CN115228480A - Hydro-hydrolysis catalyst and preparation method thereof - Google Patents
Hydro-hydrolysis catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 45
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 40
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 35
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 18
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000005096 rolling process Methods 0.000 claims description 13
- 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
- 238000001035 drying Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 8
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 8
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 6
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 26
- 230000007062 hydrolysis Effects 0.000 abstract description 24
- 125000001741 organic sulfur group Chemical group 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 38
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon disulfide Substances S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 25
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 241000219782 Sesbania Species 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 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 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000009740 moulding (composite fabrication) Methods 0.000 description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- -1 rare earth metal salt Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Health & Medical Sciences (AREA)
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Abstract
The application discloses a hydro-hydrolysis catalyst and a preparation method thereof, belonging to the technical field of sulfur recovery. The embodiment of the application provides a hydro-hydrolysis catalyst, which comprises a carrier and an active component, wherein the preparation raw material of the carrier comprises aluminum hydroxide quick-release powder, pseudo-boehmite, a pore-expanding agent and a connecting agent, the active component comprises at least one of lanthanum, cerium, molybdenum and cobalt, and the active component can uniformly cover the surface of the carrier. The hydrogenation hydrolysis catalyst has higher activity on organic sulfur hydrolysis reaction, and can remove organic sulfur in the Claus tail gas through the organic sulfur hydrolysis reaction, thereby improving the treatment efficiency of the Claus tail gas.
Description
Technical Field
The application relates to the technical field of sulfur recovery. In particular to a hydro-hydrolysis catalyst and a preparation method thereof.
Background
At present, in order to meet the requirements of environmental protection standards, strict requirements are placed on the concentration of sulfur dioxide in the Claus tail gas discharged from oil refineries and natural gas purification plants, and the sulfur dioxide must be discharged up to the standard. In order to realize the standard emission of sulfur dioxide, most oil refineries and natural gas purification plants adopt a tail gas treatment device to treat the sulfur dioxide, thereby realizing the standard emission of the sulfur dioxide. In the case of a tail gas treatment device, the performance of the catalyst used in the device directly affects the treatment efficiency of the claus tail gas.
In the related art, nickel is mainly used as an active component to be loaded on an alumina carrier, so that the catalyst is prepared.
However, the catalyst in the related art has low activity for hydrolysis reaction of organic sulfur in claus tail gas, so that organic sulfur in claus tail gas cannot be removed by hydrolysis reaction of organic sulfur, resulting in low efficiency of treating claus tail gas.
Disclosure of Invention
The embodiment of the application provides a hydro-hydrolysis catalyst and a preparation method thereof, which can improve the treatment efficiency of Claus tail gas. The specific technical scheme is as follows:
in one aspect, the embodiments herein provide a hydro-hydrolysis catalyst,
the hydro-hydrolysis catalyst comprises: a carrier and an active ingredient;
the preparation raw materials of the carrier comprise quick aluminum hydroxide powder, pseudo-boehmite, a pore-expanding agent and a connecting agent;
the active component comprises at least one of lanthanum, cerium, molybdenum and cobalt;
the pore-enlarging agent comprises sesbania powder and activated carbon powder;
the connecting agent is titanyl sulfate solution.
In one possible implementation form of the method,
the lanthanum is lanthanum oxide, the cerium is cerium oxide, the molybdenum is molybdenum oxide, and the cobalt is cobalt oxide;
the hydro-hydrolysis catalyst comprises the following components in percentage by mass:
0 to 5 percent of lanthanum oxide, 0 to 5 percent of cerium oxide, 0 to 18 percent of molybdenum oxide, 0 to 8 percent of cobalt oxide, 1 to 2 percent of titanium dioxide and the balance of gamma-Al 2 O 3 ；
Wherein the titanium dioxide is obtained by roasting the titanyl sulfate solution, and the gamma-Al is 2 O 3 Is obtained by roasting the aluminum hydroxide quick-release powder and the pseudo-boehmite.
In another possible implementation manner, the mass ratio of the aluminum hydroxide quick-release powder to the pseudoboehmite is 1: (0.2-5).
In another possible implementation manner, the mass of the pore-expanding agent is 3-14% of the total mass of the pore-expanding agent, the aluminum hydroxide quick-release powder and the pseudo-boehmite.
