OR-OSHA TECHNICAL MANUAL

Section III

SAFETY HAZARDS
CHAPTER 1: OILWELL DERRICK STABILITY: GUYWIRE ANCHOR SYSTEMS PETROLEUM REFINING PROCESSES PRESSURE VESSEL GUIDELINES INDUSTRIAL ROBOTS AND ROBOT SYSTEM SAFETY

OR-OSHA TECHNICAL MANUAL

CHAPTER 2:

CHAPTER 3:

CHAPTER 4:
OR-OSHA TECHNICAL MANUAL

III

III

SECTION III: CHAPTER 1

OIL WELL DERRICK STABILITY: ANCHOR SYSTEMS

A. INTRODUCTION
Work-over Rigs are mast type devices that vary significantly from crane or other boom (mast) type equipment. Work-over Rigs experience constant and varying dynamic loading conditions. They are subjected to various compression forces, along with jarring and wind loading. Other forces induced by pipe, tubing, etc. being stacked in the derrick and workers aloft on the derrick platform, as well as an ever-changing number of lateral and vertical forces are also present. Because of a work-over rig's dynamic environment, the health and safety of the operation is dependent upon the stability of the rig and its guy anchor system.

GUYWIRE

according to the type of soil and its holding capacity, methods of installing guywire anchors, integrity of the system, and acceptable parameters in lieu of actual pull testing should be established. Investigation into each fatal incident has determined that the cause of the upset was component failure rather than total system failure. This clearly illustrates the fact that the integrity of the system is no sounder than its weakest component.

CAUSAL FACTORS
There is no specific OSHA standard that addresses the stability of derricks in the oilwell drilling and servicing industry, see Figure III:1-1. But because of the fatality record there is a need for a guideline detailing the type of temporary stability systems

A. Introduction.......................................III:1-1 B. Types of Guywire Anchors...............III:1-2 C. Stability Considerations...................III:1-3 D. Observations, directions, and Conclusions................................III:1-5 E. Bibliography.......................................III:1-6
Fi gure III:1-1. Oilwell Servicing Derrick

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INDUSTRY RECOMMENDATIONS
The American Petroleum Institute (API) in its Specification 4E "Specification for Drilling and Well Servicing Structures" sets forth a "Recommended Guying Pattern General Conditions." The Association of Oilwell Servicing Contractors. (AOSC) in its publication "Recommended Safe Procedures and Guidelines for Oil and Gas Well Servicing" recommends the same guying patterns as are set forth in API Specification 4E. Though not present in the AOSC publication the API Specification 4E provides a Recommended Guyline Anchor Spacing and Load Chart. This is discussed in detail in the Guidelines on the Stability of Well Servicing Derricks.

There has been considerable progress within the industry to design procedures to assure the integrity of the stability system without the necessity of conducting individual pull tests on each of the anchors.

APPLICATION
This chapter is intended to form the basis of a minimum safety guideline, for the use of Temporary Guywire Anchor Systems on derricks, in the oil well drilling and servicing industry. Recommended procedures, practices, equipment, and requirements have been developed based on availability, capability, adaptability, dependability, and reliability of the various types of systems.

B. TYPES OF GUYWIRE ANCHORS

MANUFACTURED ANCHORS
There are four basic types of manufactured anchors. The screw or helix anchor, expanding plate anchor, flat plate anchor, and the pivoting anchor. Holding capacity of these anchors varies; detailed information on holding capacity, comparison charts with illustrations, and characteristics specific to each design may be found in Section 2 of the support manual. When installed in conformance with manufacturer specifications and evidence thereof is provided, this would satisfy the requirement for individual pull testing. CAUTION: It should continually be emphasized that the anchor is only one component of the Rig Stability System(RSS) Screw- (helix-) type anchors have a direct correlation between anchor capacity and the torque required to install the anchor. Following the manufacturer's specific recommendations as to torquing, with proof thereof, is a valid method of determining anchor holding capacity. Torquing according to manufacturer's specifications is an acceptable nonpull-test method of determining anchor capacity.

SHOP-MADE (IN-HOUSE FABRICATED) ANCHORS

These anchors should be designed by a registered engineer and conform to accepted engineering practices. Written procedures shall be established for installation. These manufactured anchors should be proof tested for structural integrity and holding capacity. Records shall be maintained of test protocols and holding capacity based on soil type. Individual pull testing will not be required if anchors are installed in accordance with written procedures. Proof thereof will be required of installation protocols and proof-tested holding capacities.

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C. STABILITY CONSIDERATIONS
FOUNDATION
The area should be graded, leveled and maintained so that oil, water, drilling fluid, and other fluids will drain away from the working area. Safe Bearing Capacity shall be determined from the use of an appropriate table, soil core test, penetrometer test, flat-plate test, or other suitable soil test. When surface conditions are used to determine bearing capacity, care must be exercised to insure that the soil is homogeneous to a depth of at least twice the width of supplemental footing used to support the concentrated load. Supplemental footing shall be provided to distribute the concentrated loads from the mast and rig support points. The manufacturer's load distribution diagram will indicate these locations. In the absence of a manufacturer's diagram, the supplemental footing shall be designed to carry the maximum anticipated hook load, the gross weight of the mast, the mast mount, the traveling equipment, and the vertical component of guywire tension under operational loading conditions. These footings must also support the mast and mast weight during mast erection. Wellhead cellars present special foundation considerations. In addition to the obvious of collecting water and fluids that can seep into the ground, cellars also require unique mast support considerations. These should be analyzed by a qualified person to insure that an adequate mast foundation is provided. Small settlements (soil subsidence) at the beginning of rig-up is considered normal. External guywires should never be used for plumbing the mast. Rig foundations, guywire anchors and guywire tension should be checked at each tower (shift) change.

GUYWIRES
All guywires, as indicated by the manufacturer's diagram, should be in position and properly tensioned prior to commencing any work. In the absence of manufacturer recommendations, or where mast manufacturer's recommendations cannot be implemented, the diagram in Figure III:1-2 may be used. Other guying patterns may be used; however, they must be based on sound engineering principles as determined by a qualified person. These recommendations should be posted on the mast in a weatherproof container and should state the loading conditions for which they were prepared. Guywires should be 6x19 or 6x37 class, regular lay, made of improved plow steel (IPS) or better with independent wire-rope core (IWRC) and not previously used for any other application. Double saddle clips should be used, and wire rope should be installed in accordance with the manufacturer's

Figure III:1-2. Anchor Location Diagram

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recommendations. In the absence of manufacturer recommendations, API RP 9B shall be followed.

GUYWIRE ANCHORS
The mast manufacturer's recommendations shall be followed. In the absence of manufacturer recommenda-tions the location diagram, Figure III:1-3, may be used. Each zone requires an anchor of different holding capacity. If anchors are located in more than one zone, then all anchors should be of the capacity required for the greater capacity zone. For example, if one anchor is located in "ZONE C" and the remaining anchors are located in "ZONE D," all anchors shall meet the holding capacity specified in the chart for "ZONE C." See Figure III:1-4.

Figure III:1-3. Reccommended Anchor Locations

Figure III:1-4. Anchor Capacity Requirements for Each Zone

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D. OBSERVATIONS, DIRECTIONS, AND CONCLUSIONS

VISUAL OBSERVATIONS
There are characteristic visual observations that can serve as indicators of rig stability. They include, but are not limited to, the following: @ The foundation supports the rig, substructure, and all applied loads while in an operational mode, without excessive movement. Basically in a level and plumb configuration. No large movement is observable between the mast support structure and the rotary/setback support structure when the slips are set and the load is removed from the mast, or vice versa. The empty travel block hangs plumb with the centerline of the wellbore and the mast support structure remains level. The mast support structure and/or substructure does not lean to one side more than the other when the load is applied. The guywire on one side becomes noticeably taut while the guywire on the opposite side becomes slack. The guywire anchor(s) show(s) no visible signs of movement during the loading and unloading of the system while in operational mode. to supplement this chapter. It provides a detailed analysis of existing guides and standards along with state-of-the-art developments. Section 3 provides the direction and guidance necessary to evaluate and select the proper system to assure rig stability. Section 4 discusses the installation of guywire anchor systems. It is extremely important to point out that stability is dependent on the entire system, and not on a single component. In the absence of support documentation or manufacturer specifications, Section 6 sets forth the criteria for performing effective pull testing. It further identifies what would be acceptable in lieu of actual pull testing.

CONCLUSION
No set of observations or recommendations should be so restrictive or subjective as to preclude the use of innovative approaches to derrick stability systems. Properly designed substructures and base beams have been used effectively and safely as anchorages for guywires. Engineering calculations based on sound engineering principals may also be used as evidence of an acceptable alternative to pull testing. Dead weight of equipment, fabricated components (i.e., padeyes) and other appurtenances are all considerations in determining rig stability. The derrick manufacturer's specifications and recom-mendations should be the preferred and primary means of determining derrick stability. Guywire anchors, newly installed according to the manufacturer's specifications, may be used without the

The chart presented in Figure III:1-5 may be used as a guide to the pretensioning of guywires. This method is commonly referred to as the Catenary Method (guywire sag method).

SUPPORT MANUAL
The support manual, entitled Guideline on the Stability of Well Servicing Derricks, is divided into work sections and intended

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Figure III:1-5. Catenary Method requirement for actual pull testing (This would qualify as meeting the criteria as an acceptable alternative to pull testing). If, however, there is a change in conditions, e.g., frozen ground to thawed ground, or if use of the anchor has been interrupted, the anchor shall be pull tested, with documentation thereof, prior to being placed back in service.

E. BIBLIOGRAPHY
American Petroleum Institute (API). 1988. Specification 4E: Specification for Drilling and Well Servicing Structures. API: Washington, D.C. Association of Oilwell Servicing Contractors (AOSC). 1988. Recommended Safe Procedures and Guidelines for Oil and Gas Well Servicing. AOSC: Dallas. International Association of Drilling Contractors (IADC). 1990. Accident Prevention Manual. IADC: Houston. International Association of Drilling Contractors. 1979. Drilling Manual. IADC: Houston. Scardino, A. J. 1990. Guidelines on the Stability of Well Servicing Derricks. Sigma Associates Ltd.: Pass Christian, MS

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SECTION III: CHAPTER 2

PETROLEUM REFINING PROCESSES

A. INTRODUCTION
The petroleum industry began with the successful drilling of the first commercial oil well in 1859, and the opening of the first refinery two years later to process the crude into kerosene. The evolution of petroleum refining from simple distillation to today's sophisticated processes has created a need for health and safety management procedures and safe work practices. To those unfamiliar with the industry, petroleum refineries may appear to be complex and confusing places. Refining is the processing of one complex mixture of hydrocarbons into a number of other complex mixtures of hydrocarbons. The safe and orderly processing of crude oil into flammable gases and liquids at high temperatures and pressures using vessels, equipment, and piping subjected to stress and corrosion requires considerable knowledge, control, and expertise. Safety and health professionals, working with process, chemical, instrumentation, and metallurgical engineers, assure that potential physical, mechanical, chemical, and health hazards are recognized and provisions are made for safe operating practices and appropriate protective measures. These A. B. C. D. Introduction. . . . . . . . . . . . . . . . . . . . . . . . III:2-1 Overview of the Petroleum Industry. . . . . III:2-2 Petroleum Refining Operations . . . . . . . III:2-11 Description of Petroleum Refining Processes and Related Health and Safety Considerations. . . . . . . . . . . . . . III:2-15 E. Other Refinery Operations. . . . . . . . . . . III:2-49 F. Bibliography. . . . . . . . . . . . . . . . . . . . . . III:2-58 Appendix III:2-1. Glossary. . . . . . . . . . . . . .III:2-59 measures may include hard hats, safety glasses and goggles, safety shoes, hearing protection, respiratory protection, and protective clothing such as fire resistant clothing where required. In addition, procedures should be established to assure compliance with applicable regulations and standards such as hazard communications, confined space entry, and process safety management. This chapter of the technical manual covers the history of refinery processing, characteristics of crude oil, hydrocarbon types and chemistry, and major refinery products and by-products. It presents information on technology as normally practiced in present operations. It describes the more common refinery processes and includes relevant safety and health information. Additional information covers refinery utilities and miscellaneous supporting activities related to hydrocarbon processing. Field personnel will learn what to expect in various facilities regarding typical materials and process methods, equipment, potential hazards, and exposures. The information presented refers to fire prevention, industrial hygiene, and safe work practices, and is not intended to provide comprehensive guidelines for protective measures and/or compliance with regulatory requirements. As some of the terminology is industry-specific, a glossary is provided as an appendix. This chapter does not cover petrochemical processing.

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B. OVERVIEW OF THE PETROLEUM INDUSTRY

BASIC REFINERY PROCESS -DESCRIPTION AND HISTORY Petroleum refining has evolved continuously in response to changing consumer demand for better and different products. The original requirement was to produce kerosene as a cheaper and better source of light than whale oil. The development of the internal combustion engine led to the production of gasoline and diesel fuels. The evolution of the airplane created a need first for high-octane aviation gasoline and then for jet fuel, a sophisticated form of the original product, kerosene. Present-day refineries produce a variety of products including many required as feedstocks for the petrochemical industry. DISTILLATION PROCESSES The first refinery, opened in 1861, produced kerosene by simple atmospheric distillation. Its by-products included tar and naphtha. It was soon discovered that high- quality lubricating oils could be produced by distilling petroleum under vacuum. However, for the next 30 years kerosene was the product consumers wanted. Two significant events changed this situation: (1) invention of the electric light decreased the demand for kerosene, and (2) invention of the internal combustion engine created a demand for diesel fuel and gasoline (naphtha). THERMAL CRACKING PROCESSES With the advent of mass production and World War I, the number of gasoline-powered vehicles increased dramatically and the demand for gasoline grew accordingly. However, distillation processes produced only a certain amount of gasoline from crude oil. In 1913, the thermal cracking process was developed, which subjected heavy fuels to both pressure and intense heat, physically breaking the large molecules into smaller ones to produce additional gasoline and distillate fuels. Visbreaking, another form of thermal cracking, was developed in the late 1930s to produce more desirable and valuable products. CATALYTIC PROCESSES Higher-compression gasoline engines required higher-octane gasoline with better antiknock characteristics. The introduction of catalytic cracking and polymerization processes in the mid- to late 1930s met the demand by providing improved gasoline yields and higher octane numbers. Alkylation, another catalytic process developed in the early 1940s, produced more high-octane aviation gasoline and petrochemical feedstocks for explosives and synthetic rubber. Subsequently, catalytic isomerization was developed to convert hydrocarbons to produce increased quantities of alkylation feedstocks. Improved catalysts and process methods such as hydrocracking and reforming were developed throughout the 1960s to increase gasoline yields and improve antiknock characteristics. These catalytic processes also produced hydrocarbon molecules with a double bond (alkenes) and formed the basis of the modern petrochemical industry. TREATMENT PROCESSES Throughout the history of refining, various treatment methods have been used to remove nonhydrocarbons, impurities, and other constituents that adversely affect the properties of finished products or reduce the efficiency of the conversion processes. Treating can involve chemical reaction and/or physical separation. Typical examples of treating are chemical sweetening, acid treating, clay contacting, caustic washing, hydrotreating, drying, solvent extraction, and solvent dewaxing. Sweetening compounds and acids desulfurize crude oil before processing and treat products during and after processing. Following the Second World War, various reforming processes improved gasoline quality and yield and produced higher-quality products. Some of these involved the use of catalysts and/or hydrogen to change molecules and remove sulfur. A number of

Table III:2-1 HISTORY OF REFINING

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Year 1862 1870 1913 1916 1930 1932 1932 1933 1935 1935 1937 1939 1940 1940 1942 1950 1952 1954 1956 1957 1960 1974 1975

Process name Atmospheric distillation Vacuum distillation Thermal cracking Sweetening Thermal reforming Hydrogenation Coking Solvent extraction Solvent dewaxing Cat. polymerization Catalytic cracking Visbreaking Alkylation Isomerization Fluid catalytic cracking Deasphalting Catalytic reforming Hydrodesulfurization Inhibitor sweetening Catalytic isomerization Hydrocracking Catalytic dewaxing Residual hydrocracking

Purpose Produce kerosene Lubricants (original) Cracking feedstocks (1930s) Increase gasoline Reduce sulfur & odor Improve octane number Remove sulfur Produce gasoline basestocks Improve lubricant viscosity index Improve pour point Improve gasoline yield & octane number Higher octane gasoline Reduce viscosity Increase gasoline octane & yield Produce alkylation feedstock Increase gasoline yield & octane Increase cracking feedstock Convert low-quality naphtha Remove sulfur Remove mercaptan Convert to molecules with high octane number Improve quality and reduce sulfur Improve pour point Increase gasoline yield from residual Wax

By-products, etc. Naphtha, tar, etc. Asphalt, residual coker feedstocks Residual, bunker fuel Sulfur Residual Sulfur Coke Aromatics Waxes Petrochemical feedstocks Petrochemical feedstocks Increased distillate, tar High-octane aviation gasoline Naphtha Petrochemical feedstocks Asphalt Aromatics Sulfur Disulfides Alkylation feedstocks Alkylation feedstocks

Heavy residuals

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the more commonly used treating and reforming processes are described in this chapter of the manual.

crudes have varying amounts of each type of hydrocarbon. Refinery crude base stocks usually consist of mixtures of two or more different crude oils. Relatively simple crude-oil assays are used to classify crude oils as paraffinic, naphthenic, aromatic, or mixed. One assay method (United States Bureau of Mines) is based on distillation, and another method (UOP "K" factor) is based on gravity and boiling points. More comprehensive crude assays determine the value of the crude (i.e., its yield and quality of useful products) and processing parameters. Crude oils are usually grouped according to yield structure.

BASICS OF CRUDE OIL

Crude oils are complex mixtures containing many different hydrocarbon compounds that vary in appearance and composition from one oil field to another. Crude oils range in consistency from water to tar-like solids, and in color from clear to black. An "average" crude oil contains about 84% carbon, 14% hydrogen, 1-3% sulfur, and less than 1% each of nitrogen, oxygen, metals, and salts. Crude oils are generally classified as paraffinic, naphthenic, or aromatic, based on the predominant proportion of similar hydrocarbon molecules. Mixed-base

Table III:2-2. TYPICAL APPROXIMATE CHARACTERISTICS AND PROPERTIES AND GASOLINE POTENTIAL OF VARIOUS CRUDES (Representative average numbers) Naph. yield (% vol) 28 22 23 2 18 33 31 Octane number (typical) 60 40 35 60 50 55 50

Crude source Nigerian -Light Saudi -Light Saudi -Heavy Venezuela -Heavy Venezuela -Light

Paraffins (% vol) 37 63 60 35 52

Aromatics (% vol) 9 19 15 12 14 22 16

Naphthenes (% vol) 54 18 25 53 34 32 34

Sulfur (% wt) 0.2 2 2.1 2.3 1.5 0.4 1.9 0.4

API gravity (approx.) 36 34 28 30 24 40 32 37

USA -Midcont. Sweet USA -W. Texas Sour North Sea -Brent 46 50

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Crude oils are also defined in terms of API (American Petroleum Institute) gravity. The higher the API gravity, the lighter the crude. For example, light crude oils have high API gravities and low specific gravities. Crude oils with low carbon, high hydrogen, and high API gravity are usually rich in paraffins and tend to yield greater proportions of gasoline and light petroleum products; those with high carbon, low hydrogen, and low API gravities are usually rich in aromatics. Crude oils that contain appreciable quantities of hydrogen sulfide or other reactive sulfur compounds are called "sour." Those with less sulfur are called "sweet." Some exceptions to this rule are West Texas crudes, which are always considered "sour" regardless of their H2S content, and Arabian high-sulfur crudes, which are not considered "sour" because their sulfur compounds are not highly reactive.

include from one to 60 carbon atoms. The properties of hydrocarbons depend on the number and arrangement of the carbon and hydrogen atoms in the molecules. The simplest hydrocarbon molecule is one carbon atom linked with four hydrogen atoms: methane. All other variations of petroleum hydrocarbons evolve from this molecule. Hydrocarbons containing up to four carbon atoms are usually gases; those with five to 19 carbon atoms are usually liquids; and those with 20 or more are solids. The refining process uses chemicals, catalysts, heat, and pressure to separate and combine the basic types of hydrocarbon molecules naturally found in crude oil into groups of similar molecules. The refining process also rearranges their structures and bonding patterns into different hydrocarbon molecules and compounds. Therefore it is the type of hydrocarbon, (paraffinic, naphthenic, or aromatic) rather than its specific chemical compounds that is significant in the refining process.

BASICS OF HYDROCARBON CHEMISTRY

Crude oil is a mixture of hydrocarbon molecules, which are organic compounds of carbon and hydrogen atoms that may

Figure III:2-1 Typical Paraffins

THREE PRINCIPAL GROUPS OR SERIES OF HYDROCARBON COMPOUNDS THAT OCCUR NATURALLY IN CRUDE OIL

PARAFFINS The paraffinic series of hydrocarbon compounds found in crude oil have the general formula CnH2n+2 and can be either straight chains (normal) or branched chains (isomers) of

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carbon atoms. The lighter, straight-chain paraffin molecules are found in gases and paraffin waxes. Examples of straight-chain molecules are methane, ethane, propane, and butane (gases containing from one to four carbon atoms), and pentane and hexane (liquids with five to six carbon atoms). The branched-chain (isomer) paraffins are usually found in heavier fractions of crude oil and have higher octane numbers than normal paraffins. These compounds are saturated hydrocarbons, with all carbon bonds satisfied, that is, the hydrocarbon chain carries the full complement of hydrogen atoms.

AROMATICS Aromatics are unsaturated ring-type (cyclic) compounds which react readily because they have carbon atoms that are deficient in hydrogen. All aromatics have at least one benzene ring (a single-ring compound characterized by three double bonds alternating with three single bonds between six carbon atoms) as part of their molecular structure. Naphthalenes are fused double-ring aromatic compounds. The most complex aromatics, polynuclears (three or more fused aromatic rings), are found in heavier fractions of crude oil. NAPHTHENES Naphthenes are saturated hydrocarbon groupings with the general formula CnH2n, arranged in the form of closed rings (cyclic) and found in all fractions of crude oil except the very lightest. Single-ring naphthenes (monocycloparaffins) with five and six carbon atoms predominate, with two-ring naphthenes

Figure III:2-2 Typical Aromatics

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(dicycloparaffins) found in the heavier ends of naphtha. OTHER HYDROCARBONS ALKENES Alkenes are mono-olefins with the general formula CnH2n and contain only one carbon-carbon double bond in the chain. The simplest alkene is ethylene, with two carbon atoms joined by a double bond and four hydrogen atoms. Olefins are usually formed by thermal and catalytic cracking and rarely occur naturally in unprocessed crude oil. DIENES AND ALKYNES Dienes, also known as diolefins, have two carbon-carbon double bonds. The alkynes, another class of unsaturated hydrocarbons, have a carbon-carbon triple bond within the molecule. Both these series of hydrocarbons have the general formula CnH2n-2. Diolefins such as 1,2-butadiene and 1,3-butadiene, and alkynes

such as acetylene occur in C5 and lighter fractions from cracking. The olefins, diolefins, and alkynes are said to be unsaturated because they contain less than the amount of hydrogen necessary to saturate all the valences of the carbon atoms. These compounds are more reactive than paraffins or naphthenes and readily combine with other elements such as hydrogen, chlorine, and bromine. NONHYDROCARBONS SULFUR COMPOUNDS Sulfur may be present in crude oil as hydrogen sulfide (H2S), as compounds (e.g., mercaptans, sulfides, disulfides, thiophenes, etc.), or as elemental sulfur. Each crude oil has different amounts and types of sulfur compounds, but as a rule the proportion, stability, and complexity of the compounds are greater in heavier crude-oil fractions. Hydrogen sulfide is a primary contributor to corrosion in refinery processing units. Other corrosive substances are elemental sulfur and mercaptans. Moreover, the corrosive sulfur compounds have an obnoxious odor.

