Sulfuric Acid and Sulfur Trioxide Huesanw MetLue, Lurgi Metallurgic Grobll, PankfurUMain, Fed 1. Introduction 2 2 Properties 3 21. Physical Propert 3 22. Chemical Prope 7 3. Development of the Sulfuric Acid Industry 9 34. Early Development 9 32. Further Development ofthe Nitro- gen Oxide Process 9 33. Ascendeney of the Contact Process 9 34. Raw Materials Usage 0 4 Production 1 4.1. Production by Contact Processes 11 411, Reaction Kineties and Thermody- namics 1 412, Catalyss 3 41.3. Process Summary 4 413.1. Gas Drying 5 4.1.32. Catalytic Oxidation of Sulfur Diox- ide 6 4.13.3, Absorption of Sulfur Trioxide 20 4134. Acid Cooling 2 414, Practical Versions of the Contact Process 23 414.1. Double-Absorption Process Based ‘on Sulfur Combustion 24 4.142, Double- Absorption Processes Based on Metallurgical Gases 3 4.1.43, Ordinary Single-Adsorption Processes Mu 4144, Wel-Catalysis Processes 35 415, TailsGas Treatment 40 Based on the corresponding article in Ull- ‘mann, 4th ed., written by ULRICH SANDER, Ut- aici RoTHE, and Rote Kota (English Bdition: British Sulphur Corporation, 1984) 1. Introduction Of all the heavy industrial chemicals, sulfuric acid is perhaps the most fundamentally impor- tant, in thatithas anumber of large-scale uses not only within the chemical industry but in other in- dustries as well. By far the most important user 10 1002/14356007 25.535 (© 2005 Wiley-VCH Verlag GubHt & Co. KGaA, Weinheim Sulfuric Acid and Sulfur Trioxide 1 Republic of Germany Economic Factore “ Production by Nitrogen Oxide Processes 45 43. Regeneration of Spent Sulfuric Acid 48 Tntroduetion 48 43.2, Recoacenteation to 70-75 % H,SO3 50 433, Concentration to 93-98% HSO, 56 44. Production of Oleum 39 Construction Materials o ‘Metallic Materials 61 ‘Nonmetallic Materials 2 Uses of Sulfuric Acid and Eco 6 61. 8 62. Direct Uses 6 6.3. Economic Aspects 64 1 Analytical Techniques 6 71. Concentration Measurement 6 72. Measurement of Imputities 64 73. Analysis of Acid-Plant Gas Streams 65 8, Sulfur Trioxide 65 81. Properties 65 82. Manufacture or 83. Handling and Uses or 9. Toxicology os 9.1. Sulfuric Acid 68 92. Sulfur Trioxide 68 10. References oe is the phosphate fertilizer industry. Other im- portant applications of sulfuric acid are found in petroleum refining, pigment production, stecl pickling, nonferrous metals extraction, and the manufacture of explosives, detergents, plastics, and man-made fibers. Many specially areas of the chemical industry also use varying amounts of sulfuric acid including the production of dyes, pharmaceuticals, and fluorine chemicals ‘The consumption of sulfuric acid has many limes been cited as an indicator of the general slate of a nation’s economy, and although many other indicators (such as energy consumption)2 Sulfuric Acid and Sulfur Trioxide might today be regarded as more important, sul- furic acid consumption still follows general eco- nomic trends. For example, the recession that resulted from the “energy crisis" of 1974 was clearly reflected in the pattern of sulfuric acid consumption in the following three years. The recession a few years later was similarly accom- panied by a generally declining trend in sulfuric acid consumption starting in mid-1980. Sulfuric acid is manufactured from sulfur dioxide. The primary raw material for pro- ducing this intermediate is elemental sulfur (Sulfur; + Sulfur Dioxide). A large involun- tary producer of sulfur dioxide is the nonferrous metals industry, the roasting and smelting pro- cesses of which generate off-gases with a sul- ficiently high concentration of sulfur dioxide to permit direct processing to sulfuric acid as a by- product (-> Sulfur Dioxide, Chap. 5.5.) A\ significant number of sulfuric acid facil- ities have been installed in metallurgical plants for the recovery of SO, mainly for envionmen- {al reasons, To an increasing extent the acid pro- duced in such plants is replacing acid formerly obtained from elemental sulfur (or pyrite). An Important task for the years ahead is to estab- lish an infrastructure for distributing this “met- allurgical acid" to consumers, especially in the fextilizer industry. Pyrite still serves in several countries as araw material for sulfuric acid production, but produc- tion rates are no longer significant compared to the other sources described ‘Sulfur dioxide is also produced in the ther- mal decomposition stage of sulfuric acid re- generation from the heavily contaminated sul- furic acid (“spent acid”) created by certain industrial processes in which sulfuric acid is introduced(-+Sulfur Dioxide, Chap.5.6.1.). A further source of sulfur dioxide for sulfuric acid production is the combustion of waste gases containing hydrogen sulfide (-» Sulfur Dioxide, Chap. 5.7). In theory, there is enough sulfur dioxide to supply all the world’s sulfuric acid needs in ex- hast gases released during the combustion of sulfur-containing coal, fucl oil, and other fos- sil fuels in power stations and large industrial boilers. Although it is possible to recover such SO, in a concentrated form by regenerative fluc- gas desulfurization processes, of to convert it directly into HaSO,, only a minor amount of sulfuric acid is prepared by this route, Numer- fous fue-gas desulfurization plants installed re- cently as.a way of complying with environmen- tal regulations instead convert the SO, into gyp- sum, primarily for economic reasons. Unless en- vironmental regulations require desulfurization of combustion gases, fluc-gas sulfur dioxide is simply discharged into the atmosphere - where, ironically, ic is then transformed by atmospheric processes into sulfuric acid, which ultimately re- turns to earth dissolved in raintall. Essentially all sulfuric acid today is manu- factured by the contact process. The correspond ing technology is very mature, although impor- tant alterations in the detailed arrangement of the conversion and absorption stages were intro- duced commercially inthe 1960s to increase the sulfur dioxide conversion efficiency, primarily in the interest of environmental protection, Some plants are now designed fora sulfur dioxide con- version efficiency exceeding 99.8 %. Neverthe- less, the basic principle of the process remains the same today as when it was first introduced in the 1930s. Modern plants can be designed to be ex- tremely efficient in terms not only of sulfur diox- ide conversion but also energy recovery. It has been common practice for many yeats torecover 60 % or more of the total energy released in sul- furie acid production in the form of high-pres- sure steam, The energy efficiency of some plants hhas recently been very substantially increased, however, by providing for additional recovery of low-level heat from the acid system. In the attempt to comply with requirements for existing metallurgical complexes, sulfuric acid plants have been developed and constructed for teating gases containing as litte as 2 % SO (in a single-catalysis plant; $% in a double- catalysis plant see Section 4.1.4). A current ab- jective is to process sulfur dioxide gas streams with the highest SO, concentrations possible in the interest of reducing capital and operating costs and increasing further the extent of high- temperature energy recovery. At the same time, ‘quality requirements have become more strict for commercial acid. Given the large quantities of “metallurgical acid” now entering the market it will be necessary to develop new processes for eliminating such impurities as may still be present.‘Yet another important challenge facing sulf- ricacid makers the reprocessing of acid wastes from user industries. Itis a peculiarity of sulfu- ric acid that very litle of the material actually ends up in the products it is used to make. In- deed, apart from small-volume products such a pharmaceuticals, almost the only end products with sulfur values comparable to sulfuric acid are synthetic detergents ~and even they ae ulti- mately destined for the drain, Many uses result in so-called spent acid: sulfuric acid in vary- ing states of dilution as well as contamination with organic and inorganic impurities. Environ- ‘mental authorities are becoming increasingly in- tolerant of the sometimes rather casual waste- disposal methods of the past, and the industry is under pressure to accept greater amounts of used acid for reconcentration, purification, or regen- eration, Although the technology in this field is already quite extensive (see Section 4,3), further development can be expected in the use of reco- vered heat from sulfuric acid plants, 2. Properties 2.1. Physical Properties Pure sulfuric acid [7664-93-9], H2SO,, 1M, 98.08, is colorless, water-white, slightly viscous liquid, mp 104°C. bp279.6°C, and 41.8356. It can be mixed with water in any ratio. Aqueous sulfuric acid solutions are de- fined by their H,S0, content in weight-percent terms. Anhydrous (100 %) sulfuric acid is even