CN1308073C - Catalyst for improving organic sulfur hydrolysis rate, its carrier and preparation method - Google Patents
Catalyst for improving organic sulfur hydrolysis rate, its carrier and preparation method Download PDFInfo
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- CN1308073C CN1308073C CNB2004100745398A CN200410074539A CN1308073C CN 1308073 C CN1308073 C CN 1308073C CN B2004100745398 A CNB2004100745398 A CN B2004100745398A CN 200410074539 A CN200410074539 A CN 200410074539A CN 1308073 C CN1308073 C CN 1308073C
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- catalyst
- carrier
- alkaline
- oxide
- metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 28
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 28
- 125000001741 organic sulfur group Chemical group 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims description 20
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000012876 carrier material Substances 0.000 claims abstract description 29
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 23
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 18
- 239000010941 cobalt Substances 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 18
- 239000011733 molybdenum Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000011609 ammonium molybdate Substances 0.000 claims description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 230000001404 mediated effect Effects 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000011734 sodium Chemical group 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000969 carrier Substances 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052708 sodium Chemical group 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 238000006424 Flood reaction Methods 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- -1 oxide Chemical compound 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 13
- 239000011593 sulfur Substances 0.000 abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 abstract description 11
- 238000004898 kneading Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000002689 soil Substances 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 13
- 239000000395 magnesium oxide Substances 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000009466 transformation Effects 0.000 description 10
- 229910001593 boehmite Inorganic materials 0.000 description 9
- 239000000292 calcium oxide Substances 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229940072033 potash Drugs 0.000 description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 7
- 235000015320 potassium carbonate Nutrition 0.000 description 7
- 241000219782 Sesbania Species 0.000 description 6
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005470 impregnation Methods 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
This invention provides one kind of catalyst which can improve organic sulfur hydrolysis rate.First,organic sulfur hydrolysis additive and carrier material is made into alkaline material through the process of kneading drying roasting and grinding.Then,mixing the carrier material alkaline material and alkali soil material,also adding peptizing agent,the catalyst carrier can be made through the process of kneading extruding strip and roasting.The catalyst carrier cab be made into sulfur tolerant shift catalyst by impregnating active component molybdenum and cobalt either alkali metal.The outstanding advantages of this invention is that enhanceding the surface alkaline of carrier by adding alkali promoter in the carrier material, which not only improve the activities of catalyst to the organic sulfur,but also improve the low temperature activities of the catalyst.The catalyst of this invention can be used in pressure range of 1.0-5.0MPa.
Description
Technical field
The present invention relates to a kind of transformation catalyst that can improve the tempreture organic sulphur hydrolysis function, its carrier and preparation method thereof, specifically, relate to a kind of sulfur-resistant transformation catalyst that can improve the tempreture organic sulphur hydrolysis function, its carrier and preparation method thereof.
Background technology
As everyone knows, being in the synthesis gas produced of raw material with the coal, contain H
2S and based on the organic sulfur of COS.Trace amounts of CO S can have a strong impact on the quality of product, and makes and the catalyst loss of activity effectively remove way so must select for use.Desulfurizing agents such as the iron oxide that uses, active carbon, zinc oxide are at normal temperatures to removing H at present
2S has higher Sulfur capacity, but to COS directly to remove its Sulfur capacity lower, only make COS in conversion process, its hydrolysis or hydrogenolysis be become H
2S could remove it, therefore, transformation catalyst transforms the quality of organic sulfur performance, the precision of final desulfurization and the service life of follow-up workshop section catalyst will directly be influenced, particularly in recent years, along with being developing rapidly of raw material system methanol industry with the coal, organic sulfur transformed and remove to have higher requirement (requiring 0.05 * 10 in the methyl methanol syngas
-6).Therefore, the hydrolysis function of raising sulfur-resistant transformation catalyst just becomes relevant design department and uses the urgent problem of being concerned about of producer.