In another possible implementation mode, the specific surface area of the aluminum hydroxide quick-release powder is more than 280m 2 /g；
The specific surface area of the pseudo-boehmite is more than 330m 2 /g。
In another possible implementation, the particle size of the hydro-hydrolysis catalyst is 4 to 6mm.
In another possible implementation, the specific surface area of the hydro-hydrolysis catalyst is 280 to 300m 2 /g。
In another possible implementation manner, the titanyl sulfate solution is obtained by dissolving 10 to 15g of titanium sulfate and 5 to 10g of sulfuric acid in 200mL of 8 to 20% nitric acid solution.
In another aspect, embodiments of the present application provide a preparation method of a hydro-hydrolysis catalyst, where the preparation method includes:
dissolving the active component into ammonia water containing a complexing agent and having the concentration of 5-20% to obtain an impregnation liquid;
quickly removing powder of aluminum hydroxide and pseudo-boehmite according to a mass ratio of 1: (0.2-5), adding a pore-expanding agent and a connecting agent, uniformly mixing, placing in a ball rolling machine, forming, curing for 10-20 hours in a water vapor atmosphere, drying for 2-8 hours at 105-150 ℃, and roasting for 4-10 hours at 500-600 ℃ to obtain a carrier;
according to the volume ratio of 1: (1-2), soaking the carrier in the soaking solution for 2-8 hours, taking out and placing at normal temperature for 24-48 hours;
drying for 2-8 hours at 105-150 ℃, and roasting for 4-10 hours at 500-600 ℃ to obtain the hydro-hydrolysis catalyst.
In one possible implementation, the complexing agent includes at least one of ammonium oxalate, methyl glycol amine, and citric acid.
The technical scheme provided by the embodiment of the application has the following beneficial effects:
the embodiment of the application provides a hydro-hydrolysis catalyst, which comprises a carrier and an active component, wherein the preparation raw material of the carrier comprises aluminum hydroxide quick-release powder, pseudo-boehmite, a pore-expanding agent and a connecting agent, the active component comprises at least one of lanthanum, cerium, molybdenum and cobalt, and the active component can uniformly cover the surface of the carrier. The hydrogenation hydrolysis catalyst has higher activity on organic sulfur hydrolysis reaction, and can remove organic sulfur in Claus tail gas through organic sulfur hydrolysis reaction, thereby improving the treatment efficiency of the Claus tail gas.
Drawings
FIG. 1 is a flow diagram of one embodiment of the present disclosure for preparing a hydro-hydrolysis catalyst;
fig. 2 is a schematic view of a claus tail gas micro-reverse evaluation device provided in an embodiment of the present application.
The reference numerals denote:
1-a valve, 2-a flowmeter, 3-a water increasing device, 4-a mixer, 5-a pressure gauge, 6-a preheater, 7-a heating furnace, 8-a first sampling point, 9-a temperature measuring point, 10-a reactor, 11-a second sampling point, 12-a separator,
13-container, 14-condenser, 15-wet flowmeter, 16-carbon disulfide bottle, 17-burning place.
Detailed Description
In order to make the technical solutions and advantages of the present application more clear, the following describes the embodiments of the present application in further detail.
Embodiments of the present application provide a hydro-hydrolysis catalyst, including: a carrier, and an active ingredient;
the preparation raw materials of the carrier comprise aluminum hydroxide quick-release powder, pseudo-boehmite, a pore-expanding agent and a connecting agent;
the active component comprises at least one of lanthanum, cerium, molybdenum and cobalt;
the pore-expanding agent comprises sesbania powder and active carbon powder;
the connecting agent is titanyl sulfate solution.
The embodiment of the application provides a hydro-hydrolysis catalyst, which comprises a carrier and an active component, wherein the preparation raw material of the carrier comprises aluminum hydroxide quick-release powder, pseudo-boehmite, a pore-expanding agent and a connecting agent, the active component comprises at least one of lanthanum, cerium, molybdenum and cobalt, and the active component can uniformly cover the surface of the carrier. The hydrogenation hydrolysis catalyst has higher activity on organic sulfur hydrolysis reaction, and can remove organic sulfur in Claus tail gas through organic sulfur hydrolysis reaction, thereby improving the treatment efficiency of the Claus tail gas.