today sometimes refered to as “monohydrate, which simply means that i isthe monohydrate of sulfur Wioxide, Sulfuric acid will dissolve any quantity of SO, forming oleam (“fuming sulfuric acid"), The concentration of oleum is expressed in weight-percent of dissolved SO, (Cree $03") in 100 % 1,50, The physical properties of sulfuric aid and eum {13} are dependent on the HaSOx and $0, concentrations, the temperature, and the pressure. Figure I shows the densities of slfuric acid and oleum as a function of temperature and concentration [4]. At constant temperature, the density of sulfuric acid increases steeply with rising H,S0q concentration, reaching’ maxi- mum at about 98 %, From there up toa concen tration of 100% the density decreases sighly Sulfuric Acid and Sulfur Trioxide 3 but it rises again in the oleum range up to a con- ‘centration of ca. 60% free SOs 2.000] Olean (% free $0 160 Density, kg/m? 1200 i rr Tenpersture, *¢—= [igure 1 Oleum and sulfuric aid density a «function of teanpeatre and coneetration [4] (On account of the clear relationship between density and concentration at defined tempera- tures in the lower concentration range, density measurement provides a quick method for deter- ‘mining concentration up to about 95 % H,S04 Hydrometers used for this purpose were for- metly calibrated in “degrees Baume” ("Bé), and for that reason sulfuric acid concentration was often, and sometimes still i, expressed in "BE “The density p in g/cm® is given by the expres- ara rasatay (1a on ) cess lara) v= uas/ (14s 8 "2"!) (united states) ‘The electrical conductivity of sulfuric acid at 20°C as a function of concentration is shown in Figure 2 (see next page). The pe- cculiar shape of the curve is due to the vari- fous states of ionic dissociation present in the system H,O/H,SO,/SOs at different concen- Uwations. Conductivity measurement is thus also4 Sulfuric Acid and Sulfur Trioxide dm 50 H,Sa, ute tree $0, ut%. k saad Concentration —= Figure 2. Hlectica conductivity of sulfuric acid and eum ane Viscosity, Pas —e- d ‘o a0 70 a0 3000 Concentration, wt%—— Figure 3 Dynamic vscony of sufi aid (5) a)A125°C:B) ALAS"C: 6) ALGO": d) ALBO®C useful as a method for determining the concen- ation of sulfuric acid, ‘The dynamic viscosity of sulfuric acid as a function of concentration at various tempera- tures is shown in Figure 3 [5] ‘The various maxima and minima observed on the freezing point curve of sulfuric acid and oleum, shown in Figure 4 [6), are due to the ex- istence of different sulfuric acid hydrates at dif- {erent temperatures. Whereas the 98,0-98.5 % acid used for sulfur trioxide absorption in sulfu- He acid production (Section 4.1.3) solidifies at about — 1 to +1°C, commercial 96 % sulfuric acid (66°B¢) solidifies at ca. — 15°C. Commer- cial 66°BE acid in the United States contains only 93.2 wi % 1180, and has a freezing point of ca. — 29°C. This behavior is obviously of im- portance if sulfuric acd is to be stored or trans- ported under very cold conditions. Figure 5 is a phase diagram for aqueous so- lutions of sulfuric acid based on boiling point measurements by Haast and Reuse (7). The Sulfuric acid 024060 HO, wi% igure 4 Freezing point curve for sulfrie acid and leurs ist 300 2 | E200} i} e Yi i 2 fi 1 1 i I i y i I i a a OT Concentration, wi%—— Figure 5, oiling curves for sulfuric acd at 1013 mbar (7) 2) Vapor: ) Liquid lower curve shows the relationship between the boiling point of sulfuric acid and its concen- tation, while the upper curve shows the sul- furic acid concentration in vapor evolved from acid boiling at a particular temperature. When an aqueous solution of sulfuric acid is boiled, the vapor contains more water than the boil- so the concentration of the acid in-creases and its boiling point rises. This contin- ues until the boiling point reaches a maximum of ca. 339 °C at a sulfuric acid concentration of 98.3 wt % HySOq. At this point the liquid and vapor phases are identical in composition, corte- sponding to an azeotrope, sothe concentration of the boiling acid cannot increase further, As can be seen from Figure 5, if vapor in equilibrium with sulfuric acid of 85 we%, boiling at about 223°C, ig completely condensed it will contain about 7 wt % HySO,. At concentrations below ca. 75 WU% H,SOg, essentially nothing but wa- (er evaporates, The boiling behavior of sulfuric acid is especially important with respect to in- dustzial processes for thermal concentration of dilute acid, As noted above, the azeotropic con- centration (98,3 wt % HpSO4) represents the ul- timate limiting concentration that can be reached by this method, ‘The vapor above concentrated sulfuric acid containing more than 98.3 wt % HS0, includes not only a greater proportion of HSO, than the liquid but also considerable quantities of SO ‘The vapor over oleum consists almost entirely of SOs. Figure 6 shows the equilibrium vapor pressures of HO, HS04, and SOs above sul- furic acid at 60°C in the concentration range 5 so, 0 / ava oN, Noe . Sulfuric aca oteun es 909598 95 Wo 0 § Hso,% tree So, vt Concentration = igure 6.Rauilriom vapor pessres over slr ac and oleun Sulfuric Acid and Sulfur Trioxide 5 from 85 wt % HSO, to 15 % SOs oleum, based ‘on measurements made by Lucussku [8]. These vapor-pressure curves are all-important in gas drying and SOs absorption, essential steps inthe production of concentrated sulfuric acid by the ‘contact process (Section 4.1.3). Apart from the field of sulfuric acid manufac ture, the system Hy0/$03/HS0, is also of im- mense importance in connection with the com- bustion of sulfur-containing fuels, Itis essential to ensure that the temperature of the combus- tion gas does not drop below the dewpoint (9, 10] prior to discharge, since otherwise there is a danger of corrosion by condensing sulfuric acd. Various formulae have been developed {11-13} for calculating dewpoints theoretically asa fune- tion of the total gas pressure as well as the HzO, S05, and HSO, partial pressures (14). Unfortu- nately, the situation is further complicated by the possible formation of various types of hycirated and associated molecules in the gas phase [15] ‘The specific heat of sulfuric acid falls as con- centration increases, Figure 7 shows the depen- dence of specific heat on concentration and tem- perature [4]. The standard enthalpy of formation for pure liquid H2S0, is — 8.305 kfkg, and the latent heat of evaporation at the boiling point is ca, 605kI/kg [16]. Figure & (see next page) shows the enthalpies of liquid sulfuric acid and oleum over a wide concentration range at tem- peratures between 0°C and the boiling point [17], assuming an arbitrary value of OkI/kg as the enthalpy of pure water at 0°C. This diagram al ° 00 700 Figure 7. Specific heat of slur acid6 Sulfuric Acid and Sulfur Trioxide 400) 400 100% 100 soc Sulturie ace °C oteum oa ty 8080100 o 50 0 HSO0I% free SO,wI% - +“ 1 Figure 8. Eathalpy dlagsam fr solfrie acid and leu (17) provides a simple method for determining the amount of heat liberated when sulfuric acid or oleum is diluted from one concentration to an- other by addition of water. ‘The amount of heat produced by diluting con- centrated sulfuric acid with water is consider- able, so rapid mixing is important to ensure that local overheating and boiling are avoided. Ifone wishes to concentrate dilute acid, a correspond- ing amount of heat, the so-called heat of dehy- ration, must be supplied in addition o such heat as may be required to evaporate the water. Fig- ture 9, which has been calculated from enthalpy values, shows the heat of hydration evolved in the dilution of 98.3 % acid to lower concentra- tions at 20°C (or, conversely, the amount of heat theoretically required to dehydrate it from lower concentrations up to 98.3 %). The heat of hydra- tion liberated by diluting between intermediate concentrations ~ from 75 % HyS04 to 25 %, for example—is simply the difference between val- ues read off the curve opposite the appropriate concentrations 2.2, Chemical Properties Sulfuric acid is a strong acid with characteris- tic hygroscopic and oxidizing properties, Sulfu- ric acid, like the sulfate ion, is chemically and se swo igure 9, Heat of dilution or dshyéraion of sulfuric acd at thermally very table, The dehydrating effect of ‘concentrated sulfuric acids du tothe formation of hydrates. Several hydrates have been identi- fied in the solid state, and these explain the ir- regular variation of some of the physical prop. ‘erties of sulfuric acid with concentration, such as its freezing temperature (see Fig. 4). Known hydrates are HaSO, - H,O (corresponding to 84.5 wt% H,S04); HaSOq - 2H,0 (71.3 we % H;S04); Hs804 - 31,0 (64.5 wt % HyS04); HS04- 4 H,0 (57.6 wt % H;S0,); and HS0, 6,0 (47.6 w% HyS0,) [1] are sulfuric acid is ionized to only a small extent as expressed by Equations (1) and (2) 1] 21,804 = 1,80} +180; © 28,50; = 40" +HS,0; 2 This is