CN1621134A - Method for preparing sulphur tail gas hydrogenation catalyst - Google Patents
Method for preparing sulphur tail gas hydrogenation catalyst Download PDFInfo
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- CN1621134A CN1621134A CN 200310105748 CN200310105748A CN1621134A CN 1621134 A CN1621134 A CN 1621134A CN 200310105748 CN200310105748 CN 200310105748 CN 200310105748 A CN200310105748 A CN 200310105748A CN 1621134 A CN1621134 A CN 1621134A
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- China
- Prior art keywords
- preparation
- catalyst
- aluminum hydroxide
- tail gas
- hydroxide solid
- Prior art date
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- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 26
- 239000005864 Sulphur Substances 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- 230000000694 effects Effects 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- -1 silica modified aluminum hydroxide Chemical class 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 26
- 229920001971 elastomer Polymers 0.000 claims description 14
- 239000000806 elastomer Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000003292 glue Substances 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- 238000004898 kneading Methods 0.000 abstract description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 23
- 235000015165 citric acid Nutrition 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 3
- 235000017491 Bambusa tulda Nutrition 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 3
- 241000219793 Trifolium Species 0.000 description 3
- 239000011425 bamboo Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- BTMQKQSSEQVSAS-UHFFFAOYSA-N cobalt;ethane-1,2-diamine Chemical compound [Co].NCCN BTMQKQSSEQVSAS-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The present invention is the preparation process of sulfur tail gas hydrogenating catalyst. The catalyst is prepared with silica modified aluminum hydroxide dry glue as main material and VIB and VIII metals as active component, and through compounding stable solution with stabilizer and mixing and kneading process to make extruded stripe. The catalyst has specific surface area greater than 300 sq m/g, porosity higher than 0.50 ml/g and cloveleaf form. It has the features of simple preparation process, low cost, high organic sulfide hydrogenolyzing activity, high CS2 and COS hydrolyzing activity and high activity stability, and may be used in the Claus tail gas hydrogenating process.
Description
Technical field
The present invention relates to the preparation method of a kind of Claus (Crouse) catalyzer for hydrogenation on tail gas, more particularly, relate to a kind of silica modified γ-AL
2O
3Be carrier, cobalt, molybdenum are the Preparation of catalysts method of active constituent.
Background technology
In the Claus+scot recovery technology of sulfur, the sulfur-bearing sour gas is after secondary Crouse transforms, enter hydrogenation reactor, under the effect of hydrogenation catalyst, elemental sulfur in the tail gas, sulfur-containing compound hydrogenation or hydrolysis are converted into hydrogen sulfide, adopt amine liquid to select to absorb then, the tail gas after the purification enters atmosphere.One of key technology that influences this technology total sulfur recovery is to adopt highly active sulfur-containing compound (or elemental sulfur) hydrogenation catalyst and CS
2With the COS hydrolyst.The at present industrial two-stage processes that adopt more, i.e. the hydrogenation reactor top hydrolyst of packing into, the bottom hydrogenation catalyst of packing into.Disclose a kind of sulfur-bearing Claus tail gas hydrogenation treatment process and catalyst as Japan Patent on May 10th, 1994 (patent No. JP06127907 A2), during two kinds of catalyst of employing were packed same reactor in this patent, top was MoO
3/ TiO
2Catalyst, wherein MoO
3Content reaches 16%; The bottom is Co-Mo/AL
2O
3Catalyst, wherein MoO
3Content reaches 13%, and CoO is 3.5%.International Shell Co. Ltd is at Chinese patents CN1230134, this patent disclosure a kind of catalyzer for hydrogenation on tail gas of sulphur, this catalyst is a carrier with silica and aluminium oxide, wherein silica content is active component greater than 25% with nickel, molybdenum, needs and COS, CS
2Hydrolytic reagent (K/TiO
2) use with being loaded in the reactor.But because two kinds of catalyst activities are all lower, need operate under higher temperature in order to take into account hydrogenation activity, catalyst amount and reactor are all bigger, and air speed can only be less than 1000h
-1Operate under the condition.
