CN102950000A - Catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and preparation method thereof - Google Patents
Catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and preparation method thereof Download PDFInfo
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- CN102950000A CN102950000A CN2011102551255A CN201110255125A CN102950000A CN 102950000 A CN102950000 A CN 102950000A CN 2011102551255 A CN2011102551255 A CN 2011102551255A CN 201110255125 A CN201110255125 A CN 201110255125A CN 102950000 A CN102950000 A CN 102950000A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 title claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 20
- 239000011593 sulfur Substances 0.000 title abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011148 porous material Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 19
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 14
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 22
- 239000005864 Sulphur Substances 0.000 claims description 20
- 239000003607 modifier Substances 0.000 claims description 19
- 230000000694 effects Effects 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 235000011187 glycerol Nutrition 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052773 Promethium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000002803 maceration Methods 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- -1 rare earth salts Chemical class 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 229910001942 caesium oxide Inorganic materials 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910001950 potassium oxide Inorganic materials 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000003245 coal Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003345 natural gas Substances 0.000 abstract description 3
- 238000005504 petroleum refining Methods 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 4
- 239000006185 dispersion Substances 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 206010013786 Dry skin Diseases 0.000 description 12
- 241000219782 Sesbania Species 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 230000001988 toxicity Effects 0.000 description 6
- 231100000419 toxicity Toxicity 0.000 description 6
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 5
- 229910020851 La(NO3)3.6H2O Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- LRZSAGKIMYFLHY-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;dihydrate Chemical compound O.O.OC(=O)CC(O)(C(O)=O)CC(O)=O LRZSAGKIMYFLHY-UHFFFAOYSA-N 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229960002413 ferric citrate Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention belongs to the technical field of sulfur recycling, and relates to a catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and a preparation method. A preparation method of a catalyst carrier comprises the steps of: based on silicon dioxide as a raw material, adding an alkali metal oxide and alkaline earth oxide composite modifying agent; and forming by using an extrusion molding mode to prepare the carrier with pore volume of more than 0.5ml/g and average pore diameter of more than 30nm. The catalyst is prepared by dipping an active component, ferric oxide is used as the active component, rare earth oxides are used as active auxiliary agents, and a promoter is added to improve dispersion of metal oxides on the carrier. The catalyst can be used for sulfur recycling devices in the industries, such as petroleum refining, natural gas purification and coal chemical industry, has the characteristics of high coal chemical industry, poor sensitivity on water and no toxicity of the active component, and is capable of improving the sulfur recycling rate of the sulfur recycling devices.
Description
Technical field
The invention belongs to the catalyst that relates in the sulphur recovery technical field, relate to a kind of hydrogen sulfide selective oxidation catalyst for sulphur and preparation method thereof, this catalyst can be used for the sulfur recovery unit of the industries such as petroleum refining, natural gas purification and Coal Chemical Industry.
Background technology
In the production process of the industries such as petroleum refining, natural gas purification and Coal Chemical Industry, can produce a large amount of H 2 S-containing gas, with hydrogen sulfide change into harmless elementary sulfur the method for extensive employing be exactly Claus method.The method is at first with about 1/3rd H
2The S burning generates SO
2In combustion furnace, the majority of organic pollutants in the air-flow is also burned falls remaining H
2S and formed SO
2Reaction generting element sulphur, its reaction equation is:
2H
2S+SO
2←→2H
2O+3/nSn
But, since the restriction of thermodynamical equilibrium, the H in this process
2S can not all change elementary sulfur into, that is to say to still have a small amount of H in the reaction end gas
2S exists.Even use high activated catalyst and three grades of catalytic conversion process, the sulfur recovery rate of Claus method technique is the highest can only to reach 97%.At present, the environmental regulation of China has not allowed discharging to contain H
2The waste gas of S, emission standards for sulfur dioxide are less than 960mg/m
3, the above-mentioned H that contains
2Discharging was not up to standard yet after the gas of S burned and becomes sulfur dioxide, so need residue H
2S is further processed, and most economical processing mode is to H at present
2S carries out direct oxidation.SuperClaus technique is a kind of in the direct oxidation process, is present successful, the most most widely used direct oxidation class technique.The SuperClaus process using improved merely H by changing in the past
2S and SO
2The method of reaction process, after traditional Crouse transformed, the afterbody conversion zone used novel hydrogen sulfide catalyst for selective oxidation, is actually a kind of tail gas treatment process, improves the sulfur recovery technology of claus process with this.The main reaction of SuperClaus technique is that hydrogen sulfide and oxygen reaction generate sulphur and water, and this reaction is not subjected to thermodynamics equilibrium limit, and after traditional Crouse transformed, the afterbody conversion zone used the hydrogen sulfide catalyst for selective oxidation, can improve the sulfur recovery rate of device, satisfy national requirements for environmental protection.At present, the built device of SuperClaus technique surpasses 100 covers both at home and abroad, and development rapidly.
