935, 53.562 11.627 B48 Bae 41.935, 532562 112627 855 B43 48.387 36.876 8.489 853 843 28.387 56.876 8.489 gaa Bas 61-290 63.340 2.089 850 645 614290 63.340 2.089 820 845 61.290 63.320 2-009 840 B45 61.290, 63.320 22049 gat 846 67.742 66.486 71.296 Bae B46 67.742, 66.446 716296 839 a7 70.968, 69.405 =16523 828 848 77.419 72.318 754101 B46 Ba, 17419 72.318 256101 Ba B49 83.871 75.08? RABID 850 B49 83.871 75.052 28.819 Ta 850 90.323, T1636 126687 Bat 850 90.323, 77,636 =126687 Bar 853 93.546 84.409, =92140 Bea 855 96.778 8.081 =8.693." G+2356 = KOLMOGOKAV-SHIRNAV ETATISTIC 285DFSCKIPTIVE STATISTICS FOR x4 MMBFK OF OBSFAVATIONS cee. seseceeseeeeneceee sees ee eee eee + 30 MEAN = XBR = SUM(XCIDI/N eeeeeeee : 977.23 MEDIAN Soosenenn 983-00 RANGE + ee 210.00 UNADJUSTED (BIASED) VAIL ANCE SUNCCKCLD=XPRI€#PIN = UE « 134965 UNADJUSTED STANDARD DFVIATION = SURTCUVRY = S cress 36.736" ADJUSTED CUNBIASED) VARIANCE = UVREN/(N@1) = AVR: 1396.0 ADJUSTED STANDARD DEVIATION = SORTCAVK? voee 97-366 SKENFSS = SUMCCXCI2=XBKI4#39/CNFUVKEETSD + 3015 KURTOSIS = SUM CCKCI=XBKI## 47 (NELUIVER EAD seeeeees 22.063 2=SIDED CONFIDENCE INTFRVALS ON MFAN & STANDARD DEVIATION STANDARD DEVIATION CONFIDENCE Lovrk UPPER: LowrR UPPER LEVEL Cisit Limit cia LIMIT 90.07 965.64 = 988.82 30-840 476815 95.02 963.28 991619 29.757 50.229, 99.08 956.43 996.04 27.819 35.547 FOk A NOhMAL DISTKIBUTION 286xa INPUT ORDFRFD ClULATIVE CUMULATIVE pata DATA PERCENTAGE NOKMAL DIFFERENCE 1 991 791 3.226 0.000 =3-226 2 992 950 62452 23.304 16.852 3 992 960 92677 32.232 22.554 a 994 968 12.903 40.241 27.338 5 968 969 16.129 41.280 25.151 6 991 970 192355 22325 22.970 7 1001 972 22.581 44.430 216850 8 1001 975 25.806 47.617 21.810 9 1000 977 29.032 49.751 20.719 964 979 32.258 51.886 19.628 1 982 980 98-710 52.951 1a.eag 981 980 38.710 52.951 1aseae 980 981 41.935 54.015, 12.079 983 9a: 45.161 38:076 g.9ta 986 983 31613 36-133 4.520 979 983 51.613 56.133, 4.520 950 964 54.839 57.186 2.347 968 986 58-065 39.275, 1211 969 988 61.290 61.339 o.04a 970 991 67.742 64.373, +3369 977 991 67.742 64.373, =3.369 975 992 Ta.19. 65.366 +8828 960 992 Taga 65.366 ~8.828 999 994. TIAN 67.319 =10-100 399 999 87,097 71.991 =18. 106 999 399 87.097 1991 715106 791 999 87.097 71.991 =15.106 980 1000 90.323, 7etges = 17438 983 1001 96.774 13.764 23.010 972 1001 96.774 73.764 =23.010 “0-3024 = KOLMAGOKOV-SMIKNOV STATISTIC 287DESCKIPTIVE STATISTICS FOR x5 NUMBER OF OBSERVATIONS « seeeeeeeees 30 MEAN = XBR = SUMOXEIDI/N eeeeee . 812.07 MEDIAN sseeseeee 813.50 RANGE 69.000 UVADJUSTED (BIASED) VARIANCE SUNCCXCII=XBRI#*29N = UVIE 186.33 UNADJUSTED STANDARD DEVIATION = SOKTCUVRD = 13.650 ADJUSTED UNBIASED) VARIANCE = UVR#N/(N=1) = AVReseeeseeee 192.75 ADJUSTED STANDARD DEVIATION = SORTCAVR) -eeeeceeeeeee 13-884 SKEWNESS = SUMC(XC1)=XBRD##39/(NSUUREHL¢5) eeeeeeeeeeeeeee =1,4408 KURTOSIS = SUMCCXCLI-XBRI##2)/(NEUVREHO) eee ee 6.2998 2-SIDED CONFIDENCE INTERVALS ON MEAN £ STANDARD DEVIATION MEAN STANDARD DEVIATION (oNF1 DENCE LOVER UPPEK Lower UPPER LEVEL Limit Limit Limit Limit 90.0% 807.76 816.37 11.461 17.767 95.02 817.25, 11.087 18.664 99.02 80S. 08 819-05, 10.335 20.640 FOK A NORMAL DISTRIBUTION 208xs INPUT Data 21 Bee 21 B22 B16 als 32 329 B26 gir B08 808 B00 08 B13 B16 163 790 800 800 Bit ait B04 826 B2e B26 800 803 B17 aia 0+1257 = KALMAGORAV-SMIANOV STATISTIC PRDEKFD DATA 163. 790 800 goo 00 800 803 Boa 808 B08 B08 git Bil B11 13 gia B16 Bie B17 nis 521 821 822 822 826 B26 B26 826 829 a2 cumuLaTive PERCENTAGE 289 3-226 6.452 192355 19.355 192355 19.355 22.581 25.806 35.484 35-484 35-484 45-161 452161 45.161 46-387 51.613 58-065 58-065 61.290, 64.516 70-968 70.968 77.419 Tas 90.323 90.323 90.323 90.323 93.528, 96.774 CUMULATIVE NORMAL, 9.020 5.598 192239 19-239 192239 19.239 25.686 28.061 38.479 38.479 382.479 426.938 46.938 46.938 52-680 35.537 612153 61.153, 632883, 6E.548 74,003, 74.003 162284 76.284 84.221 Ba.221 84.221 88.870 92.046 DIFFFRENCF -3-205 =0-853 tonite 20.116, sorte. =0.116 32106 2.255, 2.996 2.996 21996 16777 12777 “17977 45293 36925 - 3.088 3.088 22593 2.028 35036 3.036 212135 710135 762102 = 6.102 =6. 