CN113318741A - Iron-based COS hydrolysis catalyst and preparation method thereof - Google Patents
Iron-based COS hydrolysis catalyst and preparation method thereof Download PDFInfo
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- CN113318741A CN113318741A CN202110778648.1A CN202110778648A CN113318741A CN 113318741 A CN113318741 A CN 113318741A CN 202110778648 A CN202110778648 A CN 202110778648A CN 113318741 A CN113318741 A CN 113318741A
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- iron
- mixed system
- hydrolysis catalyst
- cos hydrolysis
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 49
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 5
- 238000004898 kneading Methods 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 10
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 125000001741 organic sulfur group Chemical group 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 241000219782 Sesbania Species 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
- 150000003863 ammonium salts Chemical class 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/615—
-
- 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
Abstract
The embodiment of the invention provides an iron-based COS hydrolysis catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a ferrous salt solution with a certain concentration, stirring for dissolving, and maintaining a certain temperature; adding a water-soluble emulsifier into the ferrous salt solution, uniformly stirring and forming a first mixed system; adding an active metal salt auxiliary agent into the first mixed system in the stirring process, so that the active metal salt auxiliary agent is fully dissolved and a second mixed system is formed; adding a water solution of a precipitator into the second mixed system, and uniformly stirring to form a third mixed system; adding an oxidant into the third mixed system to form a fourth mixed system, uniformly stirring and aging; and washing and separating the fourth mixed system, drying, kneading with a forming auxiliary agent and a binder, forming and drying. The invention can effectively improve the hydrolysis catalytic performance and prolong the service life.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to an iron-based COS hydrolysis catalyst and a preparation method thereof.
Background
While natural gas and coal are exploited in large quantities, resources with high sulfur content are exploited. Wherein the natural gas and synthetic gas contain organic sulfur (such as COS) 30-500mg/m3And the presence of organic sulfur (COS) can corrode equipment, cause catalyst poisoning and cause acid rain, thereby endangering health, etc. In order to effectively reduce the harm of organic sulfur to industrial production and human health, researchers have conducted a great deal of research, and certain research has been conductedApplication is carried out. However, the theoretical research and industrial application of organic sulfur in China are not sufficient and mature, and some enterprises adopt foreign products, for example, Puguang natural gas company uses hydrolysis catalyst of Johnson Matthey, which mainly comprises activated alumina and has good low-temperature hydrolysis activity, LS-04 hydrolysis catalyst developed by institute of domestic Petroleum Qilu division also has good COS-catalyzing effect, and the main active component of the LS-04 hydrolysis catalyst is impregnated activated alumina.
In the prior art, Chinese patent CN1704145A discloses COS and CS2A hydrolysis catalyst and application thereof. In the patent, the ammonium salt is loaded to gamma-Al2O3The method is used for catalyzing and hydrolyzing organic sulfur, can effectively improve the removal precision of the organic sulfur, and simultaneously, the loaded components are cheap and easy to obtain. However, the method introduces more ammonium salt (5-10%) in preparation, and ammonia nitrogen pollution is possible in the preparation and use processes; meanwhile, the method can not solve the problem of service life of the hydrolysis catalyst well, and the hydrolysis catalyst is easy to lose activity, so that the method has obvious defects.
Disclosure of Invention
The embodiment of the invention aims to provide an iron-based COS hydrolysis catalyst and a preparation method thereof, which can effectively improve hydrolysis catalytic performance and prolong service life.
In a first aspect, an embodiment of the present invention provides a method for preparing an iron-based COS hydrolysis catalyst, including the following steps:
s10: preparing a ferrous salt solution with a certain concentration, stirring for dissolving, and maintaining a certain temperature;
s20: adding a water-soluble emulsifier into the ferrous salt solution, uniformly stirring and forming a first mixed system, wherein the molar ratio of the emulsifier to the ferrous salt is (0.01-1.2): 1;
s30: adding an active metal salt auxiliary agent into the first mixed system in the stirring process, fully dissolving the active metal salt auxiliary agent and forming a second mixed system, wherein the molar ratio of the active metal salt auxiliary agent to the ferrous salt is (0.01-0.5): 1;
s40: adding a water solution of a precipitator into the second mixed system, maintaining the pH value to be 4-10, uniformly stirring to form a third mixed system, wherein the molar ratio of the precipitator to the ferrous salt is (1-2.5): 1;
s50: adding an oxidant into the third mixed system to form a fourth mixed system, uniformly stirring and aging, wherein the molar ratio of the oxidant to the ferrous salt is (0.01-100): 1;
s60: and washing and separating the fourth mixed system, drying, kneading with a forming auxiliary agent and a binder, forming and drying to obtain the iron-based COS hydrolysis catalyst.