Figure III:2-3 Typical Napthenes

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Figure III:2-4 Typical Alkenes Pyrophoric iron sulfide results from the corrosive action of sulfur compounds on the iron and steel used in refinery process equipment, piping, and tanks. The combustion of petroleum products containing sulfur compounds produces undesirables such as sulfuric acid and sulfur dioxide. C a t a l yt i c h yd r o t r e a t i n g p r o c e s s e s s u c h a s hydrodesulfurization remove sulfur compounds from refinery product streams. Sweetening processes either remove the obnoxious sulfur compounds or convert them to odorless disulfides, as in the case of mercaptans. OXYGEN COMPOUNDS Oxygen compounds such as phenols, ketones, and carboxylic acids occur in crude oils in varying amounts. Metals including nickel, iron, and vanadium are often found in crude oils in small quantities and are removed during the refining process. Burning heavy fuel oils in refinery furnaces NITROGEN COMPOUNDS Nitrogen is found in lighter fractions of crude oil as basic compounds, and more often in heavier fractions of crude oil as nonbasic compounds that may also include trace metals such as copper, vanadium, and/or nickel. Nitrogen oxides can form in process furnaces. The decomposition of nitrogen compounds in catalytic cracking and hydrocracking processes forms ammonia and cyanides that can cause corrosion . TRACE METALS

Figure III:2-5. Typcial Diolefins and Alkynes

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and boilers can leave deposits of vanadium oxide and nickel oxide in furnace boxes, ducts, and tubes. It is also desirable to remove trace amounts of arsenic, vanadium, and nickel prior to processing as they can poison certain catalysts. SALTS Crude oils often contain inorganic salts such as sodium chloride, magnesium chloride, and calcium chloride in suspension or dissolved in entrained water (brine). These salts must be removed or neutralized before processing to prevent catalyst poisoning, equipment corrosion, and fouling. Salt corrosion is caused by the hydrolysis of some metal chlorides to hydrogen chloride (HCl) and the subsequent formation of hydrochloric acid when crude is heated. Hydrogen chloride may also combine with ammonia to form ammonium chloride (NH4Cl), which causes fouling and corrosion. CARBON DIOXIDE

KERSONE Kerosene is a refined middle-distillate petroleum product that finds considerable use as a jet fuel and around the world in cooking and space heating. When used as a jet fuel, some of the critical qualities are freeze point, flash point, and smoke point. Commercial jet fuel has a boiling range of about 375-525 F, and military jet fuel 130-550 F. Kerosene, with less-critical specifications, is used for lighting, heating, solvents, and blending into diesel fuel. LIQUEFIED PETROLEUM GAS (LPG) LPG, which consists principally of propane and butane, is produced for use as fuel and is an intermediate material in the manufacture of petrochemicals. The important specifications for proper performance include vapor pressure and control of contaminants. DISTILLATE FUELS

Carbon dioxide may result from the decomposition of bicarbonates present in or added to crude, or from steam used in the distillation process. NAPHTHENIC ACIDS Some crude oils contain naphthenic (organic) acids, which may become corrosive at temperatures above 450o F when the acid value of the crude is above a certain level.

Diesel fuels and domestic heating oils have boiling ranges of about 400-700 F. The desirable qualities required for distillate fuels include controlled flash and pour points, clean burning, no deposit formation in storage tanks, and a proper diesel fuel cetane rating for good starting and combustion. RESIDUAL FUELS Many marine vessels, power plants, commercial buildings and industrial facilities use residual fuels or combinations of residual and distillate fuels for heating and processing. The two most critical specifications of residual fuels are viscosity and low sulfur content for environmental control. COKE AND ASPHALT Coke is almost pure carbon with a variety of uses from electrodes to charcoal briquets. Asphalt, used for roads and roofing materials, must be inert to most chemicals and weather conditions.

MAJOR REFINERY PRODUCTS

GASOLINE The most important refinery product is motor gasoline, a blend of hydrocarbons with boiling ranges from ambient temperatures to about 400o F. The important qualities for gasoline are octane number (antiknock), volatility (starting and vapor lock), and vapor pressure (environmental control). Additives are often used to enhance performance and provide protection against oxidation and rust formation.

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SOLVENTS A variety of products, whose boiling points and hydrocarbon composition are closely controlled, are produced for use as solvents. These include benzene, toluene, and xylene. PETROCHEMICALS Many products derived from crude oil refining such as ethylene, propylene, butylene, and isobutylene are primarily intended for use as petrochemical feedstocks in the production of plastics, synthetic fibers, synthetic rubbers, and other products. LUBRICANTS Special refining processes produce lubricating oil base stocks. Additives such as demulsifiers, antioxidants, and viscosity improvers are blended into the base stocks to provide the characteristics required for motor oils, industrial greases, lubricants, and cutting oils. The most critical quality for lubricating-oil base stock is a high viscosity index, which provides for greater consistency under varying temperatures.

COMMON REFINERY CHEMICALS

LEADED GASOLINE ADDITIVES Tetraethyl lead (TEL) and tetramethyl lead (TML) are additives formerly used to improve gasoline octane ratings but are no longer in common use except in aviation gasoline. OXYGENATES Ethyl tertiary butyl ether (ETBE), methyl tertiary butyl ether (MTBE), tertiary amyl methyl ether (TAME), and other oxygenates improve gasoline octane ratings and reduce carbon monoxide emissions. CAUSTICS Caustics are added to desalting water to neutralize acids and reduce corrosion. They are also added to desalted crude in order to reduce the amount of corrosive chlorides in the tower overheads. They are used in some refinery treating processes to remove contaminants from hydrocarbon streams. SULFURIC ACID AND HYDROFLUORIC ACID Sulfuric acid and hydrofluoric acid are used primarily as catalysts in alkylation processes. Sulfuric acid is also used in some treatment processes.

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C. PETROLEUM REFINING OPERATIONS

INTRODUCTION
Petroleum refining begins with the distillation, or fractionation, of crude oils into separate hydrocarbon groups. The resultant products are directly related to the characteristics of the crude processed. Most distillation products are further converted into more usable products by changing the size and structure of the hydrocarbon molecules through cracking, reforming, and other conversion processes as discussed in this chapter. These converted products are then subjected to various treatment and separation processes such as extraction, hydrotreat-ing, and sweetening to remove undesirable constituents and improve product quality. Integrated refineries incorporate fractionation, conversion, treatment, and blending operations and may also include petrochemical processing. @ TREATMENT Treatment processes are intended to prepare hydrocarbon streams for additional processing and to prepare finished products. Treatment may include the removal or separation of aromatics and naphthenes as well as impurities and undesirable contaminants. Treatment may involve chemical or physical separation such as dissolving, absorption, or precipitation using a variety and combination of processes including desalting, drying, hydrodesulfurizing, solvent refining, sweetening, solvent extraction, and solvent dewaxing. FORMULATING AND BLENDING Formulating and blending is the process of mixing and combining hydrocarbon fractions, additives, and other components to produce finished products with specific performance properties. OTHER REFINING OPERATIONS Other refinery operations include light-ends recovery, sour-water stripping, solid waste and wastewater treatment, process-water treatment and cooling, storage, and handling, product movement, hydrogen production, acid and tail-gas treatment, and sulfur recovery. Auxiliary operations and facilities include steam and power generation; process and fire water systems; flares and relief systems; furnaces and heaters; pumps and valves; supply of steam, air, nitrogen, and other plant gases; alarms and sensors; noise and pollution controls; sampling, testing, and inspecting; and laboratory, control room, maintenance, and administrative facilities. alteration (rear r anging) with isomerization and catalytic reforming .

REFINING OPERATIONS
Petroleum refining processes and operations can be separated into five basic areas: FRACTIONATION Fractionation (distillation) is the separation of crude oil in atmospheric and vacuum distillation towers into groups of hydrocarbon compounds of differing boiling-point ranges called "fractions" or "cuts." Conversion Conversion processes change the size and/or structure of hydrocarbon molecules. These processes include: @ @ decomposition (dividing) by thermal and catalytic cracking, unification (combining) through alkylation and polymerization, and

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III:2-12

Table III:2-3 OVERVIEW OF PETROLEUM REFINING PROCESSES Process name Action Method Purpose Feedstock(s) Product(s)

FRACTIONATION PROCESSES Atmospheric distillation Vacuum distillation Separation Separation Thermal Thermal cracking CONVERSION PROCESSES ------- DECOMPOSITION Catalytic cracking Coking Hydrocracking *Hydrogen Steam Reforming *Steam Cracking Visbreaking Alteration Polymerize Hydrogenate Decompose Decompose Decompose Gas oil, coke Gasoline,petrodistillate chemical feedstock Thermal Convert vacuResidual,heavy Naphtha, gas um residuals oil, tar oil, coke Catalytic Convert to Gas oil, cracked Lighter, higherlighter HCs oil, residual qualityproducts Thermal/cat. Produce Desulfurized Hydrogen, CO, hydrogen gas, O2, steam CO2 Thermal Crack large Atm tower hvy Cracked molecules fuel/distillate naphtha, coke,residual Thermal Reduce Atmospheric Distillate, tar viscosity tower residual Catalytic Upgrade gasoline Separate fractions Desalted crude oil Gas, gas oil, distillate,residu

Separate w/o Atmospheric Gas oil, lube tower residual stock, residual

CONVERSION PROCESSES ------- UNIFICATION Alkylation Grease compounding Polymerization Combining Combining Polymerize Unite olefins & isoparaffins Thermal Combine soaps & oils Catalytic Unite 2 or more olefins Catalytic Tower isobutane/crckr olefin Lube oil, fatty acid, alkymetal Cracker olefins naphtha, petrochemiIso-octane (alkylate) Lubricating grease High-octane cal stocks CONVERSION PROCESSES ----- ALTERATION or REARRANGEMENT Catalytic reforming Alteration/ dehydration Isomerization Rearrange Upgrade lowCoker/hydroHigh oct. octane naphtha cracker naphtha reformate/aromatic Catalytic Convert strght Butane, pentane, Isobutane/penchain to branch hexane tane/hexane Catalytic

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TREATMENT PROCESSES *Amine Treating Desalting Drying & Sweetening *Furfural ExtracTreatment Dehydration Treatment Solvent extr. Absorption Remove acidic contaminants Sour gas, HCs w/CO2 & H2S Crude oil crude Liq HCs, LPG, alky. feedstk Cycle oils & lube feedstocks High-sulfur residual/gas oil Residuals, cracked HCs Lube oil base stocks oil Sweet & dry hydrocarbons High tion quality diesel & lube oil Desulfurized olefins Cracker feed, distillate, lube High quality lube oils Heavy lube oil, asphalt basestock Highoctane gasoline Highquality distilate/ gasoline Acid free gases & liquid HCs Desalted

Absorption Remove contaminants Abspt/therm Absorption Remove H2O & sulfur cmpds Upgrade mid distillate & lubes Remove sulfur, contaminants Remv impurities saturate Hcs Improve visc. index, color Remove asphalt

Hydrodesulfurization Hydrotreating

Treatment Hydrogenation

Catalytic Catalytic

*Phenol extraction Solvent deasphalting

Solvent extr. Treatment

Abspt/therm Absorption

Solvent dewaxing Treatment Solvent Extraction Sweetening

Cool/filter

Remve wax from lube stocks

Vac. tower residual, propane Vac. tower lube Dewaxed oils lube Gas oil, reformate, distillate Untreated distillate/gasoline

Solvent extr. Treatment

Abspt/precip. Catalytic

Separate unsat. oils Remv H2S,convert mercaptan

*NOTE: These processes are not depicted in the refinery process flow chart.

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D.

DESCRIPTION OF PETROLEUM REFINING PROCESSES AND RELATED HEALTH CONSIDERATIONS

PRETREATMENT

AND

SAFETY

CRUDE OIL (DESALTING)

In both methods other chemicals may be added. Ammonia is often used to reduce corrosion. Caustic or acid may be added to adjust the pH of the water wash. Wastewater and contaminants are discharged from the bottom of the settling tank to the wastewater treatment facility. The desalted crude is continuously drawn from the top of the settling tanks and sent to the crude distillation (fractionating) tower.

Crude oil often contains water, inorganic salts, suspended solids, and water-soluble trace metals. As a first step in the refining process, to reduce corrosion, plugging, and fouling of equipment and to prevent poisoning the catalysts in processing units, these contaminants must be removed by desalting (dehydration). The two most typical methods of crude-oil desalting, chemical and electrostatic separation, use hot water as the extraction agent. In chemical desalting, water and chemical surfactant (demulsifiers) are added to the crude, heated so that salts and other impurities dissolve into the water or attach to the water, and then held in a tank where they settle out. Electrical desalting is the application of high-voltage electrostatic charges to concentrate suspended water globules in the bottom of the settling tank. Surfactants are added only when the crude has a large amount of suspended solids. Both methods of desalting are continuous. A third and less-common process involves filtering heated crude using diatomaceous earth. The feedstock crude oil is heated to between 150o and 350oF to reduce viscosity and surface tension for easier mixing and separation of the water. The temperature is limited by the vapor pressure of the crude-oil feedstock.

HEALTH AND SAFETY CONSIDERATIONS

Fire Prevention and Protection The potential exists for a fire due to a leak or release of crude from heaters in the crude desalting unit. Low boiling point components of crude may also be released if a leak occurs. Safety Inadequate desalting can cause fouling of heater tubes and heat exchangers throughout the refinery. Fouling restricts product flow and heat transfer and leads to failures due to increased pressures and temperatures. Corrosion, which occurs due to the presence of hydrogen sulfide, hydrogen chloride, naphthenic (organic) acids, and other contaminants in the crude oil, also causes equipment failure. Neutralized salts (ammonium chlorides and sulfides), when moistened by

Table III:2-4: DESALTING PROCESS Feedstocks Crude From Storage Process Typical products............ To

Treating Desalted crude..........Atmospheric distillation tower Waste water..........................Treatment

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Figure II:2-7 Electrostatic Desalting condensed water, can cause corrosion. Overpressuring the unit is another potential hazard that causes failures. Health Because this is a closed process, there is little potential for exposure to crude oil unless a leak or release occurs. Where elevated operating temperatures are used when desalting sour crudes, hydrogen sulfide will be present. There is the possibility of exposure to ammonia, dry chemical demulsifiers, caustics, and/or acids during this operation. Safe work practices and/or the use of appropriate personal Depending on the crude feedstock and the treatment chemicals used, the wastewater will contain varying amounts of chlorides, sulfides, bicarbonates, ammonia, hydrocarbons, phenol, and suspended solids. If diatomaceous earth is used in filtration, exposures should be minimized or controlled. Diatomaceous earth can contain silica in very fine particle size, making this a potential respiratory hazard. protective equipment may be needed for exposures to chemicals and other hazards such as heat, and during process sampling, inspection, maintenance, and turnaround activities.

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CRUDE OIL DISTILLATION (FRACTIONATION)

The first step in the refining process is the separation of crude oil into various fractions or straight-run cuts by distillation in atmospheric and vacuum towers. The main fractions or "cuts" obtained have specific boiling-point ranges and can be classified in order of decreasing volatility into gases, light distillates, middle distillates, gas oils, and residuum. ATMOSPHERIC DISTILLATION TOWER At the refinery, the desalted crude feedstock is preheated using recovered process heat. The feedstock then flows to a direct-fired crude charge heater where it is fed into the vertical distillation column just above the bottom, at pressures slightly above atmospheric and at temperatures ranging from 650 to 700 F (heating crude oil above these temperatures may cause undesirable thermal cracking). All but the heaviest fractions flash into vapor. As the hot vapor rises in the tower, its temperature is reduced. Heavy fuel oil or asphalt residue is taken from the bottom. At successively higher points on the tower, the various major products

including lubricating oil, heating oil, kerosene, gasoline, and uncondensed gases (which condense at lower temperatures) are drawn off. The fractionating tower, a steel cylinder about 120 feet high, contains horizontal steel trays for separating and collecting the liquids. At each tray, vapors from below enter perforations and bubble caps. They permit the vapors to bubble through the liquid on the tray, causing some condensation at the temperature of that tray. An overflow pipe drains the condensed liquids from each tray back to the tray below, where the higher temperature causes re-evaporation. The evaporation, condensing, and scrubbing operation is repeated many times until the desired degree of product purity is reached. Then side streams from certain trays are taken off to obtain the desired fractions. Products ranging from uncondensed fixed gases at the top to heavy fuel oils at the bottom can be taken continuously from a fractionating tower. Steam is often used in towers to lower the vapor pressure and create a partial vacuum. The distillation process separates the major constituents of crude oil into so-called straight-run products. Sometimes crude oil is "topped" by distilling off only the lighter fractions, leaving a heavy residue that is often distilled further under high vacuum.

Table III:2-5. ATMOSPHERIC DISTILLATION PROCESSES Feedstocks Crude From Desalting Process Separation Typical products................. To Gases.................................. Naphthas............................ Kero or distillates.............. Gas oil............................... Residual............................ Fuel or gas recovery Reforming or treating Treating Catalytic cracking Vacuum tower or visbreaker

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Figure III:2-8 Atmospheric Distillation VACUUM DISTILLATION TOWER In order further to distill the residuum or topped crude from the atmospheric tower at higher temperatures, reduced pressure is required to prevent thermal cracking. The process takes place in one or more vacuum distillation towers. The principles of vacuum distillation resemble those of fractional distillation and, except that larger-diameter columns are used to maintain comparable vapor velocities at the reduced pressures, the equipment is also similar. The internal designs of some vacuum towers are different from atmospheric towers in that random packing and demister pads are used instead of trays. A typical first-phase vacuum tower may produce gas oils, lubricating-oil base stocks, and heavy residual for propane deasphalting. A second-phase tower operating at lower vacuum may distill surplus residuum from the atmospheric tower, which is not used for lube-stock processing, and surplus residuum from the first vacuum tower not used for deasphalting. Vacuum towers are typically used to separate catalytic cracking feedstocks from surplus residuum. OTHER DISTILLATION TOWERS (COLUMNS) Within refineries there are numerous other, smaller distillation towers called columns, designed to separate specific and unique products. Columns all work on the same principles as the towers described above. For example, a depropanizer is a small column designed to separate propane and lighter gases from butane and heavier components. Another larger column is used to separate ethyl benzene and xylene. Small "bubble" towers called strippers use steam to remove trace amounts of light products from heavier product streams. HEALTH AND SAFETY CONSIDERATIONS Fire Prevention and Protection

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Even though these are closed processes, heaters and exchangers in the atmospheric and vacuum distillation units could provide a source of ignition, and the potential for a fire exists should a leak or release occur. Safety An excursion in pressure, temperature, or liquid levels may occur if automatic control devices fail. Control of temperature, pressure, and reflux within operating parameters is needed to prevent thermal cracking within the distillation towers. Relief systems should be provided for overpressure and operations monitored to prevent crude from entering the reformer charge. The sections of the process susceptible to corrosion include (but may not be limited to) preheat exchanger (HCl and H2S), preheat furnace and bottoms exchanger (H2S and sulfur compounds), atmospheric tower and vacuum furnace (H2S, sulfur compounds, and organic acids), vacuum tower (H2S and organic acids), and overhead (H2S, HCl, and water). Where sour crudes are processed, severe corrosion can occur in furnace tubing and in both atmospheric and vacuum towers where metal temperatures exceed 450 F. Wet H2S also will cause cracks in steel. When processing high-nitrogen crudes, nitrogen oxides can form in the flue gases of furnaces. Nitrogen oxides are corrosive to steel when cooled to low temperatures in the presence of water.

Chemicals are used to control corrosion by hydrochloric acid produced in distillation units. Ammonia may be injected into the overhead stream prior to initial condensation and/or an alkaline solution may be carefully injected into the hot crude-oil feed. If sufficient wash-water is not injected, deposits of ammonium chloride can form and cause serious corrosion. Crude feedstocks may contain appreciable amounts of water in suspension which can separate during startup and, along with water remaining in the tower from steam purging, settle in the bottom of the tower. This water can be heated to the boiling point and create an instantaneous vaporization explosion upon contact with the oil in the unit. Health Atmospheric and vacuum distillation are closed processes and exposures are expected to be minimal. When sour (high-sulfur) crudes are processed, there is potential for exposure to hydrogen sulfide in the preheat exchanger and furnace, tower flash zone and overhead system, vacuum furnace and tower, and bottoms exchanger. Hydrogen chloride may be present in the preheat exchanger, tower top zones, and overheads. Wastewater may contain water-soluble sulfides in high concentrations and other water-soluble compounds such as ammonia, chlorides, phenol, mercaptans, etc., depending upon the crude feedstock and the treatment chemicals. Safe work practices and/or the use of appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as heat and noise, and during sampling, inspection, maintenance, and turnaround activities.

Table III:2-6 VACUUM DISTILLATION PROCESS Feedstocks Residuals tower From Process Atmospheric Typical products................... To

Separation Gas oils................................. Catalytic cracker Lubricants............................. Hydrotreating or solvent extraction Residual................................ Deasphalter, visbreaker, or coker

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Figure III:2-9 Vacuum Distillation

SOLVENT EXTRACTION DEWAXING

AND

SOLVENT EXTRACTION The purpose of solvent extraction is to prevent corrosion, protect catalyst in subsequent processes, and improve finished products by removing unsaturated, aromatic hydrocarbons from lubricant and grease stocks. The solvent extraction process separates aromatics, naphthenes, and impurities from the product stream by dissolving or precipitation. The feedstock is first dried and then treated using a continuous countercurrent solvent treatment operation. In one type of process, the feedstock is washed with a liquid in which the substances to be removed are more soluble than in the desired resultant product. In another process, selected solvents are added to cause impurities to precipitate out of the product. In the adsorption process, highly porous solid materials collect liquid molecules on their surfaces.

Solvent treating is a widely used method of refining lubricating oils as well as a host of other refinery stocks. Since distillation (fractionation) separates petroleum products into groups only by their boiling-point ranges, impurities may remain. These include organic compounds containing sulfur, nitrogen, and oxygen; inorganic salts and dissolved metals; and soluble salts that were present in the crude feedstock. In addition, kerosene and distillates may have trace amounts of aromatics and naphthenes, and lubricating oil base-stocks may contain wax. Solvent refining processes including solvent extraction and solvent dewaxing usually remove these undesirables at intermediate refining stages or just before sending the product to storage.

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The solvent is separated from the product stream by heating, evaporation, or fractionation, and residual trace amounts are subsequently removed from the raffinate by steam stripping or vacuum flashing. Electric precipitation may be used for separation of inorganic compounds. The solvent is then regenerated to be used again in the process.

The most widely used extraction solvents are phenol, furfural, and cresylic acid. Other solvents less frequently used are liquid sulfur dioxide, nitrobenzene, and 2,2' dichloroethyl ether. The selection of specific processes and chemical agents depends on the nature of the feedstock being treated, the contaminants present, and the finished product requirements.

Table III:2-7. SOLVENT EXTRACTION PROCESS Feedstocks Naphthas Distillates Kerosene From Atm. tower Process Treating Typical products.................... High octane gasoline............... Refined Fuels.......................... Spent agents............................ To Treating or blending Treating or blending Treatment or recycle

Figure III:2-10 Aromatics Extraction

Diagrams in Figures II:2-10, 11, 12, 13, 15, and 20 reproduced with the permission of Shell International Petroleum Company Limited.

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Table III:2-8 SOLVENT DEWAXING PROCESS

Feedstocks Lube basestock

From Vacuum tower

Process Treating

Typical products................To Dewaxed lubes or wax....... Spent agents....................... Hydrotreating Treatment or recycle

SOLVENT DEWAXING Solvent dewaxing is used to remove wax from either distillate or residual basestocks at any stage in the refining process. There are several processes in use for solvent dewaxing, but all have the same general steps, which are: (1) mixing the feedstock with a solvent, (2) precipitating the wax from the mixture by chilling, and (3) recovering the solvent from the wax and dewaxed oil for recycling by distillation and steam stripping. Usually two solvents are used: toluene, which dissolves the oil and maintains fluidity at low temperatures, and methyl ethyl ketone (MEK), which dissolves little wax at low temperatures and acts as a wax precipitating agent. Other solvents that are sometimes used include benzene, methyl isobutyl ketone, propane, petroleum naphtha, ethylene dichloride, methylene chloride, and

sulfur dioxide. In addition, there is a catalytic process used as an alternate to solvent dewaxing. HEALTH AND SAFETY CONSIDERATIONS Fire Prevention and Protection Solvent treatment is essentially a closed process and, although operating pressures are relatively low, the potential exists for fire from a leak or spill contacting a source of ignition such as the drier or extraction heater. In solvent dewaxing, disruption of the vacuum will create a potential fire hazard by allowing air to enter the unit. Health Because solvent extraction is a closed process, exposures are expected to be minimal under normal operating conditions. However, there is a potential for exposure to extraction solvents such as phenol, furfural, glycols, methyl ethyl ketone, amines, and other process chemicals. Safe work practices and/or the use of appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as noise and heat, and during rep air, in sp ection, maintenance, and turnaround activities.

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Table III:2-9 VISBREAKING PROCESS

Feedstocks Residual

From

Process

Typical products................

