E INTENTS 1. INTRODUCTION 2, DIFFERENT NAME OF SODIUM SULPHATE 3. MINERALS OF SODIUM SULPHATE 4, HISTORY 5. METHOD OF PREPRATION Na,SO, AS BY PRODUCT OTHERMAYER PROCESS SYNTHETIC SALT CAKE HAGARWAVES PROCESS FROM POTASSIUM DICHOROMATE AMMONIUM SULPHATE ~SODIUM CHLORIDE PROCESS 6. SELECTED PROCESS e RAW MATERIALS © PROCESS DESCRIPTION ¢ CRYSTALIZATION PROPERTIES 7. PROPERTIES AND APPLICATIONS © PROPERTIES ONSINTRODUCTION The ultimate goal for development of the country is to provide picture of condition that will ensure maximum use of resources at minimum cost. Formic acid is produces by the action of sulphuric acid on sodium fromate along with sodium sulphate. The same method can be adopted for the production of sodium sulphate. Sulphate of sodium is industrly important material sold in three forms shown in table. In period from 1970 to 1981, over one million metric tons were consumed annually in the united state only. Sodium sulpahte is used principally 40% in soap and detergent industry. Pulp and paper manufacturers consume 25%, textile 19%, glass5% and miscellaneous industries consume 11%. About half of the sodium sulphate produced is synthetic by product of rayon, dichromate, phenol, or potash. Sodium sulphate made as a by-product referred to as synthetic. Sodium sulphate made form mirabilite, thenardite, or naturally occurring brine is called natural sodium sulphate. In 1994, about 300,000 t of sodium sulphate were produced as a by-product: an other 300,000 t were produced from natural sodium sulphate deposits.pa. 8 Historically the sulphate was low Purity, but demand for high purity and controlled particle size has forced manufacturer either to produced higher quality or go out for business. Sodium sulphate are mined commercially from three type of mineral evaporates: thenardite, mirabilie, and high sulphur brime deposits. Why different names are given to sodium sulphate Common name have been given to sodium sulphate as a result of Manufacturing methods. In rayon production, by product sodium sulphate is Separated from slurry by filtration where a7-10-cm cake forms over the filter media. Thus rayon cake term was coined for this cake. Similarly, salt cake, | chrome cake, phenol cake, and other sodium sulphate cake name were named, Li MINERALS OF SODIUM SULPHATE Minerals of sodium sulphates occur naturally throughout the world. The deposits result from evaporation of inland seas and lakes. | © Cold climates such as those found in Canda and the former sovitunnion, favor formation of mirabilite. © Warmer climates, such as those found in South America, Pakistan, Mexico, and the western united state, favors formation of thenardite. © In areas where other anions and cations are present, double salts can be found of the kinds shown belowfre 1. Glaserite 9 2. Bloedite Ness, dabieis Na,SO,MgS0,4H,0 2Na»So4 Na,CO; 4. Glauber’s salt Na,SO, 10H,0 s FS HISTORY j Three centuries ago Glauber observed that when sulphuric acid poured sr common salt even at ordinary temperature a color less sharp smelling gas obtained. The salt produced Na2SO4 10 H20 is still called “ glauber’s it”. He used his salt for medical purpose. Before the Solvay process for the manufacturing of soda ash, Leblance ess was in universal. Use. Nicholas Leblanc devised his famous process soda ash manufacturer around 1773. It was based on roasting salt cake carbon and limestone in rotary furnace. In early days Lablance made the cake in reverbratory furnace from common salt and sulphuric acid. Then d worked and muffle furnaces came into use. Many attempts were made to out the manufacture of salt cake in mechanical furnaces. Hazelnut’s hanical furnaces was patented in England in 1882.in 1887 walker’s ace was patended.the well known Mannheim mechanical furnaces was t use in 1909 at Mannheim to obtain pure arsenic free hydrochloric acid salt cake. In 1920 a modern rotary furnace was built. In 1870 Hargreaves a method of making sodium sulphate directly from sulphur dioxide common salts. This is known as Hargreaves process very good salt cake hydrochloric acid are made in the process but it