In one possible implementation, the lanthanum is lanthanum oxide, the cerium is cerium oxide, the molybdenum is molybdenum oxide, and the cobalt is cobalt oxide;
the hydro-hydrolysis catalyst comprises:
0 to 5 percent of lanthanum oxide, 0 to 5 percent of cerium oxide, 0 to 18 percent of molybdenum oxide, 0 to 8 percent of cobalt oxide, 1 to 2 percent of titanium dioxide and the balance of gamma-Al 2 O 3 ；
Wherein the titanium dioxide is prepared by roasting titanyl sulfate solution, and is gamma-Al 2 O 3 Is prepared from quickly removed aluminium hydroxide powder and pseudoboehmite through calcining.
In this implementation, the appearance of the hydro-hydrolysis catalyst is a blue-gray sphere. The particle size of the hydrogenation hydrolysis catalyst is 4-6 mm, and the specific surface area of the hydrogenation hydrolysis catalyst is 280-300 m 2 (iv) g. The catalyst has large specific surface area, and can be used for hydrogenation reaction of sulfide and hydrolysis reaction of organic sulfurAll have higher activity.
In the embodiment of the application, the mass fraction of lanthanum oxide can be 0, 1%, 2%, 3%, 4%, 5%; the mass fraction of cerium oxide may be 0, 1%, 2%, 3%, 4%, 5%; the mass fraction of the molybdenum oxide can be 0, 2%, 4%, 6%, 8%, 10%, 14%, 16%, 18%; the mass fraction of the cobalt oxide can be 0, 1%, 2%, 4%, 5%, 6%, 7%, 8%; the mass fraction of titanium dioxide can be 1%, 1.2%, 1.5%, 1.8%, 2%.
Introduction of aluminum hydroxide quick-release powder and pseudo-boehmite: in one possible implementation mode, the mass of the aluminum hydroxide quick-release powder and the pseudo-boehmite is 1: (0.2-5). For example, the mass ratio of aluminum hydroxide quick-release powder to pseudo-boehmite is 1. In the embodiments of the present application, this is not particularly limited.
The quick-release powder of aluminum hydroxide is a component with small aperture, the pseudoboehmite is a component with large aperture, and the quick-release powder of aluminum hydroxide has low cost of 5000 yuan/ton, and the pseudoboehmite has high cost of 1.5 ten thousand yuan to 2 ten thousand yuan/ton. In the embodiment of the application, the aluminum hydroxide quick-release powder and the pseudo-boehmite are compounded for use, so that the cost can be reduced, and the large-aperture component and the small-aperture component can be fully combined, so that the crushing strength of the hydro-hydrolysis catalyst is increased.
In the embodiment of the application, the crushing strength of the hydro-hydrolysis catalyst is greater than 200N/particle, and the higher crushing strength can enable the hydro-hydrolysis catalyst to have the characteristics of higher stability, difficult breakage and long service life.
In one possible implementation, the specific surface area of the aluminum hydroxide quick-release powder is more than 280m 2 (ii)/g; the specific surface area of the pseudo-boehmite is more than 330m 2 /g。
In the implementation mode, the specific surface areas of the aluminum hydroxide quick-release powder and the pseudo-boehmite are larger, and the gamma-Al obtained after roasting 2 O 3 Has a larger specific surface area and is more sufficiently contacted with the active component, so that the active component can be more uniformly loaded on the surface thereof, thereby improving the additionActivity of hydrogen hydrolysis catalyst on organic sulfur hydrolysis reaction.
Note that γ -Al 2 O 3 The active alumina is a porous and high-dispersity solid material, has a larger specific surface area, can react with the active component to disperse the active component into the carrier, and provides effective specific surface area and a proper pore structure for the active component, so that the thermal stability of the catalyst is improved.
Introduction of the linking agent: the connecting agent is mainly used for connecting the aluminum hydroxide quick-release powder, the pseudo-boehmite and the pore-expanding agent together, so that the forming is convenient, and the crushing strength and the wear resistance of the catalyst are improved. The linking agent includes a permanent linking agent and a temporary linking agent, and these two linking agents may be used alone or in combination. The permanent bonding agent may be a titanyl sulfate solution, a sulfuric acid solution, or a nitric acid solution. The temporary linking agent may be water or a cellulose-based compound. In the embodiments of the present application, this is not particularly limited.
In one possible implementation, the linking agent is a titanyl sulfate solution.