To

Atmospheric tower Decompose Vacuum tower

Gasoline or distillate...........Treating or blending Vapor.............................Hydrotreater Residue...........................Stripper or recycle Gases..............................Gas plant

THERMAL CRACKING
Because the simple distillation of crude oil produces amounts and types of products that are not consistent with those required by the marketplace, subsequent refinery processes change the product mix by altering the molecular structure of the hydrocarbons. One of the ways of accomplishing this change is through "cracking," a process that breaks or cracks

heavier, higher boiling-point petroleum fractions into more valuable products such as gasoline, fuel oil, and gas oils. The two basic types of cracking are thermal cracking, using heat and pressure, and catalytic cracking. The first thermal cracking process was developed around 1913. Distillate fuels and heavy oils were heated under pressure in large drums until they cracked into smaller molecules with better antiknock characteristics. However, this method produced large amounts of solid, unwanted coke. This early process has evolved into the following applications of thermal cracking: visbreaking, steam cracking, and coking. VISBREAKING PROCESS Visbreaking, a mild form of thermal cracking, significantly lowers the viscosity of heavy crude-oil residue without affecting the boiling point range. Residual from the atmospheric distillation tower is heated (800-950 F) at atmospheric pressure and mildly cracked in a heater. It is then quenched with cool gas oil to control overcracking, and flashed in a distillation tower. Visbreaking is used to reduce the pour point of waxy residues and reduce the viscosity of residues used for blending with lighter fuel oils. Middle distillates may also be produced, depending on product demand. The thermally cracked residue tar, which accumulates in the bottom of the fractionation tower, is vacuum flashed in a stripper and the distillate recycled.

the Figure III:2-12 Visbreaking

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STEAM CRACKING PROCESS Steam cracking is a petrochemical process sometimes used in refineries to produce olefinic raw materials (e.g., ethylene) from various feedstocks for petrochemicals manufacture. The feedstocks range from ethane to vacuum gas oil, with heavier feeds giving higher yields of by-products such as naphtha. The most common feeds are ethane, butane, and naphtha. Steam cracking is carried out at temperatures of 1,500-1,600 F, and at pressures slightly above atmospheric. Naphtha produced from steam cracking contains benzene, which is extracted prior to hydrotreating. Residual from steam cracking is sometimes blended into heavy fuels. COKING PROCESSES Coking is a severe method of thermal cracking used to upgrade heavy residuals into lighter products or distillates. Coking produces straight-run gasoline (coker naphtha) and various middle-distillate fractions used as catalytic cracking feedstocks. The process so completely reduces hydrogen that the residue is a form of carbon called "coke." The two most common processes are delayed coking and continuous (contact or fluid) coking. Three typical types of coke are obtained (sponge coke, honeycomb coke, and needle coke) depending upon the reaction mechanism, time, temperature, and the crude feedstock.

Delayed Coking In delayed coking the heated charge (typically residuum from atmospheric distillation towers) is transferred to large coke drums which provide the long residence time needed to allow the cracking reactions to proceed to completion. Initially the heavy feedstock is fed to a furnace which heats the residuum to high temperatures (900-950 F) at low pressures (25-30 psi) and is designed and controlled to prevent premature coking in the heater tubes. The mixture is passed from the heater to one or more coker drums where the hot material is held approximately 24 hours (delayed) at pressures of 25-75 psi, until it cracks into lighter products. Vapors from the drums are returned to a fractionator where gas, naphtha, and gas oils are separated out. The heavier hydrocarbons produced in the fractionator are recycled through the furnace. After the coke reaches a predetermined level in one drum, the flow is diverted to another drum to maintain continuous operation. The full drum is steamed to strip out uncracked hydrocarbons, cooled by water injection, and decoked by mechanical or hydraulic methods. The coke is mechanically removed by an auger rising from the bottom of the drum. Hydraulic decoking consists of fracturing the coke bed with high-pressure water ejected from a rotating cutter.

Table III:2-10 COKING PROCESSES Feedstocks Residual Clarified oil Tars Wastewater (sour) Gases From Atmospheric & vacuum catalytic cracker Catalytic cracker Various units Treatment Gas plant Process Decomposition Typical products............ To

Naphtha, gasoline...........Distillation column, blending Coke........................... Shipping, recycle Gas oil........................ Catalytic cracking

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HEALTH AND SAFETY CONSIDERATIONS Fire Protection and Prevention Because thermal cracking is a closed process, the primary potential for fire is from leaks or releases of liquids, gases, or vapors reaching an ignition source such as a heater. The potential for fire is present in coking operations due to vapor or product leaks. Should coking temperatures get out of control, an exothermic reaction could occur within the coker. Safety In thermal cracking when sour crudes are processed, corrosion can occur where metal temperatures are between 450 and 900 F. Above 900 F coke forms a protective layer on the metal. The furnace, soaking drums, lower part of the tower, and high-temperature exchangers are usually subject to corrosion. Hydrogen sulfide corrosion in coking can also occur when temperatures are not properly controlled above 900 F. Continuous thermal changes can lead to bulging and cracking of coke drum shells. In coking, temperature control must often be held within a 10-20 F range, as high temperatures will produce coke that is too hard to cut out of the drum. Conversely, temperatures that are too low will result in a high asphaltic-content slurry. Water or steam injection may be used to prevent buildup of coke in delayed coker furnace tubes. Water must be completely drained from the coker, so as not to cause an explosion upon recharging with hot coke. Provisions for alternate means of egress from the working platform on top of coke drums are important in the event of an emergency. Health The potential exists for exposure to hazardous gases such as hydrogen sulfide and carbon monoxide, and trace polynuclear aromatics (PNAs) associated with coking operations. When coke is moved as a slurry, oxygen depletion may occur within confined spaces such as storage silos, since wet carbon will adsorb oxygen. Wastewater may be highly alkaline and contain

Continuous Coking Continuous (contact or fluid) coking is a moving-bed process that operates at temperatures higher than delayed coking. In continuous coking, thermal cracking occurs by using heat transferred from hot, recycled coke particles to feedstock in a radial mixer, called a reactor, at a pressure of 50 psi. Gases and vapors are taken from the reactor, quenched to stop any further reaction, and fractionated. The reacted coke enters a surge drum and is lifted to a feeder and classifier where the larger coke particles are removed as product. The remaining coke is dropped into the preheater for recycling with feedstock. Coking occurs both in the reactor and in the surge drum. The process is automatic in that there is a continuous flow of coke and feedstock.

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oil, sulfides, ammonia, and/or phenol. The potential exists in the coking process for exposure to burns when handling hot coke or in the event of a steam-line leak, or from steam, hot water, hot coke, or hot slurry that may be expelled when opening cokers. Safe work practices and/or the use of appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as heat and noise, and during process sampling, inspection, maintenance, and turnaround activities. (Note: coke produced from petroleum is a different product from that generated in the steel-industry coking process.)

pressures of 10-20 psi. The catalysts used in refinery cracking units are typically solid materials (zeolite, aluminum hydrosilicate, treated bentonite clay, fuller's earth, bauxite, and silica-alumina) that come in the form of powders, beads, pellets or shaped materials called extrudites. There are three basic functions in the catalytic cracking process: Reaction: Feedstock reacts with catalyst and cracks into different hydrocarbons. Regeneration: Catalyst is reactivated by burning off coke. Fractionation: Cracked hydrocarbon stream is separated into various products. The three types of catalytic cracking processes are fluid catalytic cracking (FCC), moving-bed catalytic cracking, and Thermofor catalytic cracking (TCC). The catalytic cracking process is very flexible, and operating parameters can be adjusted to meet changing product demand. In addition to cracking, catalytic activities include dehydrogenation, hydrogenation, and isomerization. FLUID CATALYTIC CRACKING The most common process is FCC, in which the oil is cracked in the presence of a finely divided catalyst which is maintained in an aerated or fluidized state by the oil vapors. The fluid

CATALYTIC CRACKING
Catalytic cracking breaks complex hydrocarbons into simpler molecules in order to increase the quality and quantity of lighter, more desirable products and decrease the amount of residuals. This process rearranges the molecular structure of hydrocarbon compounds to convert heavy hydrocarbon feedstocks into lighter fractions such as kerosene, gasoline, LPG, heating oil, and petrochemical feedstocks. Catalytic cracking is similar to thermal cracking except that catalysts facilitate the conversion of the heavier molecules into lighter products. Use of a catalyst (a material that assists a chemical reaction but does not take part in it) in the cracking reaction increases the yield of improved-quality products under much less severe operating conditions than in thermal cracking. Typical temperatures are from 850-950 F at much lower

Table III:2-11 CATALYTIC CRACKING PROCESS Feedstock Gas oils Deasphalted recycle oils From Towers, coker Visbreaker Deasphalter Process Decomposition, alteration Typical products............................... To

Gasoline............................................Treater or blend Gases................................................Gas plant Middle distillates...............................Hydrotreat, blend, or Petrochem feedstocks.......................Petrochem or other Residue..............................................Residual fuel blend

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Figure III:2-14 Fluid Catalytic Cracking cracker consists of a catalyst section and a fractionating section that operate together as an integrated processing unit. The catalyst section contains the reactor and regenerator, which with the standpipe and riser forms the catalyst circulation unit. The fluid catalyst is continuously circulated between the reactor and the regenerator using air, oil vapors, and steam as the conveying media. A typical FCC process involves mixing a preheated hydrocarbon charge with hot, regenerated catalyst as it enters the riser leading to the reactor. The charge is combined with a recycle stream within the riser, vaporized, and raised to reactor temperature (900-1,000 F) by the hot catalyst. As the mixture travels up the riser, the charge is cracked at 10-30 psi. In the more modern FCC units, all cracking takes place in the riser. The "reactor" no longer functions as a reactor; it merely serves as a holding vessel for the cyclones. This cracking continues until the oil vapors are separated from the catalyst in the reactor cyclones. The resultant product stream (cracked product) is then charged to a fractionating column where it is separated into fractions, and some of the heavy oil is recycled to the riser. Spent catalyst is regenerated to get rid of coke that collects on the catalyst during the process. Spent catalyst flows through the catalyst stripper to the regenerator, where most of the coke deposits burn off at the bottom where preheated air and spent catalyst are mixed. Fresh catalyst is added and worn-out catalyst removed to optimize the cracking process. MOVING BED CATALYTIC CRACKING The moving-bed catalytic cracking process is similar to the FCC process. The catalyst is in the form of pellets that are moved continuously to the top of the unit by conveyor or pneumatic lift tubes to a storage hopper, then flow downward by gravity through the reactor, and finally to a regenerator. The regenerator and hopper are isolated from the reactor by steam seals. The cracked product is separated into recycle gas, oil, clarified oil, distillate, naphtha, and wet gas.

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THERMOFOR CATALYTIC CRACKING In a typical thermofor catalytic cracking unit, the preheated feedstock flows by gravity through the catalytic reactor bed. The vapors are separated from the catalyst and sent to a fractionating tower. The spent catalyst is regenerated, cooled, and recycled. The flue gas from regeneration is sent to a carbon-monoxide boiler for heat recovery. HEALTH AND SAFETY CONSIDERATIONS Fire Prevention and Protection Liquid hydrocarbons in the catalyst or entering the heated combustion air stream should be controlled to avoid exothermic reactions. Because of the presence of heaters in catalytic cracking units, the possibility exists for fire due to a leak or vapor release. Fire protection including concrete or other insulation on columns and supports, or fixed water spray or fog systems where insulation is not feasible and in areas where firewater hose streams cannot reach, should be considered. In some processes, caution must be taken to assure prevent explosive concentrations of catalyst dust during recharge or disposal. When unloading any coked catalyst, the possibility exists for iron sulfide fires. Iron sulfide will ignite spontaneously when exposed to air and therefore mus be wetted with water to prevent it from igniting vapors. Coked catalyst may be either cooled below 120 F before they are dumped from the reactor, or dumped into containers that have been purged and inerted with nitrogen and then cooled before further handling. Safety Regular sampling and testing of the feedstock, product, and recycle streams should be performed to assure that the cracking process is working as intended and that no contaminants have entered the process stream. Corrosives or deposits in the feedstock can foul gas compressors. Inspections of critical equipment including pumps, compressors, furnaces, and heat exchangers should be conducted as needed. When processing sour crude, corrosion may be expected where temperatures are

below 900o F. Corrosion takes place where both liquid and vapor phases exist, and at areas subject to local cooling such as nozzles and platform supports. When processing high-nitrogen feedstocks, exposure to ammonia and cyanide may occur, subjecting carbon steel equipment in the FCC overhead system to corrosion, cracking, or hydrogen blistering. These effects may be minimized by water wash or corrosion inhibitors. Water wash may also be used to protect overhead condensers in the main column subjected to fouling from ammonium hydrosulfide. Inspections should include checking for leaks due to erosion or other malfunctions such as catalyst buildup on the expanders, coking in the overhead feeder lines from feedstock residues, and other unusual operating conditions. Health Because the catalytic cracker is a closed system, there is normally little opportunity for exposure to hazardous substances during normal operations. The possibility exists of exposure to extremely hot (700 F) hydrocarbon liquids or vapors during process sampling or if a leak or release occurs. In addition, exposure to hydrogen sulfide and/or carbon monoxide gas may occur during a release of product or vapor. Catalyst regeneration involves steam stripping and decoking, and produces fluid waste streams that may contain varying amounts of hydrocarbon, phenol, ammonia, hydrogen sulfide, mercaptan, and other materials depending upon the feedstocks, crudes, and processes. Inadvertent formation of nickel carbonyl may occur in cracking processes using nickel catalysts, with resultant potential for hazardous exposures. Safe work practices and/or the use of appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as noise and heat; during process sampling, inspection, maintenance and turnaround activities; and when handling spent catalyst, recharging catalyst, or if leaks or releases occur.

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HYDROCRACKING
Hydrocracking is a two-stage process combining catalytic cracking and hydrogenation, wherein heavier feedstocks are cracked in the presence of hydrogen to produce more desirable products. The process employs high pressure, high temperature, a catalyst, and hydrogen. Hydrocracking is used for feedstocks that are difficult to process by either catalytic cracking or reforming, since these feedstocks are characterized usually by a high polycyclic aromatic content and/or high concentrations of the two principal catalyst poisons, sulfur and nitrogen compounds. The hydrocracking process largely depends on the nature of the feedstock and the relative rates of the two competing reactions, hydrogenation and cracking. Heavy aromatic feedstock is converted into lighter products under a wide range of very high pressures (1,000-2,000 psi) and fairly high temperatures (750-1,500 F), in the presence of hydrogen and special catalysts. When the feedstock has a high paraffinic content, the primary function of hydrogen is to prevent the formation of polycyclic aromatic compounds. Another important role of hydrogen in the hydrocracking process is to reduce tar formation and prevent buildup of coke on the catalyst. Hydrogenation also serves to convert sulfur and nitrogen compounds present in the feedstock to hydrogen sulfide and ammonia. Hydrocracking produces relatively large amounts of isobutane for alkylation feedstocks. Hydrocracking also performs isomerization for pour-point control and smoke-point control, both of which are important in high-quality jet fuel.

HYDROCRACKING PROCESS In the first stage, preheated feedstock is mixed with recycled hydrogen and sent to the first-stage reactor, where catalysts convert sulfur and nitrogen compounds to hydrogen sulfide and ammonia. Limited hydrocracking also occurs. After the hydrocarbon leaves the first stage, it is cooled and liquefied and run through a hydrocarbon separator. The hydrogen is recycled to the feedstock. The liquid is charged to a fractionator. Depending on the products desired (gasoline components, jet fuel, and gas oil), the fractionator is run to cut out some portion of the first stage reactor outturn. Kerosene-range material can be taken as a separate side-draw product or included in the fractionator bottoms with the gas oil. The fractionator bottoms are again mixed with a hydro-gen stream and charged to the second stage. Since this material has already been subjected to some hydrogen-ation, cracking, and reforming in the first stage, the operations of the second stage are more severe (higher temperatures and pressures). Like the outturn of the first stage, the second stage product is separated from the hydrogen and charged to the fractionator. HEALTH AND SAFETY CONSIDERATIONS Fire Prevention and Protection Because this unit operates at very high pressures and temperatures, control of both hydrocarbon leaks and hydrogen releases is important to prevent fires. In some processes, care is

Table III:2-12 HYDROCRACKING PROCESS Feedstocks High pour point residuals Gas oil Hydrogen plant From Catalytic cracker Atmospheric, vac. tower Vacuum tower, coker Reformer Process Decomposition Hydrogenation Heavy naphthas Typical products..................... To

Kerosene, jet fuel......................Blending Gasoline, distillates....................Blending Recycle, reformer Gas.............................................Gas

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Figure III-2:15 Two-Stage Hydrocracking needed to ensure that explosive concentrations of catalytic dust do not form during recharging. Safety Inspection and testing of safety relief devices are important due to the very high pressures in this unit. Proper process control is needed to protect against plugging reactor beds. Unloading coked catalyst requires special precautions to prevent iron sulfide-induced fires. The coked catalyst should either be cooled to below 120 F before dumping, or be placed in nitrogen-inerted containers until cooled. Because of the operating temperatures and presence of hydrogen, the hydrogen-sulfide content of the feedstock must be strictly controlled to a minimum to reduce the possibility of severe corrosion. Corrosion by wet carbon dioxide in areas of condensation also must be considered. When processing high-nitrogen feedstocks, the ammonia and hydrogen sulfide form ammonium hydrosulfide, which causes serious corrosion at temperatures below the water dew point. Ammonium hydrosulfide is also present in sour water stripping. Health Because this is a closed process, exposures are expected to be minimal under normal operating conditions. There is a potential for exposure to hydrocarbon gas and vapor emissions, hydrogen and hydrogen sulfide gas due to high-pressure leaks. Large quantities of carbon monoxide may be released during catalyst

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regeneration and changeover. Catalyst steam stripping and regeneration create waste streams containing sour water and ammonia. Safe work practices and/or the use of appropriate personal protective equipment may be needed for exposure to chemicals and other hazards such as noise and heat, during process sampling, inspection, maintenance, and turnaround activities, and when handling spent catalyst.

reactors containing a platinum catalyst. The effluent from the last reactor is cooled and sent to a separator to permit removal of the hydrogen-rich gas stream from the top of the separator for recycling. The liquid product from the bottom of the separator is sent to a fractionator called a stabilizer (butanizer). It makes a bottom product called reformate; butanes and lighter go overhead and are sent to the saturated gas plant. Some catalytic reformers operate at low pressure (50-200 psi), and others operate at high pressures (up to 1,000 psi). Some catalytic reforming systems continuously regenerate the catalyst in other systems. One reactor at a time is taken off-stream for catalyst regeneration, and some facilities regenerate all of the reactors during turnarounds. HEALTH AND SAFETY CONSIDERATIONS Fire Prevention and Protection This is a closed system; however, the potential for fire exists should a leak or release of reformate gas or hydrogen occur. Safety Operating procedures should be developed to ensure control of hot spots during start-up. Safe catalyst handling is very important. Care must be taken not to break or crush the catalyst when loading the beds, as the small fines will plug up the reformer screens. Precautions against dust when regenerating or replacing catalyst should also be considered. Also, water wash should be considered where stabilizer fouling has occurred due to the formation of ammonium chloride and iron salts. Ammonium chloride may form in pretreater exchangers and cause corrosion and fouling. Hydrogen chloride from the hydrogenation of chlorine compounds may form acid or ammonium chloride salt. Health Because this is a closed process, exposures are expected to be minimal under normal operating conditions. There is potential

CATALYTIC REFORMING
Catalytic reforming is an important process used to convert low-octane naphthas into high-octane gasoline blending components called reformate. Reforming represents the total effect of numerous reactions such as cracking, polymerization, dehydrogenation, and isomerization taking place simultaneously. Depending on the properties of the naphtha feedstock (as measured by the paraffin, olefin, naphthene, and aromatic content) and catalysts used, reformates can be produced with very high concentrations of toluene, benzene, xylene, and other aromatics useful in gasoline blending and petrochemical processing. Hydrogen, a significant by-product, is separated from the reformate for recycling and use in other processes. A catalytic reformer comprises a reactor section and a product-recovery section. More or less standard is a feed preparation section in which, by combination of hydrotreatment and distillation, the feedstock is prepared to specification. Most processes use platinum as the active catalyst. Sometimes platinum is combined with a second catalyst (bimetallic catalyst) such as rhenium or another noble metal. There are many different commercial catalytic reforming processes including platforming, powerforming, ultraforming, and Thermofor catalytic reforming. In the platforming process, the first step is preparation of the naphtha feed to remove impurities from the naphtha and reduce catalyst degradation. The naphtha feedstock is then mixed with hydrogen, vaporized, and passed through a series of alternating furnace and fixed-bed

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for exposure to hydrogen sulfide and benzene should a leak or release occur. Small emissions of carbon monoxide and hydrogen sulfide may occur during regeneration of catalyst. Safe work practices and/or

appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as noise and heat; during testing, inspecting, maintenance and turnaround activities; and when handling regenerated or spent catalyst.

Table III:2-13 CATALYTIC REFORMING PROCESS Feedstocks Desulfurized naphtha Naphthene-rich fractions Straight-run naphtha From Coker Hydrocracker Hydrodesulfur Atmospheric fractionator Process Rearrange, dehydrogenate Typical products...................... To High octane gasoline................Blending Aromatics.................................Petrochemical Hydrogen.................................Recycle, hydrotreat, etc. Gas...........................................Gas plant

Figure III:2-16 Platforming Process

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CATALYTIC HYDROTREATING
Catalytic hydrotreating is a hydrogenation process used to remove about 90% of contaminants such as nitrogen, sulfur, oxygen, and metals from liquid petroleum fractions. These contaminants, if not removed from the petroleum fractions as they travel through the refinery processing units, can have detrimental effects on the equipment, the catalysts, and the quality of the finished product. Typically, hydrotreating is done prior to processes such as catalytic reforming so that the catalyst is not contaminated by untreated feedstock. Hydrotreating is also used prior to catalytic cracking to reduce sulfur and improve product yields, and to upgrade middle-distillate petroleum fractions into finished kerosene, diesel fuel, and heating fuel oils. In addition, hydrotreating converts olefins and aromatics to saturated compounds. CATALYTIC HYDRODESULFURIZATION PROCESS Hydrotreating for sulfur removal is called hydrodesulfur-ization. In a typical catalytic hydrodesulfurization unit, the feedstock is deaerated and mixed with hydrogen, preheated in a fired heater (600-800 F) and then charged under pressure (up to 1,000 psi) through a fixed-bed catalytic reactor. In the reactor, the sulfur and nitrogen compounds in the feedstock are converted into H2S and NH3. The reaction products leave the reactor and after cooling to a low temperature enter a liquid/gas separator. The hydrogen-rich gas from the high-pressure separation is recycled to combine with the feedstock, and the low-pressure gas stream rich in H2S is sent to a gas treating unit where H2S is removed. The clean gas is then suitable as fuel for the refinery furnaces. The liquid stream is the product from hydrotreating and is normally sent to a stripping column for removal of H2S and other undesirable components. In cases where steam is used for stripping, the product is sent to a vacuum drier for removal of water. Hydrodesulfurized products are blended or used as catalytic reforming feedstock.

OTHER HYDROTREATING PROCESSES Hydrotreating processes differ depending upon the feedstocks available and catalysts used. Hydrotreating can be used to improve the burning characteristics of distillates such as kerosene. Hydrotreatment of a kerosene fraction can convert aromatics into naphthenes, which are cleaner-burning compounds. Lube-oil hydrotreating uses catalytic treatment of the oil with hydrogen to improve product quality. The objectives in mild lube hydrotreating include saturation of olefins and improvements in color, odor, and acid nature of the oil. Mild lube hydrotreating also may be used following solvent processing. Operating temperatures are usually below 600 F and operating pressures below 800 psi. Severe lube hydrotreating, at temperatures in the 600-750 F range and hydrogen pressures up to 3,000 psi, is capable of saturating aromatic rings, along with sulfur and nitrogen removal, to impart specific properties not achieved at mild conditions. Hydrotreating also can be employed to improve the quality of pyrolysis gasoline (pygas), a by-product from the manufacture of ethylene. Traditionally, the outlet for pygas has been motor gasoline blending, a suitable route in view of its high octane number. However, only small portions can be blended untreated owing to the unacceptable odor, color, and gum-forming tendencies of this material. The quality of pygas, which is high in diolefin content, can be satisfactorily improved by hydro-treating, whereby conversion of diolefins into mono-olefins provides an acceptable product for motor gas blending. HEALTH AND SAFETY CONSIDERATIONS Fire Prevention and Protection The potential exists for fire in the event of a leak or release of product or hydrogen gas.