The typical technology of preparing of catalyzer for hydrogenation on tail gas of sulphur is an infusion process, a kind of preparation method of catalyzer for hydrogenation on tail gas of sulphur is disclosed as Chinese patent (02135699.8), Preparation of Catalyst comprises aluminum hydroxide solid elastomer kneading, extrusion, oven dry, roasting is prepared into alumina support, use the solution impregnating carrier of metalline then, process such as drying, roasting is prepared into catalyst again.Complicated process of preparation, through twice drying, double roasting, the pore volume of catalyst, specific area descend bigger relatively.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of catalyzer for hydrogenation on tail gas of sulphur, under the situation that guarantees the hydrogenation activity uniform component distribution, simplifies Preparation of catalysts technology, and makes catalyst activity component high degree of dispersion.The present invention can also use silica modified aluminium hydroxide on this basis, makes catalyst not only have hydrogenation activity and also has hydrolysis COS, CS
2Activity.
The preparation method of catalyzer for hydrogenation on tail gas of sulphur of the present invention, it is characterized in that the hydrogenation activity component is group vib and VIIII family metal, it is mixed with stable reactive metal solution, mix with aluminum hydroxide solid elastomer, binding agent, expanding agent pinch, extrusion, oven dry, roasting form.
Still be common group vib and VIII family metallic element as hydrogenation activity component that catalyzer for hydrogenation on tail gas of sulphur of the present invention adopted, it is made into uniform and stable solution, make catalyst activity component high degree of dispersion, pore volume, specific area are bigger.Guaranteeing to have simplified production technology on the finely dispersed basis of active component, only need first drying, roasting process, guarantee activity of such catalysts.
The used stabilizing agent of described reactive metal solution is the oxyacid that roasting process can volatilize, its addition is 2-20g/l, oxyacid can be selected from one or more in citric acid, malic acid (hydroxysuccinic acid), hydroxymalonic acid, glyceric acid, lactic acid or the glycolic etc., and the preferred addition of stabilizing agent is 5-10g/l.Containing the group vib metal oxide in the reactive metal solution is 100～300g/L, and the group VIII metal oxide is 20～60g/L, and preferably containing the group vib metal oxide in the metallic solution is 150～250g/L, and the group VIII metal oxide is 30～50g/L.
The group vib metal generally is selected from molybdenum, tungsten, molybdenum preferably, and its predecessor can adopt ammonium molybdate, and the group vib metal oxide accounts for the 5-15% (m/m) of catalyst total amount, preferred 8～11%; VIII family metal generally is selected from cobalt, nickel, cobalt preferably, and its predecessor can adopt cobalt nitrate or cobalt acetate, and the VIII family metal oxide accounts for the 0.5-5% (m/m) of catalyst total amount, preferred 1～3%.
Aluminum hydroxide solid elastomer of the present invention is preferably silica modified aluminum hydroxide solid elastomer, SiO
2Content be 1～20%, pore volume greater than 0.80 milliliter/gram, specific surface is greater than 350 meters squared per gram, preferably SiO
2Content be 2～10%, pore volume greater than 0.90 milliliter/gram, specific surface is greater than 380 meters squared per gram.Adopt silica modified aluminum hydroxide solid elastomer, make catalyst have COS, CS preferably simultaneously
2Hydrolysing activity, SiO simultaneously
2Content is moderate, COS, CS
2The hydrolysing activity height.
Expanding agent of the present invention, binding agent all are the common selection components of catalyst, expanding agent can be the volatilizable organic matters of roasting process such as polyethylene, polyacrylamide, sesbania powder, citric acid, be preferably sesbania powder and citric acid, addition is the 2-10% (m/m) of dried glue weight, is preferably 3-6% (m/m).Binding agent can be water, nitric acid, acetate, citric acid or oxalic acid, is preferably acetate, citric acid, and its addition is the 2-10% (m/m) of dried glue weight, is preferably 3-5% (m/m).
