CN104667926A - Low-temperature carbonyl sulfide hydrolysis catalyst and preparation method thereof - Google Patents
Low-temperature carbonyl sulfide hydrolysis catalyst and preparation method thereof Download PDFInfo
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- CN104667926A CN104667926A CN201310632491.7A CN201310632491A CN104667926A CN 104667926 A CN104667926 A CN 104667926A CN 201310632491 A CN201310632491 A CN 201310632491A CN 104667926 A CN104667926 A CN 104667926A
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- feooh
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- carbonyl sulfur
- hydrolytic catalyst
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- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 title abstract description 26
- 230000007062 hydrolysis Effects 0.000 title abstract description 24
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 78
- 229910006299 γ-FeOOH Inorganic materials 0.000 claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000004898 kneading Methods 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims description 45
- 238000012986 modification Methods 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000003153 chemical reaction reagent Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 230000001376 precipitating effect Effects 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 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 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- -1 NaHCO 3 Inorganic materials 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 6
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 150000003608 titanium Chemical class 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910001570 bauxite Inorganic materials 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004567 concrete Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 3
- 229960004011 methenamine Drugs 0.000 claims description 3
- 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 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 2
- 150000002505 iron Chemical class 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 229910006540 α-FeOOH Inorganic materials 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000012266 salt solution Substances 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000413 hydrolysate Substances 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 125000001741 organic sulfur group Chemical group 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical group [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 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
- 239000003463 adsorbent Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VXWSFRMTBJZULV-UHFFFAOYSA-H iron(3+) sulfate hydrate Chemical compound O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VXWSFRMTBJZULV-UHFFFAOYSA-H 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003463 sulfur Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002631 hypothermal effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
The invention relates to a low-temperature carbonyl sulfide hydrolysis catalyst, which takes modified gamma-FeOOH as an active component, wherein the modified gamma-FeOOH catalyst is prepared by the following method: uniformly mixing ferrous salt and a modifier to form a solution, dropwise adding a precipitator into the solution under the stirring condition, adjusting the pH value to 6.5-8, aging, centrifuging, washing, adding a forming agent and a binder, kneading, forming and drying to obtain the product. Controlling the content of the modified gamma-FeOOHThe molar ratio of the modifier to the iron salt is 0.005-0.1, and the optimal molar ratio is 0.01-0.05. The carbonyl sulfide hydrolysis catalyst provided by the invention is used for hydrolyzing CO in feed gas at a low temperature of 30-80 DEG C2Under the condition of higher concentration, the COS can be efficiently removed, and the precision is high.
Description
Technical field
The present invention relates to a kind of low temperature hydrolytic catalyst of carbonyl sulfur and preparation method thereof, belong to carbonyl sulfide hydrolysis catalysis technical field.
All containing organic sulfur in the material gas produced for raw material with coal, coke, natural gas and oil etc., but organic sulfur particularly cos COS existence not only contaminated environment, corrosion pipeline equipment, affect quality of chemical products, and the poisoning and deactivation of catalyst in subsequent production process can be caused, therefore the removing sulfuldioxide of cos is paid much attention to.Because cos is in neutral or faintly acid, its chemical property torpescence, be difficult to use the method removing hydrogen sulfide to be removed, thus in current industrial production, the catalyzing hydrolysis of cos is utilized to be proved to be one of most effective method to remove cos, its fundamental reaction principle is: under the effect of hydrolytic catalyst of carbonyl sulfur, and cos COS first reacts with water and changes into H
2s, adopts zinc oxide, iron oxide, γ-Al afterwards
2o
3etc. remove agent removing H
2s.