Further, the ferrous salt is at least one of ferrous sulfate, ferrous chloride, ferrous nitrate and ferrous acetate.
Further, the emulsifier is at least one of alkylphenol ethoxylates, ethoxylated alkyl sodium sulfate, oleic acid, polypropylene, polystyrene, polyethylene glycol, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and barium stearate.
Further, the active metal salt auxiliary agent is at least one of titanium sulfate, zirconium sulfate, cobalt nitrate, molybdenum sulfate, nickel nitrate, calcium sulfate, zinc sulfate and copper sulfate.
Further, the precipitant is at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, ammonium carbonate, and urea.
Further, the concentration of the precipitant is 1-5 mol/L.
Further, the oxidant is at least one of oxygen, ozone, sodium peroxide, sodium persulfate, hydrogen peroxide, sodium hypochlorite and sodium ferrate.
Further, the forming auxiliary agent is at least one of pseudo-boehmite, kaolin, red clay and attapulgite; the binder is at least one of polyvinyl alcohol, polyacrylamide, cellulose, sesbania powder, starch, calcium sulfate and calcium oxide.
Further, the temperature in the step S10 is maintained at 10 to 80 ℃, the aging time in the step S50 is 0.5 to 8 hours, the drying temperature for the fourth mixed system in the step S60 is 70 to 110 ℃, and the drying temperature for the iron-based COS hydrolysis catalyst in the step S60 is 80 to 350 ℃.
In a second aspect, an embodiment of the present invention provides an iron-based COS hydrolysis catalyst, which is produced by using the above method for preparing an iron-based COS hydrolysis catalyst, wherein the iron-based COS hydrolysis catalyst comprises: 40-95 parts of iron-based material, 2-20 parts of forming agent, 5-30 parts of binder and 25-40 parts of water.
The invention has the beneficial effects that: the iron-based COS hydrolysis catalyst and the preparation method thereof provided by the embodiment of the invention can increase the active point position and the specific surface area of the iron-based COS hydrolysis catalyst, and have extremely high desulfurization precision, thereby improving the hydrolysis catalytic performance and prolonging the service life.
In order to make the aforementioned and other objects, features and advantages of the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the embodiments of the present invention will be described in detail and completely with reference to the accompanying drawings. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention.
The terms "first", "second", and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
Example 1
The preparation method of the iron-based COS hydrolysis catalyst provided by the embodiment of the invention mainly comprises the following steps:
s10: preparing ferrous sulfate solution with the concentration of 0.1mol/L, stirring and dissolving, and maintaining the temperature at 40 ℃.
S20: adding polyoxyethylene ether into the ferrous sulfate, wherein the molar ratio of the polyoxyethylene ether to the ferrous is 0.02:1, and uniformly stirring to form a first mixed system.
S30: adding cobalt nitrate solid into the first mixed system under continuous stirring, wherein the molar ratio of the cobalt nitrate solid to ferrous is 0.015:1, and stirring to fully dissolve the cobalt nitrate solid and the ferrous to form a second mixed system.
S40: adding an ammonia water solution with the concentration of 2mol/L into the solution of the second mixed system, maintaining the pH value to be 7.0, and uniformly stirring to form a third mixed system; wherein the molar ratio of ammonia to ferrous iron is 2.2: 1.
S50: slowly dropwise adding H into the third mixed system2O2Said H is2O2The mol ratio of the mixed solution to ferrous salt is 1:1, a fourth mixed system is formed, and the mixed solution is uniformly stirred, fully oxidized and aged.
S60: and washing and separating the fourth mixed system, drying at 80 ℃, kneading with a forming auxiliary agent and a binder, forming, and drying at 120 ℃ to obtain the iron-based COS hydrolysis catalyst.
In this example, the iron-based COS hydrolysis catalyst was composed of the following raw materials in parts by weight: 80 parts by weight of an iron-based material, 10 parts by weight of kaolin, 10 parts by weight of sesbania powder and 10 parts by weight of water.