At present, the trade mark of the hydrogen sulfide catalyst for selective oxidation of exploitation is less both at home and abroad, on the whole, existing catalyst is not high to the yield of sulphur, have following problem: there is the larger material of toxicity in (1) catalyst activity component, such as chromium, misoperation can prepare personnel to catalyst and damage with the device operating personnel; (2) catalyst is to the poor selectivity of sulphur, causes the yield of sulphur lowlyer, affects the sulfur recovery rate of sulphur unit; (3) catalyst is to water sensitive, it is larger that catalytic activity is affected by water vapour content, the catalyst that has requires to use under low water content (volume content is less than 5%) or anhydrous condition, but water vapour content can't satisfy this type of catalyst requirement more than 30% in the gas behind the secondary claus reaction.
United States Patent (USP) 4818740 disclose a kind of selective oxidation sulfur-containing compound particularly hydrogen sulfide become the catalyst of elementary sulfur, this catalyst is take alpha-aluminium oxide as carrier, the oxide of iron and chromium is active component, and the standby catalyst of this patent system has higher conversion ratio and selective.But the commercial Application actual result shows that the catalyst actual conversion is about 95%, selectively less than 80%.Since selectively relatively poor, the lower gas of sulfide hydrogen content can only be processed.
CN200810157750.4 discloses catalyst and the technique that a kind of selective oxidation of sulfureted hydrogen becomes elementary sulfur.This catalyst comprises carrier and active component, and active component adopts di-iron trioxide and/or chrome green, and carrier is the mixed oxide of titanium dioxide and alundum (Al2O3), and content of titanium dioxide is 60～95% in the carrier.The selective oxidation hydrogen sulfide that this catalyst is used for hydrogen sulfide-containing mixed gas is the reaction of elementary sulfur.Reaction condition is: 160～280 ℃ of reaction temperatures, and reaction pressure 0.02～10.0MPa, gas space velocity is 400～2000h
-1, H
2S≤3.0% (Vol%), O
2/ H
2S (mol ratio)=0.6～3.0.Because this catalyst uses titania support, to water sensitive, can only be for the treatment of the gas of anhydrous or low water content (less than 5%).
Summary of the invention
Technical problem to be solved by this invention provides a kind of hydrogen sulfide selective oxidation catalyst for sulphur and preparation method thereof, selects nontoxic rare earth element to substitute the larger crome metal of toxicity and solves the problem that there is toxicity in catalyst activity component; By selecting silica as the raw material of carrier, and add alkali metal oxide and alkaline earth oxide composite modifier, with solve catalyst not high to the yield of sulphur, to problems such as water sensitive; Use silica as the raw material of carrier, in the catalyst preparation, add promoter, can improve the decentralization of active component, promote the activity of catalyst.