the reason why the electrical conductiv- ity ofa sulfuric acid solution has its lowest value at 100 % HSO, (see Fig.2). When pure sulfu- ric acid is diluted with water, dissociation accurs increasingly according to Equation (3), 180) +140 = 40" +HS0; o ‘The conductivity rises accordingly. Between 92.wt % and 84.5 wt % HySO,, the monohydrate (H,S0¢ « H,0) exists preferentially in equilib- rium with the ionie species, so the conductivity decreases slightly. At lower H3SO, concentra tions the extent of dissociation increases, as does therefore the conductivity. ‘At high water content the second stage of dissociation becomes increasingly immportant 9.4), 150; +20= Ho" +80! ®On account of the diminishing total concentra- tion of sulfuric acid, however, the conductiv- ity reaches a maximum at ca. 30wL% H)SO4 (the exact value depends on the temperature), and decreases steeply down to Owt% H2SO; [1], Dilute sulfuric avid is the preferred elec- trolyte for industrial metal electrowinning and electroplating plants on account of its high con- ductivity and the chemical stability of the sul- fate ion. To take advantage of the electrical con- ductivity maximum, sulfuric acid of about 33°% concentration is used in lead storage batteries (Batteries, Chap. 4), Dilute sulfuric acid is a strong dibasic aci, so it will dissolve all base metals. Hydrogen is released, and the respective metal sulfates and bisulfates (hydrogensulfates) are formed. Bar- ium and lead aze exceptions, not because they ddo not react in the first place but because they become coated with an insoluble sulfate layer that protects them from further attack by the acid [1]. Hot, concentrated sulfuric acid has an oxi- ddizing effect, reacting with precious metals and with carbon, phosphorus, and sulfur, by which itis reduced to sulfur dioxide. ‘A very important property of sulfuric acid is its ability to decompose the salts of most other acids. Examples of industrial importance include: 1) Production of sodium sulfate and hydrogen chloride from sodium chloride (> Hydro- chlorie Acid, Chap.3.1.; -> Sodium Sulfates, Chap. 1.3.4) 2) Decomposition of sulfites to sulfur dioxide 3) Decomposition of phosphate rock (natural calcium phosphates) to phosphoric acid and calcium sulfate (—+Phosphoric Acid and Phosphates, Chap. 1.2.2.) ‘The reactions of concentrated sulfuric acid with organic compounds are frequently domi- nated by its oxidizing and hygroscopic proper- ties [1]. Carbohydrates, for example, are decom- posed to the point of carbonization. Organiccon- densation reactions in which water is eliminated are promoted by sulfuric acid because it effec- tively removes the water as soon as it is formed, Sulfuric acid is therefore frequently used in in- dustry for this purpose. IL also exercises a cat- alytic effect on certain reactions involving or- ganic compounds Sulfuric Acid and Sulfur Trioxide 7 Sulfuric acid is thermally extremely stable. Only at very high temperatures is it partially de- ‘composed into its anhydride, sulfur trioxide, and water vapor (Eq. 5). 804 = $05 +120 o ‘Thereverse of this reaction is the overall route by ‘which sulfuric acid is formed in the absorption section of acontact sulfuric acid plant, However, itis not possible in practice to manufacture sul- furic acid by absorbing sulfur trioxide directly into water, because the sulfur trioxide reacts with water vapor in equilibrium with the liquid near the surface, initially forming sulfuric acid vapor. ‘This quickly condenses as a mist of very fine (submicron) droplets, which are practically im- possible to collect, However, sulfuric acid itself reacts readily with sulfur trioxide to form disul- furic acid (Eg. 6), which can be converted back to sulfuric acid by reaction with water (Eq. 7), i, (04 +05 = Hy S10; © 11,8207 +120 = 211804 o Itis therefore quite feasible to absorb sulfur tri- oxide in sulfuric acid of 98 % or higher concen- ‘ation, over which the patial pressure of water vapor is very low, thus avoiding the problem of imist. However, because the vapor pressures of both HS0 and $05 increase steeply atconcen- trations above 99 % H,S03, the optimum sulfur trioxide absorption efliciency is achieved in 98— 99% acid. If sulfur tioxide is produced in a gas stream that already contains moisture, gaseous sulfu- ric acid forms progressively by eaction (5) the thermodynamic equilibrium point of which is shifted towards TSO, with decreasing temper- ature 18]. The resulting sulfuric acidcan then be ‘condensed in a controlled manner without sig- nificant mist production, This route (o sulfuric acid is also exploited in industry “The vapor pressure of sulfur trioxide over cleum or disulfuric aid is appreciable, so when cleum is exposed to ambient air, which always contains moisture, sulfuric acid mists invariably form, Ii this property that gives olewm its fa- riliar name of forning sulfuric acid Pure disulfuric acid, H2S207, which corre- sponds theoretically to oleum with 44.9 wt % free SOs, crystallizes ata. 35°C. the maximum of the freezing-point curve in the oleum range8 Sulfuric Acid and Sulfur Trioxide (ee Fig. 4). Disulfuric acid is partially dissoci- ated in sulfuric acid solution (Eq. 8), Hy$)01+H,S0, = H)S0} +H8,07 © Itis for this reason that the electrical conductiv- ity of oloum rises slightly as the SOs concen- ation is increased from 0 to about 10 wt % free S05, Sulfuric acid is oxidized both by hydro- ‘gen peroxide and anodically to diperoxysulfurie acid, H2S303, and the unstable monoperoxysul- faric acid (Caro's acid), H2S0; (Eq. 9) 102 +1504 = S05 +1120 o Since itis a strong oxidant, Cato's acid can ox- idize sulfur dioxide to sulfuric acid, a property that has been exploited in pollution control for sulfuric acid plants (the Peracidox process, Sec- tion 4.1.5). Nitrogen oxides (NO +NO,) react with sul furic acid at concentrations above 7Owt% H,S0z (give nitrosyl hydrogensulfate, NOHSO, (see Section 4.2), 3. Development of the Sulfuric Acid Industry Detailed descriptions of the development of sul- furic acid production procedures can be found in the literature [19-23] 3.1, Early Development In the late Middle Ages, sulfuric acid was ob- tained in small quantities in glass vessels in which sulfur was burned with saltpeter in a moist atmosphere. Higher rates of production first became possible with the introduction of lead chambers as reaction vessels by RoEBUCK, in Birmingham, England, in 1746. The next ma- jor step forward came in 1793, when CLEMENT and Desorstes achieved better results by intro- ducing supplemental air into the lead chamber process. They interpreted this as meaning that the nitrous gases were acting only as facilitators of the process, and that the oxidation itself was being effected by the air (i.c., oxygen) In 1827, Gay-Lussac introduced a method for absorbing nitrogen oxides from the lead- chamber off-gases, With the further develop- ment by GLOVER in 1859 of a method for re- ‘covering nitrogen oxides from the newly formed acid by stripping with incoming hot gases, it became possible to make the nitrogen oxide- catalyzed process continuous. As early as 1831, Prmtuars, in Bristol, Eng- land, had patented the oxidation of sulfur diox- ide to sulfur trioxide over a platinum catalyst at high temperature. Nevertheless, it was only af- ter oleum demand for dye manufacture began to increase ~ from about 1872 onward — that this invention was adopted by industry, and inten- sive development of the contact process began, Better solid catalysts were then sought, and the ‘chemistry and thermodynamics of the S0/SOs ‘equilibrium were investigated, Systematic stud- ies undertaken by KNtETScH at BASF on the re- action equilibrium of SQ oxidation over a plat- inum catalyst, published in 1901 [24], formed an important basis for an understanding of ther- ‘modynamic principles. 