Bake out temperature is 50-150 ℃, and be 2-20 hour drying time, is preferably 50-60 ℃, dry 2-4 hour; 1 10-120 ℃, dry 2-4 hour.Sintering temperature is 450-550 ℃, roasting time 2-8 hour, is preferably 500 ℃, roasting 4 hours.
The prepared catalyst of the present invention is preferably trifolium-shaped, reduces bed resistance, also can be common catalyst shape.
Advantage of the present invention:
Catalyst activity component high degree of dispersion, pore volume, specific area are bigger, and appearance design is a trifolium-shaped, and bed resistance reduces, and modifier content is moderate, COS, CS
2The hydrolysing activity height, the sulfur-containing compound hydrogenolysis is active high, the side pressure strength height, wear away low, water-fast Heat stability is good, anti-efflorescence ability is strong, heap is than gently, same reactor can reduce the catalyst loading amount.
The specific embodiment
Embodiment 1
Take by weighing the 7Kg ammonium molybdate, the 4.2Kg cobalt nitrate is dissolved in 60 liters the deionized water, and stirring and dissolving adds the 5Kg citric acid, and stirring and dissolving is mixed with stable metal salt solution 1.
Take by weighing 70Kg SiO
2Content is 2.5% (wt), and pore volume is 1.12 a milliliters/gram, and specific area is the aluminum hydroxide solid elastomer of 445 meters squared per gram, adds 3Kg field mountain valley with clumps of trees and bamboo powder, mixing.Add above-mentioned metal salt solution 1.Mix and to pinch, be extruded into Φ 3mm clover bar, in 110 ℃ of oven dry 4 hours, Co-Mo-SiO was made in 450-550 ℃ of roasting 4 hours
2-γ-AL
2O
3Catalyst (A), wherein molybdenum oxide (MoO
3) content is 9.3% (m/m), cobalt oxide (CoO) content is 1.80% (m/m).Its character sees Table 1.
Embodiment 2 (Comparative Examples)
Take by weighing the aluminum hydroxide solid elastomer of 70Kg, add 3Kg field mountain valley with clumps of trees and bamboo powder again, mixing by the preparation of embodiment 1 method.4.3Kg (65%) nitric acid is dissolved in 60 liters the deionized water, stirs, join in the above-mentioned mixed aluminum hydroxide solid elastomer, mediate, be extruded into Φ 3mm clover bar, in 110 ℃ of oven dry 4 hours, SiO was made in 550 ℃ of 2 roasting 4 hours
2-γ-AL
2O
3Carrier.
Get 80ml concentration and be 22～28% ammoniacal liquor, be heated to 50 ℃, add the 15g cobalt nitrate, all slowly add people 1ml ethylenediamine after the dissolving, make it to form stable cobalt ethylenediamine complex compound, then, add the 24g ammonium molybdate again, be stirred to dissolving fully, be settled to 100ml, promptly get stable cobalt molybdenum maceration extract.
Get the above-mentioned maceration extract of 70ml, join the above-mentioned 100g SiO that makes
2-γ-AL
2O
3In the carrier, flooded 1 hour, 110 ℃ of oven dry 4 hours, Co-Mo-SiO is made in 500 ℃ of roastings 4 hours
2-γ-AL
2O
3Catalyst (B), wherein molybdenum oxide (MoO
3) content is 9.4% (m/m), cobalt oxide (CoO) content is 1.82% (m/m).Its character sees Table 1.
Embodiment 3
The preparation method is with embodiment 1, but ammonium molybdate is 10Kg, and cobalt nitrate is 6.3Kg, makes Co-Mo-SiO
2-γ-AL
2O
3Carrier (C), wherein molybdenum oxide (MoO
3) content is 14.7% (m/m), cobalt oxide (CoO) content is 2.75% (m/m).Its character sees Table 1.