In this implementation, the titanyl sulfate solution can be obtained by the following preparation method: 10-15 g of soluble titanium sulfate and 5-10 g of sulfuric acid are dissolved in 200mL of 8-20% nitric acid solution.
The titanyl sulfate solution is roasted to obtain titanium dioxide, and the titanium dioxide can increase the crushing strength of the hydrogenation hydrolysis catalyst, so that the hydrogenation hydrolysis catalyst can keep higher stability in the hydrogenation hydrolysis process, reduce abrasion and prolong the service life of the hydrogenation hydrolysis catalyst.
The concentration of the nitric acid solution may be 8%, 10%, 12%, 14%, 15%, 17%, 18%, 20%.
Introduction of pore-expanding agent: the pore-enlarging agent is mainly used for removing partial substances of the carrier by reacting with the carrier, and improving the pore volume and the pore diameter.
In one possible implementation mode, the mass of the pore-expanding agent is 3-14% of the total mass of the pore-expanding agent, the aluminum hydroxide quick-release powder and the pseudo-boehmite.
In this implementation, the mass of the pore-expanding agent may be 3%, 4%, 7%, 9%, 11%, 12%, 13%, 14% of the total mass of the three. The pore-enlarging agent comprises sesbania powder and activated carbon powder, wherein the sesbania powder can account for 1-8% of the total mass, and the activated carbon powder can account for 2-6% of the total mass. For example, sesbania powder accounts for 1%, 2%, 3%, 4%, 6%, 8% of the total mass, and activated carbon powder accounts for 2%, 3%, 4%, 5%, 6% of the total mass.
The embodiment of the application provides a hydrogenation catalyst, and this hydrogenation catalyst has crushing intensity big, all has higher activity to sulphide hydrogenation and organic sulphur hydrolysis, is a high claus tail gas hydrogenation catalyst of stability, can satisfy the technical requirement of the large-scale sulphur recovery unit claus tail gas hydrogenation technology of natural gas purification trade, guarantees that tail gas emission reaches the technical standard of national regulation.
The embodiment of the application also provides a preparation method of the hydro-hydrolysis catalyst, which comprises the following steps:
step 1: dissolving the active component into ammonia water containing complexing agent and having the concentration of 5-20% to obtain impregnation liquid.
In this step, the complexing agent includes at least one of ammonium oxalate, methyl glycol amine, and citric acid. The active component may be at least one of ammonium cerium nitrate, lanthanum nitrate, cobalt nitrate and ammonium molybdate.
Correspondingly, the steps can be as follows: at least one of ammonium ceric nitrate, lanthanum nitrate, cobalt nitrate and ammonium molybdate is dissolved in 5-20% ammonia water containing at least one of ammonium oxalate, methyl glycol amine and citric acid to obtain an impregnation liquid, and the impregnation liquid is a red solution. The dipping solution is a solution containing lanthanide series rare earth metal salt and VIB group and/or VIII group metal salt.
Step 2: quickly removing powder of aluminum hydroxide and pseudo-boehmite according to a mass ratio of 1: (0.2-5), adding a pore-expanding agent and a connecting agent, uniformly mixing, placing in a ball rolling machine, molding, curing for 10-20 hours in a water vapor atmosphere, drying for 2-8 hours at 105-150 ℃, and roasting for 4-10 hours at 500-600 ℃ to obtain the carrier.
In the step, the aluminum hydroxide quick-removing powder, the pseudo-boehmite and the pore-enlarging agent are all solids, and the connecting agent is liquid, so the aluminum hydroxide quick-removing powder, the pseudo-boehmite and the pore-enlarging agent can be uniformly mixed firstly, then the mixture is placed in a ball rolling machine, the titanyl sulfate solution is slowly sprayed into the mixed solids, the ball rolling machine is rotated to form and sieve, and small balls with the diameter of 4-6 mm are sunned out. Placing the mixture in the atmosphere of 100% water vapor for curing for 10 to 20 hours, drying the mixture for 2 to 8 hours at the temperature of between 105 and 150 ℃, and roasting the mixture for 4 to 10 hours at the temperature of between 500 and 600 ℃ to obtain the carrier, wherein the carrier is shown in figure 1.
And step 3: according to the volume ratio of 1: (1-2), soaking the carrier in the soaking solution for 2-8 hours, taking out and standing at normal temperature for 24-48 hours.