Example 2
The preparation method of the iron-based COS hydrolysis catalyst provided by the embodiment of the invention mainly comprises the following steps:
s10: preparing ferrous sulfate solution with the concentration of 0.5mol/L, stirring and dissolving, and maintaining the temperature at 50 ℃.
S20: adding sodium dodecyl benzene sulfonate into ferrous sulfate, wherein the molar ratio of the sodium dodecyl benzene sulfonate to the ferrous sulfate is 0.05:1, and uniformly stirring to form a first mixed system.
S30: adding zirconium sulfate solid into the first mixed system under continuous stirring, wherein the molar ratio of the zirconium sulfate solid to ferrous sulfate is 0.08:1, and stirring to fully dissolve the zirconium sulfate solid and ferrous sulfate to form a second mixed system.
S40: adding a sodium carbonate solution with the concentration of 1mol/L into the solution of the second mixed system, maintaining the pH value to be 7.5, and uniformly stirring to form a third mixed system; the molar ratio of the sodium carbonate to the ferrous sulfate is 1.4: 1.
S50: slowly introducing O into the third mixed system3Said O is3The mol ratio of the mixed solution to ferrous salt is 3:1, a fourth mixed system is formed, and the mixed solution is continuously stirred, fully oxidized and aged.
S60: and washing and separating the fourth mixed system, drying at 90 ℃, kneading with a forming auxiliary agent and a binder, forming, and drying at 150 ℃ to obtain the iron-based COS hydrolysis catalyst.
Activity evaluation example
The hydrolysis catalyst prepared by the method is used for evaluating the performance of hydrolyzing and catalyzing COS under the anaerobic condition, and the operation steps are as follows:
drying the product at 90 deg.C for 2 hr, grinding, sieving with 60-80 mesh sieve, accurately weighing 2g (accurate value of 0.0001 g) sample, filling into a reaction tube (phi 6) with constant temperature of 80 deg.C, filling quartz sand with 60 mesh sieve at two ends, connecting one end of the reaction tube with a constant temperature (e.g. 50 deg.C) steam generator, and introducing COS (with COS concentration of 500 mg/m)320% of CO2The remainder being N2) And the tail end of the reaction tube is connected with a gas chromatograph for detecting the content of COS at an outlet. Opening the valve of the gas cylinder, controlling the airspeed at 2000h-1, and detecting the content of COS at the outlet to be more than 1mg/m when the chromatogram detects3When the reaction is completed, the reaction is stopped.
The specific surface area and hydrolytic activity of the products prepared in the above examples are shown in table 1:
TABLE 1 hydrolysis catalyst De-catalytic Performance
As can be seen from the table above, the desulfurizer of the type has excellent hydrolysis catalysis efficiency and long service life of the catalyst at 2000h < -1 >.
In this example, the iron-based COS hydrolysis catalyst was composed of the following raw materials in parts by weight: 75 parts by weight of an iron-based material, 7 parts by weight of pseudoboehmite, 5 parts by weight of attapulgite, 10 parts by weight of calcium sulfate, 3 parts by weight of cellulose and 20 parts by weight of water.
In summary, the iron-based COS hydrolysis catalyst and the preparation method thereof provided by the embodiments of the present invention can increase the active site and the specific surface area of the iron-based COS hydrolysis catalyst, thereby improving the hydrolysis catalytic performance and prolonging the service life.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of an iron-based COS hydrolysis catalyst is characterized by comprising the following steps:
s10: preparing a ferrous salt solution with a certain concentration, stirring for dissolving, and maintaining a certain temperature;
s20: adding a water-soluble emulsifier into the ferrous salt solution, uniformly stirring and forming a first mixed system, wherein the molar ratio of the emulsifier to the ferrous salt is (0.01-1.2): 1;
s30: adding an active metal salt auxiliary agent into the first mixed system in the stirring process, fully dissolving the active metal salt auxiliary agent and forming a second mixed system, wherein the molar ratio of the active metal salt auxiliary agent to the ferrous salt is (0.01-0.5): 1;
s40: adding a water solution of a precipitator into the second mixed system, maintaining the pH value to be 4-10, uniformly stirring to form a third mixed system, wherein the molar ratio of the precipitator to the ferrous salt is (1-2.5): 1;
s50: adding an oxidant into the third mixed system to form a fourth mixed system, uniformly stirring and aging, wherein the molar ratio of the oxidant to the ferrous salt is (0.01-100): 1;
s60: and washing and separating the fourth mixed system, drying, kneading with a forming auxiliary agent and a binder, forming and drying to obtain the iron-based COS hydrolysis catalyst.