102 =6.102 ~42678 4.375,DESChIPTIVE STATISTICS FAR x6 NIMBER OF ORSFRVATIONS «eee ee aon + 90 MEAN = XBR = SUNCXCIDO/N ooo 8.47.60 MEDIAN 849.50 RANGE «5 129.00 ADJUSTED CRIASED) VARIANCE. = SUC CXC? 2°XBRD##2IN = UR» 628.57 UADJUSTFD STANDARD DEVIATION = SORTCUUR? = S see 25.071 ADJUSTED (UNBIASED? VARIANCE = UVRAN/(N=1) = AVR 650.25 ADIUSTED STANDARD DEVIATION = SORTCAVK «eee 25.500 SKEWNESS = SUC CXCL)-XPRD##D) /ENAUUKOEI6S) ceesesseesseese | 7142096 KURTOSIS = SUMCCXCI>=XPRIEAD/CNEUVKHED) oe 5.9209 2-SIDED CONFIDENCE INTERVALS @N MFAN 2 STANDARD DEVIATION . FAN, STANDARD DFVIATION 2 cone 1DENCE tows UPPRR Lower UpPrR LEVEL trait Liwit creat Limit 90.02 899.69 855.51 21.050 324652 95.07 898-08 857.12 20.308 34.280 99.07 98077 860.49 18.982 37.910 2 FO @ NORMAL DISTRIRUTION 290Ks INPUT GRDF RED. CUMULATIVE CUMULATIVE DATA DATA PERCENTAGE NORMAL DIFFFRENCE 363 163 3.226 0.045, -3+180 B63 808 6.452 6.022 B63 B12 91677 Br135, Bes B15 12.903 10-055 59 830 22.581 24.504 B60 830 22.581 24.508 BRE 830 22.581 24.504 Bea 334 25.806 29.690 883 B42 29.032 412309, B90 Ras, 38.484 45.939 10.456 Ban gas, 35.4Ra 45.939 10.456 845 846 38-710 47.098, 8.789 830 Bag 45.161 50.626 5.468 Bae 848 45.161 50.626 + S68 8st a9 48.387 52.189 3.802 ase so 53.749 763 851 55.304 08 B52 58.065, 56.850 830 859 61.290 67.258 830 860 64.516 68-661 Ba 863 7ali94 72.705, Bas 863 7a.194 72.705, B34 B63 7al194 72.705, 869 Bes, 77.419 75.249 eR 67 BO. 645 77.661 867 868 83.871 7a.814 12 869 R7.097 79.933, 815 883 90.323 91.747 B48 Baa 93.508 92.398 850 ane 96.774 93.395 0.1594 = KOLMOGAKOV=SMIKNAY STATISTIC 291DFSCKIPTIVE STATISTICS FOR x7 NUMBER OF OBSERVATIONS + +s 30 MEAN = XBR = SUNCKEDDIAN woe eee a s15.83 MEDIAN «+e 20.50 BANG sees 68.000 WADJUSTED (BIASED) UakLANCE SUVCEXED@REIONEDIN HIVE : 193.87 (ADJUSTED STANDARD DEVIATION = SORTCUKD = S 7 losses POUUSTED CUNBIASED VALLANCE = UVKEN/EN=1) = AVKe 200.56 ADJUSTED STANDARD DEVIATION = SURTCAVKD « 14.162 SKEWNESS = SIMCCXCT)=XBRI##3)7(NFUVREET OS) c 1.3548 KUBTOSIS © SUNCCKCLD=XBR#RAD/CHRUVRHED) ee eeeee 5.1429 P-SIDED CONFIDENCE INTFAVALS @N MFAN & STANDARD DEVIATION MFAN — STANDARD DEVIATION q@oFieNcr LOWER CUPPER Lower "UPPER CEVA ciwtt List List Limit 90.07 ait.aa 820.29 11.690 18.123, 98.07 610.5 s21-12 11279 19.038 (99608 408-71 822.96 10.542 21,054 FOR A NORMAL DISTRIBUTION 292SSSIRaT GEIS vases 2 22 Ree B28 26 Ry 29 g x7 INPUT DATA B21 B22 821 820 81s 818 834 832 830 82a 820 818 810 gen 827 526 169. 195 gor 803 gor 80s 806 B21 821 821 193 818 833 _ 830 0.2275 = KOLMOGOROV-SHIRNOV STATISTIC ORDERED DATA 169 193 795 ‘gor B01 803 80S B06 B10 B15 gis sis B18 820 820 821 Bel B21 21 Bet sat B22 B23 826 827 830 830 832 833 34 CUMULATIVE PEKCENTAGE, 293 3-226 41,935 41.935 48.387 48.387 67-742 67.742 67.742 67.742 67.742 67.742 Ta mM 87.097 87.097 90.323 932508 96.774 CUMULATIVE NOrMAL 0.047 52345 7.063 14.745 1al7a5 18.242 22.215, 24.373 342020 476654 36-080 56.080 56.080 61-870 61.570 64.238 64-238, 64.238 64.238 64.238 64.238 66.838 692359 16.359 + 782.480 84.143, 4.143, 87.318 88.728 90.022 DIFFFRENCE =34179 =1.107 2614 21.384 21384 21113 =02366 =2.958 721954 =3.004 741821 =6.752DESCRIPTIVE STATISTICS FOK x6 NUMBER OF OBSERVATIONS arco 30 MEAN = XBR SUM(KCID9/N veer 841.30 MEDIAN ee eeeeeee eee 846-00 RANGE seeeeeeeeeeeeeeeeee | 80-000 UNADJUSTED (BIASED) VARIANCE = SUMCCXCL)=%BRI##29N = UVK eee 2ae.2t UNADJUSTED STANDARD DEVIATION = SOKTCUVR? 15-627 ADJUSTED (UNBIASED) VARIANCE = UVREN/(N=1) 252-63 ADJUSTED STANDAKD DEVIATION = SORTCAVR? « 15.894 SKEWNESS = SUMC(XC1)-XBRD#439/(N*UVREI6S) « neato 6.0694 KURT@SIS = SUNCCKCI)-XBRI##4)/(N*UVRES2) 2-SIDED CONFIDENCE INTERVALS @N MFAN £ STANDARD DEVIATION STANDARD DEVIATION CONFI DENCE LOWER UPPER LOWER UPPER LEVEL LIMIT Limit Limit Limit 90-02 836.37 846-23 13-121 20.320 95.02 835.36 Ba7-24 12.658 21.367 99.02 833.30 849.30 11.832 23.630 FOR A NORMAL DISTRIBUTION 294INPUT ORDEREL. DATA DATA B46 786 846 819 B46 821 a7 22 Bae 827 Ba 828 866 830 B63 831 B62 837 850 83s B49 a2 848 Bae 838 BAG 847 846 est 846 Ba 846 796 846 eee 3a? 830 847 831 48 928 849 827 Bao 819 B49 849 850 B46 850 846 B51 Bet ass 837 862 850 863 85S 866 163 = KOLMOGOKOV-SMIRNOV STATISTIC CUMULATIVE PERCENTAGE 295 34226 6.452 92677 12.903 16.129 192355 22.581 25-806 29.032 32.258 34.839 54.839 34.839 34.639 54.839 61-290 61-290 640516, 74.194 7a 194 Tas 194 80.645, 80.645 83.871 87.097 90.323 93.548 96.774 CUMULATIVE NORMAL, 0.025 8.031 10.077 1ivas2 18.414 20.136 23.856 25.848 39.337 41.776 51.756 512756 61.627 61.627 61.627 61.627 61.627 64.006 642006 66.332 68.597 68.597 68.597 10.794 70.794 722916 80-564 90-360 91.391 93.991 DIFFERENCE =3.201 12579 0.399 -1.671 =5.597 75.597 75.597 79.852 =9.852 -10:955, 6.533, 0.038 =2.157 2.783STATISTICAL ANALYSIS oF DUAL CONVERSION ACID PLANTS Catalytic Project 42460 EPA Contract 68-02-1322 by Dr. D. B, Nixon 296Introduction This report is concerned with analyses of and comments on several data sets containing information on sulfur dioxide emission at sulfuric acid producing plants. Data sets, figures and other computer results contained in the report and are divided into three section: A, B, and C. Each section represents a different type of analysis using the five data sets provided. The data sets examined were as follows: Data Data from ASARCO sulfuric acid plant. (Ar2,2) Data set Data from ASARCO sulfuric acid plant. (A-3) Data Set Data from Texas Gulf H,S0, No. 1 plant. Data Data from Texas Gulf H,S0, No. 2 plant. Data set Data relating to a start-up analysis des- cribed in Figure VI-1, page VI-6 Appendix VI: “Analysis of Dual-Absorption Acid Plant Continuous $0, Monitoring Data." These data sets are referenced in this section according to the above numbers (1)-(5). By way of further introduction it should be reported that the writer of this section has been completely un- biased in presentations herein from the point of view of his lack of knowledge of the operations of sulfuric acid plants. Thus, some of these results may be refuted from theoretical considerations. Some additional insights 297DATA SET 1 AND 2 COMPUTER RUN A~1 1 895, 0 850 955 770 «755-715-715 2130 oad 2 830 0 (845 880 780 AIS 775785931095, 460760 _§5 Anat @ 895 0 850 895 765 765 750 760 699 Se61 5 830 0 889 870 “79 «795 775 «765 «435 5428 ——4_-25_o. z 7 820 9 950 A70 800 825 75 790 175 418 8 885 0 850 «880 «785785 7AD 79033-2429 Yo 816 1016 826 880 75a 750 759 758 93 0400 11 895 1109 850 975-835-860 87595191 0800 13 650 665 675 700 699 700 705 745 11 0400 1a 840 1055 790 «750.615 «625 700-820. 1012 9400 16 810 1055 425 905 709 €05 775 765 26 0400 17 816 1098 812912 T4a oR 748-796 AB O00 —i1h 824 1004 _8: -Laz__7a2__31 eno 19 828 1118 834 922 768 778 758 768 182 0400 20 898 J07H 36 «818 «70> 782-760 «760 = 28 (0400. 2 2 4 16238 oson 22 890 1078 832 900 74A 794 7sa 762 28 0400 23 874 1136 840 «962 Bans 822_—TAP_—-782_— 102-0400 8; 78 a5; 20700 258701030 490 @80 770 770 735 730 139 4495 76 895 1089 349 920 8n0 815 795 400 128 aeTa 27820 soa0 Aan 919 8an 15705890 a8 3-03 28 825 1000 820 860 790 780 780 765 St 036 29 875 955 «A290 «845730 -725-«-7MS_ 710 TOL 5438, 39830 1000 439 869705780749 739k ae 31830 1015 B30 870 779 770 750 755 30 Ss6a 32.830 1070 885 930 BMS 84D TAS 77S 138 5408 38 : 73 op 688 16 aera ‘3a 898927 75a faa 7n9 AOD 700 698 209 3481 35 828 1087 874 864710758 6K? 686 ST 3450 ~-G1a__834 734778 706 702 __ag_a.58 37 «815 1960 8954S TAS «735 —~6O5 «SBS 260 470 38 890 1100 839 ATO. 7H8 765 74H 7350 BATT 39890 4080 Ado 835745 7a5__—740 AO bea 025 0 A509 8a0 840855 700 Ta? 9430 875 0 889 «ATO. BIN -835. BND «ZO. ALG Dak age tan " i 830 ‘0899805758 740 670675 2 +32 4a 890 0 fay ABD 755735 7OS 705173 Aa 45890 885 910 7g 779 7ag 780437 668 46870 0830870 7an 77 740 760 19 3432 a7 830 0 430 «835 «695-700 6907201094 49830 QO A89 880 695 719700795268 6G a9 870 0 f&9 910 8no 800. 770 +765 20 50 830 0. 849 80 779 «760 770 «780 258 Sy 315 oi 839 880779 79075576028 52780 01 Rao 745 7a5 760. 725735 di07 298DATA SET 1 AND 2 COMPUTER RUN A-2 $3 790 0 Ano 960 B1N 750 710-715-213 6422 790 a 45789785 707708 a 35 800 Ano A9O 745785 77577076 +28 56 830 9 830 «885 7H BH TEN 750 136 9495, 57__A20 geo 155 _785._ted 7en 759 2a 23a 38810 0 AIS AGS TRA -750 790 Tara 6.43 59 15 a a 69 890 9820 70775 800 _770 _780 320 61690 0849850770 A800 750 770 947 62 810 0 885 905 765 750 710 705 908 63 85 0 839 ATS TAD 785 7HS 78519 64820 Q 845 _A65 750 _780__759 745 ay 6585 0885-465 Tan 750 715 720 a3 66 840 9 950 890 750 «750 «715 «715516 6? 895 0833095 __fag_730__Pah_720 8D Neds 68788 705 6A? 766 2AG 925 825 760 70008 69 818 B18 792-694 67D 460 606596199 3402 z 4 0 O_26a2_ 569 Fags apa 853 52 738732 ana — tees 72 845 1110 330 865 «750. 