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Table III:2-14 HYDRODESULFURIZATION PROCESS Feedstocks Naphthas, distillates Sour gas oil, Residuals From Atmospheric & vacuum tower Catalytic & thermal cracker Process Treating, hydrogenation Typical products......................To Naphtha....................................Catalytic reformer Hydrogen..................................Recycle Distillates..................................Blending H2S, ammonia...........................Sulfur plant, treater Gas.............................................Gas plant

Safety Many processes require hydrogen generation to provide for a continuous supply. Because of the operating temperatures and presence of hydrogen, the hydrogen sulfide content of the feedstock must be strictly controlled to a minimum to reduce corrosion. Hydrogen chloride may form and condense as hydrochloric acid in the lower-temperature parts of the unit. Ammonium hydrosulfide may form in high-temperature, high-pressure units. Excessive contact time and/or temperature will create coking. Precautions need to be taken when unloading coked catalyst from the unit to prevent iron sulfide fires. The coked catalyst should be cooled to below 120o F before removal,

or dumped into nitrogen-inerted bins where it can be cooled before further handling. Special antifoam additives may be used to prevent catalyst poisoning from silicone carryover in the coker feedstock. Health Because this is a closed process, exposures are expected to be minimal under normal operating conditions. There is a potential for exposure to hydrogen sulfide or hydrogen gas in the event of a release, or to ammonia should a sour-water leak or spill occur. Phenol also may be present if high boiling-point feedstocks are processed. Safe work practices and/or appropriate personal protective equipment may be needed for exposures to

Figure III:2-17 Distillate Hydrodesulffurization

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chemicals and other hazards such as noise and heat; during process sampling, inspection, maintenance, and turnaround activities; and when handling amine or exposed to catalyst.

mixture is sent to a fractionator (deisobutanizer) to separate n-butane from the isobutane product. Pentane/hexane isomerization increases the octane number of the light gasoline components n-pentane and n-hexane, which are found in abundance in straight-run gasoline. In a typical C5/C6 isomerization process, dried and desulfurized feedstock is mixed with a small amount of organic chloride and recycled hydrogen, and then heated to reactor temperature. It is then passed over supported-metal catalyst in the first reactor where benzene and olefins are hydrogenated. The feed next goes to the isomerization reactor where the paraffins are catalytically isomerized to isoparaffins. The reactor effluent is then cooled and subsequently separated in the product separator into two streams: a liquid product (isomerate) and a recycle hydrogen-gas stream. The isomerate is washed (caustic and water), acid stripped, and stabilized before going to storage. SAFETY AND HEALTH CONSIDERATIONS Fire Protection and Prevention Although this is a closed process, the potential for a fire exists should a release or leak contact a source of ignition such as the heater. Safety If the feedstock is not completely dried and desulfurized, the potential exists for acid formation leading to catalyst poisoning and metal corrosion. Water or steam must not be allowed to enter areas where hydrogen chloride is present. Precautions are

ISOMERIZATION
Isomerization converts n-butane, n-pentane and n-hexane into their respective isoparaffins of substantially higher octane number. The straight-chain paraffins are converted to their branched-chain counterparts whose component atoms are the same but are arranged in a different geometric structure. Isomerization is important for the conversion of n-butane into isobutane, to provide additional feedstock for alkylation units, and the conversion of normal pentanes and hexanes into higher branched isomers for gasoline blending. Isomerization is similar to catalytic reforming in that the hydrocarbon molecules are rearranged, but unlike catalytic reforming, isomerization just converts normal paraffins to isoparaffins. There are two distinct isomerization processes, butane (C4) and pentane/hexane (C5/C6). Butane isomerization produces feedstock for alkylation. Aluminum chloride catalyst plus hydrogen chloride are universally used for the low-temperature processes. Platinum or another metal catalyst is used for the higher-temperature processes. In a typical low-temperature process, the feed to the isomerization plant is n-butane or mixed butanes mixed with hydrogen (to inhibit olefin formation) and passed to the reactor at 230-340 F and 200-300 psi. Hydrogen is flashed off in a high-pressure separator and the hydrogen chloride removed in a stripper column. The resultant butane

Table III:2-15 ISOMERIZATION PROCESSES Feedstock n-Butane n-Pentane n-Hexane From Various processes Process Rearrangement Typical products................To Isobutane.........................Alkylation Isopentane........................Blending Isohexane.........................Blending Gas.................................Gas Plant

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Figure III:2-18 C4 Isomerization

Figure II:2-19 C5 and C6 Isomerization

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needed to prevent HCl from entering sewers and drains. Health Because this is a closed process, exposures are expected to be minimal during normal operating conditions. There is a potential for exposure to hydrogen gas, hydrochloric acid, and hydrogen chloride and to dust when solid catalyst is used. Safe work practices and/or appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as heat and noise, and during process sampling, inspection, maintenance, and turnaround activities.

temperatures between 300 and 450 F at pressures from 200 psi to 1,200 psi. The reaction products leaving the reactor are sent to stabilization and/or fractionator systems to separate saturated and unreacted gases from the polymer gasoline product. NOTE: In the petroleum industry, polymerization is used to indicate the production of gasoline components, hence the term "polymer" gasoline. Furthermore, it is not essential that only one type of monomer be involved. If unlike olefin molecules are combined, the process is referred to as "copolymerization." Polymerization in the true sense of the word is normally prevented, and all attempts are made to terminate the reaction at the dimer or trimer (three monomers joined together) stage. However, in the petrochemical section of a refinery, polymerization, which results in the production of, for instance, polyethylene, is allowed to proceed until materials of the required high molecular weight have been produced. SAFETY AND HEALTH CONSIDERATIONS Fire Prevention and Protection Polymerization is a closed process where the potential for a fire could occur due to leaks or releases reaching a source of ignition. Safety The potential for an uncontrolled exothermic reaction exists should loss of cooling water occur. Severe corrosion leading to equipment failure will occur should water make contact with the phosphoric acid, such as during water washing at shutdowns. Corrosion may also occur in piping manifolds,

POLYMERIZATION
Polymerization in the petroleum industry is the process of converting light olefin gases including ethylene, propylene, and butylene into hydrocarbons of higher molecular weight and higher octane number that can be used as gasoline blending stocks. Polymerization combines two or more identical olefin molecules to form a single molecule with the same elements in the same proportions as the original molecules. Polymerization may be accomplished thermally or in the presence of a catalyst at lower temperatures. The olefin feedstock is pretreated to remove sulfur and other undesirable compounds. In the catalytic process the feedstock is either passed over a solid phosphoric acid catalyst or comes in contact with liquid phosphoric acid, where an exothermic polymeric reaction occurs. This reaction requires cooling water and the injection of cold feedstock into the reactor to control

Table III:2-16 POLYMERIZATION PROCESS Feedstocks Olefins From Cracking processes Process Unification Typical products................ To High octane naphtha...........Gasoline blending Petrochem. feedstocks.........Petrochemical Liquefied petro. gas............Storage

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reboilers, exchangers, and other locations where acid may settle out. Health Because this is a closed system, exposures are expected to be minimal under normal operating conditions. There is a potential for exposure to caustic wash (sodium hydroxide), to phosphoric

acid used in the process or washed out during turnarounds, and to catalyst dust. Safe work practices and/or appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as noise and heat, and during process sampling, inspection, maintenance, and turnaround activities.

Figure III:2-20 Polymerization Process

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ALKYLATION
Alkylation combines low-molecular-weight olefins (primarily a mixture of propylene and butylene) with isobutene in the presence of a catalyst, either sulfuric acid or hydrofluoric acid. The product is called alkylate and is composed of a mixture of high-octane, branched-chain paraffinic hydrocarbons. Alkylate is a premium blending stock because it has exceptional antiknock properties and is clean burning. The octane number of the alkylate depends mainly upon the kind of olefins used and upon operating conditions. SULFURIC ACID ALKYLATION PROCESS In cascade type sulfuric acid (H2SO4) alkylation units, the feedstock (propylene, butylene, amylene, and fresh isobutane) enters the reactor and contacts the concentrated sulfuric acid catalyst (in concentrations of 85% to 95% for good operation and to minimize corrosion). The reactor is divided into zones, with olefins fed through distributors to each zone, and the sulfuric acid and isobutanes flowing over baffles from zone to zone. The reactor effluent is separated into hydrocarbon and acid phases in a settler, and the acid is returned to the reactor. The hydrocarbon phase is hot-water washed with caustic for pH control before being successively depropanized, deisobutanized, and debutanized. The alkylate obtained from the deisobutanizer can then go directly to motor-fuel blending or be rerun to produce aviation-grade blending stock. The isobutane is recycled to the feed.

HYDROFLUORIC ACID ALKYLATION PROCESS Phillips and UOP are the two common types of hydro-fluoric acid alkylation processes in use. In the Phillips process, olefin and isobutane feedstock are dried and fed to a combination reactor/settler system. Upon leaving the reaction zone, the reactor effluent flows to a settler (separating vessel) where the acid separates from the hydrocarbons. The acid layer at the bottom of the separating vessel is recycled. The top layer of hydrocarbons (hydrocarbon phase), consisting of propane, normal butane, alkylate, and excess (recycle) isobutane, is charged to the main fractionator, the bottom product of which is motor alkylate. The main fractionator overhead, consisting mainly of propane, isobutane, and HF, goes to a depropanizer. Propane with trace amount of HF goes to an HF stripper for HF removal and is then catalytically defluorinated, treated, and sent to storage. Isobutane is withdrawn from the main fractionator and recycled to the reactor/settler, and alkylate from the bottom of the main fractionator is sent to product blending. The UOP process uses two reactors with separate settlers. Half of the dried feedstock is charged to the first reactor, along with recycle and makeup isobutane. The reactor effluent then goes to its settler, where the acid is recycled and the hydrocarbon charged to the second reactor. The other half of the feedstock also goes to the second reactor, with the settler acid being recycled and the hydrocarbons charged to the main fractionator. Subsequent processing is similar to the Phillips process. Overhead from the main fractionator goes to a depropanizer. Isobutane is recycled to the reaction zone and alkylate is sent to product blending.

Table II:2-17 ALKYLATION PROCESS Feedstocks Petroleum gas Olefins Isobutane From Distillation or cracking Cat. or hydro cracking Isomerization Process Unification Typical products............... To High octane gasoline..........Blending n-Butane & propane...........Stripper or blender

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Figure III:2-21 Sulfuric Acid Alkaylation

Figure III:2-22 Hydrogen Fluoride Alkylation

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HEALTH AND SAFETY CONSIDERATIONS Fire Protection and Prevention Alkylation units are closed processes; however, the potential exists for fire should a leak or release occur that allows product or vapor to reach a source of ignition. Safety Sulfuric acid and hydrofluoric acid are potentially hazardous chemicals. Loss of coolant water, which is needed to maintain process temperatures, could result in an upset. Precautions are necessary to ensure that equipment and materials that have been in contact with acid are handled carefully and are thoroughly cleaned before they leave the process area or refinery. Immersion wash vats are often provided for neutralization of equipment that has come into contact with hydrofluoric acid. Hydrofluoric acid units should be thoroughly drained and chemically cleaned prior to turnarounds and entry to remove all traces of iron fluoride and hydro-fluoric acid. Following shutdown, where water has been used the unit should be thoroughly dried before hydrofluoric acid is introduced. Leaks, spills, or releases involving hydrofluoric acid or hydrocarbons containing hydrofluoric acid can be extremely hazardous. Care during delivery and unloading of acid is essential. Process unit containment by curbs and drainage and isolation so that effluent can be neutralized before release to the sewer system should be considered. Vents can be routed to soda-ash scrubbers to neutralize hydrogen fluoride gas or hydrofluoric acid vapors before release. Pressure on the cooling water and steam side of exchangers should be kept below the minimum pressure on the acid service side to prevent water contamination. Some corrosion and fouling in sulfuric acid units may occur from the breakdown of sulfuric acid esters or where caustic is added for neutralization. These esters can be removed by fresh acid treating and hot-water washing. To prevent corrosion from

hydrofluoric acid, the acid concentration inside the process unit should be maintained above 65% and moisture below 4%. Health Because this is a closed process, exposures are expected to be minimal during normal operations. There is a potential for exposure should leaks, spills, or releases occur. Sulfuric acid and (particularly) hydrofluoric acid are potentially hazardous chemicals. Special precautionary emergency preparedness measures and protection appropriate to the potential hazard and areas possibly affected need to be provided. Safe work practices and appropriate skin and respiratory personal protective equipment are needed for potential exposures to hydro-fluoric and sulfuric acids during normal operations such as reading gauges, inspecting, and process sampling, as well as during emergency response, maintenance, and turnaround activities. Procedures should be in place to ensure that protective equipment and clothing worn in hydrofluoric acid activities are decontaminated and inspected before reissue. Appropriate personal protection for exposure to heat and noise also may be required.

SWEETENING PROCESSES

AND

TREATING

Treating is a means by which contaminants such as organic compounds containing sulfur, nitrogen, and oxygen; dissolved metals and inorganic salts; and soluble salts dissolved in emulsified water are removed from petroleum fractions or streams. Petroleum refiners have a choice of several different treating processes, but the primary purpose of the majority of them is the elimination of unwanted sulfur compounds. A variety of intermediate and finished products, including middle distillates, gasoline, kerosene, jet fuel and sour gases are dried and sweetened. Sweetening, a major refinery treatment of gasoline, treats sulfur compounds (hydrogen sulfide, thiophene and mercaptan) to improve color, odor and oxidation stability. Sweetening also reduces concentrations of carbon dioxide.

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Treating can be accomplished at an intermediate stage in the refining process, or just before sending the finished product to storage. Choices of a treating method depend on the nature of the petroleum fractions, amount and type of impurities in the fractions to be treated, the extent to which the process removes the impurities, and end-product specifications. Treating materials include acids, solvents, alkalis, oxidizing, and adsorption agents. ACID, CAUSTIC, OR CLAY TREATING

blending, propane is recovered for LPG, and propylene is removed for use in petrochemicals. Some mercaptans are removed by water-soluble chemicals that react with the mercaptans. Caustic liquid (sodium hydroxide), amine compounds (diethanolamine) or fixed-bed catalyst sweetening also may be used. Drying is accomplished by the use of water absorption or adsorption agents to remove water from the products. Some processes simultaneously dry and sweeten by adsorption on molecular sieves. SULFUR RECOVERY

Sulfuric acid is the most commonly used acid treating process. Sulfuric acid treating results in partial or complete removal of unsaturated hydrocarbons, sulfur, nitrogen, and oxygen compounds, and resinous and asphaltic compounds. It is used to improve the odor, color, stability, carbon residue, and other properties of the oil. Clay/lime treatment of acid-refined oil removes traces of asphaltic materials and other compounds improving product color, odor, and stability. Caustic treating with sodium (or potassium) hydroxide is used to improve odor and color by removing organic acids (naphthenic acids, phenols) and sulfur compounds (mercaptans, H2S) by a caustic wash. By combining caustic soda solution with various solubility promoters (e.g., methyl alcohol and cresols), up to 99% of all mercaptans as well as oxygen and nitrogen compounds can be dissolved from petroleum fractions. DRYING AND SWEETENING Feedstocks from various refinery units are sent to gas treating plants where butanes and butenes are removed for use as alkylation feedstock, heavier components are sent to gasoline

Sulfur recovery converts hydrogen sulfide in sour gases and hydrocarbon streams to elemental sulfur. The most widely used recovery system is the Claus process, which uses both thermal and catalytic-conversion reactions. A typical process produces elemental sulfur by burning hydrogen sulfide under controlled conditions. Knockout pots are used to remove water and hydrocarbons from feed gas streams. The gases are then exposed to a catalyst to recover additional sulfur. Sulfur vapor from burning and conversion is condensed and recovered. HYDROGEN SULFIDE SCRUBBING Hydrogen sulfide scrubbing is a common treating process in which the hydrocarbon feedstock is first scrubbed to prevent catalyst poisoning. Depending on the feedstock and the nature of contaminants, desulfurization methods vary from ambient temperature-activated charcoal absorption to high-temperature catalytic hydrogenation followed by zinc oxide treating.

Table III:2-18 SWEETENING AND TREATING PROCESSES

Feedstocks Gases Finished products Intermediates

From Various

Process Treatment

Products........................To Butane & butene..............Alkylation Propane, distillates...........Storage Gasoline........................Blending Propylene......................Petrochemical

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Figure III:2-23 Molecular Sieve Drying and Sweetening HEALTH AND SAFETY CONSIDERATIONS Fire Protection and Prevention The potential exists for fire from a leak or release of feedstock or product. Sweetening processes use air or oxygen. If excess oxygen enters these processes, it is possible for a fire to occur in the settler due to the generation of static electricity, which acts as the ignition source. Health Because these are closed processes, exposures are expected to be minimal under normal operating conditions. There is a potential for exposure to hydrogen sulfide, caustic (sodium hydroxide), spent caustic, spent catalyst (Merox), catalyst dust and sweetening agents (sodium carbonate and sodium bicarbonate). Safe work practices and/or appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as noise and heat, and during process sampling, inspection, maintenance, and turnaround activities.

UNSATURATED GAS PLANTS

Unsaturated (unsat) gas plants recover light hydrocarbons (C3 and C4 olefins) from wet gas streams from the FCC, TCC, and delayed coker overhead accumulators or fractionation receivers. In a typical unsat gas plant, the gases are compressed and treated with amine to remove hydrogen sulfide either before or after they are sent to a fractionating absorber where they are mixed into a concurrent flow of debutanized gasoline. The light fractions are separated by heat in a reboiler, the offgas is sent to a sponge absorber, and the bottoms are sent to a debutanizer. A portion of the debutanized hydrocarbon is recycled, with the balance sent to the splitter for separation. The overhead gases go to a depropanizer for use as alkylation unit feedstock.

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Table III:2-19 UNSAT GAS PLANT PROCESS Feedstock Gas Oils From FCC,TCC, Delayed coker Process Treatment Typical products.................. To Gasoline................................ Recycle or treating Gases..................................... Alkylation

HEALTH AND SAFETY CONSIDERATIONS Fire Prevention and Protection The potential of a fire exists should spills, releases, or vapors reach a source of ignition. Safety

counterflowing amine solutions (i.e., MEA, DEA, MDEA). The stripped gas or liquid is removed overhead, and the amine is sent to a regenerator. In the regenerator, the acidic components are stripped by heat and reboiling action and disposed of, and the amine is recycled. HEALTH AND SAFETY CONSIDERATIONS Fire Protection and Prevention

In unsat gas plants handling FCC feedstocks, the potential exists for corrosion from moist hydrogen sulfide and cyanides. When feedstocks are from the delayed coker or the TCC, corrosion from hydrogen sulfide and deposits in the high pressure sections of gas compressors from ammonium compounds is possible. Health Because these are closed processes, exposures are expected to be minimal under normal operating conditions. There is a potential for exposures to amine compounds such as monoethanolamine (MEA), diethanolamine (DEA) and methyldiethanolamine (MDEA) and hydrocarbons. Safe work practices and/or appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as noise and heat, and during process sampling, inspection, maintenance, and turnaround activities.

The potential for fire exists where a spill or leak could reach a source of ignition. Safety To minimize corrosion, proper operating practices should be established and regenerator bottom and reboiler temperatures controlled. Oxygen should be kept out of the system to prevent amine oxidation. Health Because this is a closed process, exposures are expected to be minimal during normal operations. There is potential for exposure to amine compounds (i.e., monoethanolamine, diethanolamine, methyldiethanol-amine), hydrogen sulfide and carbon dioxide. Safe work practices and/or appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as noise and heat, and during process sampling, inspection, maintenance and turnaround activities.

AMINE PLANTS
Amine plants remove acid contaminants from sour gas and hydrocarbon streams. In amine plants, gas and liquid hydrocarbon streams containing carbon dioxide and/or hydrogen sulfide are charged to a gas absorption tower or liquid contactor where the acid contaminants are absorbed by

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SATURATE GAS PLANTS

Saturate gas plants separate refinery gas components including butanes for alkylation, pentanes for gasoline blending, LPGs for fuel, and ethane for petrochemicals. Because sat gas processes depend on the feedstock and product demand, each refinery uses different systems, usually absorption-fractionation or straight fractionation. In absorption-fractionation, gases and liquids from various refinery units are fed to an absorber-deethanizer where C2 and lighter fractions are separated from heavier fractions by lean oil absorption and removed for use as fuel gas or petrochemical feed. The heavier fractions are stripped and sent to a debutanizer, and the lean oil is recycled back to the absorber-deethanizer. C3/C4 is separated from pentanes in the debutanizer, scrubbed to remove hydrogen sulfide, and fed to a splitter where propane and butane are separated. In fractionation sat-gas plants, the absorption stage is eliminated. HEALTH AND SAFETY CONSIDERATIONS Fire Protection and Prevention There is potential for fire if a leak or release reaches a source of ignition such as the unit reboiler. Safety Corrosion could occur from the presence of hydrogen sulfide, carbon dioxide, and other compounds as a result of prior treating. Streams containing ammonia should be dried before processing. Antifouling additives may be used in absorption oil to protect heat exchangers. Corrosion inhibitors may be used to control corrosion in overhead systems. Health Because this is a closed process, exposures are expected to be minimal during normal operations. There is potential for exposure to hydrogen sulfide, carbon dioxide, and other

products such as diethanolamine or sodium hydroxide carried over from prior treating. Safe work practices and/or appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as noise and heat, and during process sampling, inspection, maintenance, and turnaround activities.

ASPHALT PRODUCTION
Asphalt is a portion of the residual fraction that remains after primary distillation operations. It is further processed to impart characteristics required by its final use. In vacuum distillation, generally used to produce road-tar asphalt, the residual is heated to about 750 F and charged to a column where vacuum is applied to prevent cracking. Asphalt for roofing materials is produced by air blowing. Residual is heated in a pipe still almost to its flash point and charged to a blowing tower where hot air is injected for a predetermined time. The dehydrogen-ization of the asphalt forms hydrogen sulfide, and the oxidation creates sulfur dioxide. Steam, used to blanket the top of the tower to entrain the various contaminants, is then passed through a scrubber to condense the hydrocarbons. A third process used to produce asphalt is solvent deasphalting. In this extraction process, which uses propane (or hexane) as a solvent, heavy oil fractions are separated to produce heavy lubricating oil, catalytic cracking feedstock, and asphalt. Feedstock and liquid propane are pumped to an extraction tower at precisely controlled mixtures, temperatures (150-250 F), and pressures of 350-600 psi. Separation occurs in a rotating disc contactor, based on differences in solubility. The products are then evaporated and steam stripped to recover the propane, which is recycled. Deasphalting also removes some sulfur and nitrogen compounds, metals, carbon residues, and paraffins from the feedstock.

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Table III:2-20. SOLVENT DEASPHALTING PROCESS Feedstock Residual Reduced crude From Process Typical products.....................To Heavy lube oil..........................Treating or lube blending Asphalt.....................................Storage or shipping Deasphalted oil.........................Hydrotreat & catalytic cracker Propane.....................................Recycle

Vacuum tower Treatment Atmospheric tower

SAFETY AND HEALTH CONSIDERATIONS Fire Protection and Prevention The potential for a fire exists if a product leak or release contacts a source of ignition such as the process heater. Condensed steam from the various asphalt and deasphalting processes will contain trace amounts of hydrocarbons. Any disruption of the vacuum can result in the entry of atmospheric air and subsequent fire. In addition, raising the temperature of the vacuum tower bottom to improve efficiency can generate methane by thermal cracking. This can create vapors in asphalt storage tanks that are not detectable by flash testing but are high enough to be flammable. Safety Deasphalting requires exact temperature and pressure control. In addition, moisture, excess solvent, or a drop in operating temperature may cause foaming, which affects the product temperature control and may create an upset. Health Because these are closed processes, exposures are expected to be minimal during normal operations. Should a spill or release occur, there is a potential for exposure to residuals and asphalt. Air blowing can create some polynuclear aromatics. Condensed steam from the air-blowing asphalt process may also contain contaminants. The potential for exposure to hydrogen sulfide and sulfur dioxide exists in the production of asphalt. Safe work

practices and/or appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as noise and heat, and during process sampling, inspection, maintenance, and turnaround activities.