Summary of the invention
The object of the invention is to provide a kind of high-performance sulfur-resistant transformation catalyst, and this catalyst has high organic sulfur and transforms hydrolysis function and low temperature active.
A further object of the present invention is to provide a kind of preparation method of high-performance sulfur-resistant transformation catalyst.
An also purpose of the present invention is to provide a kind of used active carrier of high-performance sulfur-resistant transformation catalyst for preparing, it has added alkaline material and peptizing agent in the carrier material, strengthened the surface alkalinty of carrier, not only improve the most effective auxiliary agent of low temperature active, thereby also improved activity of such catalysts sulfur-resistant transformation catalyst.
A further object of the present invention is to provide a kind of preparation method of active carrier.
In order to realize the object of the invention, a kind of catalyst that can improve organic sulfur hydrolysis rate of the present invention is characterized in that,
1) carrier component is AL (OH)
3, r-AL
2O
3, δ-AL
2O
3, α-AL
2O
3, CaO, MgO or ZrO
2A kind of, two or three mixture.
2) active component is the oxide of cobalt and the oxide of molybdenum;
3) active ingredient in the catalyst: cobalt is counted 0.2～5.0% of catalyst total amount with CoO, and molybdenum is with MoO
3Count 1～15% of catalyst total amount, alkali metal is with M
2O (M represents alkali metal) counts 0.5～20% of catalyst total amount, and remaining composition is AL
2O
3, CaO, MgO or ZrO
2A kind of, two or three mixture.
4) preparation method is: a) preparation of alkaline material: with carrier material and hydrolysis auxiliary agent mix, roasting makes alkaline material; B) preparation of carrier: with carrier material, alkaline material and three kinds of materials of alkaline earth material add that peptizing agent is mediated, extrusion and roasting make catalyst carrier; C) will contain active component cobalt and molybdenum and the alkali metal co-impregnated solution floods described carrier, drying or roasting make catalyst then.
Prepare a kind of method that can improve the catalyst of organic sulfur hydrolysis rate of the present invention, it is characterized in that, to contain active component cobalt and molybdenum and alkali metal and be made into co-impregnated solution, dipping is mixed with the carrier of alkaline material and peptizing agent then, and final drying or roasting make finished catalyst.
The volume ratio of carrier and co-impregnated solution is 1: 0.5～1 in the Preparation of catalysts method of the present invention, is preferably 1: 1.
Described co-impregnated solution component comprises: with MoO
3Count 5～15% ammonium molybdate, with CoO count 0.5～5% cobalt nitrate, with M
2O (M represents alkali metal) counts 1～20% alkali carbonate, and concentration is 18% aqueous ammonia solvent.Wherein said alkali metal can be potassium, sodium.
Described ammoniacal liquor addition is as the criterion with complete at least lytic activity component.
Baking temperature described in the described Preparation of catalysts method is 80～200 ℃, and the time is 4～12 hours; Described sintering temperature is 400～650 ℃, and the time is 2～8 hours.
Used carrier in the catalyst of the present invention is characterized in that, can be by following method preparation:
C) carrier material and hydrolysis auxiliary agent are mixed, roasting makes alkaline material;
D) then carrier material, alkaline material and three kinds of materials of alkaline earth material are added that peptizing agent is mediated, extrusion and roasting make catalyst carrier.
The carrier component of carrier material wherein of the present invention is AL (OH)
3, r-AL
2O
3, δ-AL
2O
3, α-AL
2O
3, CaO, MgO or ZrO
2A kind of, two or three mixture.
CaO, MgO, ZrO in the carrier component
2With AL
2(OH)
3, r-AL
2O
3, δ-AL
2O
3, α-AL
2O
3In the weight ratio of any two kinds of mixtures be 0.02: 1～0.2: 1, AL
2(OH)
3, r-AL
2O
3, δ-AL
2O
3Or α-AL
2O
3In the weight ratio of any two kinds of mixtures be 0.02: 1～0.2: 1, the weight ratio of any three kinds of mixtures is 0.02～0.5: 0.5～1 in the carrier component: 1～1.5.