735 720 7253 73 835 1000 819840735 735 _ 709720 6. Ta 835 1015 830 860 TAN 785 745 755 a3 TS (835 1010 930 870 790 «780 «760 «765-2863 7 895 1077 A190 _955__825_790__*770__—75S__-222 Tr 8251015 165 820 670790 6A0_ 735 3 78 806 850 898 «784 «Sq -730 GAG AOA T9416 28770 +772 7na_710__—67a__—668 2185, Bo —Taa— Bag 78a 750710 700662682 — B73 81 686 822 -779«-758 GRA G92 GIA GAO 1863 82995 955 7A5 755645725 670660255, 83 #951680 A290 865 790 690675 685 1605 84 895 1030 830 «75 745775 TAS TAOS. 25 820 995 810 860__750__750_—rag_— 740 ate 86780640 670.780 71n 755690 715 16 87 790 760 «470-690 «6AM 710. GAD. «690 0 88 830 1075 895 AZo 745 780 Png 695134 a 90 896 990 AG «BB 77R_ 77038730 93 830 4039 mas 920790765 5. zt te ao sagen FoR Lr rrs—S—sSsi—CS*sSsSC CL ——_94__710__690 615 635 63046: 30635 __a4 95 810 1030 780 755 835 640 6an 685 3107 9% 895 981 Ang «820. FMM «6908-43092 97 895 1045 849 890765 755 710 710 99: 98895 tnia AAS 915 ANS 800775 765213 99 695 1957 AS50920 B10 «800 7AS PTS 100 830 989879460 7sn_750_—750_—760__3: 101860 109¢ 439 845 fos 715 690 685 1088 102 835 1099 a5 910-775-760 770710970 10) 825 1075 a5 890 7A 785755750278 10a 6401949 AS53920 819 _A1S TAQ 77925 105 760 «750-690-705 895705 685890 106 810955 8g 860__770__730_—=6AS__—68O_1009 10715958 _8a5 860740 725 6a0 675 350 108 850 1080 845 915790765 TAS 78073 \ 2991.2 have been gained toward the end of the project period and these are summarized under recommendations Subsection 1.6. pata set_(1) This data (A-1,2) was extracted from a rather large data set from the ASARCO Plant and essentially represents data points associated with upset conditions, during start-up, shutdown and points before and after these occurrences. Altogether, there were 108 obsezvations on the following variables: X, = First Converter Bed Inlet Temperature in °F. This is also referenced as BMI1 on some of the computer print-outs in the appendix. X, = First Converter Bed Outlet Temperature in °F. This is referenced as BNOL. = Second Converter Bed Inlet Temperature in °F, This is referenced as BMI2. Second Converter Bed Outlet Temperature in °F. This is referenced as BMO,. Third Converter Bed Inlet Temperature in °F. This is referenced as BNI3. ‘Third Converter Bed Outlet Temperature in °F, This is referenced as BMO3. = Fourth Converter Bed Inlet Temperature in °F. This is referenced as BMI4. Fourth Converter Bed Outlet Temperature in °F. This is referenced as BMO4. 300Xg = Percent SO, Entrance to Converter. This is refer- enced as PSO2E. Y = Parts per million $0, - exit stack. ‘This is refer- enced as PPMSO,, In A-l, 2 these variables are listed for each observation in the above order with the exception that X, and Y are interchanged. Data values with a value of 0. denote missing observation (these were not recorded on original charts). O£ the 108 points, only 54 contained complete data. As a first attempt to explain the dependent variable ¥ in terms of these processes parameters simple correla~ tions were computed. Also scatter plots such as A-4 were obtained. Following are the simple correlations. Correlation of ¥ with Correlation N x -0.0214 107 ca 0.0265, 70 X3 0.0147 107 Xy 0.1212 107 Xs 0.1356 107 Xe 0.1995 107 x, 0.3390 107 X, ~0.3390 107 0.4030 94 301“Hid ant s00 suet ‘4 nese 10 i iiE ie + MEAD we $0» PROC sun aT e100 Rese ns MULTIPLE LINEAR REGRESSTON awALYSIS nove 40 ' EPS Svoodoeet FoR SINGULAR MaTery TEST DEPEVOENT VaaT MALE = PPRGDT HEAnS ann STanpagy oF ytATtOWs ventaste wea steoevtaTion “err aoas07 TEI mal ePoatori = ntSetaT fal? 400.0809, 50.5030 z ROE 33050107 ——— Fos 927 g Bry T3reogne 7743620 ano} Tanessrt mira3) are 19 wee heed 704 siaee 32037 erg woamay waters ' 2 2 ‘ 5 . 53y tego ease ttaangvagny g2naeet0y7 deraecznie sosteerese Weasopeaner 1442 verse 219401 +4213 19995740572 890443957 (010000 ox0000, 5938 20077400465 15248605178 1270780916 091119800 a7rracigr2 azsesais '4+9900 ung engga a7aareessa? 173751 $80 sorrisnest aeyhs eee tanrzaerese 40000 oenagg —-oanaao 32831748593 21920340713 10339 yaayeasry +0000 ounngo 0400000000 3araKeens7? aeura Peasant? as? pp filytenn00_a2eagvezy? _zazasoas (re4n00 040000 Ganga Atysonsso00 19014814992 ses1-7000 rag tg teteoe teeta etae +0000a.9605 ponrosie x 5 e189 2 $55153 Sages now garany mM oes782 _otasz. Srato? nor n oesrv2___teog09 gan how Bed =ov00s6 nesses oseeyz____dvoate tenn 7 Bee) eaetee Baw 7 ered a sai2 __ostaar Ben83 ronda nore nesses gegnnr___geanta—_oesare aa oeraF 3950 oxpase 008058 ___oveone _ 0703 0.9747 14000003400 now 1088 g.ne7)___s9e9709__2949966 __sass628 soeh3e3 ——=0+3950—dea40e T0000 ‘COMPUTER RUNon per: mace page ofr “aieay Bars otre “pave aasts 400 ats wth THEO bare sere READ Ne 108 ROE N= 10 Ede oe SUK WT #108 —Rlaagscton carerieiears= VARTASLE COEFFICIENT. era COEFFICIENT ONSTANT ar +2799 ent sescote eer On358T S308 res wy mie