3.2. Further Development of the Nitrogen Oxide Process ‘The growth in popularity of the contact pro- cess stimulated new competitive efforts to im- prove the lead chamber process. The most signif icant development was replacement of the lead ‘chambers themselves with acid-itrigated towers, which substantially reduced the specific space requirements. The frst so-called tower plant was built by Ort. in 1907, However, widespread in- dustrial use of the tower process had to await the development of adequate acid pumps. In 1923, Perersen introduced an improved tower pro- ‘cess that remaine competitive with the contact process up to the 1950s. However. a fundamen tal disadvantage of the nitrogen oxide processes is that product concentration is limited to amax- imum of 70-75%, while the contact process produces concentrated (98 %) acid. With the de- velopment of relatively inexpensive vanadium ‘catalysts for the contact process together with in- ‘xeasing demand for concentrated sulfuric acid, the proportionate share of world sulfuric acid ‘output produced in nitrogen oxide process plants declined steadily. Around 1910, these accountedforca, 80 % of production in Western Europe and North America, By 1930 the figure had shrunk to about 73 %, by 1950t0 20-25 %, and by 1960to cea, 15 % [23]; in 1980 virtually no acid was be- ing produced in nitrogen oxide process plants in these parts of the world, Nonetheless, the nitzo- gon oxide process has continued to be the object of interest and a certain amount of development work, especially for the processing of gases with extremely low $02 content (see Section 4.2) 3.3. Ascendency of the Contact Process Platinum remained the predominant catalyst for the contact process until the 1930s. As carly as 1913, however, BASF was granted a patent [25] for a catalyst based on vanadium pentox- ide, which eventually succeeded in replacing the platinum catalyst because of its insensitivity to catalyst poisons and its considerably lower cost In 1936/37 Lurgi introduced the wet con- tact process for converting moist sulfur dioxide~ containing gases over a vanadium catalyst. This made it possible to process hot gases from the combustion of hydrogen sulfide in coking plants directly to sulfuric acid In succeeding years a number of factors affected the development of the contact pro- cess. First, the raw material basis of the indus- tuy changed progressively from mainly roaster gases to sulfur combustion gases containing higher concentrations of sulfur dioxide, Second, plant capacities increased as a result of a great rise in the consumption of sulfurie acid by the {ertilizer industry, These and other factors pro- vided a stimulus for the introduction of improve- ‘ments in the individual process steps and in the design of associated equipment (e.g, the shift to ‘way converters from tube converters) Double Absorption. In 1960, a patent appli- cation was filed by Bayer [26] for the so-called double-catalysis process, and the first plant us- ing this process, builtby Lurgi, started up in 1964 (27). By incorporating a preliminary SOs ab- sorption step ahead of the final catalytic stages, the improved contact process permitted a deci- sive increase in overall SO conversion, thus re- ducing SO, emissions substantially. Because the essential difference between this process and the Sulfuric Acid and Sulfur Trioxide 9 ordinary contact process isin the number of ab- sorption stages, iis referred to herealter as the “double-absorption” process. Environment and Energy. In the 1970s the principal industrial countries introduced more stringent regulations for environmental protec- tion, which made the use of the double-absorp- tion process more or less mandatory in new plants. Nevertheless. the conventional contact process continues to be used in countries where ‘environmental regulations are less exacting, ‘On account ofthe steep tise in energy costs, the main thrust of current development in the ‘contact process is toward increasing the recov- ‘ery and utilization of the very substantial amount of process heat, Indeed, a large, modern sulfu- rie acid plant may be looked upon not just as a ‘chemical plant but also as a thermal power plant [28-22] 3.4, Raw Materials Usage ‘The principal starting material for sulfuric acid production is sulfur dioxide, which can be ob- {ained by different methods from various za materials (~> Sulfur Dioxide, Chap. 3,). Moder- ately concentrated sulfuric acid is also produced by reconcentration and purification of so-called spent or waste sulfurie acid, Reprocessing spent acids, which are generated in large quantities in ‘many processes, and recycling the regenerated acid to the user is becoming inereasingly im- portant from an environmental protection stand- point especially inthe major industrial countries (331 Up about 1970, pyrite was the predominant raw material, maintaining a 57-62% share of the continually rising total. Thus, in 1962, out of atoll of ea 3.1 10* cof sure acid, about 1.9% 10° (62) was made from pyrite;in 1970, about 2.710" was pyrite-based, correspond. ing (0 ca. 61% of the total production of ca 44x10" [34]. Since 1970, the proportionate role of pysite has been declining relative to the total, which has continued to rise. In 1979, pyrite accounted for only ca. 24 % Since the beginning of the 1970s, production of sulfuric acid {rom elemental sulfur inthe Fed- «eral Republic of Germany has grown faster than total acid production, in step with rapid growth10 Sulfuric Acid and Sulfur Trioxide inthe production of recovered sulfur from there- fining of crude oil or purification of natural gas from the gas fields of Northern Germany. The proportion of total sulfuric acid production de- rived from elemental sulfur increased from ca. 30% in 1970 to ca, 50% in 1979, when total production stood at about 5%10 [34] Sulfuric acid manufacture basedon elemental sulfur and pyrite is, of cours, relatively sensi- tive tomarket conditions, because acid produced from these materials represents a primary prod- uct, The same is nat tue of sulfuric acid produe- tion based on any of the other sulfur-containing raw materials. In those cases, sulfuric acid is a secondary product, manufactured as a means of disposing of waste from another process, The level of production is therefore dictated not by conditions in the sulfuric acid market, but by conditions in the market for the primary prod- uct, Typical sources ofthis so-called fatal acid axe sulfuric acid plants associated with nonfer- ous metal smelters processing sulfide ores. The quantity of fatal acid produced in the Federal Republic of Germany has been rising constantly, reaching ca. 1.3% 10° Lin 1979 (ca. 26% of the ‘otal. ‘The raw material basis for sulfuric acid pro- duction in other European counties has fol- lowed a pattern generally similar to that inthe Federal Republic of Germany. Pyrite remained the dominant raw material until the 1950s, and it was only with the advent of large quantities of recovered sulfur from the Lacq natural gas fields in France, and later from natural gas oper- ations in Canada, that elemental sulfur assumed its current predominance In contrast, the United States industry has been based since the early years of this century on elemental sulfur because of development of the Frasch industry in the Gulf states (-» Sulfur, Chap.5.5,). In 1978, the various raw materials accounted for the following approximate pro- portions of the total U.S, sulfur acid production ofca. 36x10" t{35] in 1963 and of ca. 280x10" t in 1993: Nonfeous le ts om yan byogen ule ve 4, Production 4.1, Production by Contact Processes 4.1.1. Reaction Kinetics and Thermodynamics In the contact process, a gas mixture containing sulfur dioxide is passed together with oxygen over a catalyst (o oxidize the sulfur dioxide to sulfur trioxide (Eq. 10) [36} S02 +1203 = $05 AH*=- 990% 49) ‘The sulfur trioxide is then absorbed in sulfuric acid where it reacts with added water to form more sulfuric acid (Bq, 505 (g) +100) = 1804) AN” =—1825K0 (LD) “The position of equilibrium in the gas-phase ‘exothermic oxidation of sulfur dioxide (0 sul- fur wioxide (Eq. 10) depends on the prevailing temperature, total pressure, and concentrations (partial pressures) of the reactants, Thermody- namie equilibrium is determined by the equilib- rum constant K, according to the law of mass action (SOs) ** p1S02) play On account of the negative reaction enthalpy of sulfur dioxide oxidation, both K, and the SO. equilibrium conversion decrease with ris- ing temperature, The classical relationship bet- ween K,, (in atm ~°*) and temperature was de- veloped empirically by Bopexsrein and Por. [37]. although more recent data [16,38,39) show deviations. log Kp where Influences on the Conversion Equilibrium. ‘Any increase in the overall pressure will increase the extent of conversion at equilibrium, because the reaction leads to a decrease in volume. The maximum possible equilibrium sulfur dioxide conversion ata given temperature J and total pressure p depends upon the SO, and O; ‘concentrations of the supplied gases. Ifthe sulfurdioxide concentration is 2a vol % and the oxy- gen concentration b vol %, the fraction x of sul- fur dioxide oxidized to sulfur trioxide at equilib- rium can be calculated from the following equa- tion based on the law of mass action: Los fa ‘The appropriate value of K, is determined from the equation of BopeNstiin and Pout. The dependence of SO, equilibrium conversion on temperature and pressure is shown in Figure 10 for the example of sulfur combustion gas con- taining 10 vol % SOs 109 9 60 5 er wo 13 be 0, Conversion, %. , Bs foo iso 300 S80_woo 5700 Temperature, *¢—> Figure 10. Theoreial eonverson esta nthe oxida tionof $09 to $05 as afuneonoftempeatere and (deed gat composition: 10val% SO, 10901 % 03) 2) lobar: b) Boar, e)Sbar: 4) 1 Shar In accordance with the law of mass action, in creasing the oxygen partial pressure will also in- crease the