CN102335617B - Hydrolysis method for sulfur recovery and organic sulfur - Google Patents
Hydrolysis method for sulfur recovery and organic sulfur Download PDFInfo
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- CN102335617B CN102335617B CN 201010231517 CN201010231517A CN102335617B CN 102335617 B CN102335617 B CN 102335617B CN 201010231517 CN201010231517 CN 201010231517 CN 201010231517 A CN201010231517 A CN 201010231517A CN 102335617 B CN102335617 B CN 102335617B
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 22
- 239000011593 sulfur Substances 0.000 title claims abstract description 22
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 21
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000011084 recovery Methods 0.000 title claims description 10
- 125000001741 organic sulfur group Chemical group 0.000 title abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 abstract 1
- 229910000348 titanium sulfate Inorganic materials 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 28
- 239000000843 powder Substances 0.000 description 28
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 23
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 23
- 238000005303 weighing Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 241000219782 Sesbania Species 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000001404 mediated effect Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CUWODFFVMXJOKD-UVLQAERKSA-N buserelin Chemical compound CCNC(=O)[C@@H]1CCCN1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](COC(C)(C)C)NC(=O)[C@@H](NC(=O)[C@H](CO)NC(=O)[C@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CC=1NC=NC=1)NC(=O)[C@H]1NC(=O)CC1)CC1=CC=C(O)C=C1 CUWODFFVMXJOKD-UVLQAERKSA-N 0.000 description 1
- 229960002719 buserelin Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- -1 polyethylene oxirane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
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Abstract
The invention relates to a method for hydrolyzing organic sulfur by recovering sulfur, which comprises the steps of filling 20ml of catalyst into a reactor, wherein the reaction temperature is 190-360 ℃, and the inlet gas composition is H2S 2％、O21％、H2O3% and the balance of N2The gas volume space velocity is 500-6000h-1The catalyst consists of titanium oxide, activated alumina and an auxiliary agent, and the weight of the catalyst is as follows: the content of titanium oxide is 80-95%, the content of active alumina is 4-15%, the content of soluble titanium sulfate is 0.5-10%, and the content of sulfuric acid is 0.5-10%; the strength is 250-400N/cm; the specific surface area is 150-300m2(ii)/g; the bulk density is 0.6-0.8 g/ml; the content of titanium oxide on the surface is 10-30%; the catalyst has high strength, large specific surface area, small bulk density, high claus conversion rate and high organic sulfur hydrolysis rate.
Description
Technical field
The present invention relates to a kind of method of sulfur recovery organo-sulfur hydrolysis, particularly a kind of sulfur recovery organo-sulfur hydrolysis catalyst.
Background technology
U.S.P4,388,288 directly adopt pulverous TiO
2, water and moulding additive mixed-forming, this patent does not adopt colloidal sol, has 2 examples to adopt compression moldings, the reagent of interpolation is carbon black and polyethylene glycol, sintering temperature is respectively 600 ℃ and 350 ℃.The former specific area is less than 60m
2/ g, the latter's decomposition temperature does not reach the temperature that metatitanic acid is decomposed into titanium oxide, can not use as catalyst for recovering sulfur.The exemplifying embodiment of this patent is for only adding cellulose, and this example may reduce the dosage of water, but has increased the wearing and tearing of machine.
U.S.P4,113,660 mainly adopt the method for colloidal sol in preparation process, and its colloidal sol is made by hydrochloric acid and metatitanic acid in advance, and dilution is used in the preparation process afterwards.Although the catalyst strength according to the preparation of this kind method is higher, its specific area is less than normal, only has the specific surface area of catalyst of two example preparations to surpass 100m in the embodiment of its patent
2/ g has added aluminium hydroxide in preparation process, content is higher, surpasses 1:1 with the ratio of metatitanic acid.Perhaps add Ludox, clay, with the about 0.7:1 of the ratio of metatitanic acid.Mainly as the nitric oxide conversion catalyst, specific area is less than 115m in this agent
2/ g.