au08 Poe Ebert tteet tae oeyeatraatrausesecsecet COEFFIELENT np ETERUEGATION C40J} ees ge mUUETeCe Caameuirpoe coer repeat, ‘SRULTIPLE CAELATION COEPFLEIFAT C4039 Tawney Oeuratinne ayo, Wauurs oF AEanesStow cneerieienis VaRTTELE S15 SEVTIT Tow ont 3308 Story atte 120924478 aunt Or9739__ 9200 ar Orzst 907 anne Seager Bet eer Be335__8s05 AT tre $:a7 oxra or4032 nt grea 9.37 Sis Thor VARTABLE, nzeoryere “ COMPUTER RUN A-7 war rare mot oraaat ere Bead38 _ = BRU cas 1 oceans 0} sai foe ryote 388aunt fan squsers nconessto og 19 160600749h40 Tora, 55 3271012304207 Soursnewce sever of 6¢ 24 a4) a eysans 90% COMPUTER ROY A-8AALS aco Teas oar sere cao we Poe N= 16) Reve Ne Oe SUH RT 1 —— [vant of atsrousts : 08s 40s actus PReDtereD = RESTOUAL f T Tai 9008 | 2 Aiesoo0e 1 s2a.n009. r + aero800 | 3 Stsoo0e aarstze $ rai9n08 1938 tr T 2 2 2 28a Te warsiae i siazvotat 4 srn2284 eh 3 sa 260r0000—tasdeanor 3 48,0000 6a4svoer___ 257320257 1 ‘Breoom) Fane) ater TT " Teaoos —t3yvang2 447029 a s20.gon0 __1749:5nn3__*1123.5008 7 Touegon0 —— Taas7ayy——ssass7039 20 ‘Syvo000 205.2800 H saigo0n 8 to.0aL ae ‘SSrea0a ——=29rsaney 20.0821 2) sagncongn = eraconysta8bartee n pyzisane 2388 sEstsoaer ttoasr Soscosor “17 )s08o1 attscgnen __1290rd008 ‘Brasg000 —— Sans6mRe ‘5.0000 9470 resizane 12.0909 yuzene Tesoaoa “20 gene ‘oros00“izvssose — arveges Soacazoe _b0q.g771 COMPUTER ROW A-9 ‘Soassnel ——507s9091 eso? se9eoUl? eras __ $d 2048 f aa Y092c0000 aa tatAME 177008168 + —-#$___s03sangg teases uagazeta we 213.0000 shasara at rset oreS2ro000 #7ec0000 P2bsoaan 2h Bivoaoo caressa toarenz? reasons 9ataray brit Falsasra ai t3873 73.0800 incons2—ssass9032 ToRaTNMATSON O STANTSTIE © 04 COMPUTER FON A-10only the correlations between ¥ and X and Xg are sign- ificant at the five percent level. Since the difference between X, and X, is insignificant (a fact no doubt characteristic to the upset conditions which the data represent), these two variables are regarded as the same. It is felt that x, is not influencing ¥ but rather this correlation is significant because of the following xeason: When the fourth converter bed is finally brought up to temperature, $0, emission is lower, the nature of start-up. It should be observed that almost all of the above correlations are based on the full 108 observations, unfortunately not the case on omitting missing data in fitting the following model: qa Yadn + > dy X& Ker Complete results of this fit are contained in A-5,10. While this regression equation gave a significant fit to the data at the one percent level and the model accounted for approximately 44 percent of the variabil- ity in Y, its usefulness in prediction is questionable. The model does seem to predict "rather close" to the high SO, emissions, in order of magnitude, but is some- what more erratic in predicting low to medium So, emis- sions. The writer would have liked an additional data set having similar characteristics as (1) in order-to verify the reproduceability of the model. Since this 309set was not available, the 108 points were split down the middle and the model refitted to the last 54 points of which 40 were complete. These results are contained in A-11, 15 and they appear to be comparable to the original fit. In each case PS0,F was the most signifi- cant contributing variable to the regression and, in fact it shoula be noted that the correlation 0.4030 between ¥ and Xy compares with the 0.413 reported on page VI-13 of the appendix referenced in the description of Data Set (5). It is understood that the latter correla- tion was obtained from the larger ASARCO data set with upset conditions removed. In summary, the high variability in So, emission and its erractic behavior during these upset conditions seems to preclude a satisfactory explanation in terms of the process parameters considered. It is felt that the main reason for the inadequacy of the model in explaining 80, emission during upset conditions is due to the fact that data was reported at two-hour intervals and, in fact, since it is possible for a plant to shut down and start up in just a few hours, the few data points recorded does not adequately report the changing nature of S0, emission and the process parameters during these times. Data set (3) ‘This data consisted of 54 observations on-the variables described in Section 1.1 except that in this case the 310prot H 6 Reeds oe UN RT ee $1440 aes MULTIPLE Ctwean neonesston amacrsts rove vay Peuntut vAsianles EPse Seo000ee41 FOR SINGULAR waTRIY TEST DEPEVOENT VaeTame = Pasa ans tad Stasnaen orviarton MEAN sreOrvtaTtON anaes oars 95243500 Bieteaoe g Fyovoson gaat pascanes 91.0889 07 u zee, Pease WEN 037 woman watater ‘ 2 a ‘ ’ ‘ a0 T Aan0enet7a9 qasz77 4500 LAL wor ‘910000 $7A975«0999 276): e1490 "9g y08. 