Wherein, γ-Al
2o
3as a kind of porous material, not only have that specific area is large, Heat stability is good, mechanical strength advantages of higher, also to the hydrolysis of cos, there is catalytic action simultaneously, thus based on γ-Al
2o
3aluminium-based catalyst become in hydrolytic catalyst of carbonyl sulfur and study the most deep, a most popular class hydrolytic catalyst of carbonyl sulfur, compared to
x-Al
2o
3can be used for cos conversion and remove, traditional iron oxide or common alpha-feooh decompose the iron oxide that obtains as extremely low in activity during the removing of cos for micro-organic sulfur, thus commonly adopt alkali modification γ-Al in existing sulfur removal technology
2o
3cOS catalyzing hydrolysis is converted into H
2s, absorbs H with iron oxide afterwards again
2s.But it is above-mentioned based on γ-Al
2o
3hydrolytic catalyst of carbonyl sulfur when temperature is lower than 100 DEG C, its catalytic activity for hydrolysis COS obviously reduces, simultaneously CO in unstripped gas
2when concentration is higher, also can cause the significantly reduction of its desulfurized effect.
For this reason, Chinese patent literature CN101791532A discloses a kind of normal-temperature natural-gas sulphur adsorbent and preparation method thereof, and above-mentioned preparation method comprises the following steps: (1) adopts soluble ferric iron salt and carbonate generation coprecipitation reaction, generates active γ-FeOOH; (2) in the suspension of γ-FeOOH, to add in Ti, Cu, Co, Ni, Zn, Ca, Mg, Ba, Mo, Mn the soluble salt solutions homogeneous precipitation in urea liquid of one or more, obtain their oxide; (3) mixed precipitation is squeezed into required shape, then drying and moulding, cures through 400-700 DEG C, obtain the sulfur absorbent with perovskite structure composite metal oxide active component.Above-mentioned sulfur absorbent with the composite metal oxide of perovskite structure for active component, component in this perovskite structure is replaced by element portions or doping can keep causing while original structure appraising at the current rate of new lattice vacancy and other ions of coordination, thus makes this sulfur absorbent have higher CO
2tolerance, and be hydrogen sulfide at promotion sulfide catalysis organic sulfur conversion while iron oxide surface absorption, finally reach the object of organic sulfide removal.But the active component in this sulfur absorbent is the composite oxides with perovskite structure, when temperature is lower than 100 DEG C, its catalytic activity for hydrolysis COS obviously reduces.
In order to solve the problem, also disclose a kind of nano α-FeOOH catalyst one-stage process in prior art and removing COS and H
2(" nano α-FeOOH catalyst one-stage process removes COS and H to the technique of S
2the research of S performance ", the people such as Gao Lihua, " chemistry of fuel journal " the 21st volume, 3rd phase, in June, 2003), the preparation method of this nano α-FeOOH catalyst is specific as follows: (1) adopts homogeneous precipitation method to prepare nano α-FeOOH particle: take a certain amount of ferric sulfate hydrate and mix with urea, be placed in there-necked flask, add certain density diluted acid again, strong agitation, make it to dissolve, then slowly be warming up to 363K, constant temperature, utilize pH meter track record solution ph, until reading change being no more than ± 0.2 time stop reaction, product is through repeatedly washing is extremely neutral, filtration drying, obtain the alpha-feooh particle that particle diameter is 30-80nm, (2) preparation of nano α-FeOOH catalyst: with nano α-FeOOH particle for active component, add the components such as other carriers a certain amount of, by its Homogeneous phase mixing, then compression molding on hydraulic press, broken, be sieved into 40-60 order, roasting 2h obtains nano α-FeOOH catalyst at a certain temperature.To above-mentioned nano α-FeOOH catalyst at normal pressure, air speed 10000h
-1, 25-60 DEG C, COS inlet concentration be about 150mg/m
3condition under carry out the evaluation experimental of carbonyl sulfide hydrolysis activity, result shows, under normal pressure, large air speed, low temperature, have greater activity with the catalyst that nano α-FeOOH ion is prepared for active component to COS hydrolysis, meanwhile, above-mentioned catalyst also effectively can remove H while catalysis COS is hydrolyzed
2s, thus realize absorbing H by utilizing its nano effect effectively to improve it to COS hydrolysing activity and one-stage process
2s fine de-sulfur ability.