In the step, the pellets with the diameter of 4-6 mm are soaked in the soaking solution for 2-8 hours, taken out and passivated at normal temperature for 24-48 hours, so that the active components in the soaking solution are uniformly loaded on the surfaces of the carrier pellets.
And 4, step 4: drying at 105-150 deg.c for 2-8 hr, and roasting at 500-600 deg.c for 4-10 hr to obtain the hydrohydrolysis catalyst.
And drying and roasting the carrier pellets loaded with the active component to finally obtain the hydro-hydrolysis catalyst, and continuously referring to fig. 1.
In the application example, the appearance of the hydro-hydrolysis catalyst is blue gray spherical, and the specific surface area is 280-300 m 2 (ii) in terms of/g. The hydrogenation hydrolysis catalyst has a large specific surface area, can be fully contacted with Claus tail gas, and accelerates the sulfide hydrogenation reaction and the organic sulfur hydrolysis reaction.
The technical solution of the present application will be described in detail by specific embodiments below.
In the following examples, those whose operations are not subject to the conditions indicated, are carried out according to the conventional conditions or conditions recommended by the manufacturer. The raw materials are conventional products which can be obtained commercially by manufacturers and specifications.
Example 1
Respectively weighing 2Kg of aluminum hydroxide quick-release powder and pseudo-thin water1Kg of aluminum oxide, 50g of sesbania powder and 50g of activated carbon powder are mixed uniformly. Wherein the specific surface area of the aluminum hydroxide quick-release powder is 295m 2 (g) the specific surface area of the pseudo-boehmite is 340m 2 /g。
2L of nitric acid solution with the concentration of 12% is prepared, and 100g of titanium sulfate and 50g of sulfuric acid are added to prepare uniform solution. And (3) placing the mixed solid in a ball rolling machine, slowly spraying the prepared titanyl sulfate solution into the mixed solid, rotating, rolling, forming and sieving to obtain small balls with the diameter of 4-6 mm, placing the small balls in an atmosphere of 100% of water vapor for curing for 15 hours, drying at 110 ℃ for 2 hours, and roasting at 500 ℃ for 4 hours to obtain the carrier.
500g of ammonium heptamolybdate, 180g of cobalt nitrate, 300g of ammonium ceric nitrate and 120g of lanthanum nitrate were added to 10.7% strength 3L of aqueous ammonia and stirred until a red impregnation solution was formed.
0.15L of carrier is taken to be dipped in 3L of dipping solution for 2 hours, taken out to be passivated at normal temperature for 24 hours, dried for 4 hours at 110 ℃, and roasted for 4 hours at 500 ℃ to obtain the hydrogenation hydrolysis catalyst.
Example 2
Respectively weighing 2Kg of quick-release aluminum hydroxide powder, 1Kg of pseudo-boehmite, 50g of sesbania powder and 50g of activated carbon powder, and uniformly mixing. Wherein the specific surface area of the aluminum hydroxide quick-release powder is 295m 2 (g) the specific surface area of the pseudo-boehmite is 340m 2 /g。
2L of nitric acid solution with the concentration of 12% is prepared, and 100g of titanium sulfate and 50g of sulfuric acid are added to prepare uniform solution. And (3) placing the mixed solid in a ball rolling machine, slowly spraying the prepared titanyl sulfate solution into the mixed solid, rotating, rolling, forming and sieving to obtain small balls with the diameter of 4-6 mm, placing the small balls in an atmosphere of 100% of water vapor for curing for 15 hours, drying at 110 ℃ for 2 hours, and roasting at 500 ℃ for 4 hours to obtain the carrier.
500g of ammonium heptamolybdate and 180g of cobalt nitrate were added to 10.7% strength 3L of aqueous ammonia and stirred until a red impregnation solution was formed.
0.15L of carrier is taken to be dipped in 3L of dipping solution for 2 hours, taken out to be passivated at normal temperature for 24 hours, dried for 4 hours at 110 ℃, and roasted for 4 hours at 500 ℃ to obtain the hydrogenation hydrolysis catalyst.