349g 5 3759 17304940000 13566747500 11098 1 207000 40000 22605440000 14758440000 126031 32022000 234870 LSOMPUTER RUN ADL 9.0900 0000 30239349001 24914643000 san} s9509. . 9.0000 0.0000 0000 3236610999 a70ghsnnee, e40000 47000 640000 0+00004 2 4 4 5 4 nowt we *14p000___osaeyy__ge7675__avsagg __gen978___guzara Bearea———g-oa? ose? 940380 now 2 oagose 909 nsarig _narere oe Oeuntg ocean OT 785 tow assrie___tennoo __asnris___ouseay_-_guagre Tor Prise OvtzS——0vAN50 81196 ‘ousas2___ 047979 gsnrs8___anoga.___o564___ ose ‘9x6b08——Osnaze ean? _——=00097 now 5 fosszre___ovtero_ovsezt__ovnaye___tso000___ ov Baths —orsa78 Bs 308 now 6 'os92?1___ostg79_natgre __ovngso__ov0743___ 9000 00027) 99249 +9838 00872 now 7 fosareo __oeaszt_ 09158 __os4no8___vst395__oso2r Te9000 ——9x8989 —— 919738 —— F017 now fesyoe?___osaesz__ovaan8_nagaza onze ous Beko —— 1169008097 Oe T81e ee fen saan ssn ox20n8 eae 5335} 2 10 . 009360___atr93 ott soanasr son0are =o ge BST ‘etree 150000 LcoMPUsER RUN Aci?ate edge aE its . oe biti gfee “gaye aAsts_ 4,0 ACgntsston correictevise YaRTAOLE COCFFYCIENT acre coErrrerte® eouaTaaT ath 0 gaz moe wovaare rayo1n9 tango or estates [—boeeeieteti ar Be rtdc tear iat COEFFICIENT ap OETERVIyAT {DM (4009, MULTIALE ener ua Efereny [CHaETFtE-EBaSRLAT Intent eter ast FENDA Sevier rows ayo,7 vaunes oF REaneSsinn enerriciewis= Vaataare 370 EVI nt ign ONDER Pantin Cosnclatios coter ano ePencvere sa-otvere oe arr ano ota mot aise onseat etry oeinge _geszy ‘noe Totter — 003319 mn Seroser e388 fey coudee__9:5878 ere 7nd —0n567o fuoe savose —9s38 eae ashes u38AmauyStS OF vantance TaMLe Somee _neFe _ ove Sat aeonession 9 1653s! wears wean sousees 5 1877 aaa Gowrtornce Lever oF F¢ te COMPUTER FUN AWAeit SS “ahah me sant at ata : ; : i i si = 270 22. $4c0000 2ese1e03 3 trioo0e tienes), 3a {hsga%n 338 3% ‘tss000 roe a 2140000 sss7.0s08 32 ssnrioane maar 25 to07 0000 Ona 2 995-0000, eae : 30 12.0090 1 39.000 2 3310000 3b sena2g99n tsa Srosoon1 ——Tosned785 228.0079 tages tert 20900 COMPUTER pu Anis 2000138, sae thee Br 1120 2 198 ie the iH 9108. = Tee —1350s00 a2 2 oars 4301209100 3h tear ar on 63612 Az8 430400 Sto he 83 B98 Aza 83 ated sto__Aos tag ang 29 oak ok 30 ae 239 a0 30 830 190 830 se wat —206 ania ar the a 23095 COMPUTER RUN A-3 ‘80055100 33199or ere sess mart age Here “STi08 on gate fre “bave wRALYSS#—wuLTe ee) outa sere t READ we Sas ROE Mtueme Oe sea e 38 MULTIPLE UEWEAR REGRESSION ANALYSTS onov> vo AGUOE TMACPEaneMT yasreaees 9 fe Se00008—11 FoR SINGULAR MarerX TEST DEPENDENT Vantaa © FPWSOF _nians ann stunnaan peytatious wanttoLe + MEAN sreoevrATrON a7 1219203 2 tzaae Praste mona, matatye 1 2 2 . 5 ‘ : 25571538 7640769 P5aea8z8 arraeanes w2erseassa *9142307 “103140764 fete 0900 navex076 sszteress ssahtans —"saioaag 040200 0000 200740769 azoteavee Gt : ee COMPUTER HUN Avi6 ans +9900 040000, 123000386 ato. “riseaet rs 2. +9900 040000940000» 04000 39848185 n2es}538__pazestors —eessaiS '0s4000 049000 040000040000, ovo000 4747293839690 ana 0000 or000 non ghrt00® 352701538 =Fhen08 2" 5 x950 as 0000 70550 —— os 000 TOOT 10000 © 0v0000 Ont r98 [rormecnrror Tart 7 4 2 2 . i. now esse oo 19¢ 3068 Sp eee sonny __snegona separ [St 8883 hs a tae foe 3 009879 __ov0309 osen19 Oe Be8505 332 now ‘oeaose__sos1923_os0113_tsno00_ovazzw 9.9860 vant soesaee noe 5 . osg341___eoatray 924720____4s0000 z Boksa —— 9180 son35t Steed peiry eee ovtery enn ahaa Braue soseTe foe oegroe oars 2689 oust 110000 bs Fa7e or028 foe 8 yegese __navg00 2s04%e auaTe 110000 now Sou nees 2 a now 10, 301 ons708 2479 eesees 042521 ‘rages ——~os9421 04630 19000 2272, COMPUTER UM A-17RHALYSI Se aCe Dara se, : MEAD ne Suen Se Arsene sare 38 Wert —Aiaarsstnu torecreess VARIAQLE COCFFTeLeNT era enerrterenr covenant 1tensg0te matt tar cuss ont anne eu nang oF esta COEFFICIENT AF OTERTWATIONee sss eeee Gacrrtetenr a Gereavtaat ioe cada}. AROELATION COEFFICIEMT obs H MUCHTECE conaecattow eaerrterrar casas sore ETNgAGS OEVTAT OWS Ay9_Y VALUES OF REGRESSION ENEFFTETEATS™ VaaTagee a0 OFVEN pe ame St? Oa kage vantage TEAL CORR CNEF — R2MDELETE aT oos508 aunt