Although above-mentioned nano α-FeOOH catalyst also can reach certain COS hydrolysing activity at low temperatures, but present inventor finds in long-term practice and research, above-mentioned catalyst of the prior art easy inactivation after long-term use, present inventor thinks and causes the reason of this phenomenon to be hydrolytic catalyst of carbonyl sulfur of the prior art while hydrolyzing carbonyl sulfur also easily and the hydrolysate H of cos
2s reacts, and generates iron sulphur compounds, thus causes hydrolyst fast deactivation; And catalyst of the prior art is to CO in unstripped gas
2tolerance lower, as CO in unstripped gas
2when concentration is higher, CO
2the surface of hydrolyst can be adsorbed in a large number thus destroy the carbonyl sulfide hydrolysis active sites that its surface has, and then causing that its carbonyl sulfide hydrolysis is active to be reduced rapidly.In this case, how to provide a kind of and there is high carbonyl sulfide hydrolysis activity at low temperatures, also there is higher CO simultaneously
2tolerance and not with H
2the catalyst that S reacts is this area urgent problem.
Summary of the invention
The technical problem that the present invention solves adopts nano α-FeOOH particle to be active component, as CO in unstripped gas for hydrolytic catalyst of carbonyl sulfur in prior art
2when concentration is higher, its carbonyl sulfide hydrolysis activity can reduce rapidly and above-mentioned catalyst is easy and the hydrolysate H of cos
2s reacts, and generates iron sulphur compounds, thus causes hydrolyst fast deactivation.For this reason, the invention provides a kind of CO
2high and the low temperature hydrolytic catalyst of carbonyl sulfur that is not easy in inactivation and preparation method thereof of tolerance.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
The invention provides a kind of low temperature hydrolytic catalyst of carbonyl sulfur, it is with modification γ-FeOOH for active component, and described low temperature hydrolytic catalyst of carbonyl sulfur comprises following component:
Modification γ-FeOOH, 70-90 weight portion;
Forming agent, 2-10 weight portion;
Binding agent, 1-6 weight portion;
Described modification γ-FeOOH adopts and prepares with the following method:
(1) in the solution of ferrous salt, the mixture of aluminum soluble salt, zirconates or titanium salt one or more is added as modifier, the mol ratio controlling described modifier and ferrous salt is 0.005-0.1, mix the transparent mixed liquor of rear formation, reaction temperature 40-60 DEG C;
(2) in described transparent mixed liquor, drip precipitating reagent under stirring condition, the mol ratio controlling described precipitating reagent and described ferrous salt is 0.5-1, mixes and regulates pH to be 6.5-8, and through ageing, centrifugal, washing, drying obtains described modification γ-FeOOH.
Described ferrous salt is FeCl
24H
2o, FeSO
47H
2the mixture of one or more of O or ferrous acetate.
Described aluminum soluble salt is selected from one or several the mixing in aluminum sulfate, aluminium chloride or aluminum nitrate; Solubility zirconates is selected from one or several the mixing in zirconyl nitrate, zirconium oxychloride or zirconium oxysulfate; Solubility titanium salt is selected from one or several the mixing in titanium sulfate, titanium tetrachloride, butyl titanate.
Described precipitating reagent is NaOH, NaHCO
3, NH
3h
2the mixture of one or more in O, urea or methenamine.
The consumption of described modifier and the mol ratio of ferrous salt are 0.005-0.09.
The molar ratio of described ferrous salt and precipitating reagent is 0.5-1.
Described forming agent is one or several mixing in cement, boehmite, kaolin or natural bauxite.
Described binding agent is the mixture of one or more in polyvinyl alcohol, polyacrylamide, sesbania powder.
Further, the preparation method of described low temperature hydrolytic catalyst of carbonyl sulfur is also provided, its concrete steps are: in the described modification γ-FeOOH of above-mentioned weight portion, add the described forming agent of above-mentioned weight portion and described binding agent successively, add the deionized water of 2-10 weight portion afterwards, mix, after kneading, shaping, drying, obtain described low temperature hydrolytic catalyst of carbonyl sulfur.
The temperature of described drying process is 80-110 DEG C, and the dry time is 2-5h.