Hydroxide, oxide, nitrate, carbonate or sulfate that described hydrolysis auxiliary agent is alkali metal or alkaline-earth metal, preferably alkali-metal nitrate.The addition of hydrolysis auxiliary agent is counted carrier material 1～10% with oxide, and preferably 5%, be to be benchmark to make the required carrier inventory of alkaline material herein.Be good wherein earlier the hydrolysis auxiliary agent is made the aqueous solution.
The sintering temperature of alkaline material is 400～1200 ℃, is preferably 600～800 ℃.
The present invention adopts the way of adding the basic hydrolysis auxiliary agent in the carrier material, strengthened the surface alkalinty of carrier, not only improved the hydrolysis function of catalyst widely to organic sulfur, and, because alkali metal is the most effective auxiliary agent of low temperature active that improves sulfur-resistant transformation catalyst, thereby has also improved activity of such catalysts.
Oxide, hydroxide or carbonate that alkaline earth material of the present invention is an alkaline-earth metal are good with the oxide of alkaline-earth metal.The addition of alkaline earth material is counted carrier material 3～40% with oxide, and preferably 15%.
In the process of preparing carriers, the carrier material is 1: 0.01～0.1 with the ratio of the addition of alkaline material.
Described peptizing agent is the nitrate or the sulfate of nitric acid, alkali metal, alkaline-earth metal, transition metal, is preferably alkali metal, alkaline earth nitrate.Addition is 0.5～10% (Wt%) of carrier material, is preferably 0.5～3% (Wt%).
The adding peptizing agent can make between the carrier material and be easy to connecting shaping, has improved the intensity and the strength stability of carrier.When carrier material and peptizing agent kneading, can add pore creating material, described pore creating material can be an organic pore-forming agents, as organic pore-forming agents such as sesbania powder, citric acid or methyl methacrylates; Addition is 2%～10% of a carrier material.
Sintering temperature described in the preparing carriers is 400～650 ℃, and the time is 2～8 hours.
Mixing of the present invention, kneading, extrusion are those skilled in the art's known technology and equipment.
The present invention passes through to add the hydrolysis auxiliary agent in the carrier, and steeps carrier with the co-impregnated solution that contains active component, and active ingredient in the catalyst: cobalt is counted 0.2～5.0% of catalyst total amount with CoO, and molybdenum is with MoO
3Count 1～15% of catalyst total amount, alkali metal is with M
2O (M represents alkali metal) counts 0.5～20% of catalyst total amount, and remaining composition is Al
2O
3, CaO, MgO or ZrO
2A kind of, two or three mixture.
Outstanding advantage of the present invention is to have added alkaline material when preparing carriers, owing to add alkaline material, the surface alkalinty of carrier is obviously increased, not only improved the activity that catalyst transforms organic sulfur greatly, and, because alkali metal is the most effective auxiliary agent of low temperature active that improves sulfur-resistant transformation catalyst, thereby also improved the low temperature active of catalyst.The catalyst that the present invention makes can use in the pressure limit of 1.0-5.0Mpa, and the percent hydrolysis and the low-temperature conversion activity of the organic sulfur of the catalyst that makes with this method all are higher than industrial catalyst A.
Catalyst performance method of testing of the present invention:
Utilize normal pressure little anti--the organic sulfur conversion ratio and the intrinsic activity of anti-spectral apparatus detecting catalyst.