A kind of hydrogen sulfide selective oxidation of the present invention catalyst for sulphur, it is characterized in that silica is the raw material of preparation carrier, adds alkali metal oxide and alkaline earth oxide composite modifier, take iron oxide as active component, rare earth oxide is as coagent, wherein:
Composite modifier accounts for 0.5～5% of carrier mass content, and the molar ratio of alkali metal oxide and alkaline earth oxide is 4: 1 to 1: 2 in the composite modifier;
The specific surface of silica is 100～200m
2/ g, pore volume are 0.5～1.4ml/g;
Iron oxide content accounts for catalyst quality content 2～10%;
Rare earth oxide content accounts for catalyst quality content 0.5～3%, and rare earth oxide is selected from the oxide of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium or gadolinium.
More specific scheme is:
Take silica as carrier, add alkali metal oxide and alkaline earth oxide composite modifier, be prepared into carrier through moulding, oven dry, roasting, take iron oxide as active component, rare earth oxide is as coagent, add promoter, the employing impregnating method preparation technique is prepared from, wherein active component, promoter and coagent join in the deionized water, form activity component impregnation liquid, promoter is selected from glycerine, ethylene glycol or phosphoric acid, and its addition is 5～20% of the long-pending content of activity component impregnation liquid.
Yield on sulphur is not high because existing hydrogen sulfide catalyst for selective oxidation exists, catalyst activity is subjected to water vapour content to affect large, catalyst activity component to have the problems such as toxicity, invented a kind of catalyst and preparation method for hydrogen sulfide Selective Oxidation sulphur.Select nontoxic rare earth element to substitute the larger crome metal of toxicity by optimization and solve the problem that there is toxicity in catalyst activity component; By selecting silica as the raw material of carrier, and add alkali metal oxide and alkaline earth oxide composite modifier, can solve catalyst not high to the yield of sulphur, to problems such as water sensitive; Use silica as the raw material of carrier, in the catalyst preparation, add promoter, can improve the decentralization of active component, promote the activity of catalyst.
The preparation method of catalyst of the present invention comprises:
Be 100～200m with specific surface
2/ g, pore volume are that the silica of 0.5～1.4ml/g is after expanding agent, composite modifier and water kneading, through extrusion, drying, roasting and make carrier.Add active component promoter and active component salt in the deionized water, form activity component impregnation liquid, carrier is behind activity component impregnation liquid dipping, and further hydrogen sulfide selective oxidation catalyst for sulphur is made in drying, roasting.
Expanding agent is polyvinyl alcohol, polyacrylamide, sesbania powder, citric acid, starch etc., preferred sesbania powder.Is its addition 1～5% of carrier mass content?
Promoter is glycerine, ethylene glycol or phosphoric acid, and its amount is 5～20% of maceration extract volume content.
Composite modifier accounts for carrier mass content 0.5～5%, is preferably 1～3%.
Alkali metal oxide and alkaline earth oxide ratio are 4: 1 to 1: 2 (oxide mol ratio) in the composite modifier, are preferably 2: 1 to 1: 1.
Alkali metal oxide is mainly the oxide of lithium, sodium, potassium, rubidium, caesium etc. in the composite modifier, is preferably the oxide of potassium, sodium.
Alkaline earth oxide is mainly the oxide of beryllium, magnesium, calcium, strontium, barium etc. in the composite modifier, is preferably calcium oxide.
The sintering temperature of carrier is 500～700 ℃, preferred 600 ℃.
The carrier pore volume that makes should be greater than 0.5ml/g, and average pore size is greater than 30nm.
The carrier outward appearance is preferably bar shaped.
The equi-volume impregnating preparation is adopted in the catalyst preparation.
The active constituent of catalyst is iron oxide, and iron oxide content accounts for catalyst quality content 2～10%, is preferably 4～7%, and iron oxide adds with the form of the soluble ferric iron salt such as ferric nitrate, ferric citrate, iron chloride.
The catalyst activity auxiliary agent is rare earth oxide, and rare earth oxide is mainly the oxide of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium etc., is preferably the oxide of lanthanum and cerium, and rare earth oxide adds with the form of the soluble ferric iron salt such as nitrate.