degree of conversion. However, when air alone is used as the source of oxygen in SO production, asis usually the case, the oxygen and sulfur dioxide concentrations are inversely re- lated, so the greater the oxygen concentration in the combustion gases the lower will be the sulfur dioxide content, The essential factor determin- ing the aliainable SO, conversion is thus the vol- tumettic O/SO; ratio inthe feed gases. Whercas Sulfuric Acid and Sulfur Trioxide " sulfur dioxide oxidation requires a stoichiomet- ric O/SO2 ratio of only 0.5: 1, in industry itis normal practice to use a ratio of at least 1:1 ‘The presence of excess oxygen not only raises the $02 equilibrium conversion but is also an ‘essential prerequisite for maintaining the activ- ity of the vanadium catalyst. There are, however, practical Limits on the amount of extra air that can be added, because nitrogen present in the air dilutes the sulfur dioxide to the point where the economics of the process are impaired. Al- though it would be technically feasible to avoid nitrogen dilution by using oxygen instead of air, as is sometimes done in pyrometallurgical pro- ‘cesses that produce high-strength byproduct sul- fur dioxide gas streams, itis usually difficult justify in a sulfur-burning installation (40), Another practical expedient for improving the conversion of sulfur dioxide to sulfur triox- ide isto remove, at an intermediate stage in the process, the sulfur trioxide already formed, In a double-absorption type sulfuric acid plant this is accomplished by routing the reaction gases af ter two of three stages of catalytic conversion trough an intermediate absorption stage and then through one or two subsequent catalytic ‘conversion stages. Because of the large (100 %) stoichiometric oxygen excessiin the original feed gas and the diminished sulfur dioxide concentra- tion, the O2/SO2 ratio at this point is about six times more favorable than atthe start, Influences on Reaction Rate. In an indus- sia plant, actual sulfurdioxide conversion never reaches the theoretical equilibrium value. Gas- phase oxidation of sulfur dioxide is kinetically inhibited, and virtually impossible at any tem- perature without a catalyst, At ordinary temper- atures the reaction is so slow that, in practical terms, it does not occur at all. Increasing the temperature increases the rate of reaction, but si- multancously shifts the position of equilibrium in an unfavorable way away fom sulfur tiox- ide and toward sulfur dioxide and oxygen. With- outa catalyst, the temperature required to make the system react ata practical rate is so high that ‘conversion is very poor. Even with present-day catalysts, a temperature of ca, 400 °C is neces- sary to initiate a self-sustaining reaction, “The reaction mechanism varies depending on the catalyst used, Reaction with a platinum cata- lyst involves heterogencous gas solid catalysis12 Sulfuric Acid and Sulfur Trioxide [22.23.26]. In contrast, according to present un- derstanding, oxidation over a vanadium catalyst is a homogeneous reaction that takes place in a liquid melt of active components on both the ex- temal and internal surfaces of an inert solid cata- lystcarrier [41,42]. The reaction mechanism and the chemical structures ofthe active components hhave not yet been clearly defined. According to the model of Mazs and Mazssex (43), reaction in the melt takes place by way of the intermedi- ate steps shown in Equations (12) and (13). 80; +2V8* 40% =2v!* 4505 2) 050242v4* 3 2V" 408 a The validity of kinetic equations derived from this and other reaction models is limited to cer- tain temperature ranges [44], However, the rate of the catalytic oxidation of sulfur dioxide de- pends not only on the chemical mechanism but also on mass and heat wansfer at the gas—liquid interface of the catalyst [42,45], 2a| m nT) Figure 11. Comparison of) theoretical equlibium SO conversion for sulfucturmer gates (10% SOp, 109% O2) tth (actual $03 conversion ataned over a specific ct alys Other purely technical parameters. such as the gas velocity, gas distribution, and residence time in the catalyst bed, help to determine how closely sulfur dioxide conversion in practice will approach the theoretical equilibrium. To esti- ‘mate the sulfur dioxide conversion that can be achieved in reality in comparison with the ther- modynamic equilibrium conversion, a correc- tion function is used that takes into account the influences of the individual variables. Figure 1] is a plot against temperature of the theoretical sulfur dioxide equilibrium conversion and atyp- ical observed sulfur dioxide conversion fun tion, Actual conversion characteristics are sig- nificantly influenced by the specific catalyst ac- livity, which must be determined empirically for ‘each individual catalyst, 4.1.2. Catalysts (177] Apart {rom catalyst activity, other factors inelud- ing thermal stability, service life, and mechan- ical strength are of practical importance (20- 23,42,44-47), OF all substances tested for cat- alytic activity toward sulfur dioxide oxidation, only vanadium compounds, platinum, and iron oxide have proven to be technically satisfactory. ‘Today, vanadium pentoxide is used almost ex- clusively. Commercial catalysts contain 4-9 wt% vanadium pentoxide, V2O5, as the active com- ponent, together with alkali-metal sulfate pro- ‘moters, Under operating conditions these form the liquid melt in which the oxidation of sulfur dioxide is thought actually to take place. Potas- sium sulfate is used most often in a KV mo- lar proportion of ca. 2.5-3,5. Some catalysts also contain sodium sulfate to reduce the melt- ing point. The carrier material is silica in the form of diatomaceous earth, silica gel, or 2e0- lites, all of which present especially large spe- cific surface areas. Cesium-doped catalysts have also been developed and installed in vatious fa- cilities. Cesium sulfate asa promoter reduces the melting point of the active components, result- ing in significantly lower temperature limits for sustainable stable activity ‘The catalyst components are mixed together to form a paste, which is then usually extruded into solid cylindrical pellets or rings. These are dried and baked at elevated temperature, Other catalyst forms less common in industry include spheres and tablets, Pellettype catalysts were used almost exclusively until the mid 1980s, bat plants today are usually equipped with ring-shaped (or “star-ring”) catalysts. The advantage of a ring-type catalyst is a lower pressure drop; compared to pellet-lype catalysts the pressure drop is reduced by more than half. Furthermore, a ring-shaped catalyst is less sensitive to dust blockages. The relationship linking gas velocity with pressure-drop for different catalyst forms is illustrated in Figure 12. id 200 00] + 500] a 7) 3100 200] » ‘60 120 4 199 a 203 4 0s0e G8 10 Gas velocity, m/s—= Figure 12. Presta drops for various clay yes perme: lef of eaalyst depth BASF) 2) Pellets (Sm); b) Rings (10/Smmm); «) Slarninge (4mm) Operating Temperature Range. An impor- tant property of the vanadium catalyst is the low-temperature limit at which stable opera- tion is possible under fixed gas conditions. This emperature is ca. 410-430 °C for a conven- tional catalyst and ca, 380~ 390°C for acesium- doped catalyst. Low-temperature activity de- pends mainly on the melting point and the chem- ical properties of the mixture of active con- stituents, TThe upper operating-temperatuse limit is de- termined by the thermal stability of the catalyst Above ca. 600—650 °C catalyst activity may be lost irreversibly because of damage to the struc- ture of the carrier and reduction of its internal surface. Sulfuric Acid and Sulfur Trioxide 13 Service Life, The average service life quoted by most catalyst producers [46] is about ten years, Service life is generally determined not 50 much by progressive loss of activity as by catalyst losses incurred when filling and emp- tying the reactor and during routine screening. Depending on the dust load of the gas enter- ing the converter, the size and shape of the cata- lyst grains, and the properties of the active melt, dust will accumulate in the catalyst bed over the ‘course of time. This dust eventually increases the gas-pressure drop through the catalyst bed and reduces both gas throughput and SO, conversion cfliciency. That is the reason why the catalyst ‘must be screened from time to time to remove dust [48]. When catalysts withdrawn, screened, ang returned to the reactor, a certain amount is bound to be lost as a result of abrasion. The pro- ‘ise amount depends on the handling method used and the stability of the catalyst, This loss must be compensated by the addition of new cat- alyst. In contrast to platinum, vanadium catalyst is largely insensitive (o catalyst poisons [49]. Flu- rine compounds in elevated concentrations will attack the cartier materia, leading