Embodiment 4
Take by weighing the aluminum hydroxide solid elastomer of 70Kg by the preparation of embodiment 1 method, add 3.0Kg field mountain valley with clumps of trees and bamboo powder again, 7.0Kg ammonium molybdate, 4.2Kg cobalt nitrate, 5.0Kg citric acid, stirring and evenly mixing adds 60 liters deionized water, mediates, be extruded into Φ 3mm clover bar, in 110 ℃ of oven dry 4 hours, Co-Mo-SiO was made in 550 ℃ of roastings 4 hours
2-γ-AL
2O
3Catalyst (D), wherein molybdenum oxide (MoO
3) content is 9.3% (m/m), cobalt oxide (CoO) content is 1.80% (m/m).Its character sees Table 1.
The physico-chemical property of table 1 catalyst
| Project | A | B | C | D |
| Outward appearance | Color is even | Color is even | Color is even | Irregular colour is even |
| Cobalt oxide, % | 1.80 | 1.82 | 2.75 | 1.80 |
| Molybdenum trioxide, % | 9.3 | 9.4 | 14.7 | 9.3 |
| Pore volume, (ml/g) | 0.61 | 0.53 | 0.52 | 0.57 |
| Specific area (m 2/g) | 350 | 298 | 290 | 329 |
| Intensity, N/cm | 192 | 233 | 160 | 172 |
| Crystalline phase | No crystalline phase | No crystalline phase | No crystalline phase | No crystalline phase |
As can be seen from Table 1, bigger by catalyst A pore volume, the specific area of preparation technology's preparation of the present invention under the situation of identical active component content, obviously be better than catalyst prepared B.It is not too even to adopt common mixed kneading to be equipped with the distribution of catalyst E active component of technology preparation.
Embodiment 5
Catalyst desulfurizing activity and contrast test:
Get each 800.0 milliliters of the above-mentioned 4 kinds of catalyst of example, length is 3-5mm, is loaded in the industrial side line reactor, adopts conventional unstripped gas presulfurization (reactor outlet H
2S content is more than or equal to inlet, and sulfuration finishes), conditions of vulcanization is: 300 ℃ of temperature, volume space velocity 600h
-1, hydrogen content is 0.5-5% (v/v) in the unstripped gas.
Sulfuration switches to Claus tail gas after finishing.At 260 ℃ of reaction temperatures, volume space velocity 2000h
-1, hydrogen content is under the reaction condition greater than 1% (v/v) in the hydrogenation tail gas, assaying reaction device gateway H
2S, COS, SO
2, CO
2Content is:
Several activity of such catalysts of table 2 relatively
The hydrogen-catalyst reactor inlet gas is formed, and (v/v) the % reactor outlet gas is formed, (v/v) %
H
2S?????COS??????SO
2????H
2???????CO
2????H
2S????COS????SO
2??????H
2???????CO
2
A?????0.23?????0.05?????0.54????2.98??????8.16??????1.18????-??????-????????1.32??????9.66
B?????0.59?????0.06?????0.28????1.88??????6.68??????0.85????-??????-????????1.02??????7.36
C?????0.46?????0.04?????0.66????2.96??????7.26??????1.32????-??????-????????1.82??????8.72
D?????0.32?????0.06?????0.68????4.25??????6.98??????1.29????-??????-????????3.10??????7.56
Embodiment 6
Catalyst desulfurizing activity and contrast test:
Get above-mentioned 4 kinds of catalyst on industrial side line device, after the sulfuration of the method among the embodiment 5, temperature is transferred to 300 ℃, volume space velocity 4000h
-1, hydrogen content is under the reaction condition greater than 1% (v/v) in the hydrogenation tail gas, assaying reaction device gateway H
2S, COS, SO
2, CO
2Content is:
Several catalyst high-speed of table 3 specific activity
The hydrogen-catalyst reactor inlet gas is formed, and (v/v) the % reactor outlet gas is formed, (v/v) %
H
2S?????COS??????SO
2??????CO
2?????H