Rare earth oxide content accounts for catalyst quality content 0.5～3%, is preferably 0.5～1.5%.
The ratio of lanthana and cerium oxide is 2: 1 to 1: 4 (oxide mol ratio) in the rare earth oxide, is preferably 1: 1 to 1: 2;
Add promoter in the catalyst impregnating solution, promoter is glycerine, ethylene glycol, phosphoric acid etc., is preferably glycerine.
The sintering temperature of catalyst is 300～600 ℃, and preferred temperature is 400 ℃.
The concrete preparation process of the present invention is as follows:
1, the preparation of carrier
Choosing specific surface is 100～200m
2/ g, pore volume are the silica of 0.5～1.4ml/g, and composite modifier, water, expanding agent add kneader.Said mixture is through mediating, and ф 3mm stripe shape orifice plate extruded moulding in 110～150 ℃ of oven dry 2～4 hours, in 600 ℃ of roastings 2～5 hours, can be made into carrier.The pore volume of carrier should be greater than 0.5ml/g, and average pore size is greater than 30nm.Use N
2Determination of adsorption method pore volume and average pore size.
2, catalyst preparation
Get a certain amount of deionized water, add active component promoter, add soluble ferric iron salt and the rare earth salts of aequum under constantly stirring, make it to form stable solution, be stirred to fully dissolving, constant volume namely gets activity component impregnation liquid.Get a certain amount of above-mentioned co-impregnated solution, impregnated carrier 10 minutes～3 hours preferably 0.5～1 hour, in 110～150 ℃ of oven dry 2～6 hours, in 300～600 ℃ of roastings 2～6 hours, namely gets catalyst of the present invention.What the catalyst preparation was adopted is equi-volume impregnating.
Advantage of the present invention:
Adopt the catalyst of the present invention's preparation to have catalytic activity height,, the advantage such as active constituent nontoxic poor to water sensitivity.Use this catalyst under certain condition the hydrogen sulfide conversion ratio can reach more than 99%, sulfur dioxide selectively reaches more than 90%, the sulphur yield can reach more than 90%, thereby improves the sulfur recovery rate of sulfur recovery unit, has significant economic benefit and social benefit.
The specific embodiment
Embodiment 1: (specific area is 145m with 200 gram silica
2/ g, pore volume is 1.2ml/g) mix with 0.8 gram calcium oxide, 8.4 gram citrate dihydrate trisodiums, 4 gram sesbania powder, 300 gram distilled water, extruded moulding on banded extruder was 120 ℃ of dryings 4 hours, 650 ℃ of roastings 6 hours, the carrier specific area that makes thus was 75m
2/ g, pore volume are 0.61ml/g, and average pore size is 35nm.
With 65.2 gram Fe (NO
3)
3.9H
2O, 2.86 gram Ce (NO
3)
3.6H
2O, 2.86 gram La (NO
3)
3.6H
2O, 20ml glycerine join in the 180 gram water, mix, and with the carrier that the step on the solution impregnation that obtains makes, dip time is 10 hours, and 120 ℃ of dryings 10 hours, 500 ℃ of lower roastings 6 hours, the specific surface area of catalyst that makes thus was 67m
2/ g, pore volume are 0.53ml/g, and average pore size is 32nm, and catalyst oxidation iron amount is 6% (quality), and rare earth oxide content is 1% (quality).
Embodiment 2: (specific area is 145m with 200 gram silica
2/ g, pore volume is 1.2ml/g) mix with 0.8 gram calcium oxide, 8.4 gram citrate dihydrate trisodiums, 4 gram sesbania powder, 300 gram distilled water, extruded moulding on banded extruder was 120 ℃ of dryings 4 hours, 650 ℃ of roastings 6 hours, the carrier specific area that makes thus was 75m
2/ g, pore volume are 0.61ml/g, and average pore size is 35nm.