required a large amountpecause of increase demand of sodium sulphate Kraft peat acture synthetic salt ' ni cake has resulted salt cake is prepared by fusing a ash and elemental sulphur in molecular proportions Because the expending Kraft Paper industry and its use in synthetic gents on large scale, the development of sodium sulphate from natural ources has been greatly stimulated. The chief sources of sodium sulphate the lakes in Canda In India sodium sulphate has been extracted from reh or kallar in last ntury at Auodh and united state of Agra. The salt known as khari has been ed for medicinal purpose as purgative. It has also been used for treating s, where it was found batter than common salt.ICET LIBRARY, UNIVERSITY OF PUNJAB, LAHORE METHOD OF PREPRATION1. SODIUM SULPHATE AS A BY PRODUCT SODIUM SULPHATE FROM HYDROCHLORIC ACID INDUSTRY The important method for t he production of salt cake or crude sodium ulphate is through the action of Sulphuric acid to obtain hydrochloric acid. At emperature in range of 300°F the Product is the acid sulphate and may be call niter cake, as it is similar to the solid product of salt peter-sulphuric acid process for the manufacture of nitric acid. At temperature in the range of 1000°F the product is normal sulphate and may be called in the trade salt cake. Complete decomposition occurs at red heat in the presence of slight excess of sulphuric acid. The acid sulphate may be substituted for the sulphuric acid in ihe higher temperature reaction. The reaction involves are as follows 2NaCl+H2SO,4 —————» _ Na)S0,+2HCl1 ¢ SALT CAKE FURNACES: The decomposition of salt by sulphuric acid for the formation of salt Cake and hydrochloric acid takes place in two steps, in the first step of which acid sulphate is formed. Whether this first step is performed in separate as it may be or whether both steps are performed in ne salt cake the latter is the principal part of the equipment. It is the mostive part to build expansive Pi and to operate, All other parts of the proc h . waited 0" the development of the furnace. ee ¢ Hand worked reverbratory furnac For many year alkali was all by the Leblanc process. Its first operation is the preparation of salt cake. In the early days Leblanc made it in a simple reverbratory furnace. Salt and acid were mixed in the hearth and the flue gas from the coal fire on the adjacent grade passed directly over the charge, rapidly effecting conversion and sweeping the hydrogen chloride up the stack. In England the law abated the nuisance by the establishment of a permissible minimum of the acid in the escaping gas. To comply the manufacturers drew the gas up large towers built of stone slates and packed with cake, through which water was trickled. As uses developed for all of hydrochloric acid the design and operation of tower were modified, but the methods adopted did not yield a product of strength and purity obtained in muffle furnaces. Moreover a demand came for salt cake of a quality also through obtainable at that time only a muffle. 'e POST AND MUFFLE FURNACE: were hand worked like the reverbratories, but ‘The first muffle furnaces : pot in which the first step of the reaction With them came the addition of the. D, rformed. Pot had been att 14 was PO ached to o, a Pen fire fy ces i iatanees- But the standard farina furnaces in some NY yea e year was the pot and muffle furnace. se fur although these naces are now a days rarely buikt so 7 some are still in use. 2. THE OTHERMAYER PROCESS: The other Mayer uses muffle without pots at all. Bisulphate is used for composing alt. The two are mixed and ground to a fine powder and then eated in muffle without any stirring the temperature of the cake must be 50-S000F. It makes good salt but at low capacity muffle area. 3. SYNTHETIC SALT CAKE: ecause of the increase demand of sodium sulphate in the Kraft paper anufacture synthetic salt cake. Synthetic salt cake is a sintered mixture of oda ash and sulphur proportions of 3 parts of sulphur to 10 soda ash. CO; +S + 1.50. ————» _Na,SO,+CO, is product is not satisfactory as a substitute for sodium sulphate in plications other than craft paper industry. 