a 3 COMPUTER RUN. 18meaysts OF vantance Taste _— Saat outs sum Sousgre wean sovanes meanession 9 tee2 neers zgatezte 9478 anne sa "SS0es3eay $90f 888 Yara 78 —aye000 3407 ener tornes crves of FC 9 14) © roos908 SSONPUTER HUN A=19)8 ere ast oage Bere Gare sere MEAD we Say PRO Shy egy Se tame_ot-atsiousts 00s wo sews, PReniereo ——atstouat 1 Tievaooe ae 7 1 20 + ———Tietoaae Teves 3 tetlooen 123080 a iattonoe : fosn009 ‘Socaoas ‘aianeo 92-0000 ines 1 30 1 ay.n000 3 Vise0909 a inaearor 3 ieg2479) cz tosesree % 9010009 top4a35 DuRpINwaTSOy 0 statistic # 145653 : COMPUTER UW AW20plant was considered in normal operating mode. The same model as in Section 1.1 was fitted to the 26 points having complete data. The results are given in A-16, 20. In this case the regression is significant at the one Fercent level and accounts for approximately 85 per~ cent of the variability in $0, emission. In addition (See A-20), the model very nicely predicts $0, emission. Estimates of the coefficients in the model are given at the top of A-18. No attempt was made to reduce the set of independent variables to a smaller set and this may be possible through additiona? analyses. In view of the interdependence between the process parameters it is quite reasonable not to expect signs of particular coefficients to have some a'priori value (+ or -). In fact, the usual interpretation that. a given regression coefficient measures the change in the dependent variable with the cther variables held constant is not appropriate for highly correlated independent variables. The model simple presents the best linear fit over the range of values observed. Data Sets (3) - (4) ‘These data, obtained from two similar plants of Texas Gulf, offered the opportunity to examine the effect of catalyst aging over time. Each set has one to three Pieces of data for most months from March 1968 through Decomber, 1973. In addition, these data contain values 322of $03, not previously considered in this section. Graphs of SO, and SO, versus time (B1, B2, B3) suggest, for the So, data at least, that there are definite trends starting at what appears to be the catalyst cleaning month, CCM, In order to test the hypothesis that 50, is linearly related to time the following model was YaarRT Where Y = mg S0,/SCF and T = month since CCM. It was used: assumed that the CCM for Data Set (3) occurred in June, 1968, August, 1969, and August, 1972, and for Data set (4) occurred July, 1968, August, 1969, and June, 1972. ‘Two comparable samples were extracted from each of the data sets and all observations for a particular month were averaged to obtain one value for each T. The re~ lationships are shown in Bl, B2, B3, and the results are summarized in the following table: 80, Versus T (from CCH) From (3) Frem (4) Sample 1 Sample 2 Sample 1 sample 2 13 4 12 a7 2.9 17.9 8.0 15.7 a2.t 36.3 127.8 33.2 correlation +79 -87 “22 78 std. error 24.7 47.4 29.0 72.4 Each of these regressions is significant at the five \ ss \percent level. Interestingly, there is no significant difference between comparable samples from Data Sets (3) and (4) indicating that this measure of catalyst effect is the same for the two similar plants. The ‘fact that the slopes for Sample 2 were about twice that for Sample 1 was apparently due to the fact that these plants burned “dirty sulfur" during the period October, 1972 through August, 1973. Unfortunately, this fact masks any conclu- sion of a catalyst effect difference over years. The 80, data for Sample 1 from (3) and (4) dia not correlate with 7; moreover, no trend was examined for Sample 2 trom the two data sets due to any trend line being obscurred by “dirty sulfur" burning. A comparison of SO, means for the "dirty sulfur" period versus the other months for each of the data sets showed an extreme difference (for Data Set (2) these means were 22.7 and 1.4 respect- ively). A comparison of overall S0, and SO, means between Data Sets (2) and (3) showed no significant difference. Analysis of variance of the S0, data (B4, BS, B6, B7) illustrates significant month and year effect for each of the data sets except for the month effect for Data Set (3). Tt has been suggested that a reason for this is the fact that ‘there was a less controlled operation of Plant Number 1. The writer understands that the latter statement will be verified and the burning of "dirty sulfur” will be investigated on