With 65.2 gram Fe (NO
3)
3.9H
2O, 20ml glycerine join in the 180 gram water, mix, with going on foot the carrier that makes on the solution impregnation that obtains, dip time is 10 hours, 120 ℃ of dryings 10 hours, 500 ℃ of lower roastings 6 hours, the catalyst oxidation iron amount that makes thus was 6% (quality).
Embodiment 3: (specific area is 145m with 200 gram silica
2/ g, pore volume is 1.2ml/g) mix with 0.8 gram calcium oxide, 8.4 gram citrate dihydrate trisodiums, 4 gram sesbania powder, 300 gram distilled water, extruded moulding on banded extruder was 120 ℃ of dryings 4 hours, 650 ℃ of roastings 6 hours, the carrier specific area that makes thus was 75m
2/ g, pore volume are 0.61ml/g, and average pore size is 35nm.
With 65.2 gram Fe (NO
3)
3.9H
2O, 2.86 gram Ce (NO
3)
3.6H
2O, 2.86 gram La (NO
3)
3.6H
2O is added in the 180 gram water, mix, with going on foot the carrier that makes on the solution impregnation that obtains, dip time is 10 hours, 120 ℃ of dryings 10 hours, 500 ℃ of lower roastings 6 hours, the catalyst oxidation iron amount that makes thus was 6% (quality), and rare earth oxide content is 1% (quality).
Embodiment 4: (specific area is 145m with 200 gram silica
2/ g, pore volume are 1.2ml/g) mix with 4 gram sesbania powder, 300 gram distilled water, extruded moulding on banded extruder, 120 ℃ of dryings 4 hours, 650 ℃ of roastings 6 hours, the carrier specific area that makes thus was 75m
2/ g, pore volume are 0.61ml/g, and average pore size is 35nm.
With 65.2 gram Fe (NO
3)
3.9H
2O, 2.86 gram Ce (NO
3)
3.6H
2O, 2.86 gram La (NO
3)
3.6H
2O, 20ml glycerine join in the 180 gram water, mix, with going on foot the carrier that makes on the solution impregnation that obtains, dip time is 10 hours, 120 ℃ of dryings 10 hours, 500 ℃ of lower roastings 6 hours, the catalyst oxidation iron amount that makes thus was 6% (quality), and rare earth oxide content is 1% (quality).
Embodiment 5: (specific area is 145m with 200 gram silica
2/ g, pore volume are 1.2ml/g) mix with 4 gram sesbania powder, 300 gram distilled water, extruded moulding on banded extruder, 120 ℃ of dryings 4 hours, 650 ℃ of roastings 6 hours, the carrier specific area that makes thus was 75m
2/ g, pore volume are 0.61ml/g, and average pore size is 35nm.
With 42.2 gram Fe (NO
3)
3.9H
2O, 2.86 gram Ce (NO
3)
3.6H
2O, 2.86 gram La (NO
3)
3.6H
2O, 20ml glycerine join in the 180 gram water, mix, with going on foot the carrier that makes on the solution impregnation that obtains, dip time is 10 hours, 120 ℃ of dryings 10 hours, 500 ℃ of lower roastings 6 hours, the catalyst oxidation iron amount that makes thus was 4% (quality), and rare earth oxide content is 1% (quality).
Embodiment 6: (specific area is 145m with 200 gram silica
2/ g, pore volume are 1.2ml/g) mix with 4 gram sesbania powder, 300 gram distilled water, extruded moulding on banded extruder, 120 ℃ of dryings 4 hours, 650 ℃ of roastings 6 hours, the carrier specific area that makes thus was 75m
2/ g, pore volume are 0.61ml/g, and average pore size is 35nm.
With 65.2 gram Fe (NO
3)
3.9H
2O, 5.72 gram Ce (NO
3)
3.6H
2O, 20ml glycerine join in the 180 gram water, mix, with going on foot the carrier that makes on the solution impregnation that obtains, dip time is 10 hours, 120 ℃ of dryings 10 hours, 500 ℃ of lower roastings 6 hours, the catalyst oxidation iron amount that makes thus was 6% (quality), and cerium oxide content is 1% (quality).