HYDROGEN PRODUCTION
High-purity hydrogen (95-99%) is required for hydro-desulfurization, hydrogenation, hydrocracking, and petrochemical processes. Hydrogen, produced as a by-product of refinery processes (principally hydrogen recovery from catalytic reformer product gases), often is not enough to meet the total refinery requirements, necessitating the manufacturing of additional hydrogen or obtaining supply from external sources. In steam-methane reforming, desulfurized gases are mixed with superheated steam (1,100-1,600 F) and reformed in tubes containing a nickel base catalyst. The reformed gas, which consists of steam, hydrogen, carbon monoxide, and carbon dioxide, is cooled and passed through converters containing an iron catalyst where the carbon monoxide reacts with steam to form carbon dioxide and more hydrogen. The carbon dioxide is removed by amine washing. Any remaining carbon monoxide in the product stream is converted to methane. Steam-naphtha reforming is a continuous process for the production of hydrogen from liquid hydrocarbons and is, in fact, similar to steam-methane reforming. A variety of naphthas in the gasoline boiling range may be employed, including fuel containing up to 35% aromatics. Following pretreatment to

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Table III:2-21. STEAM REFORMING PROCESS Feedstock Desulfurized refinery gas From Various treatment units Process Decomposition Typical products.....................To Hydrogen.................................Processing Carbon dioxide........................Atmosphere Carbon monoxide....................Methane

remove sulfur compounds, the feedstock is mixed with steam and taken to the reforming furnace (1,250-1,500 F) where hydrogen is produced. HEALTH AND SAFETY CONSIDERATIONS Fire Protection and Prevention The possibility of fire exists should a leak or release occur and reach an ignition source. Safety The potential exists for burns from hot gases and superheated steam should a release occur. Inspections and testing should be considered where the possibility exists for valve failure due to contaminants in the hydrogen. Carryover from caustic scrubbers should be controlled to prevent corrosion in preheaters. Chlorides from the feedstock or steam system should be prevented from entering reformer tubes and contaminating the catalyst. Health Because these are closed processes, exposures are expected to be minimal during normal operating conditions. There is a potential for exposure to excess hydrogen, carbon monoxide, and/or carbon dioxide. Condensate can be contaminated by process materials such as caustics and amine compounds, with resultant exposures. Depending on the specific process used, safe work practices and/or appropriate personal protective equipment may be needed for exposures to chemicals and other

hazards such as noise and heat, and during process sampling, inspection, maintenance, and turnaround activities.

BLENDING
Blending is the physical mixture of a number of different liquid hydrocarbons to produce a finished product with certain desired characteristics. Products can be blended in-line through a manifold system, or batch blended in tanks and vessels. In-line blending of gasoline, distillates, jet fuel, and kerosene is accomplished by injecting proportionate amounts of each component into the main stream where turbulence promotes thorough mixing. Additives including octane enhancers, metal deactivators, anti-oxidants, anti-knock agents, gum and rust inhibitors, detergents, etc. are added during and/or after blending to provide specific properties not inherent in hydrocarbons. HEALTH AND SAFETY CONSIDERATIONS Fire Prevention and Protection Ignition sources in the area need to be controlled in the event of a leak or release. Health Safe work practices and/or appropriate personal protective equipment may be needed for exposures to chemicals and other hazards such as noise and heat; when handling additives; and during inspection, maintenance, and turnaround activities.

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LUBRICANT, WAX, AND GREASE MANUFACTURING PROCESSES

Lubricating oils and waxes are refined from the residual fractions of atmospheric and vacuum distillation. The primary objective of the various lubricating oil refinery processes is to remove asphalts, sulfonated aromatics, and paraffinic and isoparaffinic waxes from residual fractions. Reduced crude from the vacuum unit is deasphalted and combined with straight-run lubricating oil feedstock, preheated, and solvent-extracted (usually with phenol or furfural) to produce raffinate. WAX MANUFACTURING PROCESS Raffinate from the extraction unit contains a considerable amount of wax that must be removed by solvent extraction and crystallization. The raffinate is mixed with a solvent (propane) and precooled in heat exchangers. The crystallization temperature is attained by the evaporation of propane in the chiller and filter feed tanks. The wax is continuously removed by filters and cold solvent-washed to recover retained oil. The solvent is recovered from the oil by flashing and steam stripping. The wax is then heated with hot solvent, chilled, filtered, and given a final wash to remove all oil. LUBRICATING OIL PROCESS The dewaxed raffinate is blended with other distillate fractions and further treated for viscosity index, color, stability, carbon residue, sulfur, additive response, and oxidation stability in extremely selective extraction processes using solvents (furfural,

phenol, etc.). In a typical phenol unit, the raffinate is mixed with phenol in the treating section at temperatures below 400 F. Phenol is then separated from the treated oil and recycled. The treated lube-oil base stocks are then mixed and/or compounded with additives to meet the required physical and chemical characteristics of motor oils, industrial lubricants, and metal working oils. GREASE COMPOUNDING Grease is made by blending metallic soaps (salts of long-chained fatty acids) and additives into a lubricating oil medium at temperatures of 400-600 F. Grease may be either batch-produced or continuously compounded. The characteristics of the grease depend to a great extent on the metallic element (calcium, sodium, aluminum, lithium, etc.) in the soap and the additives used. SAFETY AND HEALTH CONSIDERATIONS Fire Protection and Prevention The potential for fire exists if a product or vapor leak or release in the lube blending and wax processing areas reaches a source of ignition. Storage of finished products, both bulk and packaged, should be in accordance with recognized practices. While the potential for fire is reduced in lube oil blending, care must be taken when making metal-working oils and compounding greases due to the use of higher blending and compounding temperatures and lower flash point products.

Table III:2-22 LUBRICATING OIL AND WAX MANUFACTURING PROCESSES Feedstock Lube feedstock and additives From Vacuum tower, solvent dewaxing, hydrotreating solvent extraction, etc. Process Treatment Typical products................To Lube blend or compound Grease compounding Wax............................... Storage or shipping Dewaxed raffinate.............

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Safety Control of treater temperature is important as phenol can cause corrosion above 400 F. Batch and in-line blending operations require strict controls to maintain desired product quality. Spills should be cleaned and leaks repaired to avoid slips and falls. Additives in drums and bags need to be handled properly to avoid strain. Wax can clog sewer or oil drainage systems and interfere with wastewater treatment.

Health When blending, sampling, and compounding, personal protection from steam, dusts, mists, vapors, metallic salts, and other additives is appropriate. Skin contact with any formulated grease or lubricant should be avoided. Safe work practices and/or appropriate personal protection may be needed for exposures to chemicals and other hazards such as noise and heat; during inspection, maintenance, and turnaround activities; and while sampling and handling hydrocarbons and chemicals during the production of lubricating oil and wax.

E. OTHER REFINERY OPERATIONS

HEAT EXCHANGERS, COOLERS, AND PROCESS HEATERS
HEATING OPERATIONS Process heaters and heat exchangers preheat feedstocks in distillation towers and in refinery processes to reaction temperatures. Heat exchangers use either steam or hot hydrocarbon transferred from some other section of the process for heat input. The heaters are usually designed for specific process operations, and most are of cylindrical vertical or box-type designs. The major portion of heat provided to process units comes from fired heaters fueled by refinery or natural gas, distillate, and residual oils. Fired heaters are found on crude and reformer preheaters, coker heaters, and large-column reboilers. COOLING OPERATIONS Heat also may be removed from some processes by air and water exchangers, fin fans, gas and liquid coolers, and overhead condensers, or by transferring heat to other systems. The basic mechanical vapor-compression refrigeration system, which may serve one or more process units, includes an evaporator, compressor, condenser, controls, and piping. Common coolants are water, alcohol/water mixtures, or various glycol solutions. HEALTH AND SAFETY CONSIDERATIONS Fire Protection and Prevention A means of providing adequate draft or steam purging is required to reduce the chance of explosions when lighting fires in heater furnaces. Specific start-up and emergency procedures are required for each type of unit. If fire impinges on fin fans, failure could occur due to overheating. If flammable product escapes from a heat exchanger or cooler due to a leak, fire could occur. Safety Care must be taken to ensure that all pressure is removed from heater tubes before removing header or fitting plugs. Consideration should be given to providing for pressure relief in heat-exchanger piping systems in the event they are blocked off while full of liquid. If controls fail, variations of temperature and pressure could occur on either side of the heat exchanger. If heat exchanger tubes fail and process pressure is greater than heater pressure, product could enter the heater with downstream consequences. If the process pressure is less than heater

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pressure, the heater stream could enter into the process fluid. If loss of circulation occurs in liquid or gas coolers, increased product temperature could affect downstream operations and require pressure relief. Health Because these are closed systems, exposures under normal operating conditions are expected to be minimal. Depending on the fuel, process operation, and unit design, there is a potential for exposure to hydrogen sulfide, carbon monoxide, hydrocarbons, steam boiler feed-water sludge, and water-treatment chemicals. Skin contact should be avoided with boiler blowdown, which may contain phenolic compounds. Safe work practices and/or appropriate personal protective equipment against hazards may be needed during process maintenance, inspection, and turnaround activities and for protection from radiant heat, superheated steam, hot hydrocarbon, and noise exposures.

off-gas is collected from process units and combined with natural gas and LPG in a fuel-gas balance drum. The balance drum provides constant system pressure, fairly stable Btu-content fuel, and automatic separation of suspended liquids in gas vapors, and it prevents carryover of large slugs of condensate into the distribution system. Fuel oil is typically a mix of refinery crude oil with straight-run and cracked residues and other products. The fuel-oil system delivers fuel to process-unit heaters and steam generators at required temperatures and pressures. The fuel oil is heated to pumping temperature, sucked through a coarse suction strainer, pumped to a temperature-control heater, and then pumped through a fine-mesh strainer before being burned. In one example of process-unit heat generation, carbon monoxide boilers recover heat in catalytic cracking units as carbon monoxide in flue gas is burned to complete combustion. In other processes, waste-heat recovery units use heat from the flue gas to make steam. STEAM DISTRIBUTION The distribution system consists of valves, fittings, piping, and connections suitable for the pressure of the steam transported. Steam leaves the boilers at the highest pressure required by the process units or electrical generation. The steam pressure is then reduced in turbines that drive process pumps and compressors. Most steam used in the refinery is condensed to water in various types of heat exchangers. The condensate is reused as boiler feedwater or discharged to wastewater treatment. When refinery steam is also used to drive steam turbine generators to produce electricity, the steam must be produced at much higher pressure than required for process steam. Steam typically is generated by heaters (furnaces) and boilers combined in one unit. FEEDWATER Feedwater supply is an important part of steam generation. There must always be as many pounds of water entering the system as there are pounds of steam leaving it. Water used in steam generation must be free of contaminants including

STEAM GENERATION
HEATER AND BOILER OPERATIONS Steam is generated in main generation plants, and/or at various process units using heat from flue gas or other sources. Heaters (furnaces) include burners and a combustion air system, the boiler enclosure in which heat transfer takes place, a draft or pressure system to remove flue gas from the furnace, soot blowers, and compressed-air systems that seal openings to prevent the escape of flue gas. Boilers consist of a number of tubes that carry the water-steam mixture through the furnace for maximum heat transfer. These tubes run between steam-distribution drums at the top of the boiler and water-collecting drums at the bottom of the boiler. Steam flows from the steam drum to the superheater before entering the steam distribution system. HEATER FUEL Heaters may use any one or combination of fuels including refinery gas, natural gas, fuel oil, and powdered coal. Refinery

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minerals and dissolved impurities that can damage the system or affect its operation. Suspended materials such as silt, sewage, and oil, which form scale and sludge, must be coagulated or filtered out of the water. Dissolved gases, particularly carbon dioxide and oxygen, cause boiler corrosion and are removed by deaeration and treatment. Dissolved minerals including metallic salts, calcium, carbonates, etc., that cause scale, corrosion, and turbine blade deposits are treated with lime or soda ash to precipitate them from the water. Recirculated cooling water must also be treated for hydrocarbons and other contaminants. Depending on the characteristics of raw boiler feedwater, some or all of the following six stages of treatment will be applicable: (1) (2) (3) (4) (5) (6) Clarification Sedimentation Filtration Ion exchange Deaeration Internal treatment

scale on turbine blades and superheater tubes. Care must be taken not to overheat the superheater during startup and shut-down. Alternate fuel sources should be provided in the event of loss of gas due to refinery unit shutdown or emergency. Knockout pots provided at process units remove liquids from fuel gas before burning. Health Safe work practices and/or appropriate personal protective equipment may be needed for potential exposures to feedwater chemicals, steam, hot water, radiant heat, and noise, and during process sampling, inspection, maintenance, and turnaround activities.

PRESSURE-RELIEF AND FLARE SYSTEMS

PRESSURE-RELIEF SYSTEMS Pressure-relief systems control vapors and liquids that are released by pressure-relieving devices and blow-downs. Pressure relief is an automatic, planned release when operating pressure reaches a predetermined level. Blowdown normally refers to the intentional release of material, such as blowdowns from process unit startups, furnace blowdowns, shutdowns, and emergencies. Vapor depressuring is the rapid removal of vapors from pressure vessels in case of fire. This may be accom-plished by the use of a rupture disc, usually set at a higher pressure than the relief valve. SAFETY RELIEF VALVE OPERATIONS Safety relief valves, used for air, steam, and gas as well as for vapor and liquid, allow the valve to open in proportion to the increase in pressure over the normal operating pressure. Safety valves designed primarily to release high volumes of steam usually pop open to full capacity. The overpressure needed to open liquid-relief valves where large-volume discharge is not required increases as the valve lifts due to increased spring resistance. Pilot-operated safety relief valves, with up to six times the capacity of normal relief valves, are used where tighter

HEALTH AND SAFETY CONSIDERATIONS Fire Protection and Prevention The most potentially hazardous operation in steam generation is heater startup. A flammable mixture of gas and air can build up as a result of loss of flame at one or more burners during light-off. Each type of unit requires specific startup and emergency procedures including purging before lightoff and in the event of misfire or loss of burner flame. Safety If feedwater runs low and boilers are dry, the tubes will overheat and fail. Conversely, excess water will be carried over into the steam distribution system and damage the turbines. Feedwater must be free of contaminants that could affect operations. Boilers should have continuous or intermittent blowdown systems to remove water from steam drums and limit buildup of

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sealing and larger volume discharges are required. Nonvolatile liquids are usually pumped to oil-water separation and recovery systems, and volatile liquids are sent to units operating at a lower pressure. FLARE SYSTEMS

(3)

Rapid vaporization and pressure increase from injection of a lower boiling-point liquid including water into a process vessel operating at higher temperatures. Expansion of vapor and resultant over-pressure due to overheated process steam, malfunctioning heaters, or fire. Failure of automatic controls, closed outlets, heat exchanger failure, etc. Internal explosion, chemical reaction, thermal expansion, or accumulated gases.

(4) A typical closed pressure release and flare system includes relief valves and lines from process units for collection of discharges, knockout drums to separate vapors and liquids, seals, and/or purge gas for flashback protection, and a flare and igniter system which combusts vapors when discharging directly to the atmosphere is not permitted. Steam may be injected into the flare tip to reduce visible smoke. PRESSURE RELIEF CONSIDERATIONS HEALTH AND SAFETY

(5) (6)

Fire Protection and Prevention Vapors and gases must not discharge where sources of ignition could be present. Safety Liquids should not be discharged directly to a vapor disposal system. Flare knockout drums and flares need to be large enough to handle emergency blowdowns. Drums should be provided with relief in the event of over pressure. Pressure relief valves must be provided where the potential exists for overpressure in refinery processes due to the following causes: (1) Loss of cooling water, which may greatly reduce pressure in condensers and increase the pressure in the process unit. Loss of reflux volume, which may cause a pressure drop in condensers and a pressure rise in distillation towers because the quantity of reflux affects the volume of vapors leaving the distillation tower.

Maintenance is important because valves are required to function properly. The most common operating problems are listed below. (1) Failure to open at set pressure, because of plugging of the valve inlet or outlet, or because corrosion prevents proper operation of the disc holder and guides. Failure to reseat after popping open due to fouling, corrosion, or deposits on the seat or moving parts, or because solids in the gas stream have cut the valve disc. Chattering and premature opening, because operating pressure is too close to the set point.

(2)

(3)

Health Safe work practices and/or appropriate personal protective equipment may be needed to protect against hazards during inspection, maintenance, and turnaround activities.

(2)

WASTEWATER TREATMENT
Wastewater treatment is used for process, runoff, and sewerage water prior to discharge or recycling. Wastewater typically contains hydrocarbons, dissolved materials, suspended solids,

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phenols, ammonia, sulfides, and other compounds. Wastewater includes condensed steam, stripping water, spent caustic solutions, cooling tower and boiler blowdown, wash water, alkaline and acid waste neutralization water, and other process-associated water. PRETREATMENT OPERATIONS

activated carbon adsorption, etc. Compressed oxygen is diffused into wastewater streams to oxidize certain chemicals or to satisfy regulatory oxygen-content requirements. Wastewater that is to be recycled may require cooling to remove heat and/or oxidation by spraying or air stripping to remove any remaining phenols, nitrates, and ammonia. HEALTH AND SAFETY CONSIDERATIONS

Pretreatment is the separation of hydrocarbons and solids from wastewater. API separators, interceptor plates, and settling ponds remove suspended hydrocarbons, oily sludge, and solids by gravity separation, skimming, and filtration. Some oil-in-water emulsions must be heated first to assist in separating the oil and the water. Gravity separation depends on the specific gravity differences between water and immiscible oil globules, which allows free oil to be skimmed off the surface of the wastewater. Acidic wastewater is neutralized using ammonia, lime, or soda ash. Alkaline wastewater is treated with sulfuric acid, hydrochloric acid, carbon dioxide-rich flue gas, or sulfur. SECONDARY TREATMENT OPERATIONS After pretreatment, suspended solids are removed by sedimentation or air flotation. Wastewater with low levels of solids may be screened or filtered. Flocculation agents are sometimes added to help separation. Secondary treatment processes biologically degrade and oxidize soluble organic matter by the use of activated sludge, unaerated or aerated lagoons, trickling filter methods, or anaerobic treatments. Materials with high adsorption characteristics are used in fixed-bed filters or added to the wastewater to form a slurry which is removed by sedimentation or filtration. Additional treatment methods are used to remove oils and chemicals from wastewater. Stripping is used on wastewater containing sulfides and/or ammonia, and solvent extraction is used to remove phenols. TERTIARY TREATMENT OPERATIONS Tertiary treatments remove specific pollutants to meet regulatory discharge requirements. These treatments include chlorination, ozonation, ion exchange, reverse osmosis,

Fire Protection and Prevention The potential for fire exists if vapors from wastewater containing hydrocarbons reach a source of ignition during treatment. Health Safe work practices and/or appropriate personal protective equipment may be needed for exposures to chemicals and waste products during process sampling, inspection, maintenance, and turnaround activities as well as to noise, gases, and heat.

COOLING TOWERS
Cooling towers remove heat from process water by evaporation and latent heat transfer between hot water and air. The two types of towers are crossflow and counterflow. Crossflow towers introduce the airflow at right angles to the water flow throughout the structure. In counterflow cooling towers, hot process water is pumped to the uppermost plenum and allowed to fall through the tower. Numerous slats or spray nozzles located throughout the length of the tower disperse the water and help in cooling. Air enters at the tower bottom and flows upward against the water. When the fans or blowers are at the air inlet, the air is considered to be forced draft. Induced draft is when the fans are at the air outlet.

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COOLING WATER Recirculated cooling water must be treated to remove impurities and dissolved hydrocarbons. Because the water is saturated with oxygen from being cooled with air, the chances for corrosion are increased. One means of corrosion prevention is the addition of a material to the cooling water that forms a protective film on pipes and other metal surfaces. HEALTH AND SAFETY CONSIDERATIONS Fire Prevention and Protection When cooling water is contaminated by hydrocarbons, flammable vapors can be evaporated into the discharge air. If a source of ignition is present, or if lightning occurs, a fire may start. A potential fire hazard also exists where there are relatively dry areas in induced-draft cooling towers of combustible construction. Safety Loss of power to cooling tower fans or water pumps could have serious consequences in the operation of the refinery. Impurities in cooling water can corrode and foul pipes and heat exchangers, scale from dissolved salts can deposit on pipes, and wooden cooling towers can be damaged by microorganisms. Health Cooling-tower water can be contaminated by process materials and by-products including sulfur dioxide, hydrogen sulfide, and carbon dioxide, with resultant exposures. Safe work practices and/or appropriate personal protective equipment may be needed during process sampling, inspection, maintenance, and turnaround activities; and for exposure to hazards such as those related to noise, water-treatment chemicals, and hydrogen sulfide when wastewater is treated in conjunction with cooling towers.

ELECTRIC POWER
Refineries may receive electricity from outside sources or produce their own power with generators driven by steam turbines or gas engines. Electrical substations receive power from the utility or power plant for distribution throughout the facility. They are usually located in nonclassified areas, away from sources of vapor or cooling-tower water spray. Transformers, circuit breakers, and feed-circuit switches are usually located in substations. Substations feed power to distribution stations within the process unit areas. Distribution stations can be located in classified areas, providing that classification requirements are met. Distribution stations usually have a liquid-filled transformer and an oil-filled or air-break disconnect device. HEALTH AND SAFETY CONSIDERATIONS Fire Protection and Prevention Generators that are not properly classified and are located too close to process units may be a source of ignition should a spill or release occur. Safety Normal electrical safety precautions including dry footing, high-voltage warning signs, and guarding must be taken to protect against electrocution. Lockout/tagout and other appropriate safe work practices must be established to prevent energization while work is being performed on high-voltage electrical equipment. Health Safe work practices and/or the use of appropriate personal protective equipment may be needed for exposures to noise, for exposure to hazards during inspection and maintenance activities, and when working around transformers and switches that may contain a dielectric fluid which requires special handling precautions.

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GAS AND AIR COMPRESSORS

Both reciprocating and centrifugal compressors are used throughout the refinery for gas and compressed air. Air compressor systems include compressors, coolers, air receivers, air dryers, controls, and distribution piping. Blowers are used to provide air to certain processes. Plant air is provided for the operation of air-powered tools, catalyst regeneration, process heaters, steam-air decoking, sour-water oxidation, gasoline sweetening, asphalt blowing, and other uses. Instrument air is provided for use in pneumatic instruments and controls, air motors and purge connections. HEALTH AND SAFETY CONSIDERATIONS Fire Protection and Prevention Air compressors should be located so that the suction does not take in flammable vapors or corrosive gases. There is a potential for fire should a leak occur in gas compressors. Safety Knockout drums are needed to prevent liquid surges from entering gas compressors. If gases are contaminated with solid materials, strainers are needed. Failure of automatic compressor controls will affect processes. If maximum pressure could potentially be greater than compressor or process-equipment design pressure, pressure relief should be provided. Guarding is needed for exposed moving parts on compressors. Compressor buildings should be properly electrically classified, and provisions should be made for proper ventilation. Where plant air is used to back up instrument air, interconnections must be upstream of the instrument air drying system to prevent contamination of instruments with moisture. Alternate sources of instrument air supply, such as use of nitrogen, may be needed in the event of power outages or compressor failure.

Health Safe work practices and/or appropriate personal protective equipment may be needed for exposure to hazards such as noise and during inspection and maintenance activities. The use of appropriate safeguards must be considered so that plant and instrument air is not used for breathing or pressuring potable water systems.

MARINE, TANK CAR, AND TANK TRUCK LOADING and UNLOADING

Facilities for loading liquid hydrocarbons into tank cars, tank trucks, and marine vessels and barges are usually part of the refinery operations. Product characteristics, distribution needs, shipping requirements, and operating criteria are important when designing loading facilities. Tank trucks and rail tank cars are either top- or bottom-loaded, and vapor-recovery systems may be provided where required. Loading and unloading liquefied petroleum gas (LPG) require special considerations in addition to those for liquid hydrocarbons. HEALTH AND SAFETY CONSIDERATIONS Fire Protection and Prevention The potential for fire exists where flammable vapors from spills or releases can reach a source of ignition. Where switch-loading is permitted, safe practices need to be established and followed. Bonding is used to equalize the electrical charge between the loading rack and the tank truck or tank car. Grounding is used at truck and rail loading facilities to prevent flow of stray currents. Insulating flanges are used on marine dock piping connections to prevent static electricity buildup and discharge. Flame arrestors should be installed in loading rack and marine vapor-recovery lines to prevent flashback.

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Safety Automatic or manual shutoff systems at supply headers are needed for top and bottom loading in the event of leaks or overfills. Fall protection such as railings are needed for top-loading racks where employees are exposed to falls. Drainage and recovery systems may be provided for storm drainage and to handle spills and leaks. Precautions must be taken at LPG loading facilities not to overload or overpressurize tank cars and trucks. Health The nature of the health hazards at loading and unloading facilities depends upon the products being loaded and the products previously transported in the tank cars, tank trucks, or marine vessels. Safe work practices and/or appropriate personal protective equipment may be needed to protect against hazardous exposures when loading or unloading, cleaning up spills or leaks, or when gauging, inspecting, sampling, or performing maintenance activities on loading facilities or vapor-recovery systems.

devices. Consideration should be given to providing governors and overspeed control devices on turbines. Health Safe work practices and/or appropriate personal protective equipment may be needed for noise, steam and heat exposures, and during inspection and maintenance activities.