CN101069582 has described a kind of catalyst for clause recovering sulfur and preparation method thereof.Mainly be to add aluminosilicate and ammonium sulfate, the catalyst oxidation Ti content that this patent is produced is lower, be 65%-85%, and only the COS conversion ratio is higher under certain condition.
CN1126595 discloses a kind of TiO
2Base double-function sulfur recovery catalyst and preparation method thereof, this catalyst is mixed together evenly by the precursor solution of metatitanic acid, aluminium oxide or aluminium hydroxide and the alkaline earth oxide that configures, by the banded extruder extruded moulding, get finished catalyst after drying, the roasting.Titanium oxide content is 10-90%, and activated alumina is 9.5-89.5%, and alkaline earth oxide content is 0.5-10%, compares with the conventional oxidation Al catalysts, has large, the intensity advantages of higher of specific area, but CS
2Hydrolysing activity is lower in the situation of high-speed.The direct oxidation of hydrogen sulfide performance is also lower.
Representative external organic sulfur hydrolyst is the CRS-31 catalyst that Luo Na-Rhone-Poulenc produces at present, is widely applied at commercial plant.But this catalyst bulk density is about 1.0g/ml, and is relatively high, and has data to show its mechanical strength less stable.
Summary of the invention
The method that the purpose of this invention is to provide a kind of sulfur recovery organo-sulfur hydrolysis, its catalyst have high strength, high-ratio surface, have a high CS simultaneously
2/ COS percent hydrolysis, high Crouse activity and higher direct oxidation performance.
The method of a kind of sulfur recovery organo-sulfur hydrolysis of the present invention is to be broken into the 8-12 purpose catalyst 20ml reactor that stainless steel tube makes of packing into, and reaction temperature is 320 ℃, and inlet gas consists of H
2S4%, SO
22.5%, CS
21%, O
20.2%, CO
220%, H
2O25%, all the other are N
2, the gas volume air speed is 5000h
-1It is characterized in that: its catalyst is comprised of titanium oxide, activated alumina and auxiliary agent, and take catalyst weight: the content of titanium oxide is as 80-95%, and activated alumina content is 4-15%, auxiliary agent solubility titanium sulfate salt content is 0.5-10%, and auxiliary agent sulfuric acid is 0.5-10%;
The intensity of described catalyst is 250-400N/cm; Specific area is 150-300m
2/ g; Bulk density is 0.6-0.8g/ml; The free titanium oxide content on surface, duct is 10-30%.
Described solubility sulfuric acid titanium salt is Ti(SO
4)
2, TiOSO
4In a kind of or both mixtures wherein.
Catalyst of the present invention is comprised of titanium oxide, activated alumina and auxiliary agent, and take catalyst weight 100%: titanium oxide content is as 80-95%; Be preferably 80-85%; Activated alumina content is 4-20%, is preferably 4-15%; Solubility titanium sulfate salt content is 0.5-10%, and sulfuric acid is 0.5-10%.Titanium oxide described in the present invention derives from the metatitanic acid that adopts Production By Sulfuric Acid Process, or derives from industrial TiCl
4The metatitanic acid that obtains after the hydrolysis, the metatitanic acid that preferably adopts the industrial sulphuric acid method to produce.Activated alumina of the present invention derives from the aluminium hydroxide of industrial use, or the industrial activated alumina that obtains through the fast method of taking off, or derives from aluminium hydroxide such as the boehmite of special construction, preferably adopts boehmite to do predecessor.Other auxiliary agents of the present invention derive from TiOSO
4, Ti (SO
4)
2, VOSO4, be preferably TiOSO
4
Catalyst of the present invention can make by hydraulic pressure extrusion technique, is about to the sulfuric acid titanium salt and is dissolved in acid solution (such as H
2SO
4, H
3PO
4, HCl, HNO
3Deng) in, the mixed liquor of formation joins in the mixture of metatitanic acid and aluminium hydroxide (also can be aluminium oxide or boehmite) after stirring, mediating, with screw rod banded extruder or hydraulic press extruded moulding, and again drying and roasting and make after drying in the shade.In the extrusion process, can add the extrusion aids such as CMC, hydroxyethylcellulose, polyethylene glycol, sesbania, polyethylene oxirane, poly-propyl alcohol, poly-buserelin, so that the catalyst bar smooth surface that the extrusion process is smooth and easy and assurance is extruded.The addition of extrusion aid is generally the 0.5-2% of gross weight.The baking temperature of catalyst of the present invention is 100-160 ℃, and be 8-20 hour drying time, and sintering temperature is 400-700 ℃, and roasting time is 2-15 hour.