The test of organic sulfur conversion ratio; Represent the quality of catalyst hydrolysis function with the size of conversion ratio of COS before and after the reaction, its calculating formula is: S%=Y
0COS-Y
COS/ Y
0COS* 100
Y
0COSThe molar fraction (butt) of-Reactor inlet gas COS;
Y
COSThe molar fraction of-reactor outlet gas COS (butt);
The test of intrinsic activity: with the height of CO interconversion rate (XCO%) size expression catalyst activity, its computational methods are shown below:
X
CO％＝(Y
0CO-Y
CO)/(Y
0CO×(1+Y
CO))×100
Y
OCO--the molar fraction (butt) of-Reactor inlet gas CO;
Y
CO--the molar fraction (butt) of-reactor outlet gas CO;
The catalyst performance evaluation condition:
Catalyst loading amount 0.6g; Air speed 5000h-1; Water/gas 0.5; Reaction temperature 2500C, 3500C; Unstripped gas is formed CO45～50% (V/V); CO21～5% (V/V); H
2S2000～4000ppm; COS200～300ppm; Surplus is hydrogen.
The specific embodiment
Following embodiment is for further describing the present invention, but described embodiment only is used to illustrate the present invention rather than restriction the present invention.
Embodiment 1
Get KNO
350 grams are dissolved in the 200ml water, add aluminium hydroxide 800 grams, and metatitanic acid 30 grams are mediated, dried in 600 ℃ of roastings 3 hours, pulverize 180 orders, and it is stand-by to get alkaline material.
Get 20 gram alkaline materials, add boehmite 1000 gram again, MgO 200 grams, sesbania powder 50 grams mix, and restrain with 30 that 10% salpeter solution is mediated, extrusion, and make carrier in 3 hours in 500 ℃ of roastings.
Get carrier 50 grams, with ammonium molybdate 6 grams, cobalt nitrate 3.0 grams and potash 16 grams, the ammoniacal liquor with 18% is made into co-impregnated solution, makes catalyst with solution incipient impregnation carrier and in 400 ℃ of roastings, and wherein cobalt is counted 1.0% of catalyst total amount with CoO, and molybdenum is with MoO
3Count 4.8% of catalyst total amount, potassium is with K
2O counts 12% of catalyst total amount.
The catalyst call number that makes is SJB-1, and its COS conversion ratio and activity rating data are as shown in table 1.
Embodiment 2
Get MgSO
480 grams are dissolved in the 200ml water, add r-AL
2O
3800 grams are mediated, are dried in 800 ℃ of roastings 2.5 hours, pulverize 180 orders, and it is stand-by to get alkaline material.
Get 100 gram alkaline materials, and then add gibbsite 1000 grams, CaO 200 grams, sesbania powder 40 grams mix, and restrain 10% salpeter solution with 10 and mediate, and extrusion also made carrier in 3 hours in 500 ℃ of roastings.
Get carrier 50 grams, with ammonium molybdate 10 gram, cobalt nitrate 1 gram and potash 10 grams, be made into co-impregnated solution with 29 18% the ammoniacal liquor that restrain, make catalyst with solution incipient impregnation carrier and in 400 ℃ of roastings, wherein cobalt is counted 0.8% of catalyst total amount with CoO, and molybdenum is with MoO
3Count 9% of catalyst total amount, potassium is with K
2O counts 5% of catalyst total amount.
The catalyst call number that makes is SJB-2, and its COS conversion ratio and activity rating data are as shown in table 1.
Embodiment 3
The preparation method is with embodiment 1, and different is with KNO
350 grams change Ca (NO into
3) 240 grams, catalyst be numbered SJB-3, its performance comparison is as shown in table 1.
Embodiment 4
The preparation method is with embodiment 1, and different is with KNO
350 grams change NaOH20 gram into, catalyst be numbered SJB-4, its performance comparison is as shown in table 1.
Embodiment 5
The preparation method is with embodiment 4, and different is to change the MgO200 gram into MgCO
3150 grams, the catalyst of making be numbered SJB-5.Its performance comparison is as shown in table 1.
Comparative Examples of the present invention is industrial catalyst A, is active component with the oxide of cobalt and the oxide of molybdenum wherein, and carrier is AL
2O
3Carrier, the preparation method: will contain active component cobalt and molybdenum and alkali metal and be made into co-impregnated solution, impregnated carrier then, last roasting makes finished catalyst A.