4. HARGRWAVES PROCESS: The Hargrwaves process introduced in England in I century, promised for a time to become an important source of salt cake hydrochloric acid. It eliminated the necessity for agitating the reaction ast half of thepowever being work Successfully in | Ouisiana ‘The reactants are salt, sulphurdioxide as air and water vapors. the reaction involved id S+0, > so; 4NaCl + 280) + O2 + 21,0 > 2Na,SO,+ 4HCL The reactors are exothermic and sufficient heat is evolved to maintain Process, once the reactions are brought to the temperature. The process onsist of passing a mixture of sulphur dioxide and air through stocks of salt Uriquets lying on perforated false bottoms within vertical chambers. The tion of the process is cyclic; a chamber containing spent salts is removed 0 be replaced one containing fresh salt at the end of each cycle. The chamber so manifolded that strong sulphur dioxide contacts spent salt in the chamber to be removed and the weak sulphur dioxide contacts raw sulphate in the chamber newly installed. The passage of gas through the chamber is thus current with respect to salt. Sulphur dioxide is obtain by burning of F ry god salt cake and acid can make by this method but it could not for the large amount ‘of hand labour involved in the5. Potassium dichromate: . The modern method for the manufacturing of potassium dichromate nsists in ab eds Sodiumdichroamte, which is then converted into the yassium dichromate by reaction with potassium chloride. In the anufacturing of sodium dichromate a large amout of sodiumsulphate is duced as by product. The raw material used is in the following proportion chromite 2700- 100 Ib, soda ash 1600-2400Ib, lime 0-1 I1b and sulfuric=acid 850-1500Ib As a by product 1200-1800 Ibs of salt cake is produced. Aluminum is so recovered as a by product 6. AMMONIUM SULPHATE-SODIUM CHLORIDE PROCESS : Sodium sulpahte is prepare as a by production manufacturing of onium chloride by double decomposition of ammonium sulphate with lium chloride, the reaction is as follow (NH,4).S04+2NaCL ————» 2NH,CI+Na,SO,4 is process is used because ammonium sulphate is most readily av hloride are ailable monium salts. In this process ammonium sulphate and sodium c troduced into solution together. The amount of sodium chloride should be in hate used. The cess by S%of the quantity equivalent to ammoniumsulp! is maintained hot and agitated vegriously for some time. The pasty is filtered by use of suction. Sodium sulphate from the vacuum filter as such or may be recrystallised if pure sodium sulphate is required. fiery [OrySELECTED PROCESSzAW MATERIAL: ye rhe raW material required for this Process is |, SODUM FORMAT 2, SULPHURIC ACID pROCESS DETAILS: Sodium sulphate can be produced by the action of the sulphuric acid on the sodium format. the basic equation for the reaction is as follows 2HCOONa + H2SO,——® 2HCOOH + NaSO, According to the reaction 136kg of sodium format required 98 kg of sulphuric acid so 1300kg required918kg of sulphuric acid which is equal to 508 liter. The reaction is carried out in the reaction tank having cooling jacket outside in which cooling water is circulated to maintain the temperature of the reaction mass into the range of 45°C-50°C. because above 650C formic acid decompose into the CO and H,O At a time addition of the reactants are ®oided because the reaction is highly exothermic and by the addition of all ‘olves will evaporate all the formic acid ain in the tank. So some quantity of rate is so adjusted that all the reactants at a time the heat ev Produced and the solid mass will rem ‘odium format is added and the sulphuri Ne tequired sulphuric acid go into the ta ic acid is already added to the tank | "Setion the vapor evolves, absorb into the I ic acid flow nk in required time. Some quantity of 9 avoid solid mass formation. During lean formic aid solution.INVL NOLLVTILSIG Flow chart of formic acid lantlum. Steam is applied outside the jet. The vapors of formic acid obtained are condensed i the de mister. ifi i iene oust » Purifier, and iron separator