to increased abrasion loss. Chlorine compounds, especially atelevated temperatures, will volatilize the vana- dium and consequently decrease the activity, Ar- senic, which may be presentin the feed gases that result from roasting arsenical pyrites, will accu- rmulate in the catalyst, but it will only cause an observable decrease in activity ifthe As03 con- ‘centration in the catalyst mass exceeds 15 wt % 20} ‘Water vapor in the feed gas is not deleterious toa vanadium catalyst so long as the temperature is sufficiently high to prevent condensation of sulfuric acid. Atlow temperature (during plant stoppages, for example, or when the catalyst is ‘exposed to humid air) there is a danger that wa- ter will be absorbed by the hygroscopic active ‘constituents, and this can impair the mechanical stzength of the catalyst 4.1.3, Process Summary ‘There are four main process steps inthe produc- tion of sulfuric acid from sulfur dioxide-con- taining gases by the contact process: 1) Gas drying14 Sulfuric Acid and Sulfur Trioxide 2) Catalytic conversion of sulfur dioxide to sul- fur tioxide 3) Absorption of sulfur trioxide 4) Acid cooling ‘The gas-drying stage is not applicable to a plant of the wet-catalysis type, Almost without exception, contact plants operate under essen- ally atmospheric pressure; compression is te- guired only for driving the gases through the plant. 4. Gas Drying Gas drying is an important process step in con- ventional contact plants {in contrast (0 wel- catalysis plants), It protects cooler parts of the plant, such as heat exchangers, against corrosion by acid condensation, and it safeguards against the formation of sulfuric acid mist, which can be very difficult o absorb. It also protects the cat- alyst from ill effects of acid condensation when the plant is shut down for any reason. Therefore, both the operating performance (especially tail- gs purity) and the service life of the plant de- pend in large measure on an efficient and reliable gas-drying stage In sulfur-burning plants the molten sulfur used is dry from the outset, because its melting point is well above the boiling point of water, and any moisture originally present will have been driven off in the melter. The combustion air, however, must be dried, In the usual arrange- ment, filtered air from the atmosphere is drawn through a drying tower by the main blower, When the {eed gas is derived from smelter waste gases or pyrite roasting, cold, humid, sulfur dioxide-containing gas irom the gas- cleaning system (> Sulfur Dioxide, Chap. 6.) is mixed with such additional air as may be re- quized to bring the Oz/S03 ratio to the opti- ‘mum process value before the gas mix enters the drying section, Similar gas-drying equipment is used in both situations. ‘The gases are in most cased dried in coun- (erourrent with fairly concentrated sulfuric acid in irrigated packed towers [20-22]. The sulfuric acid is circulated. The residual water content of the gases after drying corresponds theoretically to the partial pressure of water vapor above the ddrying-tower acid at the prevailing temperature and concentration. For purposes of achieving high drying efficiency, the temperature of the imigation acid is normally maintained at S0- 60°C. A substantial amount of heat~not simply the heat of dilution of the sulfuric acid but also the heat of condensation of the water—is liberated in the gas-drying stage. For this reason the cit- ‘culated acid is generally cooled by inditect heat ‘exchange before returning to the dryer. Water Balance. The sulfuric acid concentra tion of dryer acid is usually between 93 and 98%, depending on the production conditions and the plant concept, This level is maintained constant by bleeding off part of the dilute acid leaving the dryer and exchanging it for a corre- sponding amount of concentrated acid (98.5 %) from the absorber circuit. When the desired product-acid strength is 93—95 % H3S04, prod- uct acid can be taken ditectly from the drying circuit. Inthe case ofa sulfur-burning plant, pro- ‘coss water may even need to be added to the dry- ing acid circuit to prevent the acid concentration from rising, and itis then not necessary to wans- fer dryer acid back to the absorber circuit. Occa- sionally, 98 % acid is used in the drying tower; this arrangement permits a common pump tank tw be used for both dryer and absorption circuits instead of the usual separate pump tanks [50] ‘Water absorbed by the dryer acid is thus used as process water for sulfuric acid formation be- ‘cause of connections between the dryer and ab- sorption systems, When processing metallurgi- cal off-gases, the water content of the feed gas ‘entering the dryer must be contralled by cool- ing in the gas-cleaning plant so that it does not exceed the stoichiometric requirement for pro- duction of H,SO, based on the amount of SO to be absorbed, Otherwise, the water balance in the contact plant will not be maintained, and the ‘concentration of eitculating acid will drop below the minimum level required for proper plant op- eration. ‘The permissible water content for feed gases is determined by the concentration of the prod- ‘uct acid, the sulfur dioxide content of the con- tact gases, and the sulfur dioxide conversion ef- ficiency. Figure 13 illustrates how the allowable feed-gas moisture content (represented by the ‘gas temperature at the inlet of the drying tower, to which is is related) varies with sulfur dioxidecontent for two different product-acid strengths I-can be seen that the lower the sulfur dioxide content of the gas, the cooler (Le. the less moist) the gas must be before it enters the drying tower. Gas temperature at dying tower inet, *¢ a ' we feed gas, vol%—= + 20 0, content o Figure 13. Maximum permissible temperature of moist gas eying Lower nll of roaster gas-based douhleabsor- ti salfce ad plata function of ges SO> content abd desig product ati suength 18) 93% HS0q product ) 98.5% H,SO. product In the case of metallurgical gases with ex- tremely low SO concentrations it is some times technically difficult and uneconomical to cool the feed gas to the low temperature re- quired to maintain the correct water balance For such cases Lurgi has developed a predryer- reconcentrator system that has been proven in service [51]. In the predryer, upstream from the main drying tower, surplus water is removed from the metallurgical gas by washing with sul- Juric acid of medium concenteation (30-60%), This acid does not circulate to the main acid- plant dryer and absorber circuit. Instead, itcircu- lates in aclosed circuit between the predryer and a reconcentrator immediately downstream from the final SOs absorber in the main acid plant, where itgives up moisture to tail gas released to the atmosphere (see the description ofthe venturi process in Section 4.3.2), Alernatively, a water roffigeration plant would be required to adjust the gas temperature to the appropriate level. Drying-Tower Design. The dryers used to- day ate, as a general rule, vertical eyelindrical towers, Their steel shells are lined with acid- proof bricks. In the lower part of most such tow- cers aplastic foil (polyisobutylene) is applied bet- ween the steel shell and the bricks in order to prevent acid from penetrating through the bricks to the steel shell. A grate of acid-proof material Sulfuric Acid and Sulfur Trioxide 18 supports the packing. Normally, Raschig rings or Intalox saddles of ceramic material are used as packing, The dryer design is determined by a number of interacting parameters, such as the surface character and geometry of the packing, the packing height, the gas velocity, and the ir- rigation rate, The efficiency of moisture absorp- tion by the sulfuric acid depends mainly on the diffusion resistance at the gas—acid interface. ‘The gas flow velocity is best kept well above the region of laminar flow, because this induces turbulence that not only lowers the diffusion re- sistance but also improves distribution ofthe liq- wid. ‘A lower limit on the irrigation density is set by the minimum amount of acid requited for uniform wetting of the entize packing surface. ‘The maximum level is defined by the flooding limit, which is itself a function of the gas veloc= ity, and must be determined empirically for each packing type. ‘An important factor in ensuring uniform acid distribution over the entire tower cross-section isthe nature of the acd irrigation system. Prefer- ably, this should be located in the upper part of the packing layer, and it should consist of cast iron or stainless steel nozzle tubes with lateral oblique openings directed upward. As a general rule, a wite-mesh filter of plastic of stainless steel is installed above the packing layer (o sep- arate entrained acid droplets. formally, a residual moisture content of 50 mg/m? in the dry gas is considered satisfac- tory. 4.1.3.2. Catalytic Oxi Dioxide ion of Sulfur ‘The