2?????H
2S?????COS???????SO
2??????CO
2??????H
2
A?????????0.75?????0.06?????0.23??????7.12??????4.1??????2.24??????-????????-?????????10.0??????2.3
B?????????0.14?????0.06?????0.34??????6.24??????3.1??????1.60??????-????????-?????????6.48??????1.5
C?????????0.24?????0.02?????0.39??????7.52??????5.5??????1.16??????-????????-?????????7.98??????4.5
D?????????0.28?????0.06?????0.39??????6.78??????4.1??????0.96??????-????????0.08??????7.08??????2.9
Embodiment 7
Catalyst desulfurizing activity and contrast test:
Get above-mentioned 4 kinds of catalyst on industrial side line device, after the sulfuration of the method among the embodiment 5, temperature is transferred to 300 ℃, volume space velocity 2000h
-1, hydrogen content is under the reaction condition less than 1% (v/v) in the hydrogenation tail gas, assaying reaction device gateway H
2S, COS, SO
2, CO
2Content is:
Several catalyst low hydrogen content of table 4 specific activity
The hydrogen-catalyst reactor inlet gas is formed, and (v/v) the % reactor outlet gas is formed, (v/v) %
H
2S?????COS??????SO
2????CO
2??????H
2???????H
2S?????COS???SO
2???????CO
2?????H
2
A?????0.51?????0.06?????0.26????8.00??????1.5????????1.22??????-?????-??????????8.26?????0.2
B?????0.07?????-????????0.13????6.88??????2.3????????1.41??????-?????-??????????8.32?????0.2
C?????0.23?????0.04?????0.38????5.86??????1.8????????1.29??????-?????-??????????6.10?????0.0
D?????0.12?????0.06?????0.36????6.28??????2.0????????0.68??????-?????0.06???????6.86?????0.2
From table 3, table 4 data as can be seen, the D catalyst can not satisfy the requirement of high-speed, low hydrogen content.Activity is relatively poor relatively.
Embodiment 8
Method for preparing catalyst is with embodiment 1, and solution stabilizer 5 gram citric acids wherein change 6 gram malic acid into.That prepares is solution-stabilized.
Embodiment 9
Method for preparing catalyst is with embodiment 1, and solution stabilizer 5 gram citric acids wherein change 4 gram glyceric acid into.That prepares is solution-stabilized.
Claims (11)
1, a kind of preparation method of catalyzer for hydrogenation on tail gas of sulphur, it is characterized in that the hydrogenation activity component is group vib and VIII family metal, it is mixed with stable reactive metal solution, mix with aluminum hydroxide solid elastomer, binding agent, expanding agent pinch, extrusion, oven dry, roasting form.
2, preparation method according to claim 1 is characterized in that the used stabilizing agent of described reactive metal solution is the oxyacid that roasting process can volatilize, and its addition is 2-20g/l.
3, preparation method according to claim 2 is characterized in that described stabilizing agent is selected from one or more in citric acid, malic acid, hydroxymalonic acid, glyceric acid, lactic acid or the glycolic, and the addition of stabilizing agent is 5-10g/l.
4, preparation method according to claim 1 is characterized in that the group vib metal oxide accounts for the 5-15% of catalyst total amount (m/m), and the VIII family metal oxide accounts for the 0.5-5% (m/m) of catalyst total amount.
5, preparation method according to claim 4 is characterized in that the group vib metal is selected from molybdenum, tungsten, and VIII family metal is selected from cobalt, nickel.
6, preparation method according to claim 5 is characterized in that the group vib metal is a molybdenum, and its predecessor is an ammonium molybdate, and VIII family metal is a cobalt, and its predecessor is cobalt nitrate or cobalt acetate.