2. The method of preparing an iron-based COS hydrolysis catalyst as claimed in claim 1, wherein the ferrous salt is at least one of ferrous sulfate, ferrous chloride, ferrous nitrate and ferrous acetate.
3. The method of preparing an iron-based COS hydrolysis catalyst as claimed in claim 1, wherein the emulsifier is at least one of alkylphenol ethoxylates, sodium ethoxyalkylsulfate, oleic acid, polypropylene, polystyrene, polyethylene glycol, cetyltrimethylammonium bromide, sodium dodecylsulfate, and barium stearate.
4. The method of preparing an iron-based COS hydrolysis catalyst as claimed in claim 1, wherein the active metal salt promoter is at least one of titanium sulfate, zirconium sulfate, cobalt nitrate, molybdenum sulfate, nickel nitrate, calcium sulfate, zinc sulfate and copper sulfate.
5. The method of preparing an iron-based COS hydrolysis catalyst as claimed in claim 1, wherein the precipitant is at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, aqueous ammonia, ammonium carbonate and urea.
6. The method of preparing an iron-based COS hydrolysis catalyst as claimed in claim 5, wherein the concentration of the precipitant is 1-5 mol/L.
7. The method of preparing an iron-based COS hydrolysis catalyst as claimed in claim 1, wherein the oxidant is at least one of oxygen, ozone, sodium peroxide, sodium persulfate, hydrogen peroxide, sodium hypochlorite and sodium ferrate.
8. The method for preparing an iron-based COS hydrolysis catalyst as claimed in claim 1, wherein the forming aid is at least one of pseudoboehmite, kaolin, red clay and attapulgite; the binder is at least one of polyvinyl alcohol, polyacrylamide, cellulose, sesbania powder, starch, calcium sulfate and calcium oxide.
9. The method of preparing an iron-based COS hydrolysis catalyst as claimed in claim 1, wherein the temperature in step S10 is maintained at 10-80 ℃, the aging time in step S50 is 0.5-8 hours, the drying temperature for the fourth mixed system in step S60 is 70-110 ℃, and the drying temperature for the iron-based COS hydrolysis catalyst in step S60 is 80-350 ℃.
10. An iron-based COS hydrolysis catalyst produced by the method for preparing an iron-based COS hydrolysis catalyst according to any one of claims 1 to 9, wherein the iron-based COS hydrolysis catalyst comprises: 40-95 parts of iron-based material, 2-20 parts of forming agent, 5-30 parts of binder and 25-40 parts of water.
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| CN114196448A (en) * | 2022-02-16 | 2022-03-18 | 北京中航天业科技有限公司 | Full-flow dry type blast furnace gas fine desulfurization system and method |
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| FR2608458A1 (en) * | 1986-12-23 | 1988-06-24 | Rhone Poulenc Chimie | CERIUM OXIDE CATALYST AND PROCESS FOR PROCESSING INDUSTRIAL GASES CONTAINING SULFUR COMPOUNDS |
| CN104667926A (en) * | 2013-11-29 | 2015-06-03 | 福建三聚福大化肥催化剂国家工程研究中心有限公司 | Low-temperature carbonyl sulfide hydrolysis catalyst and preparation method thereof |
| CN105056719A (en) * | 2015-07-30 | 2015-11-18 | 福州大学化肥催化剂国家工程研究中心 | Preparation method of FeOOH low-temperature desulfurizer and desulfurizer prepared through same |
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| FR2608458A1 (en) * | 1986-12-23 | 1988-06-24 | Rhone Poulenc Chimie | CERIUM OXIDE CATALYST AND PROCESS FOR PROCESSING INDUSTRIAL GASES CONTAINING SULFUR COMPOUNDS |
| CN104667926A (en) * | 2013-11-29 | 2015-06-03 | 福建三聚福大化肥催化剂国家工程研究中心有限公司 | Low-temperature carbonyl sulfide hydrolysis catalyst and preparation method thereof |
| CN105056719A (en) * | 2015-07-30 | 2015-11-18 | 福州大学化肥催化剂国家工程研究中心 | Preparation method of FeOOH low-temperature desulfurizer and desulfurizer prepared through same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114196448A (en) * | 2022-02-16 | 2022-03-18 | 北京中航天业科技有限公司 | Full-flow dry type blast furnace gas fine desulfurization system and method |
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