Comparative example 1
Weighing 2Kg of quick-release aluminum hydroxide powder, 1Kg of pseudo-boehmite, 50g of sesbania powder and 50g of activated carbon powder respectively, and uniformly mixing. Wherein the specific surface area of the aluminum hydroxide quick-release powder is 295m 2 Perg, the specific surface area of the pseudo-boehmite is 340m 2 /g。
Preparing a nitric acid solution with the concentration of 12%, placing the mixed solid in a ball rolling machine, slowly spraying the prepared nitric acid solution into the mixed solid, rotating, rolling, forming, sieving to obtain small balls with the diameter of 4-6 mm, placing the small balls in an atmosphere of 100% water vapor for curing for 15 hours, drying for 2 hours at the temperature of 110 ℃, and roasting for 4 hours at the temperature of 500 ℃ to obtain the carrier.
500g of ammonium heptamolybdate, 180g of cobalt nitrate, 300g of ammonium ceric nitrate and 120g of lanthanum nitrate were added to 10.7% strength 3L of aqueous ammonia and stirred until a red impregnation solution was formed.
0.15L of carrier is taken to be soaked in 3L of soaking liquid for 2 hours, taken out to be passivated for 24 hours at normal temperature, dried for 4 hours at 110 ℃, and roasted for 4 hours at 500 ℃ to obtain the catalyst.
Comparative example 2
Weighing 3Kg of pseudo-boehmite, 50g of sesbania powder and 50g of activated carbon powder, and uniformly mixing. Wherein the specific surface area of the aluminum hydroxide quick-release powder is 295m 2 (g) the specific surface area of the pseudo-boehmite is 340m 2 /g。
2L of nitric acid solution with the concentration of 12% is prepared, and 100g of titanium sulfate and 50g of sulfuric acid are added to prepare uniform solution. And (3) placing the mixed solid in a ball rolling machine, slowly spraying the prepared titanyl sulfate solution into the mixed solid, rotating, rolling, forming and sieving to obtain small balls with the diameter of 4-6 mm, placing the small balls in an atmosphere of 100% of water vapor for curing for 15 hours, drying at 110 ℃ for 2 hours, and roasting at 500 ℃ for 4 hours to obtain the carrier.
500g of ammonium heptamolybdate, 180g of cobalt nitrate, 300g of ammonium ceric nitrate and 120g of lanthanum nitrate were added to 10.7% strength 3L of aqueous ammonia and stirred until a red impregnation solution was formed.
0.15L of carrier is taken to be dipped in 3L of dipping solution for 2 hours, taken out to be passivated at normal temperature for 24 hours, dried for 4 hours at 110 ℃ and roasted for 4 hours at 500 ℃ to obtain the catalyst.
Application example 1
This application example was mainly used to evaluate the crush strength of the catalysts prepared in examples 1 to 2 and comparative examples 1 to 2.
The crush strength of the catalyst prepared in example 1 was 201N/particle and the crush strength of the catalyst prepared in comparative example 1 was only 133N/particle, see table 1. The preparation of the catalysts according to example 1 and comparative example 1 shows that: in comparison with comparative example 1, in the case of preparing a hydro-hydrolysis catalyst in example 1, the linking agent is a titanyl sulfate solution, while the linking agent used in comparative example 1 is a nitric acid solution, and the rest is the same. It is thus understood that the titanyl sulfate solution can enhance the crush strength of the catalyst.
The crush strength of the catalyst prepared in example 2 was 210N/particle and the crush strength of the catalyst prepared in comparative example 2 was only 113N/particle, with continued reference to table 1. In contrast to comparative example 2, in the case of preparing the hydro-hydrolysis catalyst in example 2, the raw materials for preparing the carrier mainly include aluminum hydroxide quick-release powder and pseudo-boehmite, while the raw materials for preparing the carrier in comparative example 2 include only pseudo-boehmite, and the others are the same. Therefore, the crushing strength of the catalyst can be enhanced by compounding the aluminum hydroxide quick-release powder and the pseudo-boehmite.
In addition, it can be seen from Table 1 that the catalysts prepared in examples 1 and 2 have high specific surface areas, both greater than 280m 2 The active components can be uniformly distributed on the surface of the carrier, so that the activity of the hydrogenation hydrolysis catalyst on sulfide hydrogenation reaction and organic sulfur hydrolysis reaction is improved.