and at the end from plate condenser. This formic acid is in the concentration range of 90% to 98%. hich is marketed after reducing the concentration to 85%? The jsf distillation is carried out under =a joncentration reduction carries out by adding dilute formic acid; obtain from absorption of formic acid vapors into the water. The solid mass obtain after the distillation is called as raw sulphate and is in the form of powder. The pH of this raw sulphate is acidic in nature an can be market as such or after making the crystals. Crystallization proces A 40% solution is made by dissolving raw sulphate obtain after the distillation. Then after maintaining the pH of the solution in basic reason the olution is send to the storage tank. In storage tank oily material are removed ‘ad the solution is filter by using horizontal filter. The solution is pumped ‘tough the filter and the filtrate obtained is send to the storage tank. The ; 's send to the evaporators. ‘sodium sulphate having pH 9-6 i " ged for the porpose of evaporation ar B=TeraIY OPS with agitator and heating coils. Crystallization is » to 30%water, obtain from theNS” OO , 2 The filter used for the purpose is called Natsha filter. It contain two the upper sieve have big hole and the lower sieve have small holes. The dropped on the sieve has big holes and water is filtered through the tnoles leaving behind the sodium sulphate’s crystals. Then by employing the vacuum the remaining moisture is removed. The crystals obtain from the filter still contains moisture. To remove this moisture and to make the granular of crystals the unit used is rotary drier. Crystals of sodium sulphate are into the drier along with the hot air. Air is heated by using steam coils. In rotary dryer crystals and air move co-currently and the crystals attain form of granular which are drawn off from the 2™ end of the dryer which classified by using vibrating screen and the crystals which blown off with air are recovered by using cyclone separators and bag filters. Sodium obtain is 99% pure and market in 50kg packing. The flow chart of the process of making raw sulphate and its crystalline10 I" ( centr } ~ ruon 4 ¢— vies | > Da — EVAPORATER a STORAGE A TANK . - (4 as | -“™ : a | NATSHA “ -_ ROTARY DRIER FHFER---- -- THIS LINE SHOW THE 40% SOLUTION OF THE SODIUM SULPHATE THS LINE SHOWS THE SOLUTION LINE AFTER MAINTANINIG THE pH THIS LINE SHOWS THE ‘(0 CENTRIFUGAL, AND TO THE RECOVERY TANK > THIS LINE SHOWS THE SOLUTION AFTER FILTERATION THIS LINE SHOWS THE SLURRY AFTER EVAPORATION —--— > ‘THIS LINE SHOWS THE SODIUM SULPHATE CRYSTALSjum sulpahte reaches the market in three forms 1. Anhydrous refined sodium sulphate 2. Technical grade sodium sulphate known as salt cake 3, Dehydrate known as Gauber’s salt SICAL CONTENTS Molecular weight 142.059 Melting point 8430C Heat of solution at 1000C 780 calories Heat of formation 328,600 calories Specific heat .232 Sodium sulphat partly volatilizes at 14000C Anhydrous sodium sulphate thenardite forms rhombic bipyramidal stals with a sp. gf of 2.70 at 1000C a transition occurs to monoclinic cture; at 5000C a transition to hexagonal structure takes place. Solubility of sodium sulphate in water increases from 0 to 32.280C, and gradually decreases to 103.50C, which is boiling point of saturated lution. Under 180C anhydrous sodium sulphate cannot exit in the presence Water but is converted into hm hydrate (Na2S047H20) or decahydrate 10H20). The solubility of heptads hydrate increases withiransition temperature is lowered by the presence of other salts, thus with italite NaK) 2804 it is 30.10C, with sodium chloride 17090C and with sodium chloride and aphthit a litte only 16.320C. Super saturated solution of sodium format is easily formed. When ium sulphate solution saturated at its boiling point is hermetically seeded No crystals are deposited on cooling. The same is true if the flash is closed by tton wool and often by merely covering it in a beaker with each glass ardor utting a layer of oil on the solution. Addition of a crystal of Glauber salt “ause crystallization. The solubility of sodium