Embodiment 7: on sulphur micro anti-evaluation device the catalyst of embodiment 1 to embodiment 6 preparation carried out activity rating, the reactor of micro-reactor is that the stainless steel tube of 20mm is made by internal diameter, and reactor is placed in the insulating box.Loaded catalyst is 10ml, the quartz sand mixing preheating of top filling same particle sizes.Adopt H in Japanese Shimadzu GC-2014 gas chromatograph on-line analysis reactor inlet and the exit gas
2S, SO
2And O
2Content, adopt the GDX-301 carrier to analyze sulfide, adopt the 5A molecular sieve to analyze O
2Content, 120 ℃ of column temperatures adopt thermal conductivity detector (TCD), do carrier gas with hydrogen, flow velocity 25ml/min behind the post.
With 2H
2S+O
2→ 2S+2H
2O, 2H
2S+3O
2→ 2SO
2+ 2H
2O is the index reaction, investigates the catalytic activity of catalyst, and inlet gas consists of H
2S1%, O
21.5%, H
2O30%, all the other are N
2, the gas volume air speed is 1600h
-1,, according to the H of following formula calculating catalyst
2S conversion ratio η
Act:
M wherein
0, M
1Then represent respectively entrance and exit H
2The volumetric concentration of S.
Calculate the H of catalyst according to following formula
2S transforms the selective η that generates sulphur
Sel:
M wherein
0, M
1Then represent respectively entrance and exit H
2The volumetric concentration of S, C
0Volumetric concentration for exit sulfur dioxide.
Calculate the H of catalyst according to following formula
2S transforms and generates sulphur productive rate η
Yld:
η
Yld＝η
Act×η
Sel
Embodiment 1 catalyst
| Reaction temperature/℃ | Conversion ratio η Act％ | Selective η Sel％ | Yield η Yld％ |
| 180 | 98 | 95 | 93 |
| 200 | 100 | 95 | 95 |
| 220 | 100 | 93 | 93 |
| 240 | 100 | 89 | 90 |
| 260 | 100 | 83 | 83 |
Embodiment 2 catalyst
| Reaction temperature/℃ | Conversion ratio η Act％ | Selective η Sel％ | Yield η Yld％ |
| 180 | 98 | 93 | 91 |
| 200 | 100 | 92 | 92 |
| 220 | 100 | 90 | 90 |
| 240 | 100 | 85 | 85 |
| 260 | 100 | 80 | 80 |
Embodiment 3 catalyst
| Reaction temperature/℃ | Conversion ratio η Act％ | Selective η Sel％ | Yield η Yld％ |
| 180 | 97 | 95 | 92 |
| 200 | 98 | 94 | 92 |
| 220 | 99 | 92 | 91 |
| 240 | 99 | 89 | 88 |
| 260 | 100 | 82 | 82 |
Embodiment 4 catalyst
| Reaction temperature/℃ | Conversion ratio η Act％ | Selective η Sel％ | Yield η Yld％ |
| 180 | 98 | 92 | 90 |
| 200 | 100 | 91 | 91 |
| 220 | 100 | 90 | 90 |
| 240 | 100 | 83 | 83 |
| 260 | 100 | 79 | 79 |
Embodiment 5 catalyst
| Reaction temperature/℃ | Conversion ratio η Act％ | Selective η Sel％ | Yield η Yld％ |
| 180 | 96 | 95 | 91 |
| 200 | 98 | 95 | 93 |
| 220 | 98 | 93 | 91 |
| 240 | 99 | 89 | 88 |
| 260 | 100 | 83 | 83 |
Embodiment 6 catalyst
| Reaction temperature/℃ | Conversion ratio η Act％ | Selective η Sel％ | Yield η Yld％ |
| 180 | 98 | 94 | 92 |
| 200 | 100 | 94 | 94 |
| 220 | 100 | 91 | 91 |
| 240 | 100 | 86 | 86 |
| 260 | 100 | 82 | 82 |
Claims (13)
1. hydrogen sulfide selective oxidation catalyst for sulphur, it is characterized in that take silica as carrier, add alkali metal oxide and alkaline earth oxide composite modifier, be prepared into carrier, take iron oxide as active component, rare earth oxide is as coagent, composite modifier accounts for 0.5～5% of carrier mass content, the molar ratio of alkali metal oxide and alkaline earth oxide is 4: 1 to 1: 2 in the composite modifier, iron oxide content accounts for 2～10% of catalyst quality content, and rare earth oxide content accounts for catalyst quality content 0.5～3%.