The contrast of table 1. catalyst performance
| Hydrolytic reagent | COS conversion ratio %, 165 ℃ | Normal pressure intrinsic activity, % | |
| 250 | 350 | ||
| SJB-1 SJB-2 SJB-3 SJB-4 SJB-5 industrial catalyst | 98.2 98.6 99.1 98.3 98.2 85.9 | 8.9 9.2 8.8 8.5 9.6 7.0 | 39.6 41.2 45.2 38.7 42.9 31.2 |
Embodiment 6-11
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Implement 11 | ||
| Alkaline material (wherein percentage is total amount with the carrier material) | The carrier material | r-AL 2O 3, MgO and boehmite | AL(OH) 3And r-AL 2O 3 | δ-AL 2O 3, CaO and boehmite | ZrO 2、r- AL 2O 3And boehmite | r-AL 2O 3And boehmite | r-AL 2O 3, MgO and ZrO 2 |
| Ratio | 0.5∶0.1∶2 | 1∶1 | 0.02∶0.6∶1.2 | 0.5∶2∶3 | 4∶5 | 2∶0.1∶0.01 | |
| Hydrolysis auxiliary agent (by oxide) | 3％K 2O | 6% sodium nitrate | 2% magnesia | 8% potash | 1% magnesium hydroxide | 10% sodium sulphate | |
| Sintering temperature (℃) | 400 | 550 | 850 | 600 | 500 | 1200 | |
| Time (h) | 8 | 6 | 2 | 3 | 5 | 2 | |
| Carrier (wherein percentage is total amount with the carrier material) | The carrier material | r-AL 2O 3, MgO and boehmite | AL(OH) 3And r-AL 2O 3 | δ-AL 2O 3, CaO and boehmite | ZrO 2、r- AL 2O 3And boehmite | r-AL 2O 3And boehmite | r-AL 2O 3, MgO and ZrO 2 |
| Ratio | 0.5∶0.1∶2 | 1∶1 | 0.02∶0.6∶1.2 | 0.5∶2∶3 | 4∶5 | 2∶0.1∶0.01 | |
| Alkaline earth material (by oxide) | 15% magnesia | 3% calcium carbonate | 40% calcium oxide | 20% magnesium hydroxide | 10% magnesium carbonate | 30% calcium hydroxide | |
| Peptizing agent | 5% nitric acid | 3% ferric nitrate | 10% potassium sulfate | 1% magnesium nitrate | 0.5% cobaltous sulfate | 8% calcium nitrate | |
| Pore creating material | 2% sesbania powder | 5% citric acid | 10% sesbania powder | 3% methyl methacrylate | 6% citric acid | 8% sesbania powder | |
| Sintering temperature (℃) | 400 | 550 | 650 | 600 | 500 | 450 | |
| Time (h) | 8 | 6 | 2 | 3 | 5 | 8 | |
| Co-impregnated solution (wherein active component content is all in its oxide) | 6% ammonium molybdate, 1% cobalt nitrate and 2% sodium carbonate, the ammoniacal liquor with 18% | 8% ammonium molybdate, 0.5% cobalt nitrate and 5% sodium carbonate, the ammoniacal liquor with 18% | 15% ammonium molybdate, 2% cobalt nitrate and 3% potash, the ammoniacal liquor with 18% | 10% ammonium molybdate, 5% cobalt nitrate and 10% potash, the ammoniacal liquor with 18% | 12% ammonium molybdate, 3% cobalt nitrate and 5% potash, the ammoniacal liquor with 18% | 5% ammonium molybdate, 4% cobalt nitrate and 20% potash, the ammoniacal liquor with 18% | |
| Carrier immersion liquid volume ratio together | 1∶0.6 | 1∶0.8 | 1∶0.7 | 1∶1 | 1∶0.8 | 1∶0.5 | |
| Sintering temperature (℃) | 200 (dryings) | 200 (dryings) | 650 | 500 | 120 (dryings) | 550 | |
| Time (h) | 5 | 6 | 2.5 | 6 | 10 | 4 | |
| Catalyst (is total amount with the catalyst) | Cobalt counts 1.8% with CoO, and molybdenum is with MoO 3Count 5.2%, Na is with Na 2O counts 1.6% | Cobalt counts 2% with CoO, and molybdenum is with MoO 3Count 6%, Na is with Na 2O counts 3% | Cobalt counts 1.5% with CoO, and molybdenum is with MoO 3Count 10%, K is with K 2O counts 0.50% | Cobalt counts 3.0% with CoO, and molybdenum is with MoO 3Count 5%, K is with K 2O counts 5% | Cobalt counts 0.5% with CoO, and molybdenum is with MoO 3Count 12%, K is with K 2O counts 1% | Cobalt counts 2% with CoO, and molybdenum is with MoO 3Count 1%, K is with K 2O counts 15% | |