The specific area of catalyst of the present invention is 150-300m
2/ g, average crushing strength is 250-400N/cm, and the bulk density of catalyst is 0.6-0.8g/ml, and catalyst body titanium oxide absolute content is at 80-95%, the free titanium oxide content on surface, duct is the 10-30%(XPS test).
Catalyst of the present invention has overcome pure TiO
2The shortcomings such as specific surface area of catalyst is little, bulk density is higher, intensity difference and the catalyst based easy Sulphated Poisoning of conventional aluminum, have that intensity is higher, specific area is large, bulk density is little, claus conversion ratio and organic sulfur hydrolysis rate be all higher and have the characteristics of preferably direct oxidation performance, is a kind of high-performance sulfur recovery organo-sulfur hydrolysis catalyst.
The specific embodiment
Embodiment 1
Metatitanic acid and aluminium hydroxide were dried 8 hours under 110 ℃ of conditions, obtain metatitanic acid and aluminium hydroxide dry powder.Take by weighing metatitanic acid dry powder 270g and aluminium hydroxide dry powder 60 grams and fully mix, after wherein adding 9 gram sesbania powder, fully mix.Measure 130ml concentration and be rare nitric acid of 10%, join in the said mixture, fully stir rear after single-screw extruder is mediated 1 hour, at hydraulic press ф 4mm orifice plate extruded moulding, dried in the shade 48 hours, then 130 ℃ of lower oven dry 10 hours, 450 ℃ of lower roastings namely got catalyst sample A in 3 hours.This sample specific area 135m
2/ g, bulk density 0.75g/ml, average crushing strength 70N/cm.
Embodiment 2
Metatitanic acid and aluminium hydroxide were dried 8 hours under 110 ℃ of conditions, obtain metatitanic acid and aluminium hydroxide dry powder.Take by weighing metatitanic acid dry powder 270g and aluminium hydroxide dry powder 60 grams and fully mix, after wherein adding 9 gram sesbania powder, fully mix.Take by weighing 7.1gTiOSO4 and 10gH
2It is in rare nitric acid of 10% that SO4 is dissolved in 130ml concentration, it is joined in the above-mentioned powder mixture, fully stir rear after single-screw extruder is mediated 1 hour, at hydraulic press ф 4mm orifice plate extruded moulding, dried in the shade 48 hours, then 130 ℃ of lower oven dry 10 hours, 450 ℃ of lower roastings namely got catalyst sample B in 3 hours.This sample specific area 190m
2/ g, bulk density 0.70g/ml, average crushing strength 405N/cm.
Embodiment 3
Metatitanic acid and aluminium hydroxide were dried 8 hours under 110 ℃ of conditions, obtain metatitanic acid and aluminium hydroxide dry powder.Take by weighing metatitanic acid dry powder 270g and aluminium hydroxide dry powder 60 grams and fully mix, after wherein adding 9 gram sesbania powder, fully mix.Take by weighing 10.6gTi(SO4)
2And 10gH
2It is in rare nitric acid of 10% that SO4 is dissolved in 130ml concentration, it is joined in the above-mentioned powder mixture, fully stir rear after single-screw extruder is mediated 1 hour, at hydraulic press ф 4mm orifice plate extruded moulding, dried in the shade 48 hours, then 130 ℃ of lower oven dry 10 hours, 450 ℃ of lower roastings namely got catalyst sample C in 3 hours.This sample specific area 170m
2/ g, bulk density 0.72g/ml, average crushing strength 262N/cm.