2. catalyst according to claim 1, it is characterized in that take silica as carrier, add alkali metal oxide and alkaline earth oxide composite modifier, through moulding, oven dry, roasting is prepared into carrier, take iron oxide as active component, rare earth oxide is as coagent, add promoter, the employing impregnating method preparation technique is prepared from, active component wherein, promoter and coagent join in the deionized water, form activity component impregnation liquid, promoter is selected from glycerine, ethylene glycol or phosphoric acid, its addition are 5～20% of the long-pending content of activity component impregnation liquid.
3. catalyst according to claim 1, the specific surface that it is characterized in that silica is 100～200m
2/ g, pore volume are 0.5～1.4ml/g.
4. catalyst according to claim 1 is characterized in that composite modifier accounts for 1～3% of carrier mass content, and the molar ratio of alkali metal oxide and alkaline earth oxide is 2: 1 to 1: 1 in the composite modifier.
5. catalyst according to claim 1 is characterized in that iron oxide content accounts for catalyst quality content 4～7%.
6. catalyst according to claim 1 is characterized in that rare earth oxide is selected from, in the oxide of cerium, praseodymium, neodymium, promethium, samarium, europium or gadolinium one or both.
7. catalyst according to claim 6 is characterized in that rare earth oxide is comprised of lanthana and cerium oxide, and the molar ratio of lanthana and cerium oxide is 2: 1 to 1: 4.
8. catalyst according to claim 1 is characterized in that alkali metal oxide is the oxide of lithium, sodium, potassium, rubidium or caesium, and alkaline earth oxide is the oxide of beryllium, magnesium, calcium, strontium or barium.
9. catalyst according to claim 8 is characterized in that alkali metal oxide is the oxide of lithium or sodium, potassium, and alkaline earth oxide is the oxide of calcium.
10. a method for preparing one of claim 1-9 described catalyst is characterized in that comprising the steps:
(1), the preparation of carrier
Silica and composite modifier, water, expanding agent mix, and through mediating, extrusion molding in 110～150 ℃ of oven dry 2～4 hours, in 500～700 ℃ of roastings 2～5 hours, is made carrier;
(2), catalyst preparation
Add active component promoter in the deionized water, the soluble ferric iron salt and the rare earth salts that under constantly stirring, add aequum, make it to form stable solution, obtain activity component impregnation liquid, with maceration extract impregnated carrier 10 minutes～3 hours, in 110～150 ℃ of oven dry 2～6 hours, in 300～600 ℃ of roastings 2～6 hours, namely get catalyst of the present invention.
11. preparation method according to claim 10 is characterized in that expanding agent is selected from one or more in polyvinyl alcohol, polyacrylamide, sesbania powder, citric acid, the starch, its addition is 1～5% of carrier mass content.
12. preparation method according to claim 10 is characterized in that promoter is glycerine, ethylene glycol or phosphoric acid, its addition is 5～20% of maceration extract volume content.
13. preparation method according to claim 10 is characterized in that the carrier outward appearance is in strip.
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| CN104248966A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Catalyst for selectively oxidizing hydrogen sulfide to prepare sulfur and preparation method thereof |
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