Although the present invention has been done detailed explanation and has quoted some instantiations as proof, for a person skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (11)
1, a kind of catalyst that can improve organic sulfur hydrolysis rate is characterized in that,
1) active ingredient is grouped into by following one-tenth in the described catalyst: cobalt is counted 0.2～5.0% of catalyst total amount with CoO, and molybdenum is with MoO
3Count 1～15% of catalyst total amount, alkali metal is with M
2O counts 0.5～20% of catalyst total amount, and M represents alkali metal; Remaining composition is by Al
2O
3, CaO, MgO and ZrO
2In a kind of, two or three mixture form;
2) described Preparation of catalysts method may further comprise the steps:
1. the preparation of alkaline material: with carrier material and hydrolysis auxiliary agent mix, roasting makes alkaline material;
2. the preparation of carrier: with carrier material, alkaline material and alkaline earth material add that peptizing agent is mediated, extrusion and roasting make catalyst carrier;
3. will contain active component and alkali-metal co-impregnated solution floods described carrier, drying or roasting make catalyst then; Described carrier material is Al (OH)
3, r-Al
2O
3, δ-Al
2O
3, α-Al
2O
3, CaO, MgO and ZrO
2In a kind of, two or three mixture;
Hydroxide, oxide, nitrate, carbonate or sulfate that described hydrolysis auxiliary agent is alkali metal or alkaline-earth metal; The addition of hydrolysis auxiliary agent is counted carrier material 1～10% with oxide;
Oxide, hydroxide or carbonate that described alkaline earth material is an alkaline-earth metal; The addition of alkaline earth material is counted carrier material 3～40% with oxide;
Described peptizing agent is the nitrate or the sulfate of nitric acid, alkali metal, alkaline-earth metal, transition metal; Addition is 0.5～10% weight ratio of carrier material;
Described active component is the oxide of cobalt and the oxide of molybdenum.
2, catalyst according to claim 1 is characterized in that, described hydrolysis auxiliary agent is alkali-metal nitrate; The addition of hydrolysis auxiliary agent is 5%.
3, catalyst according to claim 1 is characterized in that, described alkaline earth material is the oxide of alkaline-earth metal; The addition of alkaline earth material is 15%.
4, catalyst according to claim 1 is characterized in that, described peptizing agent is an alkali metal or alkaline earth metal nitrate; Addition is 0.5～3% weight ratio of carrier material.
5, catalyst according to claim 1 is characterized in that, describedly contains active component and alkali-metal co-impregnated solution component comprises: with MoO
3Count 5～15% ammonium molybdate, with CoO count 0.5～5% cobalt nitrate, with M
2O counts 1～20% alkali carbonate, and concentration is 18% aqueous ammonia solvent, and wherein said alkali metal M is potassium or sodium.
6, catalyst according to claim 5 is characterized in that, described step in 3. carrier and the volume ratio of co-impregnated solution be 1: 0.5-1.