Embodiment 4
Metatitanic acid and aluminium hydroxide were dried 8 hours under 110 ℃ of conditions, obtain metatitanic acid and aluminium hydroxide dry powder.Take by weighing metatitanic acid dry powder 270g and aluminium hydroxide dry powder 60 grams and fully mix, after wherein adding 9 gram sesbania powder, fully mix.Take by weighing 7.1gTiOSO4 and 10gH
2It is in 10% the watery hydrochloric acid that SO4 is dissolved in 130ml concentration, it is joined in the above-mentioned powder mixture, fully stir rear after single-screw extruder is mediated 1 hour, at hydraulic press ф 4mm orifice plate extruded moulding, dried in the shade 48 hours, then 130 ℃ of lower oven dry 10 hours, 450 ℃ of lower roastings namely got catalyst sample D in 3 hours.This sample specific area 105m
2/ g, bulk density 0.74g/ml, average crushing strength 305N/cm.
Embodiment 5
Metatitanic acid and aluminium hydroxide were dried 8 hours under 110 ℃ of conditions, obtain metatitanic acid and aluminium hydroxide dry powder.Take by weighing metatitanic acid dry powder 270g and aluminium hydroxide dry powder 60 grams and fully mix, after wherein adding 9 gram sesbania powder, fully mix.Taking by weighing 7.2gVOSO4, to be dissolved in 130ml concentration be in rare nitric acid of 10%, it is joined in the above-mentioned powder mixture, fully stir rear after single-screw extruder is mediated 1 hour, at hydraulic press ф 4mm orifice plate extruded moulding, dried in the shade 48 hours, then 130 ℃ of lower oven dry 10 hours, 450 ℃ of lower roastings namely got catalyst sample F in 3 hours.This sample specific area 160m
2/ g, bulk density 0.72g/ml, average crushing strength 293N/cm.
Embodiment 6
Metatitanic acid and aluminium hydroxide were dried 8 hours under 110 ℃ of conditions, obtain metatitanic acid and aluminium hydroxide dry powder.Take by weighing metatitanic acid dry powder 270g and aluminium hydroxide dry powder 60 grams and fully mix, after wherein adding 9 gram hydroxyethylcelluloses, fully mix.Taking by weighing 7.1gTiOSO4, to be dissolved in 130ml concentration be in rare nitric acid of 10%, it is joined in the above-mentioned powder mixture, fully stir rear after single-screw extruder is mediated 1 hour, at hydraulic press ф 4mm orifice plate extruded moulding, dried in the shade 48 hours, then 130 ℃ of lower oven dry 10 hours, 450 ℃ of lower roastings namely got catalyst sample G in 3 hours.This sample specific area 180m
2/ g, bulk density 0.73g/ml, average crushing strength 285N/cm.
Embodiment 7
(carry out the activity rating of catalyst among the φ 25 * 2.5mm) with being broken into the above-mentioned catalyst sample 20ml of the 8-12 purpose reactor that stainless steel tube makes of packing into.320 ℃ of reaction temperatures, inlet gas consists of H
2S4%, SO
22.5%, CS
21%, O
20.2%, CO
220%, H
2O25%, all the other are N
2, the gas volume air speed is 5000h
-1, claus conversion ratio and the tempreture organic sulphur hydrolysis of investigating simultaneously catalyst are active.Calculate claus conversion ratio and the CS of catalyst according to following formula
2Percent hydrolysis, volume correction factor Kv calculates by formula (1):
In the formula: Kv---volume correction factor;
---each component contents on dry basis of unstripped gas, %;
---each component contents on dry basis of tail gas, %.
Glaus conversion η
SPressing following formula (2) calculates:
In the formula: η
SBe Glaus conversion, %.
