vironmental lanagement Burner/fire box design improves sulfur recovery Controt of side reactions necessary for required recoveries Fischer, Lurgi Mineraloeltechni: GmbH, Frankfurt, est Germany Proper DEstoN of burners and fire boxes can increase recovery of sulfur in two catalyst stage Claus units to a level not normally achieved in three stage units, Such designs also eliminate formation of carbon on the catalyst and settling out of ammonium salts when processing sour gases containing ammonia, ‘The sulfur recovery process as developed by C.F. Claus, improved by H. Bahr and commercially applied for the first time in 1986, is usually based only on the throe reactions 3HS 49/20, > 38-+3H,0 — 159% (1) HS +3/20; + SO,+H,O ~ 124keal (2) 2US+SO, 3 3S+2H,O ~ 5keal (3) With this design basis, sulfur recovery of 80 to 85 percent results and consequently causes air pollution which is unsatisfactory today. Now recovery rates of greater than 99 percent are needed to meet environmental protection requirements. This objective makes it necessary to investi- gate side reactions caused by other constituents in the sour gas such as carbon dioxide (COs), methane (CH,), higher hydrocarbons (C,H), ammonia (NH), ete DESIGN Price factors often play a greater role than optimum design in building sulfur recovery plants which leads to ‘miniatuce combustion chambers ineluding tubes in Scotch boilers. Also a variety of available burner types including Hyprocanuon Processine October 1974 Se fa es ©. MSL SiNsnAGS Fig, 1—Equiltium COS in combustion chamber (molst basis) 125BURNER/FIRE BOX DESIGN 40 SPS GAS = om ASWOLA NOES Fig. 2—Equilbrium OS; in" Gombustion ehamber (moist Basis! von ncesscas oul MSO. PSO EAS Fig, $Equllibrium H. in combustion chamber (moist basis} use of a simple central feed pipe for sour gas, neglect proper mixing of gas and air, Under these circumstances an equilibrium approach of individual reactions is not attained and there is danger of carbon formation when processing sour gases contaiviing hydrocarbons as well as Ganger of formation of ammoniacal sulfur compounds, sach as ammonium bisulfite, ammonium bisulfate and ammonium thiosulfate in the presence of ammonia. These side reactions disturb the process in the catalytic phase and impair operational safety and optimum sulfur eign of combustion chamber and burner i, ehetefore, 126 ‘ao, SOS Fig. 5—Equlibrium ¥, In combustion chamber (moist basic). of utmost importance for the plant efficiency. Practical operation has shown that improper design of combustion chamber and burner results in only 15.0 20 percent conversion where above 70 percent conversion should be attainable based on the HS concentration in the sour gas. These designs include use of Scotch type boilers, too sinall combustion chambers anda central sour gas supply via one single large size pipe. Moreover, these October 1974 Hyprocarnon Proorssixeplants incur the hazard of process freezing due to grey the combustion chamber front wall is very satisfactory for surfaces of the waste heat boiler. this purpose, Injection burners of high grade refractory ‘Maximum conversion rates are attained by mixing the material have realized cycle times of several years of required stoichiometric amount of air with the sour gas Continuous operation when sour gas is injected to the before entering the combustion chamber such that the -~ oxygen is bonded just behind the burner mouth. A multi- dumer system disiributed over the entire crosssection of #8 Ey 0 YOL Smomoesscas Hs. scum s Fig, 8—Equlrium H.0 in combustion chamber (moist basis). 3 a 2 3 a ‘1S.NOL INSURES Fig, 7—Equilorium & in combustion chamber (moist basis). Fig. @ Equilibrium CO. in combustion chamber (moist basis). Hypkocarson Processing October 1974 127BURNER/FIRE BOX DESIGN enter of the bumer bricks and air enters the burner bricks through the ring slot, the major portion of the atmospheric oxygen is already bonded within 20 to 30 centimeters behind the burner mouth, The time depends, fon the reaction according to Equation 2 ‘A major advantage of such burners is their wide load range (Irom 100 to 10 percent) at reasonable pressure top in the maximum range (200-250 mm wg) Other burner designs may also be used but care should be taken that oxygen bonding is terminated just after the bumer. This criterion determines the number of burners, Fite box diameter depends on the number of burners NLP 64S Fig. 10—Ni afaite ioe erase toate Saati fe Nw to mi 0 2 a “60 = ww s,s SDORGES Fig, 11—Combustion chambor tomparature (basis: radiation foes equal 50 kcal/Nm* sour gas). 