further contact 324CONTACT ACID PLANT SINGLE ABSORPTION (CHEMICO) SQ EMISSIONS RRM. COMPUTER RUN 8-1 woroines SF FREES ode from ESRB2 i : z i 8 3 ‘SO, EMISSIONS RRM. COMPUTER RUN B:2Aci MIST So, my /SCE COMPUTER RUN BS i 327 reer eeCOMPUTER RUN 8-34 ACID MIST SO} My/SCH ceedStuy OF YEAR EFFECT SAMPLE 1 sll BEES *"83) ugerbdas anor4| "Ht att saga merger Isat ttscareary HHhra, BR en emeswoeen_antn j 4 ; (ene i i pay ANALYSIS. OF VARIANCE TABLE =" Soest FReCUOW dali - { a | *enates : Sioo_saseete var | = a9.00 Tove.8 1 !age «Mor OF vEen error sueeue 2 oilt . rrr—~—r——CO"NCCsCsSCiaCzasézs.CC sii EEE oieatects *™ sygpay emecysts S*HAECECPECHPtacarwenty P8@rsore. SuumaRy OF EAC OF THE 6 TREATMENT GROUPS. WAUESPL owtua— meamty3 ——-SOEVEUI wants {— vase ANALYSIS OF VARIANCE TABLE 020 vaso —— FRET IM — HES 232r29.80 3.00 9305.98 1 aS stat $4321 CONFIDENCE LEVEL OF FC 5» 097H100,008,STUOY OF MONTH EFFECT SAMPLE 1 meet PMEES 58 tap ne tor, PROC M307) EJ Ms OST 107 OUGHT AMALYStS PC LEPHECE CECH FFacarwenty PRraace. ‘SUINARY OF CAGH OF THE 12 TREATMENT GROUPS, — RBG MYERS cys weanesy seve? varcay 4 jog j ved $ Set ii yt verses ae ot _ SABO 73176097 00 | ONFLOENCE LevrL AFF WOT COMPUTED. Fa1.00 COMPUTER RUN 8-6STUDY OF MONTH EFFECT SAMPLE 2 race HLS shit acap ne os) PROC MOS) AE Ne SU Tn vn clFfecarweury $Stamce, eee — SUNVARY OF EACH OF THE 12 TREATACNT GROUPS, 8005 MMUESPE oweyywcaneya— soeveut vantay {reeerereveretsnenverwe EUALTSTS OP-VARTANEE TABLE Sererwrees eS sete7 00: rears s30—~ a [au ose aise roses | : roTALs, 717958038 94,00 | CONFIOENCE euFL OF £4 11+ ADV= 09.008. errr enn N ner rrrere ree rrr etre erremrrrenere tower ree Ter renner rewith Texas Gulf. Data Set (5) No attempt was made to find a model to fit the smooth curves shown in the referenced report (see (5) Section 1.1); however, a two-way analysis of variance was per- formed (B4 to B7) using the six length of shutdown groups as one category and time into start-up as the other category. As a B4 to B7 shows there is a signifi- cant group and a significant time effect with 0, emis- sion treated as the response variable. Regressions were obtained for each of the separate groups (C1 to C6) and +pr ‘the results are summarized below. The model ¥ for each group. Group N Correlation 1 - 10.3 106.8 12 -0.430 1-2 - 12.6 178.07 30 “0.154 2-6 - 92.4 757.0 18 0.266 6-10 - 79.8 627.1 1s -0.372 20-15 -229.2 1417.3 24 -0.512* 1s -287.6 1969.0 36 -0.515* *Significant at five percent level. ‘The use of these regression equations to predict the time after start-up at which the piant reaches the com- pliance limit is questionable. Since this time is the important variable, it was suggested that means and 333Creme) mths BH we READ Me 2p ROE N @ Ry RE Mey WT Ha That SeatTER ruoT OsREGRESSION (IME ENOPOIATS. ‘COMPUTER RUW C-1Ale Ata We suc ate “Hoth pase “pact 120,ae PROC Ne 18 RE eT Tees SeATTER PLOT GRESSION LINE ENDPOINTS ‘COMPUTER ROW C-3rat ate: on une SeaTTER PLOT ‘DeAEGRESSION LINE EnoPOINTS (COMPUTER RUN C=fit HEE BAHT ech acto mu wate Me fs hefk ona) Me Re ey Su aT eae vane w= OeREGRESSLON LINC ENDPOINTS SeATTER PLOT ‘COMPUTER RUN C-6variance of this quantity be computed Problems and Reconnendations Major problems associated with this study were: (a) The complicated nature of the procegs and relation- ships studied made full investigation of the acid plant system too time consuming for the type of task approved. (b) The number of plants from which data was gathered was insufficient to discover plant to plant vari- ability. (c) All of the data looked at vepresented data gathered after the fact so that no experimentation in manipu- lating the process parameters was accomplished. Any additional studies which may be performed on the SO, emissions should consider the need for expanded data collection mentioned above with the exception of (c) as it may be impossible to find plants willing to manipulate Process parameters to force high emissions. at this writing it is felt that any future analysis of the So, emissions as a function of process parameters should begin with data at approximately five minute intervals. ‘The availability of this data would provide the ability to study a time-lag effect in explaining SO, emission. ‘The high interdependence between the process parameters, and the observations of several continuous time charts on these parameters suggest a time-lag model might be appropriate. 340