PUMPS, PIPING AND VALVES

Centrifugal and positive-displacement (i.e., reciprocating) pumps are used to move hydrocarbons, process water, fire water, and wastewater through piping within the refinery. Pumps are driven by electric motors, steam turbines, or internal combustion engines. The pump type, capacity, and construction materials depend on the service for which it is used. Process and utility piping distribute hydrocarbons, steam, water, and other products throughout the facility. Their size and construction depend on the type of service, pressure, temperature, and nature of the products. Vent, drain, and sample connections are provided on piping, as well as provisions for blanking. Different types of valves are used depending on their operating purpose. These include gate valves, bypass valves, globe and ball valves, plug valves, block and bleed valves, and check valves. Valves can be manually or automatically operated. HEALTH AND SAFETY CONSIDERATIONS

TURBINES
Turbines are usually gas- or steam-powered and are typically used to drive pumps, compressors, blowers, and other refinery process equipment. Steam enters turbines at high temperatures and pressures, expands across and drives rotating blades while directed by fixed blades. HEALTH AND SAFETY CONSIDERATIONS Safety

Fire Protection and Prevention Steam turbines used for exhaust operating under vacuum should have safety relief valves on the discharge side, both for protection and to maintain steam in the event of vacuum failure. Where maximum operating pressure could be greater than design pressure, steam turbines should be provided with relief The potential for fire exists should hydrocarbon pumps, valves, or lines develop leaks that could allow vapors to reach sources of ignition. Remote sensors, control valves, fire valves, and isolation valves should be used to limit the release of hydrocarbons at pump suction lines in the event of leakage and /or fire.

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Safety Depending on the product and service, backflow prevention from the discharge line may be needed. The failure of automatic pump controls could cause a deviation in process pressure and temperature. Pumps operated with reduced or no flow can overheat and rupture. Pressure relief in the discharge piping should be provided where pumps can be overpressured. Provisions may be made for pipeline expansion, movement, and temperature changes to avoid rupture. Valves and instruments that require servicing or other work should be accessible at grade level or from an operating platform. Operating vent and drain connections should be provided with double-block valves, a block valve and plug, or blind flange for protection against releases. Health

hydrocarbons (during the process), and finished products. Tanks are also provided for fire water, process and treatment water, acids, additives, and other chemicals. The type, construction, capacity and location of tanks depends on their use and materials stored. HEALTH AND SAFETY CONSIDERATIONS Fire Prevention and Protection The potential for fire exists should hydrocarbon storage tanks be overfilled or develop leaks that allow vapors to escape and reach sources of ignition. Remote sensors,control valves, isolation valves, and fire valves may be provided at tanks for pump-out or closure in the event of a fire in the tank, or in the tank dike or storage area. Safety

Safe work practices and/or appropriate personal pro-tective equipment may be needed for exposure to haz-ards such as those related to liquids and vapors when opening or draining pumps, valves, and/or lines, and during product sampling, inspection, and maintenance activities.

Tanks may be provided with automatic overflow control and alarm systems, or manual gauging and checking procedures may be established to control overfills. Health

TANK STORAGE
Atmospheric storage tanks and pressure storage tanks are used throughout the refinery for storage of crudes, intermediate

Safe work practices and/or appropriate personal protective equipment may be needed for exposure to hazards related to product sampling, manual gauging, inspection, and maintenance activities including confined-space entry where applicable.

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F. BIBLIOGRAPHY
American Petroleum Institute. 1971. Chemistry and Petroleum for Classroom Use in Chemistry Courses. Washington, D.C.: American Petroleum Institute. __________. 1973. Industrial Hygiene Monitoring Manual for Petroleum Refineries and Selected P e t r o c h e mica l Op era t i o n s . Manual 2700-1/79-1M. Washington, D.C.: American Petroleum Institute. __________. 1980. Facts About Oil. Manual 4200-10/80-25M. Washington, D.C.: American Petroleum Institute. __________. 1990. Management of Process Hazards. RP 750. Washington, D.C.: American Petroleum Institute. __________. 1990. Inspection of Piping, Tubing, Valves and Fittings. RP 574. Washington, D.C.: American Petroleum Institute. __________. 1991. Inspection of Fired Boilers and Heaters. RP 573. Washington, D.C.: American Petroleum Institute. __________. 1992. Inspection of Pressure Vessels. RP 572. Washington, D.C.: American Petroleum Institute. __________. 1992. Inspection of Pressure Relieving Devices RP 576. Washington, D.C.: American Petroleum Institute. __________. 1994. Fire Protection in Refineries. Sixth Edition. RP 2001. Washington, D.C.: American Petroleum Institute. Armistead, George, Jr. 1950. Safety in Petroleum Refining and Related Industries. New York: John G. Simmons & Co., Inc. Exxon Company, USA. 1987. Encyclopedia for the User of Petroleum Products. Lubetext D400. Houston: Exxon Company, USA. Hydrocarbon Processing. 1988. Refining Handbook. Houston: Gulf Publishing Co. __________. 1992. Refining Handbook. Houston: Gulf Publishing Co. IARC. [No date given.] Occupational Exposures in Petroleum Refining. IARC Monographs, Volume 45. Kutler, A. A. 1969. "Crude distillation." Petro/Chem Engineering. New York: John G. Simmonds & Co., Inc. Mobil Oil Corporation. 1972. Light Products Refining, Fuels Manufacture. Mobil Technical Bulletin, 1972. Fairfax, Virginia: Mobil Oil Corporation. Parmeggiani, Luigi, Technical Editor. 1983. Encyclopaedia of Occupational Health and Safety. Third Edition. Geneva: International Labour Organization. Shell International Petroleum Company Limited. 1983. The Petroleum Handbook. Sixth Edition. Amsterdam: Elsevier Science Publishers B.V. Speight, James G. 1980. The Chemistry and Terminology of Petroleum. New York: Marcel Dekker, Inc. Vervalin, Charles H., Editor. 1985. Fire Protection Manual for Hydrocarbon Processing Plants. Volume 1, Third edition. Houston: Gulf Publishing Co.

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APPENDIX III:2-1. GLOSSARY

ABSORPTION The disappearance of one substance into another so that the absorbed substance loses its identifying characteristics, while the absorbing substance retains most of its original physical aspects. Used in refining to selectively remove specific components from process streams. ACID TREATMENT A process in which unfinished petroleum products such as gasoline, kerosene, and lubricating oil stocks are treated with sulfuric acid to improve color, odor, and other properties. ADDITIVE Chemicals added to petroleum products in small amounts to improve quality or add special characteristics. ADSORPTION Adhesion of the molecules of gases or liquids to the surface of solid materials. AIR FIN COOLERS A radiator-like device used to cool or condense hot hydrocarbons; also called fin fans. ALICYCLIC HYDROCARBONS Cyclic (ringed) hydrocarbons in which the rings are made up only of carbon atoms. ALIPHATIC HYDROCARBONS Hydrocarbons characterized by open-chain structures: ethane, butane, butene, acetylene, etc. ALKYLATION A process using sulfuric or hydro-fluoric acid as a catalyst to combine olefins (usually butylene) and isobutane to produce a high-octane product known as alkylate. API GRAVITY An arbitrary scale expressing the density of petroleum products. AROMATIC Organic compounds with one or more benzene rings. ASPHALTENES The asphalt compounds soluble in carbon disulfide but insoluble in paraffin naphthas. ATMOSPHERIC TOWER A distillation unit operated at atmospheric pressure. BENZENE An unsaturated, six-carbon ring, basic aromatic compound. BLEEDER VALVE A small-flow valve connected to a fluid process vessel or line for the purpose of bleeding off small quantities of contained fluid. It is installed with a block valve to determine if the block valve is closed tightly. BLENDING The process of mixing two or more petroleum products with different properties to produce a finished product with desired characteristics. BLOCK VALVE A valve used to isolate equipment. BLOWDOWN The removal of hydrocarbons from a process unit, vessel, or line on a scheduled or emergency basis by the use of pressure through special piping and drums provided for this purpose. BLOWER Equipment for moving large volumes of gas against low-pressure heads. BOILING RANGE The range of temperature (usually at atmospheric pressure) at which the boiling (or distillation) of a hydrocarbon liquid commences, proceeds, and finishes. BOTTOMS Tower bottoms are residue remaining in a distillation unit after the highest boiling-point material to be distilled has been removed. Tank bottoms are the heavy materials that accumulate in the bottom of storage tanks, usually comprised of oil, water, and foreign matter.

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BUBBLE TOWER A fractionating (distillation) tower in which the rising vapors pass through layers of condensate, bubbling under caps on a series of plates. CATALYST A material that aids or promotes a chemical reaction between other substances but does not react itself. Catalysts increase reaction speeds and can provide control by increasing desirable reactions and decreasing undesirable reactions. CATALYTIC CRACKING The process of breaking up heavier hydrocarbon molecules into lighter hydrocarbon fractions by use of heat and catalysts. CAUSTIC WASH A process in which distillate is treated with sodium hydroxide to remove acidic contaminants that contribute to poor odor and stability. CHD UNIT See Hydrodesulfurization. COKE A high carbon-content residue remaining from the destructive distillation of petroleum residue. COKING A process for thermally converting and upgrading heavy residual into lighter products and by-product petroleum coke. Coking also is the removal of all lighter distillable hydrocarbons that leaves a residue of carbon in the bottom of units or as buildup or deposits on equipment and catalysts. CONDENSATE The liquid hydrocarbon resulting from cooling vapors. CONDENSER A heat-transfer device that cools and condenses vapor by removing heat via a cooler medium such as water or lower-temperature hydrocarbon streams. CONDENSER REFLUX Condensate that is returned to the original unit to assist in giving increased conversion or recovery. COOLER A heat exchanger in which hot liquid hydrocarbon is passed through pipes immersed in cool water to lower its temperature.

CRACKING The breaking up of heavy molecular-weight hydrocarbons into lighter hydrocarbon molecules by the application of heat and pressure, with or without the use of catalysts. CRUDE ASSAY A procedure for determining the general distillation and quality characteristics of crude oil. CRUDE OIL A naturally occurring mixture of hydrocarbons that usually includes small quantities of sulfur, nitrogen, and oxygen derivatives of hydrocarbons as well as trace metals. CYCLE GAS OIL Cracked gas oil returned to a cracking unit. DEASPHALTING Process of removing asphaltic materials from reduced crude using liquid propane to dissolve nonasphaltic compounds. DEBUTANIZER A fractionating column used to remove butane and lighter components from liquid streams. DE-ETHANIZER A fractionating column designed to remove ethane and gases from heavier hydrocarbons. DEHYDROGENATION A reaction in which hydro-gen atoms are eliminated from a molecule. Dehydro-genation is used to convert ethane, propane, and butane into olefins (ethylene, propylene, and butenes). DEPENTANIZER A fractionating column used to remove pentane and lighter fractions from hydrocarbon streams. DEPROPANIZER A fractionating column for removing propane and lighter components from liquid streams. DESALTING Removal of mineral salts (most chlorides, e.g., magnesium chloride and sodium chloride) from crude oil. DESULFURIZATION A chemical treatment to remove sulfur or sulfur compounds from hydrocarbons.

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DEWAXING The removal of wax from petroleum products (usually lubricating oils and distillate fuels) by solvent absorption, chilling, and filtering. DIETHANOLAMINE A chemical (C4H11O2N) used to remove H2S from gas streams. DISTILLATE The products of distillation formed by condensing vapors. DOWNFLOW Process in which the hydrocarbon stream flows from top to bottom. DRY GAS Natural gas with so little natural gas liquids that it is nearly all methane with some ethane. FEEDSTOCK Stock from which material is taken to be fed (charged) into a processing unit. FLASHING The process in which a heated oil under pressure is suddenly vaporized in a tower by reducing pressure. FLASH POINT Lowest temperature at which a petroleum product will give off sufficient vapor so that the vapor-air mixture above the surface of the liquid will propagate a flame away from the source of ignition. FLUX Lighter petroleum used to fluidize heavier residual so that it can be pumped. FOULING Accumulation of deposits in condensers, exchangers, etc. FRACTION One of the portions of fractional distillation having a restricted boiling range. FRACTIONATING COLUMN Process unit that separates various fractions of petroleum by simple distillation, with the column tapped at various levels to separate and remove fractions according to their boiling ranges. FUEL GAS Refinery gas used for heating.

GAS OIL Middle-distillate petroleum fraction with a boiling range of about 350-750 F, usually includes diesel fuel, kerosene, heating oil, and light fuel oil. GASOLINE A blend of naphthas and other refinery products with sufficiently high octane and other desirable characteristics to be suitable for use as fuel in internal combustion engines. HEADER A manifold that distributes fluid from a series of smaller pipes or conduits. HEAT As used in the Health Considerations sections of this document, heat refers to thermal burns for contact with hot surfaces, hot liquids and vapors, steam, etc. HEAT EXCHANGER Equipment to transfer heat between two flowing streams of different temperatures. Heat is transferred between liquids or liquids and gases through a tubular wall. HIGH-LINE OR HIGH-PRESSURE GAS High-pressure (100 psi) gas from cracking unit distillate drums that is compressed and combined with low-line gas as gas absorption feedstock. HYDROCRACKING A process used to convert heavier feedstocks into lower-boiling, higher-value products. The process employs high pressure, high temperature, a catalyst, and hydrogen. HYDRODESULFURIZATION A catalytic process in which the principal purpose is to remove sulfur from petroleum fractions in the presence of hydrogen. HYDROFINISHING A catalytic treating process carried out in the presence of hydrogen to improve the properties of low viscosity-index naphthenic and medium viscosity-index naphthenic oils. It is also applied to paraffin waxes and microcrystalline waxes for the removal of undesirable components. This process consumes hydrogen and is used in lieu of acid treating.

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HYDROFORMING Catalytic reforming of naphtha at elevated temperatures and moderate pressures in the presence of hydrogen to form high-octane BTX aromatics for motor fuel or chemical manufacture. This process results in a net production of hydrogen and has rendered thermal reforming somewhat obsolete. It represents the total effect of numerous simultaneous reactions such as cracking, polymerization, dehydrogenation, and isomerization. HYDROGENATION The chemical addition of hydrogen to a material in the presence of a catalyst. INHIBITOR Additive used to prevent or retard undesirable changes in the quality of the product, or in the condition of the equipment in which the product is used. ISOMERIZATION A reaction that catalytically converts straight-chain hydrocarbon molecules into branched-chain molecules of substantially higher octane number. The reaction rearranges the carbon skeleton of a molecule without adding or removing anything from the original material. ISO-OCTANE A hydrocar b o n mo l ecu l e (2,2,4-trimethylpentane) with excellent antiknock characteristics on which the octane number of 100 is based. KNOCKOUT DRUM A vessel wherein suspended liquid is separated from gas or vapor. LEAN OIL Absorbent oil fed to absorption towers in which gas is to be stripped. After absorbing the heavy ends from the gas, it becomes fat oil. When the heavy ends are subsequently stripped, the solvent again becomes lean oil. LOW-LINE or LOW-PRESSURE GAS Low-pressure (5 psi) gas from atmospheric and vacuum distillation recovery systems that is collected in the gas plant for compression to higher pressures. NAPHTHA A general term used for low boiling hydrocarbon fractions that are a major component of gasoline. Aliphatic naphtha refers to those naphthas containing less than 0.1% benzene and with carbon numbers from C3 through C16. Aromatic naphthas have carbon numbers from C6 through C16 and contain significant quantities of aromatic hydrocarbons such as benzene (>0.1%), toluene, and xylene.

NAPHTHENES Hydrocarbons (cycloalkanes) with the general formula CnH2n, in which the carbon atoms are arranged to form a ring. OCTANE NUMBER A number indicating the relative antiknock characteristics of gasoline. OLEFINS A family of unsaturated hydrocarbons with one carbon-carbon double bond and the general formula CnH2n. PARAFFINS A family of saturated aliphatic hydrocarbons (alkanes) with the general formula CnH2n+2. POLYFORMING The thermal conversion of naphtha and gas oils into high-quality gasoline at high temperatures and pressure in the presence of recirculated hydrocarbon gases. POLYMERIZATION The process of combining two or more unsaturated organic molecules to form a single (heavier) molecule with the same elements in the same proportions as in the original molecule. PREHEATER Exchanger used to heat hydrocarbons before they are fed to a unit. PRESSURE-REGULATING VALVE A valve that releases or holds process-system pressure (that is, opens or closes) either by preset spring tension or by actuation by a valve controller to assume any desired position between fully open and fully closed. PYROLYSIS GASOLINE A by-product from the manufacture of ethylene by steam cracking of hydrocarbon fractions such as naphtha or gas oil. PYROPHORIC IRON SULFIDE A substance typically formed inside tanks and processing units by the corrosive

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interaction of sulfur compounds in the hydrocarbons and the iron and steel in the equipment. On exposure to air (oxygen) it ignites spontaneously. QUENCH OIL Oil injected into a product leaving a cracking or reforming heater to lower the temperature and stop the cracking process. RAFFINATE The product resulting from a solvent extraction process and consisting mainly of those components that are least soluble in the solvents. The product recovered from an extraction process is relatively free of aromatics, naphthenes, and other constituents that adversely affects physical parameters. REACTOR The vessel in which chemical reactions take place during a chemical conversion type of process. REBOILER An auxiliary unit of a fractionating tower designed to supply additional heat to the lower portion of the tower. RECYCLE GAS High hydrogen-content gas returned to a unit for reprocessing. REDUCED CRUDE A residual product remaining after the removal by distillation of an appreciable quantity of the more volatile components of crude oil. REFLUX The portion of the distillate returned to the fractionating column to assist in attaining better separation into desired fractions. REFORMATE An upgraded naphtha resulting from catalytic or thermal reforming. REFORMING The thermal or catalytic conversion of petroleum naphtha into more volatile products of higher octane number. It represents the total effect of numerous simultaneous reactions such as cracking, polymerization, dehydrogenation, and isomerization. REGENERATION In a catalytic process the reactivation of the catalyst, sometimes done by burning off the coke deposits

under carefully controlled conditions of temperature and oxygen content of the regeneration gas stream. SCRUBBING Purification of a gas or liquid by washing it in a tower. SOLVENT EXTRACTION The separation of materials of different chemical types and solubilities by selective solvent action. SOUR GAS Natural gas that contains corrosive, sulfur-bearing compounds such as hydrogen sulfide and mercaptans. STABILIZATION A process for separating the gaseous and more volatile liquid hydrocarbons from crude petroleum or gasoline and leaving a stable (less-volatile) liquid so that it can be handled or stored with less change in composition. STRAIGHT-RUN GASOLINE Gasoline produced by the primary distillation of crude oil. It contains no cracked, polymerized, alkylated, reformed, or visbroken stock. STRIPPING The removal (by steam-induced vaporization or flash evaporation) of the more volatile components from a cut or fraction. SULFURIC ACID TREATING A refining process in which unfinished petroleum products such as gasoline, kerosene, and lubricating oil stocks are treated with sulfuric acid to improve their color, odor, and other characteristics. SULFURIZATION Combining sulfur compounds with petroleum lubricants. SWEETENING Processes that either remove obnoxious sulfur compounds (primarily hydrogen sulfide, mercaptans, and thiophens) from petroleum fractions or streams, or convert them, as in the case of mercaptans, to odorless disulfides to improve odor, color, and oxidation stability.

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SWITCH LOADING The loading of a high static-charge retaining hydrocarbon (i.e., diesel fuel) into a tank truck, tank car, or other vessel that has previously contained a low-flash hydrocarbon (gasoline) and may contain a flammable mixture of vapor and air. TAIL GAS The lightest hydrocarbon gas released from a refining process. THERMAL CRACKING The breaking up of heavy oil molecules into lighter fractions by the use of high temperature without the aid of catalysts. TURNAROUND A planned complete shutdown of an entire process or section of a refinery, or of an entire refinery to perform major maintenance, overhaul, and repair operations and to inspect, test, and replace process materials and equipment.

VACUUM DISTILLATION The distillation of petroleum under vacuum which reduces the boiling temperature sufficiently to prevent cracking or decomposition of the feedstock. VAPOR The gaseous phase of a substance that is a liquid at normal temperature and pressure. VISBREAKING Viscosity breaking is a low-temperature cracking process used to reduce the viscosity or pour point of straight-run residuum. WET GAS A gas containing a relatively high proportion of hydrocarbons that are recoverable as liquids.

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SECTION III: CHAPTER 3

PRESSURE VESSEL GUIDELINES

A. INTRODUCTION
Recent inspection programs for metallic pressure containment vessels and tanks have revealed cracking and damage in a considerable number of the vessels inspected. Safety and hazard evaluations of pressure vessels, as also presented in PUB 8-1.5, need to consider the consequences of a leakage or a rupture failure of a vessel. Two consequences result from a complete rupture: @ @ Blast effects due to sudden expansion of the pressurized fluid; and Fragmentation damage and injury, if vessel rupture occurs. @ @ For a leakage failure, the hazard consequences can range from no effect to very serious effects: @ Suffocation or poisoning, depending on the nature of the contained fluid, if the leakage occurs into a closed space; Fire and explosion for a flammable fluid are included as a physical hazard; and Chemical and thermal burns from contact with process liquids.

A. Introduction.........................................III:3-1 B. Recent Cracking Experience in Pressure Vessels..........................III:3-2 C. Nondestructive Examiniation Methods.......................................III:3-6 D. Information for Safety Assessment..................................III:3-9 E. Bibliography........................................III:3-9 Appendix II:3-1. Recordkeeping Data for Steel Vessels and LowPressure Storage Tanks..........III:3-10

Only pressure vessels and low pressure storage tanks widely used in process, pulp and paper, petroleum refining, and petrochemical industries and for water treatment systems of boilers and steam generation equipment are covered in this chapter. Excluded are vessels and tanks used in many other applications and also excludes other parts of a pressure containment system such as piping and valves. The types and applications of pressure vessels included and excluded in this chapter are summarized in Table III:3-1. An illustration of a schematic pressure vessel is presented in Figure III:3-1. NOTE: Though this review of pressure vessels excludes inspection or evaluation of safety release valves, the compliance officer should be aware that NO valves or T-fittings should be present between the vessel and the safety relief valve.

III:3-1

Pressure Vessel Design Codes. Most of the pressure or storage vessels in service in the United States will have been designed and constructed in accordance with one of the following two design codes: @ The ASME Code, or Section VIII of the ASME (American Society of Mechanical Engineers) Boiler and Pressure Vessel Code; or The API Standard 620 or the American Petroleum Institute Code which provides rules for lower pressure vessels not covered by the ASME Code.

In addition, some vessels designed and constructed between 1934 to 1956 may have used the rules in the "API-ASME Code for Unfired Pressure Vessels for Petroleum Liquids and Gases." This code was discontinued in 1956. Vessels certification can only be performed by trained inspectors qualified for each code. Written tests and practical experience are required for certification. Usually, the compliance office is not equipped for this task, but is able to obtain the necessary contract services.

TABLE III:3-1. VESSEL TYPES Vessels included: Stationary and unfired Used for pressure containment of gases and liquids Constructed of carbon steel or low alloy steel Operated at temperatures between -75 and 315 C (-100 and 600 F) Vessel types specifically excluded: Vessels used as fired boilers Vessels used in high-temperature processes (above 315 C, 600 F) or at very low and cryogenic temperatures Vessels and containers used in transportable systems Storage tanks that operate at nominally atmospheric pressure Piping and pipelines Safety and pressure-relief valves Special-purpose vessels, such as those for human occupancy.

B.

RECENT CRACKING EXPERIENCE IN PRESSURE VESSELS

Deaerators are widely used in many industrial applications including power generation, pulp and paper, chemical, and petroleum refining and in many public facilities such as hospitals and schools where steam generation is required. In actual practice, the deaerator vessel can be separate from the

DEAERATOR SERVICE
Deaeration refers to the removal of noncondensible gases, primarily oxygen, from the water used in a steam generation system.