128 “aS tron #8670, pete rssetie ee Fig. 12—Mukiplication factor for sour gas to determine process ‘928 quaniiy, ase snares Fig. 13—Multiptication factor for sour gas to determine com- bustion alr. October 1974 Hyprocarson ProcessixeHS, VOL. % IN SOUR GAS: Fig. 14—Convarsion to sulfur in combustion chamber. and its length on the residence time of the gas in the hot combustion chamber zone wheve the side reactions take place. veeThe thickness of the refractory fining is set such that tae combustion chamber extemal skin temperature is ahove the sulfuric acid dew point (> 250°C) or below the sulfur solidification point (< 110°C) to eliminate A radiation sersen needs to be arzanged at the end of the combustion chamber and the flanged waste heat boiler to protect the waste heat boiler against intensive flame radiation and to prevent that grey, highly absorbing, surfaces create cold zones in the combustion chamber TABLE 1—Equilibrium constants for cher So that individual reactions in the combustion charmber ‘ate frozen THEORY ‘The formation of GOS, OS., H, and CO is dependent on the CO, and GH, content in the sour gas. These rela tionships are shown (Fig. 1-4) for typical conditions of a sour gas temperature of 40° C and a water content of 5.6 percent volume. Along with equilibrium conditions for the occurrence af FF8, 802, 8, HzO, GOs anc Ne (Fig. 5-10) ‘The fire box temperature is also a function of concen: ‘als reactions {ideat gases—Topsoe-Watzen) Rene [3066 + 55267. soya] 20M * WARE waa]! BRE To ao]? C%* ABLE. nn] MS LREELa no imo ae eee [C SGfe eee ae Lee ae | dae ie BEE ihe | Ba ee ee October 1974 Hyproearnon Processmo 129BURNER/FIRE BOX DESIGN fa iii! ral {iis ce les i 2 al isla S240. uSAEST CO, 260 3 2 & faa sees Hs. voL sy saunas Fig. 15—Reaction heat on cooling the process gas to 200° C. tvution in the sour gas (Fig. 11}. Fig. 12 gives the multi- plication factor for determining the process gas and Fig, 13, the multiplication factor for calculating the combus: tion air. Fig; LH shows the conversion to elemental sullur and Fig. 15, the heat released on cooling the process gas to 200° C. Equilibrium constants given in Table 1 and ideal enthalpy of formation from Table 2 were used in caleu- Jating the reactions to develop Fig. 1-9. The results ccomcide well with experimental data from commercial operations involving properly designed burners and com: bustion chambers. ‘The only exception is the CSs where the figures in the diagram are 260 times the calculated values to adapt them to aneasured results. This is necessary heeause of other reactions that possibly occur to form CS: that were not considered here, ex, CO, + 1.58, 6S, + $0, Sulfur formation versus the residence time of the pro- About the author HY, Piscner diaa born @ ohief engineer with Lurgi, Frankfurt (Main), West Germany since 1978 where his dition tn clude process engineering for sulfur re- covery. Prior to this asseeiasion he was a department manager im the Gas Divi- Sion of Pintsch Baniag AG, Butzbacky, Weet. Germany. 180 fOseUE wMsaEsTCD ay S53 Sas fest oS BEPC) StS WOL AHS H2VOL e0S RST BS) 6B 4528404 OH RST CO BET) | atvo. WHS fest ca R600 : SSA9VOL WHS IB TSAO SOM RESTO 870, Zz24vO. NS ZAVOL MOH REST 0D, CE 7 SEE Tne, seen Fig. 16—Effect of nol zone residence time on the conversion of HS to sulfur TABLE 2—Ideal enthalpy of formation (keal/kmol) Tempe] 700 as 137 sit cess gas in the fire box is shown in Fig, 16, These figures ‘were measured in several commercial plants. The diagram illustrates the importance the residence time has for the recovery rate in sulfur plants. In all instances, the gas saniples were taken from the first catalytic stage at tem peratures of about 260° C. Intermediate cooling to 165° C was only applied in one case which yielded somewhat better results Unfortunately, it was not possible to determine the exact composition of the gas at the fire box outlet as suitable measuring methods at such high temperatures are not available. The figures plotted in the diagram are in most casts better than normally in the fire box as the reaction to yield elemental sulfur contimaes due to the cooling of the gases (more favorable equilibrium condi- tions with decreasing temperature). For this reason, a line is shown in this diagram representing the theoretical equilibrium, . October 1974 Hypaocarsow Processie