reactor in which sulfur dioxide is oxidized catalytically to sulfur trioxide is known as the converter. Itis the heart ofthe sulfuric acid plant, In the design and construction of any con- verter intended (o assure maximum sulfur diox- ide conversion, proper attention (o removal of the very considerable reaction heat is of vital im- portance, The reaction is generally carried out under adiabatic conditions, so the temperature of the solid catalyst bed rises, thereby determin- ing, and at the same time limiting, the attainable level of SO, conversion consistent with thermo- dynamic equilibrium (see Fig. 10). To achieve a16 Sulfuric Acid and Sulfur Trioxide high final SO, conversion, the total catalyst mass is divided up into several catalyst beds (ays), and hot gas leaving each bed is cooled to the min- imum working temperature ofthe catalyst before it enters the next bed. Tubular converters oper- ating at nearly isothermal conditions have now almost completely fallen out of use in sulfuric acid plants. Isothermal fluidized bed converters are under development, however, and some have reached the point of industrial use, Conversion, %e 0; gh = Loo is3 saa $80 soo Catalyst bed outlet temper 30700 Figure 14, Comparison ofeaction profile and SO> conver: sion fr F-bed nana contact (single absorption abd (+2) Aouble-absorption processes led gas: 83 v0 S02) $5) Double-abrorption process equim curve ater inter ‘mediate absorption b) Baum curve for normal contact process;e) Adlabaie reaction in bed I: €) Adiabatic eacuon {bed ) Cooling and inermediate absorption; ) Cooling 2) Bed3:8) Bed Figure 14 shows the reaction profile foracon- verter comprising four beds and operating under adiabatic conditions, together with the SO, con- version attainable in each bed within the gon- eral limits of actual conversion characteristics A profile for the normal contact process with- out intermediate absorption (single absorption) is compared with that for a double-absorption process with intermediate absorption after the second bed. Itis evident that the overall conver- sion ultimately obtained in the double-absorp- tion process is substantially greater than in a single-absorption process with the same number of catalyst beds, In the single-absorption pro- ‘cess, the maximum achievable SO, conversion with a typical four-bed converter is ca. 98 %. (The exact figure depends on the feed-gas com- position.) This contrasts with afinal SO, conver- sion > 99,5 % in the double-absorption process, ‘The normal configuration for a double-ab- sorption plant using a fixed-bed converter is ei- ther (2+2) or (3-41). That is (o say, the inter- mediate $0; absorber can be placed after either the second or the third bed. If an Oz conver- sion efficiency > 99.7 % must be guaranteed, a five-bed converter in a (3+2) or (4+1) con uration may be preferred [52]. Further improve- ments in conversion efficiency, especially in a single-catalysis plant, can be achieved with ce- sium doping (see Section 4.1.2). The resulting ‘considerable increase in low-temperature activ- ity permits a conversion efficiency of ca, 99% in a single-catalysis plant and >99.7% in a double-catalysis plans. However, the applicabil- ity of such catalysts is limited by high cost ‘The double-absorption method has another significant advantage as well, in that i can pro- cess feed gases with a higher sulfur dioxide content and correspondingly lower O2/S02 ra- tio than the single-absorption process. On ac- ‘count of a lower specific gas-flow rate for a given nominal HS, production capacity, equipment for the double-absorption process can also be smaller. Converter Design. The process design for a converter [22,45] requires careful optimization because of the large number of interacting pa- rameters, Ithas been considerably simplified by the development of appropriate computer pro- ‘grams[53-S5]. The mostimportant variables are the sulfur dioxide concentration and gas-flow rate, the number of beds, the specific catalyst ‘quantity and its distribution between the individ- ual beds, the gas-pressure drop, and the gas-inlet temperatures at the individual bed. In ariving ata inal design, due consideration must be given to the relationship between equipment costs and ‘energy costs. The specific catalyst quantity required for production of 11d of sulfuric acid is ea. 200 2601 for a “normal” contact single-absorption) plantand about 150 2001. fora double-absorp- tion plant. The distribution of the catalyst bet-ween the individual beds can vary widely as a function of the gas concentration and the way the gas is routed. The catalyst bed height may vary from ca. 200mm to 100mm. Different catalysts may also be used in different beds; the choice depends on the thermal stresses prevail- ing at each stage, Tae preferred grain size de- pends on pressure-drop considerations and the permissible dust load The optimum method of cooling the reac tion gas between the catalyst beds is a func- tion of the composition and initial temperature of the feed gas, and thus its origin, It is nor- mally preferable to use indirect heat exchange Ina“cold-gas” plant running on off-gases froma ‘metallurgical or spent-acid decomposition plant, virtually all the surplus reaction heat is trans- ferred to the feed gas in a series of gas—gas heat exchangers to raise the gas temperature to the reaction temperature of the first catalyst bed Modern plants processing gases with higher SO loads (> 8 vol %) are equipped with boiler ele- ‘ments as a way of removing excess reaction heat ‘This improves the overall energy efficiency and maintains the gas temperature atthe inlet of the absorption tower within reasonable limits. In a sulfur-burning plant, where the feed gas is al- ready hot, surplus reaction heat from the cat- alytic section is recovered in steam generators and boiler {eed-water preheaters (economizers) In all double-absorption plants, however, gas passing from the converter to the intermediate absorber and back is cooled and reheated in in- direct gas— gas heat exchangers. Direct injection of cold feed gas or quench air may be employed (oa limited extent under certain circumstances, cither after the first catalyst bed for the purpose of limiting the outlet gas temperature and thus the thermal stress on the first heat exchanger or steam generator, or in later stages if the amount of available heat is insufficient to warrant provi- sion of an inditect heat exchanger ot feed-water preheater. ‘The idea of mounting at least some of the heat exchangers inside or around the converter shell has become altractive once again even though it was abandoned in the 1970s and 1980s, Convert- cs fabricated entirely of stainless stecl provide sufficient flexibility from a design and construc~ tion standpoint to permit such heat exchangers toe incorporated into the converter vessel. The advantage of this arrangement is of course elim- Sulfuric Acid and Sulfur Trioxide 17 ination of some of the gas ducts, including ex- pansion joints, supports, etc. However, no gen- ‘eral rule is available to cover all types of plants; the design engineer must consider carefully the relative advantages of fewer gas ducts versus a more complicated converter vessel. Normally, the converter is designed as a ver- tical cylindrical vessel, with the catalyst beds mounted above one another in separate, virtu- ally gas-tight compartments. Gases enter and leave through lateral nozzles, passing upward and downward through the beds. ‘The catalyst mass is supported by a metal- lic bed grate. A base layer of ceramic packing prevents direct contact between the catalyst and the grate, which could give rise to corrosion, ‘The catalyst bed is itself covered with another layer of packing. This serves the dual purpose of helping to ensure uniform gas and temperature distribution over the surface of the catalyst and preventing the catalyst from blowing around and leaving cavities inthe bed, which might also ad- versely affect gas and temperature distribution in the main body of the catalyst bed. The con- verters are usually lined with ceramic material in the catalyst areas. ‘Three principal types of converter are in use: stainless steel (wath or without heat exchangers), steel, and brick-lined (56) The stainless-steel converter (Fig. 15, see ext page), consisting ofthe shell, the tray sep- arators, and the tays, is fabricated entitely of sainless steel or heat-resistant steel, A central tube is often used to support the trays. Heat ex- ‘changers (also made of stainless steel) can either be incorporated into the central tube or arranged around the shell. ‘The steel converter (Fig. 16, see next page) corresponds in principle to the stainless-steel ‘converter, but boilerplate or equivalentis used as the construction material for the shell, the sepa- rations, and tays for those layers with lower op- ‘rating temperatures. A sleel converter