Organic sulfur hydrolysis rate (mainly is CS
2Percent hydrolysis) η
OPressing following formula (3) calculates:
In the formula: η
OBe CS
2Conversion ratio, %.
The activity rating of above-mentioned catalyst A-G the results are shown in the table 1, and activity data wherein is all the data of 10 hours continuous operations.
The activity contrast of table 1. different catalysts sample
| Catalyst sample | A | B | C | D | E | F | G |
| The Claus conversion ratio, % | 77 | 81 | 79 | 78 | 77 | 78 | 78 |
| CS 2Percent hydrolysis, % | 91 | 97 | 95 | 92 | 92 | 91 | 91 |
Embodiment 8
According to the evaluation method that embodiment 8 describes, different air speeds have been investigated to catalyst CS
2The impact of percent hydrolysis the results are shown in table 2.By table 2 column data as can be known, in 1000-5000 air speed scope, the CS of catalyst
2Percent hydrolysis changes little, still can keep higher organic sulfur hydrolysis rate under the high-speed.
Table 2 air speed is to catalyst B CS
2The impact of hydrolysing activity
Embodiment 9
(carry out the direct oxidation performance evaluation of catalyst among the φ 25 * 2.5mm) with being broken into the 8-12 purpose catalyst sample 20ml reactor that stainless steel tube makes of packing into.220 ℃ of reaction temperatures, inlet gas consists of H
2S2%, O
21%, H
2O3%, all the other are N
2, the gas volume air speed is 5000h
-1, the total sulfur conversion ratio of investigating catalyst is the direct oxidation performance, the results are shown in the table 3.By table 3 column data as can be known, in 1000-5000 air speed scope, the direct oxidation activity of catalyst is all higher.
Table 3 air speed is on the impact of catalyst B direct oxidation performance
Claims (2)
1. the method for a sulfur recovery organo-sulfur hydrolysis will be broken into the 8-12 purpose catalyst 20ml reactor that stainless steel tube makes of packing into, and reaction temperature is 320 ℃, and inlet gas consists of H
2S 4%, SO
22.5%, CS
21%, O
20.2%, CO
220%, H
2O 25%, all the other are N
2, the gas volume air speed is 5000h
-1It is characterized in that: its catalyst is comprised of titanium oxide, activated alumina and auxiliary agent, and take catalyst weight: the content of titanium oxide is as 80-95%, and activated alumina content is 4-15%, auxiliary agent solubility titanium sulfate salt content is 0.5-10%, and auxiliary agent sulfuric acid is 0.5-10%;
The intensity of catalyst is 250-400N/cm; Specific area is 150-300m
2/ g;
Bulk density is 0.6-0.8g/ml;
The free titanium oxide content on surface, duct is 10-30% through the Xps test.
2. according to the method for sulfur recovery organo-sulfur hydrolysis claimed in claim 1, it is characterized in that: solubility sulfuric acid titanium salt is Ti(SO
4)
2, TiOSO
4In a kind of or both mixtures wherein.
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| CN103894175B (en) * | 2012-12-27 | 2016-06-08 | 中国石油天然气股份有限公司 | Hydrolysis catalyst for recovering organic sulfur from middle-low temperature sulfur, preparation and application thereof |
| CN105032393B (en) * | 2015-07-31 | 2018-07-13 | 青岛联信催化材料有限公司 | A kind of high water/gas Sulfur Contained Raw Gas organic sulfur conversion catalyst of high pressure |
| CN114433049A (en) * | 2022-02-11 | 2022-05-06 | 射洪科瑞沃环保技术有限公司 | Titanium oxide sulfur recovery catalyst with high specific surface area and preparation method thereof |
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| CN1126595C (en) * | 2001-04-27 | 2003-11-05 | 中国石化集团齐鲁石油化工公司 | Double-function sulphur recovering catalyst and its prepn |
| CN1210201C (en) * | 2002-12-31 | 2005-07-13 | 中国石油化工股份有限公司齐鲁分公司 | Multifunction sulfur recovery catalyst and its preparing method |
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