sulphate varies slightly with the pressure thus: ‘Solution saturated at 0OC contain 4.4 parts of dodium sulphate per 100 parts of Water at 1 atomosphre and 4.53 parts at 20 atmospheres, and a solution Saturateq at 15aaoc contain 11.32 parts at I atmosphere and 10.33 at 40 Pheres. It dissolved in a solution of ammonium chloride, ammonium ium copper act. And also in some organic esi "tate Potassium, and magn : and ethyl 'S such as alcohol and glycerin. to asolution of potassium chloride it thro asol but not in acetone or methyl es out potassiumsulphate. Sodium sulphate dissolves in sulphuric acid from whichsolution ae = q can be crystalised as Glauber’s salt. ELECTROLYSIS: Sodium sulphate can be dectrohysed in ordinary chlorine cell to produced caustic soda and dilute sulphuric acid. At efll and Fuwa state that the production cost of caustic soda made by electrolysis of sodium sulphate solution compares favorably with that from sodium chloride, and there is saving in raw material when waste solutions of sodium sulphate are used for the production of caustic soda and sulphuric acid for local consumption HEALTH AND SAFETY Environmental concern have influenced Na2SO4 manufacturing .for example whereas waste Na2S04 was historically discharged into water ways, regulations prohibit discharges of liquid containing sulphate into the environment. This affects the paper producers well as bye product producer. In general, Na,SO, is not considered an environmentally dangerous material, but the Mannheim and Hargreaves process are practically nonexistent in the USA because it is difficult to keep emission of particulate Na,SO, low keep HCI from escaping to the atmosphere. Sodium sulphate in the moderation is used as a diuretic and aesthetic for | humans and animals. It is also used in consumer products such as laxatives, laundry antacid, and as natural filler it is used extensively in powdered I detergent facturing of paper, soap, The princi le uses of sodium sulphate are in the manu se umption from 1990 to . These accounted for 65% of U.S cons'1995, representing a signifi 26 sibel cant shift from 1980 when Paper production : ‘ulp and paper consume only 155. The kraft process uses a mixture of sodium sulphide and sodium hydroxide to digest wood chip. Both . Bot ‘consumed 67%, ra nd hydroxide are generated, starting with sodium sulphate asthe At low temperature sodium sulphate is non reactive because of this and given its relatively low cost, it is used as a filler in household soap and detergents. Detergents average about 20% sodium sulphate but some grade have much higher content.besidr adding a bulk to the detergents, particle size and whiteness of the sulphate improved appearance, handling characteristics and assist the detergent in its ability to clean. Properties of sodium sulphate help speed up the melting process in the glassmaking. Its use reduced the tendency for alkaline gas bubbles to form in the glass and provides less expensive form of Na2Othan soda ash. Sodium sulphate improves the working properties of high silica glasses. Both sodium sulphate and sodium bisulphate are use to adjust pH and dilute dyes. Sodium sulphate is used in cattle fee, in cellulose-sponge, as a cement and plaster hardener, and as an aid in metallurgy refining. Glauber’s salt has a higher heat of crystallization. This fact together with its low cost has made it a candidate as melts, absorbing large quantit heat. Because of its incongruent pro a mean of a storing solar energy. When heated, Bit y of heat. When cool, itrecrystalize, releasing its perty the energy storing capability of the plication. Researchers are working to ff salt has not met with commercial ap develop ways to use it as an affective energy-storing salt.BIBLIOGRAPHY he KIRK OTHMER Encyclopedia of chemical technology Vol 22 the — inter sciences encyclopedia Inc. 2 SHREVES, R.N; The chemical process industries Vol 2 McGraw Hill book company Inc 3. JMCOULSON& Chemical engineering Vol 2 J F RICHARDSON 4, MECATA Encyclopedia of chemical engineering session SICET library, SIAL11-15 U niversity of : Injab, lahore.