III:3-2

Figure III:3-1. Some Major Parts of a Pressure Vessel storage vessel or combined with a storage vessel into one unit. Typical operational conditions for deaerator vessels range up to about 300 psi and up to about 150 C (300 F). Nearly all of the vessels are designed to ASME Code resulting in vessel wall thicknesses up to but generally less than 25 mm (1 in). The vessel material is almost universally one of the carbon steel grades. Analysis of incident survey data and other investigations has determined the following features about the deaerator vessel cracking. @ @ @ Water hammer is the only design or operational factor that correlates with cracking. Cracking is generally limited to weld regions of vessels that had not been postweld heat treated. Corrosion fatigue appears to be the predominant mechanism of crack formation and growth. The failures and the survey results have prompted TAPPI (Technical Association of Pulp and Paper Industry), the National Board of Boiler and Pressure Vessel Inspectors, and NACE (National Association of Corrosion Engineers) to prepare inspection, operation and repair recommendations. For inspection, all recommendations suggest: @ @ Special attention to the internal surface of all welds and heat-affected zones (HAZ); and Use of the wet fluorescent magnetic particle (WFMT) method for inspection.

The TAPPI and the NACE recommendations also contain additional items, such as: @ Inspection by personnel certified to American Society for Nondestructive Testing's SNT-TC-1A minimum Level I and interpretation of the results by minimum Level II; and Reinspection within one year for repaired vessels, 1-2 years for vessels with discontinuities but unrepaired,

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and 3-5 years for vessels found free of discontinuities.

AMINE SERVICE
The amine process is used to remove hydrogen sulfide (H2S) from petroleum gases such as propane and butane. It is also used for carbon dioxide (CO2) removal in some processes. Amine is a generic term and includes monoethanolamine (MEA), diethanolamine (DEA) and others in the amine group. These units are used in petroleum refinery, gas treatment and chemical plants. The operating temperatures of the amine process are generally in the 38 to 93 C (100 to 200 F) range and therefore the plant equipment is usually constructed from one of the carbon steel grades. The wall thickness of the pressure vessels in amine plants is typically about 25 mm (1 in). Although the possibility of cracking of carbon steels in an amine environment has been known for some years, real concern about safety implications was highlighted by a 1984 failure of the amine process pressure vessel. Overall, the survey found about 40% cracking incidence in a total of 294 plants. Cracking had occurred in the absorber/contactor, the regenerator and the heat exchanger vessels, and in the piping and other auxiliary equipment. Several of the significant findings of the survey were: @ @ @ @ All cracks were in or near welds.

Information from laboratory studies indicate that pure amine does not cause cracking of carbon steels but amine with carbon dioxide in the gas phase causes severe cracking. The presence or absence of chlorides, cyanides, or hydrogen sulfide may also be factors but their full role in the cracking mechanism are not completely known at present.

WET HYDROGEN SULFIDE

Wet Hydrogen Sulfide refers to any fluid containing water and hydrogen sulfide (H2S). Hydrogen is generated when steel is exposed to this mixture and the hydrogen can enter into the steel. Dissolved hydrogen can cause cracking, blistering, and embrittlement. The harmful effects of hydrogen generating environments on steel have been known and recognized for a long time in the petroleum and petrochemical industries. In particular, sensitivity to damage by hydrogen increases with the hardness and strength of the steel and damage and cracking are more apt to occur in high strength steels. @ Significant cracks can start from very small hard zones associated with welds; these hard zones are not detected by conventional hardness tests. Initially small cracks can grow by a stepwise form of hydrogen blistering to form through thickness cracks. NACE/API limits on weld hardness may not be completely effective in preventing cracking. Thermal stress relief (postweld heat treatment, PWHT) appears to reduce the sensitivity to and the severity of cracking.

@ @

Cracking occurred predominantly in stressed or unrelieved (not PWHT) welds. @ Cracking occurred in all amine vessel processes but was most prevalent in MEA units. WFMT and UT (ultrasonic test) were the predominant detection methods for cracks; internal examination by WFMT is the preferred method.

Wet hydrogen sulfide has also been found to cause service cracking in liquified petroleum gas (LPG) storage vessels. The service cracking in the LPG vessels occurs predominantly in the weld heat affected zone (HAZ). The vessels are usually

III:3-4

spherical with wall thickness in the 20 mm to 75 mm (0.8 in to 3 in) range. Recommendations for new and existing wet hydrogen- sulfide vessels to minimize the risk of a major failure include: @ @ @ @ Use lower-strength steels for new vessels; Schedule an early inspection for vessels more than five years in service; Improve monitoring to minimize breakthrough of hydrogen sulfide; and Replace unsafe vessels or downgrade to less- severe, usually lower-pressure, service.

PULP DIGESTER SERVICE

The kraft pulping process is used in the pulp and paper industry to digest the pulp in the papermaking process. The operation is done in a relatively weak (a few percent) water solution of sodium hydroxide and sodium sulfide typically in the 110 to 140 C (230 to 285 F) temperature range. Since the early 1950s, a continuous version of this process has been widely used. Nearly all of the vessels are ASME Code vessels made using one of the carbon steel grades with typical design conditions of 175 to 180 C (350 to 360 F) and 150 psig. These vessels had a very good service record with only isolated reports of cracking problems until the occurrence of a sudden rupture failure in 1980. The inspection survey has revealed that about 65% of the properly inspected vessels had some cracking. Some of the cracks were fabrication flaws revealed by the use of more sensitive inspection techniques but most of the cracking was service-induced. The inspection survey and analysis indicates the following features about the cracking. @ @ All cracking was associated with welds. Wet fluorescent magnetic particle (WFMT) testing with proper surface preparation was the most effective method of detecting the cracking. Fully stress-relieved vessels were less susceptible. No clear correlation of cracking and noncrack-ing could be found with vessel age and manufacture or with process variables and practices. Analysis and research indicate that the cracking is due to a caustic stress corrosion cracking mechanism although its occurrence at the relatively low caustic concentrations of the digester process was unexpected.

AMMONIA SERVICE
Commercial refrigeration systems, certain chemical processes, and formulators of agricultural chemicals will be sites of ammonia service tanks. Careful inspections of vessels used for storage of ammonia (in either vapor or liquid form) in recent years have resulted in evidence of serious stress corrosion cracking problems. The vessels for this service are usually constructed as spheres from one of the carbon steel grades, and they operate in the ambient temperature range. The water and oxygen content in the ammonia has a strong influence on the propensity of carbon steels to crack in this environment. Cracks have a tendency to be found to be in or near the welds in as-welded vessels. Cracks occur both transverse and parallel to the weld direction. Thermal stress relieving seems to be a mitigating procedure for new vessels, but its efficacy for older vessels after a period of operation is dubious partly because small, undetected cracks may be present.

@ @

Currently, preventive measures such as weld cladding, spray coatings, and anodic protection are being studied, and

III:3-5

considerable information has been obtained. In the meantime, the recommended guideline is to perform an annual examination.

@ @ @

Welds and adjacent regions; Vessels that have not been thermally stress relieved (no PWHT of fabrication welds); and Repaired vessels, especially those without PWHT after repair.

SUMMARY OF SERVICE CRACKING EXPERIENCE

The preceding discussion shows a strong influence of chemical environment on cracking incidence. This is a factor that is not explicitly treated in most design codes. Service experience is the best and often the only guide to in-service safety assessment. For vessels and tanks within the scope of this document, the service experience indicates that the emphasis of the inspection and safety assessment should be on: @ Vessels in deaerator, amine, wet H2S, ammonia and pulp digesting service;

The evaluation of the severity of the detected cracks can be done by fracture mechanics methods. This requires specific information about stresses, material properties, and flaw indications. Generalized assessment guidelines are not easy to formulate. However, fortunately, many vessels in the susceptible applications listed above operate at relatively low stresses, and therefore, cracks have a relatively smaller effect on structural integrity and continued safe operation.

C. NONDESTRUCTIVE EXAMINATION METHODS

Of the various conventional and advanced nondestructive examination (NDE) methods, five are widely used for the examination of pressure vessels and tanks by certified pressure vessel inspectors. The names and acronyms of these common five methods are: @ @ @ @ @ VT Visual Examination, PT Liquid Penetrant Test, MT Magnetic Particle Test, RT Gamma and X-ray Radiography, and UT Ultrasonic Test. It is very useful for assessing the general condition of the equipment and for detecting some specific problems such as severe instances of corrosion, erosion, and hydrogen blistering. The obvious requirements for a meaningful visual examination are a clean surface and good illumination. referred to as "surface" examination methods and the last two as "volumetric" methods. Table II of PUB 8-1.5 summarizes the main features of these five methods. VISUAL EXAMINATION (VT) A visual examination is easy to conduct and can cover a large area in a short time.

VT, PT and MT can detect only those discontinuities and defects that are open to the surface or are very near the surface. In contrast, RT and UT can detect conditions that are located within the part. For these reasons, the first three are often

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LIQUID PENETRANT TEST (PT)

This method depends on allowing a specially formulated liquid (penetrant) to seep into an open discontinuity and then detecting the entrapped liquid by a developing agent. When the penetrant is removed from the surface, some of it remains entrapped in the discontinuities. Application of a developer draws out the entrapped penetrant and magnifies the discontinuity. Chemicals which fluoresce under black (ultraviolet) light can be added to the penetrant to aid the detectability and visibility of the developed indications. The essential feature of PT is that the discontinuity must be "open," which means a clean, undisturbed surface. The PT method is independent of the type and composition of the metal alloy so it can be used for the examination of austenitic stainless steels and nonferrous alloys where the magnetic particle test is not applicable.

of sensitivity since it is highly dependent on magnetizing current, material, and geometry and size of the defect. A very crude approximation would be a depth no more than 1.5 mm to 3 mm (1/16 in to 1/8 in). A very important precaution in performing MT is that corners and surface irregularities also perturb the magnetic field. Therefore, examining for defects in corners and near or in welds must be performed with extra care. Another precaution is that MT is most sensitive to discontinuities which are oriented transverse to the magnetic flux lines and this characteristic needs to be taken into account in determining the procedure for inducing the magnetic field.

RADIOGRAPHY (RT)
The basic principle of radiographic examination of metallic objects is the same as in any other form of radiography such as medical radiography. Holes, voids, and discontinuities decrease the attenuation of the X-ray and produce greater exposure on the film (darker areas on the negative film). Because RT depends on density differences, cracks with tightly closed surfaces are much more difficult to detect than open voids. Also, defects located in an area of a abrupt dimensional change are difficult to detect due to the superimposed density difference. RT is effective in showing defect dimensions on a plane normal to the beam direction but determination of the depth dimension and location requires specialized techniques. Since ionizing radiation is involved, field application of RT requires careful implementation to prevent health hazards.

MAGNETIC PARTICLE TEST (MT)

This method depends on the fact that discontinuities in or near the surface perturb magnetic flux lines induced into a ferromagnetic material. For a component such as a pressure vessel where access is generally limited to one surface at a time, the "prod" technique is widely used. The magnetic field is produced in the region around and between the prods (contact probes) by an electric current (either AC or DC) flowing between the prods. The ferromagnetic material requirement basically limits the applicability of MT to carbon and low- alloy steels. The perturbations of the magnetic lines are revealed by applying fine particles of a ferromagnetic material to the surface. The particles can be either a dry powder or a wet suspension in a liquid. The particles can also be treated to fluoresce under black light. These options lead to variations such as the "wet fluorescent magnetic particle test" (WFMT). MT has some capability for detecting subsurface defects. However, there is no easy way to determine the limiting depth

ULTRASONIC TESTING (UT)

The fundamental principles of ultrasonic testing of metallic materials are similar to radar and related methods of using electromagnetic and acoustic waves for detection of foreign objects. The distinctive aspect of UT for the inspection of

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metallic parts is that the waves are mechanical, so the test equipment requires three basic components. @ @ Electronic system for generating electrical signal. Transducer system to convert the electrical signal into mechanical vibrations and vice versa and to inject the vibrations into and extract them from the material. Electronic system for amplifying, processing and displaying the return signal.

DETECTION PROBABILITIES AND FLAW SIZING

The implementation of NDE (nondestructive examination) results for structural integrity and safety assessment involves a detailed consideration of two separate but interrelated factors. @ @ Detecting the discontinuity. Identifying the nature of the discontinuity and determining its size.

Very short signal pulses are induced into the material and waves reflected back from discontinuities are detected during the "receive" mode. The transmitting and detection can be done with one transducer or with two separate transducers (the tandem technique). Unlike radiography, UT in its basic form does not produce a permanent record of the examination. However, more recent versions of UT equipment include automated operation and electronic recording of the signals. Ultrasonic techniques can also be used for the detection and measurement of general material loss such as by corrosion and erosion. Since wave velocity is constant for a specific material, the transit time between the initial pulse and the back reflection is a measure of the travel distance and the thickness.

Much of the available information on detection and sizing capabilities has been developed for aircraft and nuclear power applications. This kind of information is very specific to the nature of the flaw, the material, and the details of the test technique, and direct transference to other situations is not always warranted. The overall reliability of NDE is obviously an important factor in a safety and hazard assessment. Failing to detect or undersizing existing discontinuities reduces the safety margin while oversizing errors can result in unnecessary and expensive outages. High reliability results from a combination of factors. @ @ @ Validated procedures, equipment and test personnel. Utilization of diverse methods and techniques. Application of redundancy by repetitive and independent tests.

Finally, it is useful to note that safety assessment depends on evaluating the "largest flaw that may be missed, not the smallest one that can be found."

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D. INFORMATION FOR SAFETY ASSESSMENT

This chapter and PUB 8-1.5 has a large amount of information on the design rules, inspection requirements, and service experience, relevant to pressure vessels and low pressure storage tanks used in general industrial applications. Though the compliance officer is not usually qualified as a pressure vessel inspector, as a summary and a reminder, Appendix III:3-1 outlines the information, data, and recordkeeping that are necessary, useful, or indicative of safe management of operating vessels and tanks. These records, besides the construction and maintenance logs usually are kept by the plant engineer, maintenance supervisor, or facility manager, will be indicative of the surveillance activities around safe operation of pressure vessels.

E. BIBLIOGRAPHY
Chuse, R. 1984. Pressure Vessels: The ASME Code Simplified. 6th ed. McGraw-Hill: New York. Forman, B. Fred. 1981. Local Stresses in Pressure Vessels. Pressure Vessel Handbook Publishing, Inc.: Tulsa. Hammer, W. 1981. Pressure Hazards in Occupational Safety Management and Engineering. 2nd ed. Prentice-Hall: New York. McMaster, R. C. and McIntire, P. (eds.) 1982-1987. Nondestructive Testing Hand-book. 2nd ed., Vols. 1-3. American Society for Metals/American Society of Nondestructive Testing: Columbus. Megyesy, E. F. 1986. Pressure Vessel Handbook. 7th ed. Pressure Vessel Handbook Publishing Inc.: Tulsa. OSHA Instruction Pub 8-1.5. 1989. Guidelines for Pressure Vessel Safety Assessment. Occupational Safety and Health Administration: Washington, D.C. Thielsch, H. 1975. Defects and Failures in Pressure Vessels and Piping. 2nd ed., Chaps. 16 and 17. Reinhold: New York. Yokell, S. 1986. Understanding the Pressure Vessel Code. Chemical Engineering 93(9):75-85.

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APPENDIX III:3-1.

RECORDKEEPING DATA FOR STEEL VESSELS AND LOW PRESSURE STORAGE TANKS
@ @ Date vessel was placed in service Interruption dates if not in continuous service.

INTRODUCTION AND SCOPE

This outline summarizes information and data that will be helpful in assessing the safety of steel pressure vessels and low pressure storage tanks that operate at temperatures between -75 and 315 C (-100 and 600 F).

DESIGN AND INFORMATION

CONSTRUCTION

VESSEL IDENTIFICATION DOCUMENTATION

AND

Information that identifies the specific vessel being assessed and provides general information about it include the following items: @ @ Current owner of the vessel Vessel location -Original location and current location if it has been moved Vessel identification -Manufacturer's serial number -National Board number if registered with NB Manufacturer identification -Name and address of manufacturer -Authorization or identification number of the manufacturer Date of manufacture of the vessel Data report for the vessel -ASME U-1 or U-2, API 620 form or other applicable report

Information that will identify the code or standard used for the design and construction of the vessel or tank and the specific design values, materials, fabrication methods, and inspection methods used include the following items: @ Design code -ASME Code Section and Division, API Standard or other design code used Type of construction -Shop or field fabricated or other fabrication method VIII, division 1 or 2 vessels -Maximum allowable pressure and temperature -Minimum design temperature API 620 vessels -Design pressure at top and maximum fill Additional requirements included such as -Appendix Q (Low-Pressure Storage Tanks For Liquified Hydrocarbon Gases) and -Appendix R (Low-Pressure Storage Tanks for Refrigerated Products)

@ @

@ @

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Other design code vessels -Maximum design and allowable pressures -Maximum and minimum operating temperatures Vessel materials -ASME, ASTM, or other specification names and numbers for the major parts Design corrosion allowance Thermal stress relief (PWHT, postweld heat treatment) -Design code requirements -Type, extent, and conditions of PWHT performed Nondestructive examination (NDE) of welds -Type and extent of examination performed -Time when NDE was performed (before or after PWHT or hydrotest)

Vessel history -Alterations, reratings, and repairs performed -Date(s) of changes or repairs

IN-SERVICE INSPECTION
Information about inspections performed on the vessel or tank and the results obtained that will assist in the safety assessment include the following items: @ @ Inspection(s) performed -Type, extent, and dates Examination methods -Preparation of surfaces and welds -Techniques used (visual, magnetic particle, penetrant test, radiography, ultrasonic) Qualifications of personnel -ASNT (American Society for Nondestructive Testing) levels or equivalent of examining and supervisory personnel Inspection results and report -Report form used (NBIC NB-7, API 510 or other) -Summary of type and extent of damage or cracking -Disposition (no action, delayed action or repaired)

@ @

SERVICE HISTORY
Information on the conditions of operating history of the vessel or tank that will be helpful in safety assessment include the following items: @ Fluids handled -Type and composition, temperature and pressures Type of service -Continuous, intermittent or irregular Significant changes in service conditions -Changes in pressures, temperatures, and fluid compositions and the dates of the changes @

@ @

SPECIFIC APPLICATIONS
Survey results indicate that a relatively high proportion of vessels in operations in several specific applications have experienced inservice related damage and cracking. Information on the following items can assist in assessing the safety of vessels in these applications:

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Service application -Deaerator, amine, wet hydrogen sulfide, ammonia, or pulp digesting Industry bulletins and guidelines for this application -Owner/operator awareness of information Type, extent, and results of examinations -Procedures, guidelines and recommendations used -Amount of damage and cracking -Next examination schedule Participation in industry survey for this application

Problem mitigation -Written plans and actions

@ @

EVALUATION OF INFORMATION
The information acquired for the above items is not adaptable to any kind of numerical ranking for quantitative safety assessment purposes. However, the information can reveal the owner or user's apparent attention to good practice, careful operation, regular maintenance, and adherence to the recommendations and guidelines developed for susceptible applications. If the assessment indicated cracking and other serious damage problems, it is important that the inspector obtain qualified technical advice and opinion.

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SECTION III: CHAPTER 4

INDUSTRIAL ROBOTS AND ROBOT SYSTEM SAFETY

A. INTRODUCTION
Industrial robots are programmable multifunctional mechanical devices designed to move material, parts, tools, or specialized devices through variable programmed motions to perform a variety of tasks. An industrial robot system includes not only industrial robots but also any devices and/or sensors required for the robot to perform its tasks as well as sequencing or monitoring communication interfaces. Robots are generally used to perform unsafe, hazardous, highly repetitive, and unpleasant tasks. They have many different functions such as material handling, assembly, arc welding, resistance welding, machine tool load and unload functions, painting, spraying, etc. See Appendix III:4-1 for common definitions. Most robots are set up for an operation by the teach-and-repeat technique. In this mode, a trained operator (programmer) typically uses a portable control device (a teach pendant) to teach a robot its task manually. Robot speeds during these programming sessions are slow. This instruction includes safety considerations necessary to operate the robot properly and use it automatically in conjunction with other peripheral equipment. This instruction applies to fixed industrial robots and robot systems only. See Appendix III:4-2 for the systems that are excluded.

A. Introduction........................................III:4-1 B. Types and Classification of Robots.....................................III:4-2 C. Hazards................................................III:4-7 D. Investigation Guidelines..................III:4-10 E. Control and Safeguarding Personnel..................................III:4-10 F. Bibliography.....................................III:4-13 Appendix III:4-1. Glossary for Robotics and Robotic System.......................................III:4-14 Appendix III:4-2. Other Robotic Systems.....................................III:4-18

ACCIDENTS: PAST STUDIES

Studies in Sweden and Japan indicate that many robot accidents do not occur under normal operating conditions but, instead during programming, program touch-up or refinement, maintenance, repair, testing, setup, or adjustment. During many of these operations the operator, programmer, or corrective maintenance worker may temporarily be within the robot's working envelope where unintended operations could result in injuries.

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Typical accidents have included the following: @ @ A robot's arm functioned erratically during a programming sequence and struck the operator. A materials handling robot operator entered a robot's work envelope during operations and was pinned between the back end of the robot and a safety pole. A fellow employee accidentally tripped the power switch while a maintenance worker was servicing an assembly robot. The robot's arm struck the maintenance worker's hand.

use, programming, and maintenance operations. Among the factors to be considered are the tasks a robot will be programmed to perform, start-up and command or programming procedures, environmental conditions, location and installation requirements, possible human errors, scheduled and unscheduled maintenance, possible robot and system malfunctions, normal mode of operation, and all personnel functions and duties. An effective safeguarding system protects not only operators but also engineers, programmers, maintenance personnel, and any others who work on or with robot systems and could be exposed to hazards associated with a robot's operation. A combination of safeguarding methods may be used. Redundancy and backup systems are especially recommended, particularly if a robot or robot system is operating in hazardous conditions or handling hazardous materials. The safeguarding devices employed should not themselves constitute or act as a hazard or curtail necessary vision or viewing by attending human operators.

ROBOT SAFEGUARDING
The proper selection of an effective robotic safeguarding system should be based upon a hazard analysis of the robot system's

B. TYPES AND CLASSIFICATION OF ROBOTS

Industrial robots are available commercially in a wide range of sizes, shapes, and configurations. They are designed and fabricated with different design configurations and a different number of axes or degrees of freedom. These factors of a robot's design influence its working envelope (the volume of working or reaching space). Diagrams of the different robot design configurations are shown in Figure III:4-1. Nonservo robots do not have the feedback capability, and their axes are controlled through a system of mechanical stops and limit switches.

TYPE OF PATH GENERATED

Industrial robots can be programmed from a distance to perform their required and preprogrammed operations with different types of paths generated through different control techniques. The three different types of paths generated are Point-to-Point Path, Controlled Path, and Continuous Path. POINT-TO-POINT PATH Robots programmed and controlled in this manner are programmed to move from one discrete point to another within

SERVO AND NONSERVO

All industrial robots are either servo or nonservo controlled. Servo robots are controlled through the use of sensors that continually monitor the robot's axes and associated components for position and velocity. This feedback is compared to pretaught information which has been programmed and stored in the robot's memory.

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Regulator Coordinate Robot

Cylindrical Roordinate Robot

Spherical Coordinate Robot

Arituclated Arm Robot

Gantry Robot

SCARA Robot Figure III:4-1. Robot Arm Design Configurations.

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the robot's working envelope. In the automatic mode of operation, the exact path taken by the robot will vary slightly due to variations in velocity, joint geometries, and point spatial locations. This difference in paths is difficult to predict and therefore can create a potential safety hazard to personnel and equipment. CONTROLLED PATH The path or mode of movement ensures that the end of the robot's arm will follow a predictable (controlled) path and orientation as the robot travels from point to point. The coordinate transformations required for this hardware management are calculated by the robot's control system computer. Observations that result from this type of programming are less likely to present a hazard to personnel and equipment. CONTINUOUS PATH A robot whose path is controlled by storing a large number or close succession of spatial points in memory during a teaching sequence is a continuous path controlled robot. During this time, and while the robot is being moved, the coordinate points in space of each axis are continually monitored on a fixed time base, e.g., 60 or more times per second, and placed into the control system's computer memory. When the robot is placed in the automatic mode of operation, the program is replayed from memory and a duplicate path is generated.

sensors. The physical dimensions, design, and weight-carrying ability depend on application requirements. POWER SOURCES Energy is provided to various robot actuators and their controllers as pneumatic, hydraulic, or electrical power. The robot's drives are usually mechanical combinations powered by these types of energy, and the selection is usually based upon application requirements. For example, pneumatic power (low-pressure air) is used generally for low weight carrying robots. Hydraulic power transmission (high-pressure oil) is usually used for medium to high force or weight applications, or where smoother motion control can be achieved than with pneumatics. Consideration should be given to potential hazards of fires from leaks if petroleum-based oils are used. Electrically powered robots are the most prevalent in industry. Either AC or DC electrical power is used to supply energy to electromechanical motor-driven actuating mechanisms and their respective control systems. Motion control is much better, and in an emergency an electrically powered robot can be stopped or powered down more safely and faster than those with either pneumatic or hydraulic power.