TABLE 1 physicochemical Properties of catalysts prepared in examples 1 to 2 and comparative examples 1 to 2
| Catalyst and process for preparing same | Example 1 | Comparative example 1 | Example 2 | Comparative example 2 |
| Appearance of the product | Spherical shape | Spherical shape | Spherical shape | Spherical shape |
| Size, mm | Φ4.0-6.0 | Φ4.0-6.0 | Φ4.0-6.0 | Φ4.0-6.0 |
| Specific surface area, m 2 /g | 289 | 284 | 298 | 291 |
| Strength, N/grain | 201 | 133 | 113 | 210 |
| Cobalt oxide% | 4.3 | 4.3 | 4.5 | 4.5 |
| Molybdenum oxide,% of | 6.8 | 6.8 | 7.1 | 7.1 |
| Lanthanum oxide,% | 1.6 | 1.6 | / | / |
| Cerium oxide,% of | 2.2 | 2.2 | / | / |
Application example 2
This application example was evaluated mainly on the hydrogenation catalytic activity and organic sulfur hydrolysis activity of the hydrogenation hydrolysis catalysts prepared in examples 1 and 2.
For convenience of description, before evaluating the hydro-hydrolysis catalyst, a claus tail gas micro-reverse evaluation device will be described, referring to fig. 2.
The valves 1 of the respective transfer lines are opened, the gas enters the mixer 4, the carbon dioxide presses the carbon disulfide in the carbon disulfide bottle 16 into the mixer 4, the nitrogen presses the water in the water booster 3 into the preheater 6, and the flow rate of the nitrogen is measured by the flow meter 2. The gas in mixer 4 is then fed to preheater 6 along with the carbon disulphide and the pressure of the gas and carbon disulphide is measured by pressure gauge 5. The preheater 6 is heated by the heating furnace 7, and when the heating temperature reaches a preset temperature, the preheater is introduced into the reactor 10, and the reactor 10 is filled with a hydro-hydrolysis catalyst, so that the hydro-hydrolysis catalyst catalyzes the reaction. Before being introduced into the reactor 10, a sample is taken at the inlet of the reactor 10, i.e. at the first sampling point 8, and the concentration of the gas is determined. After passing into the reactor 10, the temperature of the gas is measured inside the reactor 10 at the temperature measuring point 9. After the reaction is completed, a sample is taken at the outlet of the reactor 10, i.e., at the second sampling point 11, and the concentration of the gas is measured. The catalyst is introduced into the separator 12, the gas is introduced into the container 13, the container 13 is filled with alkali liquor, the alkali liquor can be sodium hydroxide solution or sodium carbonate solution, the gas is absorbed by the alkali liquor, and the gas coming out of the reactor 10 has higher temperature, so the gas can be condensed by the condenser 14, and the gas can fully react with the alkali liquor. The unreacted gas is then subjected to a burning treatment 17, and the flow rate of the gas may also be measured by the wet flowmeter 15 before the burning treatment 17.
In the examples of the present application, the loading of the catalyst in the reactor was 10mL, and the claus tail gas was presulfided by hydrogen sulfide gas before being treated. The prevulcanization conditions are as follows: the temperature is 350 ℃, and the space velocity is 650h -1 ，H 2 S concentration is 0.4-10%, when the reactor outlet H 2 The S content is greater than or equal to the inlet, the prevulcanisation is finished and the conversion is to claus tail gas, the component names and compositions of which can be seen in table 2. In this application example, the hydro-hydrolysis activity of the hydro-hydrolysis catalyst in the low-temperature claus reaction at the reactor inlet temperature of 240 ℃ and the hydro-hydrolysis activity in the normal-temperature claus reaction at 260 ℃ can be separately tested, and specific data can be seen in table 3.
In the application example, the hydrogenation catalytic activity of the catalyst can be evaluated through the conversion rate of sulfur dioxide, and the hydrolysis catalytic activity of the catalyst can be evaluated through the hydrolysis rate of carbon disulfide. Accordingly, the conversion of sulfur dioxide and the hydrolysis of carbon disulfide can be calculated by the following formulas:
wherein, measureAt a fixed conversion of sulfur dioxide, M 0 And M 1 Respectively representing the volume concentration of sulfur dioxide at the inlet and the outlet of the reactor; when the hydrolysis rate of carbon disulfide is measured, M 0 And M 1 The volume concentrations of carbon disulphide at the inlet and outlet of the reactor are indicated respectively.