is more ‘economical compared with a stainless-steel con- verter and is appropriate for weatment of gases with lower SO) loads The brick-lined converter (Fig. 17, see fol- lowing page) is completely lined internally with acid-proof bricks. The compartment separators are self-supporting domed structures made of18 Sulfuric Acid and Sulfur Trioxide Dutlet toed 1 t LZZZZZZ4 CI f U Figure 15. Lug conver in stainless steel with intersted heat exchangers shaped bricks. These carry. brick columns that support the catalyst-bed grates. The brick-lined converter represents a conservative design guar- antecing long lifetime together with ahigh “ther- ‘mal inertia.” This facilitates operation with fluc- tuating gas loads as well as start-up after idle periods. o Figure 16. Foured all-stel converter 3) lle (bed) 6) Quench inlet ) Tat (bed, &) Int (ed 3);e) net bed): Catalyst: ) Outlet (bed?) Ou- Jet el 3)) Outlet (bed) 3) Centel he support abe ‘The cast-iron converter that for many years constituted the standard design— specifically in the United States—has now been practically climinated from sulfuric acid plants, Tubular converters (—> Tubular Reactors), which were in common use in sulfuric acid plants until the 1960s, have the inherent advan- tage over bed converters that reaction conditions ‘can be made almost isothermal, but they aze quite unsuitable for use in today’s large-capacity acid plants on account of several seri-ous disadvan- tages. In particular, in order to ensure that heat is dissipated efficiently from the catalyst itis nec- ‘essary (o use a large number of narrow- Fluidized-Bed Reactors). It is possible to conduct sulfur dioxide oxidation Sulfuric Acid and Sulfur Trioxide 19 in this way at a constant temperature in the op- limum operating range of the catalyst. The te- leased heat of reaction is removed from the flu- idized bed by immersed tube bundles that gener- ate steam. One great advantage of the fluidized- bed converter is that cold feed gases from met- allurgical processes or other sources need not be preheated to the reaction temperature; instead the conditions in the fluidized bed are simply adjusted to provide any heat necessary to the in- ‘coming gas. A further attraction of this type of ‘converter is that it can process feed gases with much higher sulfur dioxide concentrations rela- tive to a fixed-bed converter [57] Because of the favorable thermodynamic ‘conditions in a fluidized-bed converter, the con- version altainable in a single stage may equal that achieved in the first three beds of a con- ventional fixed-bed converter. The fluidized-bed converter is therefore ideally suited foruse ahead of the imermediate SOy-absorption stage in a double-absorption plant. However, itdoes re- ‘quire an extremely abrasion-resistant catalyst [58]. Bayer AG has developed a spherical cat- alyst for this purpose [59], and has used it in ‘wo fluidized-bed converter plants since 1971 and 1976, respectively, apparently with success {60} 4.1.3.3. Absorption of Sulfur Trioxide Sulfur trioxide formed by the catalytic oxidation of sulfur dioxide is absorbed in sulfuric acid of at least 98 % concentration, in which i€ reacts with existing or added water to form more sul- furic acid [20-23]. The optimum concentration of the absorber acid corresponds to the azeotrope (ee Section 2.1), where the partial pressures of S05, HSO,, and waler vapor are all at a min- imum, At lower acid concentrations the water- vapor partial pressure is higher, and there is a correspondingly greater risk that sulfuric acid ist will form as a result of direct reaction of sulfur trioxide in the gas phase with water va- por above the acid, Atacid concentrations above the azeotropic point the tail gas will contain in- creased amounts of sulfur trioxide and sulfuric acid on account of theit higher partial pressures. In the original contact (single-absorption) process, process gas passes through all the con- verter beds before the sulfur trioxide is absorbed20 Sulfuric Acid and Sulfur Trioxide in a single absorption unit. In the double-ab- sorption modification, now routinely practiced in both new and “revamped” plants, most of the sulfur trioxide is removed from the process gas in an extra absorption step at an intermediate stage. As explained above, this may occur after cither the second orthe third converter bed. Inthe (2+2)configuration, ca. 85 % ofthe original sul- fur dioxide content of the feed gas has been con- verted to sulfur trioxide by the time the gas en- {ers the intermediate absorber, and in the (3+ 1) configuration even mote of the total amount of sulfur trioxide (ca, 93-95 %) is removed by the intermediate absorber. Sulfur trioxide formed in the last bed or beds from the small quantity of residual sulfur dioxide is absorbed in the final absorber, Most absorbers are packed rowers, usually ‘operating in countercurrent. The gases pass from bottom (o top through a bed of packing, which is uniformly irrigated from the top with concen- twated sulfuric acid. Process gas leaving the con- verter system is cooled by a gas—gas heat ex- changer or a steam generator, preferably in con- junction with a feed-water preheater, to a tem- perature of ca. 180-220°C before entering the absorber. Itis essential that the wall temperature in the gas coolers never drops below the acid dewpoint (ca. 110 160°C, depending on the gas composition); otherwise, there is an acute danger of corrosion due to condensing acid, as well as mist formation. Gasentering the absorber is therefore not completely cold, and it releases heat to the absorber acid as it passes through the absorber; by the time it reaches the outlet itis at virtually the same temperature as the incoming absorber acid, ‘Acsubstantial amount ofheatis also generated in the absorber acid from absorption of sulfur ti- oxide and formation of sulfuric acid, and the acid temperature rises in consequence by an extent that depends on the acid-circulation rate, Effi cient sulfur trioxide absorption depends not only fon uniform acid and gas distribution in the ab- sorber but also on ensuring that the temperature and concentration of the absorber acid remain at the optimum values. The acid concentration is held constant by adding process water or dryer acid to acid leaving the absorber, ata rate con- trolled by a device that measures the electrical conductivity or density. The optimum acid-inlet temperature depends on design conditions, but itis ca. 60~80°C in most plants, maintained at thatlevel by indiect cooling. The atainable SO, absorption efliiency is generally > 99.9 % Innigated packed-tower absorbers are not effi- cient at removing sulfuric acid mist (1). In spite of efficient gas drying and optimum conditions for sulfur trioxide absorption, its often impos- sible to prevent mist formation completely, es- pecially when processing high-bitumen sulfur or ‘metallurgical feed gases with elevated hydrocar- boncontents[61],orwhen starting up or shutting, down the plant. Furthermore, in plants with an leur tower upsteeam from the intermediate ab- sorber, sulfuric acid mists may form with aerosol particle sizes in the submicron range owing to covercooling of the process gas. In such cases the mists may already have formed in the in- termediate absorber. Ordinary wire-mesh spray separators have no effect on these mists, 0 spe- ial mist eliminators rust be installed to avoid corrosion in the downstream heat exchangers and further mist formation in the final absorber. “There ate various designs for mist eliminators, and not all operate on the same principle. The ‘most appropriate type depends on the nature of the mist, especially its particle size. For exam- ple, impingement separators are best for trap- ping particles above 1-3 um, while submnicron particles are more efficiently tapped by diffu. sion on Brownian-motion separators [61-65] Glass fibers of varying degrees of fineness are preferentially used as the filter material “The design principle underlying conventional absorption towers is similar to that for drying towers. Such towers have welded cylindrical steel shells lined on the inside with avid-proof bricks and silica-based, acid-proof mortar. Of ten the lower part of the tower around the acid sump is further protected by polytetrafluorocth- ylene (PTFE) shecting sandwiched between the stecl shell and the amultlayer brick Lining. As with the dryer, itis essential to ensure that gas and acid distribution are uniform over the en- tire tower cross-section, and thatthe acid flow zate is sufficiently high to wet the entire packing layer completely. Depending on gas conditions, the packing layer may have a height of 4~ 6m, ‘The development of special stainless steels cover the past few years has permitted the in- stallation of stel absorption towers without any brick lining. This is a particularly great advan- tage when towers must be replaced during main-