CONTROL SYSTEMS
Either auxiliary computers or embedded microprocessors are used for practically all control of industrial robots today. These perform all of the required computational functions as well as interface with and control associated sensors, grippers, tooling, and other associated peripheral equipment. The control system performs the necessary sequencing and memory functions for on-line sensing, branching, and integration of other equipment. Programming of the controllers can be done on-line or at remote off-line control stations with electronic data transfer of programs by cassette, floppy disc, or telephone modem.

ROBOT COMPONENTS
Industrial robots have four major components: the mechanical unit, power source, control system, and tooling (Figure III:4-2): MECHANICAL UNIT The robot's manipulative arm is the mechanical unit. This mechanical unit is also comprised of a fabricated structural frame with provisions for supporting mechanical linkage and joints, guides, actuators (linear or rotary), control valves, and

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Figure III:4-2. Industrial Robots: Major Components Self-diagnostic capability for troubleshooting maintenance greatly reduces robot system downtime. and

ROBOT PROGRAMMING BY TEACHING METHODS

A program consists of individual command steps which state either the position or function to be performed, along with other informational data such as speed, dwell or delay times, sample input device, activate output device, execute, etc. When establishing a robot program, it is necessary to establish a physical or geometrical relationship between the robot and other equipment or work to be serviced by the robot. To establish these coordinate points precisely within the robot's

Some robot controllers have sufficient capacity, in terms of computational ability, memory capacity, and input-output capability to serve also as system controllers and handle many other machines and processes. Programming of robot controllers and systems has not been standardized by the robotics industry; therefore, the different manufacturers use their own proprietary programming languages which require special training of personnel.

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working envelope, it is necessary to control the robot manually and physically teach the coordinate points. To do this as well as determine other functional programming information, three different teaching or programming techniques are used: lead-through, walk-through, and off-line. LEAD-THROUGH PROGRAMMING OR TEACHING This method of teaching uses a proprietary teach pendant (the robot's control is placed in a "teach" mode), which allows trained personnel physically to lead the robot through the desired sequence of events by activating the appropriate pendant button or switch. Position data and functional information are "taught" to the robot, and a new program is written (Figure III:4-3). The teach pendant can be the sole source by which a program is established, or it may be used in conjunction with an additional programming console and/or the robot's controller. When using this technique of teaching or programming, the person performing the teach function can be within the robots working envelope with operational safeguarding devices deactivated or inoperative.

WALK-THROUGH PROGRAMMING OR TEACHING

A person doing the teaching has physical contact with the robot arm and actually gains control and walks the robot's arm through the desired positions within the working envelope (Figure III:4-4). During this time, the robot's controller is scanning and storing coordinate values on a fixed time basis. When the robot is later placed in the automatic mode of operation, these values and other functional information are replayed and the program run as it was taught. With the walk-through method of programming, the person doing the teaching is in a potentially hazardous position because the operational safeguarding devices are deacti-vated or inoperative. OFF-LINE PROGRAMMING The programming establishing the required sequence of functional and required positional steps is written on a remote computer console (Figure III:4-5). Since the console is distant from the robot and its controller, the written program has to be transferred to the robot's controller and precise positional data established to achieve the actual coordinate information for the robot and other equipment. The program can be transferred directly or by cassette or floppy discs. After the program has been completely transferred to the robot's controller, either the lead-through or walk-through technique can be used for obtaining actual positional coordinate information for the robot's axes. When programming robots with any of the three techniques discussed above, it is generally required that the program be verified and slight modifications in positional information made. This procedure is called program touch-up and is normally carried out in the teach mode of operation. The teacher manually leads or walks the robot through the programmed steps. Again, there are potential hazards if safeguarding devices are deactivated or inoperative.

Figure III:4-3. Robot Lead-Through Programming or Teaching.

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DEGREES OF FREEDOM
Regardless of the configuration of a robot, movement along each axis will result in either a rotational or a translational movement. The number of axes of movement (degrees of freedom) and their arrangement, along with their sequence of operation and structure, will permit movement of the robot to

any point within its envelope. Robots have three arm movements (up-down, in-out, side-to-side). In addition, they can have as many as three additional wrist movements on the end of the robot's arm: yaw (side to side), pitch (up and down), and rotational (clockwise and counterclockwise).

C. HAZARDS
The operational characteristics of robots can be significantly different from other machines and equipment. Robots are capable of high-energy (fast or powerful) movements through a large volume of space even beyond the base dimensions of the robot (see Figure II:4-6). The pattern and initiation of movement of the robot is predictable if the item being "worked" and the environment are held constant. Any change to the object being worked (i.e., a physical model change) or environmental changes can affect the programmed movements. Some maintenance and programming personnel may be required to be within the restricted envelope while power is available to actuators. The restricted envelope of the robot can overlap a portion of the restricted envelope of other robots or work zones of other industrial machines and related equipment. Thus, a worker can be hit by one robot while working on another, trapped between them or peripheral equipment, or hit by flying objects released by the gripper. A robot with two or more resident programs can find the current operating program erroneously calling another existing program with different operating parameters such as velocity, acceleration, or deceleration, or position within the robot's

Figure III:4-4. Walk-through Programming and Teacher. Figure III:4-5. Off-line Programming or Teaching

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Figure III:4-6. A Robots Work Envelope. restricted envelope. The occurrence of this might not be predictable by maintenance or programming personnel working with the robot. A component malfunction could also cause an unpredictable movement and/or robot arm velocity. Additional hazards can also result from the malfunction of, or errors in, interfacing or programming of other process or peripheral equipment. The operating changes with the process being performed or the breakdown of conveyors, clamping mechanisms, or process sensors could cause the robot to react in a different manner. IMPACT OR COLLISION ACCIDENTS Unpredicted movements, component malfunctions, or unpredicted program changes with the robot's arm or peripheral equipment can result in contact accidents. CRUSHING AND TRAPPING ACCIDENTS A worker's limb or other body part can be trapped between a robot's arm and other peripheral equipment, or the individual may be physically driven into and crushed by other peripheral equipment. MECHANICAL PART ACCIDENTS The breakdown of the robot's drive components, tooling or end-effector, peripheral equipment, or its power source is a mechanical accident. The release of parts, failure of gripper mechanism, or the failure of end-effector power tools (e.g., grinding wheels, buffing wheels, deburring tools, power screwdrivers, and nut runners) are a few types of mechanical failures.

TYPES OF ACCIDENTS
Robotic incidents can be grouped into four categories: a robotic arm or controlled tool causes the accident, places an individual in a risk circumstance, an accessory of the robot's mechanical parts fails, or the power supplies to the robot are uncontrolled.

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OTHER ACCIDENTS Other accidents can result from working with robots. Equipment that supplies robot power and control represents potential electrical and pressurized fluid hazards. Ruptured hydraulic lines could create dangerous high-pressure cutting streams or whipping hose hazards. Environmental accidents from arc flash, metal spatter, dust, electromagnetic, or radio-frequency interference can also occur. In addition, equipment and power cables on the floor present tripping hazards.

UNAUTHORIZED ACCESS Entry into a robot's safeguarded area is hazardous because the person involved may not be familiar with the safeguards in place or their activation status. MECHANICAL FAILURES Operating programs may not account for cumulative mechanical part failure, and faulty or unexpected operation may occur. ENVIRONMENTAL SOURCES Electromagnetic or radio-frequency interference (transient signals) should be considered to exert an undesirable influence on robotic operation and increase the potential for injury to any person working in the area. Solutions to environmental hazards should be documented prior to equipment start-up. POWER SYSTEMS Pneumatic, hydraulic, or electrical power sources that have malfunctioning control or transmission elements in the robot power system can disrupt electrical signals to the control and/or power-supply lines. Fire risks are increased by electrical overloads or by use of flammable hydraulic oil. Electrical shock and release of stored energy from accumulating devices also can be hazardous to personnel. IMPROPER INSTALLATION The design, requirements, and layout of equipment, utilities, and facilities of a robot or robot system, if inadequately done, can lead to inherent hazards.

SOURCES OF HAZARDS
The expected hazards of machine to man can be expected with several additional variations. HUMAN ERRORS Inherent prior programming, interfacing activated peripheral equipment, or connecting live input-output sensors to the microprocessor or a peripheral can cause dangerous, unpredicted movement or action by the robot from human error. The incorrect activation of the "teach pendant" or control panel is a frequent human error. The greatest problem, however, is overfamiliarity with the robot's redundant motions so that an individual places himself in a hazardous position while programming the robot or performing maintenance on it. CONTROL ERRORS Intrinsic faults within the control system of the robot, errors in software, electromagnetic interference, and radio frequency interference are control errors. In addition, these errors can occur from faults in the hydraulic, pneumatic, or electrical subcontrols associated with the robot or robot system.

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D. INVESTIGATION GUIDELINES
MANUFACTURED, REMANUFACTURED, AND REBUILT ROBOTS
All robots should meet minimum design requirements to insure safe operation by the user. Consideration needs to be given to a number of factors in designing and building the robots to industry standards. If older or obsolete robots are rebuilt or remanufactured, they should be upgraded to conform to current industry standards. Every robot should be designed, manufactured, remanufactured, or rebuilt with safe design and manufacturing considerations. Improper design and manufacture can result in hazards to personnel if minimum industry standards are not conformed to on mechanical components, controls, methods of operation, and other required information necessary to insure safe and proper operating procedures. To insure that robots are designed, manufactured, remanufactured, and rebuilt to insure safe operation, it is recommended that they comply with Section 4 of the ANSI/RIA R15.06-1992 standard for Manufacturing, Remanufacture, and Rebuild of Robots.

INSTALLATION
A robot or robot system should be installed by the users in accordance with the manufacturer's recommendations and in conformance to acceptable industry standards. Temporary safeguarding devices and practices should be used to minimize the hazards associated with the installation of new equipment. The facilities, peripheral equipment, and operating conditions which should be considered are: @ @ @ @ @ @ @ Installation specifications, Physical facilities, Electrical facilities, Action of peripheral equipment integrated with the robot, Identification requirements, Control and emergency stop requirements, and Special robot operating procedures or conditions.

To insure safe operating practices and safe installation of robots and robot systems, it is recommended that the minimum requirements of Section 5 of the ANSI/RIA R15.06-1992, Installation of Robots and Robot Systems be followed. In addition, OSHA's Lockout/ Tagout standards (29 CFR 1910.147 and 1910.333) must be be followed for servicing and maintenance.

E. CONTROL AND SAFEGUARDING PERSONNEL

For the planning stage, installation, and subsequent operation of a robot or robot system, one should consider the following. There are different system and personnel safeguarding requirements at each stage. The appropriate level of safeguarding determined by the risk assessment should be applied. In addition, the risk assessments for each stage of development should be documented for future reference.

RISK ASSESSMENT
At each stage of development of the robot and robot system a risk assessment should be performed.

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SAFEGUARDING DEVICES
Personnel should be safeguarded from hazards associated with the restricted envelope (space) through the use of one or more safeguarding devices: @ @ @ @ @ Mechanical limiting devices, Nonmechanical limiting devices, Presence sensing safeguarding devices, Fixed barriers (which prevent contact with moving parts), and Interlocked barrier guards.

OPERATOR SAFEGUARDS
The system operator should be protected from all hazards during operations performed by the robot. When the robot is operating automatically, all safeguarding devices should be activated, and at no time should any part of the operator's body be within the robot's safeguarded area. For additional operator safeguarding suggestions, see the ANSI/RIA R15.06-1992 standard, Section 6.6.

ATTENDED CONTINUOUS OPERATION

When a person is permitted to be in or near the robots restricted envelope to evaluate or check the robots motion or other operations, all continuous operation safeguards must be in force. During this operation, the robot should be at slow speed, and the operator would have the robot in the teach mode and be fully in control of all operations. Other safeguarding requirements are suggested in the ANSI/RIA R15.06-1992 standard, Section 6.7.

AWARENESS DEVICES
Typical awareness devices include chain or rope barriers with supporting stanchions or flashing lights, signs, whistles, and horns . They are usually used in conjunction with other safeguarding devices.

SAFEGUARDING THE TEACHER

Special consideration must be given the teacher or person who is programming the robot. During the teach mode of operation, the person performing the teaching has control of the robot and associated equipment and should be familiar with the operations to be programmed, system interfacing, and control functions of the robot and other equipment. When systems are large and complex, it can be easy to activate improper functions or sequence functions improperly. Since the person doing the training can be within the robot's restricted envelope, such mistakes can result in accidents. Mistakes in programming can result in unintended movement or actions with similar results. For this reason, a restricted speed of 250 mm/sec. or 10 in/sec. should be placed on any part of the robot during training to minimize potential injuries to teaching personnel. Several other safeguards are suggested in the ANSI/RIA R15.06-1992 standard to reduce the hazards associated with teaching a robotic system.

MAINTENANCE & REPAIR PERSONNEL

Safeguarding maintenance and repair personnel is very difficult because their job functions are so varied. Troubleshooting faults or problems with the robot, controller, tooling, or other associated equipment is just part of their job. Program touchup is another of their jobs as is scheduled maintenance, and adjustments of tooling, gages, recalibration, and many other types of functions. While maintenance and repair is being performed, the robot should be placed in the manual or teach mode, and the maintenance personnel perform their work within the safeguarded area and within the robots restricted envelope. Additional hazards are present during this mode of operation

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because the robot system safeguards are not operative. To protect maintenance and repair personnel, safeguarding techniques and procedures as stated in the ANSI/RIA R15.06-1992 standard, Section 6.8, are recommended.

SAFETY TRAINING
Personnel who program, operate, maintain, or repair robots or robot systems should receive adequate safety training, and they should be able to demonstrate their competence to perform their jobs safely. Employers can refer to OSHA's publication 2254 (Revised), "Training Requirements in OSHA Standards and Training Guidelines."

MAINTENANCE
Maintenance should occur during the regular and periodic inspection program for a robot or robot system. An inspection program should include, but not be limited to, the recommendations of the robot manufacturer and manufacturer of other associated robot system equipment such as conveyor mechanisms, parts feeders, tooling, gages, sensors, and the like. These recommended inspection and maintenance programs are essential for minimizing the hazards from component malfunction, breakage, and unpredicted movements or actions by the robot or other system equipment. To insure proper maintenance, it is recommended that periodic maintenance and inspections be documented along with the identity of personnel performing these tasks.

GENERAL REQUIREMENTS
To ensure minimum safe operating practices and safeguards for robots and robot systems covered by this instruction, the following sections of the ANSI/RIA R15.06-1992 must also be considered: @ @ @ @ Section 6 - Safeguarding Personnel Section 7 - Maintenance of Robots and Robot Systems Section 8 - Testing and Start-up of Robots and Robot Systems Section 9 - Safety Training of Personnel

Robots or robotic systems must comply with the following regulations: Occupational Safety and Health Administration, OSHA 29 CFR 1910.333 and OSHA 29 CFR Part 1910.147, "Control of Hazardous Energy Source (Lockout/Tagout); Final Rule."

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F. BIBLIOGRAPHY
American National Standards Institute (ANSI) American National Safety Standard ANSI/ RIA R15.06-1992. Industrial Robots and Robot Systems - Safety Requirements. American National Standards Institute, Inc., 1430 Broadway, New York, New York 10018 National Institute for Occupational Safety and Health (NIOSH) Alert Publication No. 85103. Request for Assistance in Preventing the Injury of Workers by Robots. National Institute for Occupational Safety and Health, Division of Safety Research, 944 Chestnut Ridge Road, Morgantown, West Virginia 26505 Occupational Safety and Health Administration Publication No. 3067. Concepts and Techniques of Machine Safeguarding. U.S. Department of Labor, 1980 (reprinted 1983). Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20210 Robotic Industries Association, 900 Victors Way, P.O. Box 3724, Ann Arbor, Michigan 48106 Occupational Safety and Health Administration Publication No. 2254 (Revised). Training Requirements in OSHA Standards and Training Guidelines. Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20210 National Safety Council Data Sheet 1-717-85. Robots. National Safety Council, 444 N. Michigan Avenue, Chicago, Illinois 60611 National Institute for Occupational Safety and Health (NIOSH) Technical Report Publication No. 880108. Safe Maintenance Guidelines for Robotic Workstations. National Institute for Occupational Safety and Health, Division of Safety Research, 944 Chestnut Ridge Road, Morgantown, West Virginia 26505 OSHA Instruction Publication No. 8-1.3. 1987. Guideline for Robotics Safety. Occupational Safety and Health Administration, Washington, DC

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APPENDIX III:4-1.

GLOSSARY FOR ROBOTICS AND ROBOTIC SYSTEMS

Barrier A physical means of separating persons from the restricted envelope (space). Control Device Any piece of control hardware providing a means for human intervention in the control of a robot or robot system, such as an emergency-stop button, a start button, or a selector switch. Control Program The inherent set of control instructions that defines the capabilities, actions and responses of the robot system. This program is usually not intended to be modified by the user. Coordinated Straight Line Motion Control wherein the axes of the robot arrive at their respective end points simultaneously, giving a smooth appearance to the motion. Control wherein the motions of the axes are such that the Tool Center Point (TCP) moves along a prespecified type of path (line, circle, etc.) Device Any piece of control hardware such as an emergency-stop button, selector switch, control pendant, relay, solenoid valve, sensor, etc. Drive Power The energy source or sources for the robot actuators. Emergency Stop The operation of a circuit using hardware-based components that overrides all other robot controls, removes drive power from the robot actuators, and causes all moving parts to stop.

Actuator A power mechanism used to effect motion of the robot; a device that converts electrical, hydraulic, or pneumatic energy into robot motion. Application Program The set of instructions that defines the specific intended tasks of robots and robot systems. This program may be originated and modified by the robot user. Attended Continuous Operation The time when robots are performing (production) tasks at a speed no greater than slow speed through attended program execution. Attended Program Verification The time when a person within the restricted envelope (space) verifies the robot's programmed tasks at programmed speed. Automatic Mode The robot state in which automatic operation can be initiated. Automatic Operation The time during which robots are performing programmed tasks through unattended program execution. Awareness Barrier Physical and/or visual means that warns a person of an approaching or present hazard. Awareness Signal A device that warns a person of an approaching or present hazard by means of audible sound or visible light. Axis The line about which a rotating body such as tool turns.

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Enabling Device A manually operated device that permits motion when continuously activated. Releasing the device stops robot motion and motion of associated equipment that may present a hazard. End-effector An accessory device or tool specifically designed for attachment to the robot wrist or tool mounting plate to enable the robot to perform its intended task. (Examples may include gripper, spot-weld gun, arc-weld gun, spray- paint gun, or any other application tools.) Energy Source Any electrical, mechanical, hydraulic, pneumatic, chemical, thermal, or other source. Envelope (Space), Maximum The volume of space encompassing the maximum designed movements of all robot parts including the end-effector, workpiece, and attachments. Restricted Envelope (Space) That portion of the maximum envelope to which a robot is restricted by limiting devices. The maximum distance that the robot can travel after the limiting device is actuated defines the boundaries of the restricted envelope (space) of the robot. NOTE: The safeguarding interlocking logic and robot program may redefine the restricted envelope (space) as the robot performs its application program. (See Appendix D of the ANSI/RIA R15.06-1992 Specification).

Hazardous Motion Any motion that is likely to cause personal physical harm. Industrial Equipment Physical apparatus used to perform industrial tasks, such as welders, conveyors, machine tools, fork trucks, turn tables, positioning tables, or robots. Industrial Robot A reprogrammable, multifunctional manipulator designed to move material, parts, tools, or specialized devices through variable programmed motions for the performance of a variety of tasks. Industrial Robot System A system that includes industrial robots, the end-effectors, and the devices and sensors required for the robots to be taught or programmed, or for the robots to perform the intended automatic operations, as well as the communication interfaces required for interlocking, sequencing, or monitoring the robots. Interlock An arrangement whereby the operation of one control or mechanism brings about or prevents the operation of another. Joint Motion A method for coordinating the movement of the joints such that all joints arrive at the desired location simultaneously. Limiting Device A device that restricts the maximum envelope (space) by stopping or causing to stop all robot motion and is independent of the control program and the application programs. Maintenance The act of keeping the robots and robot systems in their proper operating condition.

Operating Envelope (Space) That portion of the restricted envelope (space) that is actually used by the robot while performing its programmed motions. Hazard A situation that is likely to cause physical harm.

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Mobile Robot A self-propelled and self-contained robot that is capable of moving over a mechanically unconstrained course. Muting The deactivation of a presence-sensing safeguarding device during a portion of the robot cycle. Operator The person designated to start, monitor, and stop the intended productive operation of a robot or robot system. An operator may also interface with a robot for productive purposes. Pendant Any portable control device, including teach pendants, that permits an operator to control the robot from within the restricted envelope (space) of the robot. Presence-Sensing Safeguarding Device A device designed, constructed, and installed to create a sensing field or area to detect an intrusion into the field or area by personnel, robots, or other objects. Program 1. (noun) A sequence of instructions to be executed by the computer or robot controller to control a robot or robot system; 2. (verb) to furnish (a computer) with a code of instruction; 3. (verb) to teach a robot system a specific set of movements and instructions to accomplish a task. Rebuild To restore the robot to the original specifications of the manufacturer, to the extent possible. Remanufacture To upgrade or modify robots to the revised specifications of the manufacturer and applicable industry standards. Repair To restore robots and robot systems to operating condition after damage, malfunction, or wear.

Robot Manufacturer A company or business involved in either the design, fabrication, or sale of robots, robot tooling, robotic peripheral equipment or controls, and associated process ancillary equipment. Robot System Integrator A company or business who either directly or through a subcontractor will assume responsibility for the design, fabrication, and integration of the required robot, robotic peripheral equipment, and other required ancillary equipment for a particular robotic application. Safeguard A barrier guard, device, or safety procedure designed for the protection of personnel. Safety Procedure An instruction designed for the protection of personnel. Sensor A device that responds to physical stimuli (such as heat, light, sound, pressure, magnetism, motion, etc.) and transmits the resulting signal or data for providing a measurement, operating a control, or both. Service To adjust, repair, maintain, and make fit for use. Single Point of Control The ability to operate the robot such that initiation or robot motion from one source of control is possible only from that source and cannot be overridden from another source. Slow Speed Control A mode of robot motion control where the velocity of the robot is limited to allow persons sufficient time either to withdraw the hazardous motion or stop the robot. Start-up Routine application of drive power to the robot or robot system.

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Start-up, Initial Initial drive power application to the robot or robot system after one of the following events: @ @ @ @ Manufacture or modification Installation or reinstallation Programming or program editing Maintenance or repair

Teach Mode The control state that allows the generation and storage of positional data points effected by moving the robot arm through a path of intended motions. Teacher A person who provides the robot with a specific set of instructions to perform a task. Tool Center Point (TCP) The origin of the tool coordinate system. User A company, business, or person who uses robots and who contracts, hires, or is responsible for the personnel associated with robot operation.

Teach The generation and storage of a series of positional data points effected by moving the robot arm through a path of intended motions.

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APPENDIX III:4-2.

OTHER ROBOTIC SYSTEMS NOT COVERED BY THIS CHAPTER

Automatic conveyor and shuttle systems are comprised of various types of conveying systems linked together with various shuttle mechanisms for the prime purpose of conveying materials or parts to prepositioned and predetermined locations automatically. Teleoperators are robotic devices comprised of sensors and actuators for mobility and/or manipulation and are controlled remotely by a human operator. Mobile robots are freely moving automatic programmable industrial robots Prosthetic robots are programmable manipulators or devices for missing human limbs. Numerically controlled machine tools are operated by a series of coded instructions comprised of numbers, letters of the alphabet, and other symbols. These are translated into pulses of electrical current or other output signals that activate motors and other devices to run the machine.

Service robots are machines that extend human capabilities. Automatic guided-vehicle systems are advanced material-handling or conveying systems that involve a driverless vehicle which follows a guide-path. Undersea and space robots include in addition to the manipulator or tool that actually accomplishes a task, the vehicles or platforms that transport the tools to the site. These vehicles are called remotely operated vehicles (ROVs) or autonomous undersea vehicles (AUVs); the feature that distinguishes them is, respectively, the presence or absence of an electronics tether that connects the vehicle and surface control station. Automatic storage and retrieval systems are storage racks linked through automatically controlled conveyors and an automatic storage and retrieval machine or machines that ride on floor-mounted guide rails and power-driven wheels.

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