TABLE 2 component names and compositions of Claus tail gas
TABLE 3 Hydrohydrolysis Activity of the Hydrohydrolysis catalysts prepared in examples 1-2 at different temperatures
As can be seen from table 3: the hydro-hydrolysis catalysts prepared in examples 1 and 2 have high hydrogenation conversion rate and carbon disulfide hydrolysis rate, which shows that the hydro-hydrolysis catalysts have high hydrogenation catalytic activity and hydrolysis catalytic activity. And, at an inlet temperature of 260 ℃, a space velocity of 1500h -1 Under the condition of typical Claus tail gas composition, the total sulfur content in the hydrogenated process gas except hydrogen sulfide is less than 50ppm, and the national tail gas emission standard can be reached.
In summary, the hydro-hydrolysis catalyst provided by the embodiment of the application has high hydro-catalytic activity and hydrolysis catalytic activity, and also has high crushing strength, and is a catalyst with high stability and long service life.
The above description is only for facilitating the understanding of the technical solutions of the present application by those skilled in the art, and is not intended to limit the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A hydro-hydrolysis catalyst, wherein the hydro-hydrolysis catalyst comprises: a carrier and an active ingredient;
the preparation raw materials of the carrier comprise quick aluminum hydroxide powder, pseudo-boehmite, a pore-expanding agent and a connecting agent;
the active component comprises at least one of lanthanum, cerium, molybdenum and cobalt;
the pore-enlarging agent comprises sesbania powder and activated carbon powder;
the connecting agent is titanyl sulfate solution.
2. The hydrohydrolysis catalyst as recited in claim 1 wherein the lanthanum is lanthanum oxide, the cerium is cerium oxide, the molybdenum is molybdenum oxide, and the cobalt is cobalt oxide;
the hydro-hydrolysis catalyst comprises the following components in percentage by mass:
0 to 5 percent of lanthanum oxide, 0 to 5 percent of cerium oxide, 0 to 18 percent of molybdenum oxide, 0 to 8 percent of cobalt oxide, 1 to 2 percent of titanium dioxide and the balance of gamma-Al 2 O 3 ；
Wherein the titanium dioxide is obtained by roasting the titanyl sulfate solution, and the gamma-Al is 2 O 3 Is obtained by roasting the aluminum hydroxide quick-release powder and the pseudo-boehmite.
3. The hydro-hydrolysis catalyst as recited in claim 1, wherein the mass ratio of the aluminum hydroxide fast-falling powder to the pseudo-boehmite is 1: (0.2-5).
4. The hydrohydrolysis catalyst according to claim 3, wherein the pore-enlarging agent is 3 to 14% by mass of the total mass of the pore-enlarging agent, the aluminum hydroxide quick-release powder and the pseudo-boehmite.
5. The hydrohydrolysis catalyst according to claim 1, wherein the aluminum hydroxide fast-removing powder has a specific surface area of more than 280m 2 /g；
The specific surface area of the pseudo-boehmite is more than 330m 2 /g。
6. The hydrohydrolysis catalyst according to claim 1, wherein the particle size of the hydrohydrolysis catalyst is 4 to 6mm.
7. The hydrohydrolysis catalyst according to claim 1, wherein the specific surface area of the hydrohydrolysis catalyst is 280 to 300m 2 /g。
8. The hydrohydrolysis catalyst according to claim 1, wherein the titanyl sulfate solution is prepared by dissolving 10 to 15g of titanium sulfate and 5 to 10g of sulfuric acid in 200mL of a 8 to 20% nitric acid solution.
9. A method for preparing a hydro-hydrolysis catalyst according to any one of claims 1 to 8, comprising:
dissolving the active component into ammonia water containing a complexing agent and having the concentration of 5-20% to obtain an impregnation liquid;
quickly removing powder of aluminum hydroxide and pseudo-boehmite according to a mass ratio of 1: (0.2-5), adding a pore-expanding agent and a connecting agent, uniformly mixing, placing in a ball rolling machine, molding, curing for 10-20 hours in a steam atmosphere, drying for 2-8 hours at 105-150 ℃, and roasting for 4-10 hours at 500-600 ℃ to obtain a carrier;
according to the volume ratio of 1: (1-2), soaking the carrier in the soaking solution for 2-8 hours, taking out the carrier, and standing the carrier at normal temperature for 24-48 hours;
drying for 2-8 hours at 105-150 ℃, and roasting for 4-10 hours at 500-600 ℃ to obtain the hydro-hydrolysis catalyst.
10. The method of claim 9, wherein the complexing agent comprises at least one of ammonium oxalate, methyl glycol amine, and citric acid.
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