7, catalyst according to claim 6 is characterized in that, described volume ratio is 1: 0.5.
8, catalyst according to claim 1 is characterized in that, described step 1. in the alkaline material preparation sintering temperature be 400-1200 ℃.
9, catalyst according to claim 8 is characterized in that, described sintering temperature is 600-800 ℃.
10, catalyst according to claim 1 is characterized in that, the described step 2. sintering temperature in the preparing carriers process is 400-650 ℃, and roasting time is 2-8 hour.
11, catalyst according to claim 1 is characterized in that, 2. described step adds pore creating material in the preparing carriers process, and the addition of described pore creating material is 2%～10% of a carrier material; Described pore creating material is sesbania powder, citric acid or methyl methacrylate.
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| CNB2004100745398A CN1308073C (en) | 2004-03-16 | 2004-09-07 | Catalyst for improving organic sulfur hydrolysis rate, its carrier and preparation method |
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| CN200410008740 | 2004-03-16 | ||
| CN200410008740.6 | 2004-03-16 | ||
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| CN107552061A (en) * | 2016-06-30 | 2018-01-09 | 中国石油化工股份有限公司 | Activated carbon base sulfur-resistant transformation catalyst and preparation method thereof |
| CN106268849B (en) * | 2016-08-15 | 2019-04-12 | 青岛联信催化材料有限公司 | A kind of cobalt molybdenum system CO sulfur-resistant transformation catalyst and preparation method thereof |
| CN109261159B (en) * | 2018-10-19 | 2021-04-30 | 青岛联信催化材料有限公司 | Organic sulfur conversion type sulfur-tolerant shift catalyst and preparation method thereof |
| CN113145104A (en) * | 2021-04-21 | 2021-07-23 | 山西普丽环境工程股份有限公司 | Preparation method of hydrolysis desulfurization catalyst |
| CN115646529B (en) * | 2022-10-31 | 2024-03-12 | 湖北禾谷环保有限公司 | Pre-sulfurized CO sulfur-tolerant shift catalyst and preparation method and application thereof |
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| CN1123310A (en) * | 1994-11-25 | 1996-05-29 | 中国石化齐鲁石油化工公司 | Hydrocarbon hydrodesulfurization catalyst and preparation method thereof |
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| CN1067917C (en) * | 1996-01-11 | 2001-07-04 | 中国石化齐鲁石油化工公司 | Novel CO sulfur-tolerant shift catalyst and preparation method thereof |
| CN1352229A (en) * | 2000-11-08 | 2002-06-05 | 中国石油化工股份有限公司 | Heavy oil hydrogenating treatment catalyst and its preparing method |
| CN1458236A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Process for preparing demetalizing and desulfurizing catalyst of heavy oil hydrogenation |
-
2004
- 2004-09-07 CN CNB2004100745398A patent/CN1308073C/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123310A (en) * | 1994-11-25 | 1996-05-29 | 中国石化齐鲁石油化工公司 | Hydrocarbon hydrodesulfurization catalyst and preparation method thereof |
| JPH08173809A (en) * | 1994-12-16 | 1996-07-09 | China Petrochem Corp | Catalyst for conversion of carbon monoxide and method using the same |
| CN1067917C (en) * | 1996-01-11 | 2001-07-04 | 中国石化齐鲁石油化工公司 | Novel CO sulfur-tolerant shift catalyst and preparation method thereof |
| CN1283524A (en) * | 1999-08-04 | 2001-02-14 | 中国石化集团齐鲁石化公司 | Sulfur transform resistant macroreticular catalyst and its preparing process |
| CN1352229A (en) * | 2000-11-08 | 2002-06-05 | 中国石油化工股份有限公司 | Heavy oil hydrogenating treatment catalyst and its preparing method |
| CN1458236A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Process for preparing demetalizing and desulfurizing catalyst of heavy oil hydrogenation |
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