7, preparation method according to claim 1 and 2, it is characterized in that containing in the reactive metal solution group vib metal oxide is 100～300g/L, the group VIII metal oxide is 20～60g/L.
8, preparation method according to claim 1 is characterized in that described aluminum hydroxide solid elastomer is silica modified aluminum hydroxide solid elastomer, SiO
2Content be 1～20%, pore volume greater than 0.80 milliliter/gram, specific surface is greater than 350 meters squared per gram.
9, preparation method according to claim 1, the addition that it is characterized in that described expanding agent are the 2-10% (m/m) of aluminum hydroxide solid elastomer weight, and the addition of binding agent is the 2-10% (m/m) of aluminum hydroxide solid elastomer weight.
10, preparation method according to claim 1 is characterized in that described bake out temperature is 50-150 ℃, and be 2-20 hour drying time, and sintering temperature is 450-550 ℃, roasting time 2-8 hour.
11, preparation method according to claim 1 is characterized in that described catalyst is a trifolium-shaped.
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| CN 200310105748 CN1268719C (en) | 2003-11-28 | 2003-11-28 | Method for preparing sulphur tail gas hydrogenation catalyst |
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| CN 200310105748 CN1268719C (en) | 2003-11-28 | 2003-11-28 | Method for preparing sulphur tail gas hydrogenation catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100438971C (en) * | 2005-10-19 | 2008-12-03 | 中国石油化工股份有限公司 | A silicone modified aluminum hydroxide solid elastomer and preparation method thereof |
| CN103480355A (en) * | 2012-06-12 | 2014-01-01 | 中国石油化工股份有限公司 | Organic sulfur hydrolysis catalyst applicable to natural gas large-scale sulfur recovery device and preparation method thereof |
| CN107469836A (en) * | 2016-06-08 | 2017-12-15 | 中国石油化工股份有限公司 | Catalyzer for hydrogenation on tail gas of sulphur and preparation method thereof |
| CN109433219A (en) * | 2018-10-31 | 2019-03-08 | 沈阳三聚凯特催化剂有限公司 | A kind of Organic sulphur hydrogenation catalyst and preparation method thereof, application |
| CN113289602A (en) * | 2021-06-01 | 2021-08-24 | 清华大学 | Catalyst for carbonyl sulfide hydrolysis in blast furnace gas and preparation method and application thereof |
-
2003
- 2003-11-28 CN CN 200310105748 patent/CN1268719C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100438971C (en) * | 2005-10-19 | 2008-12-03 | 中国石油化工股份有限公司 | A silicone modified aluminum hydroxide solid elastomer and preparation method thereof |
| CN103480355A (en) * | 2012-06-12 | 2014-01-01 | 中国石油化工股份有限公司 | Organic sulfur hydrolysis catalyst applicable to natural gas large-scale sulfur recovery device and preparation method thereof |
| CN103480355B (en) * | 2012-06-12 | 2015-07-15 | 中国石油化工股份有限公司 | Organic sulfur hydrolysis catalyst applicable to natural gas large-scale sulfur recovery device and preparation method thereof |
| CN107469836A (en) * | 2016-06-08 | 2017-12-15 | 中国石油化工股份有限公司 | Catalyzer for hydrogenation on tail gas of sulphur and preparation method thereof |
| CN109433219A (en) * | 2018-10-31 | 2019-03-08 | 沈阳三聚凯特催化剂有限公司 | A kind of Organic sulphur hydrogenation catalyst and preparation method thereof, application |
| CN109433219B (en) * | 2018-10-31 | 2021-08-06 | 沈阳三聚凯特催化剂有限公司 | Organic sulfur hydrogenation catalyst, preparation method and application thereof |
| CN113289602A (en) * | 2021-06-01 | 2021-08-24 | 清华大学 | Catalyst for carbonyl sulfide hydrolysis in blast furnace gas and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1268719C (en) | 2006-08-09 |
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