Technique scheme of the present invention has the following advantages compared to existing technology:
(1) low temperature hydrolytic catalyst of carbonyl sulfur of the present invention, its with modification γ-FeOOH for active component, described modification γ-FeOOH in the preparation by adding aluminum soluble salt in ferrous salt solution, one or more of zirconates or titanium salt are as modifier, add precipitating reagent after mixing to prepare through co-precipitation, the described modification γ-FeOOH prepared through above-mentioned technique not only maintains unique layer structure that γ-FeOOH inherently has, its strong basicity end oxygen hydroxyl (type I type) perpendicular to surface and lewis acidity position is also made all to be rolled up, therefore, on the one hand, the active sites that a large amount of type I type strong basicity hydroxyls that described modification γ-FeOOH exists on the surface react as carbonyl sulfide hydrolysis, be conducive to the efficient adsorption of cos during hydrolysis, thus effective hydrolysis that also can realize at low temperatures COS.The nano α-FeOOH used in prior art or iron oxide surface also have a small amount of the type hydroxyl, therefore possess certain hydrolyzing carbonyl sulfur performance, but also there is a large amount of oxygen defect position, because such defect removes H on their surface simultaneously
2the high activity center of S, when utilizing nano α-FeOOH or iron oxide hydrolysis removes cos, the hydrolysate H of absorbing carbonyl sulfur while of hydrolytic reagent meeting
2s, generates iron sulphur compounds, thus loses the type I type strong basicity hydroxyl on hydrolytic reagent surface, cause hydrolyst fast deactivation.γ-FeOOH in low temperature hydrolytic catalyst of carbonyl sulfur of the present invention is a kind of modification γ-FeOOH of high-crystallinity, and through modified γ-FeOOH surface based on type I type strong basicity hydroxyl, oxygen defect position is few.Which ensure that hydrolyst can adsorb and hydrolyzing carbonyl sulfur, but do not adsorb carbonyl sulfide hydrolysis product H
2s, thus the service life significantly extending catalyst.
On the other hand, a large amount of lewis acidity positions that the γ of modification described in the present invention-FeOOH surface exists have the effect that promotion carbonyl sulfide hydrolysis intermediate product thiocarbonic acid hydrogen salt carries out decomposing, and then can promote that carbonyl sulfide hydrolysis molecular balance moves to positive direction, and due to the catabolite of described thiocarbonic acid hydrogen salt be CO
2and H
2s, thus extraneous carbon dioxide can also be suppressed in the absorption on hydrolyst agent surface while effective facilitation of hydrolysis reaction is carried out, ensure in high concentration carbon dioxide atmosphere, also keep the high activity to carbonyl sulfide hydrolysis reaction, hydrolytic catalyst of carbonyl sulfur compared to prior art, the low temperature hydrolytic catalyst of carbonyl sulfur that is active component with modification γ-FeOOH of the present invention, extraneous carbon dioxide can also be suppressed in the absorption on hydrolyst agent surface while its surface of lifting is to the adsorption capacity of cos, thus make it under the cryogenic conditions of 30-80 DEG C, high concentration carbon dioxide atmosphere also to have higher hydrolyzing carbonyl sulfur active.The hydrolytic process of cos on hydrolytic reagent surface mainly includes CO absorption S, formation thiocarbonic acid hydrogen salt intermediate product and intermediate product and is decomposed into CO
2and H
2s tri-steps.Low temperature carbonyl sulfide hydrolysis speed mainly determines by the rate of adsorption of reactant and the decomposition rate of intermediate product.The type I type strong basicity hydroxyl that in the present invention, the modification γ-FeOOH surface of high-crystallinity is a large amount of fine and close, can efficient adsorption reactant cos; Pass through the modified of aluminium, zirconium or titanium simultaneously, the lewis acidity position on γ-FeOOH surface can be increased, promote the decomposition of dithioformate intermediate product, suppress the absorption of carbon dioxide on hydrolytic reagent surface, so greatly improve the efficiency of catalyst de-cos in the carbon dioxide enriched atmosphere of low temperature.
(2) low temperature hydrolytic catalyst of carbonyl sulfur of the present invention, be 0.005-0.1 by controlling the mol ratio of described modifier and ferrous salt, thus be beneficial to and carry out modified optimization on the surface at γ-FeOOH and generate type I type strong basicity hydroxyl and lewis acidity position, and then making the low temperature hydrolytic catalyst of carbonyl sulfur being active component with modification γ-FeOOH of the present invention, it is all optimized lifting to the absorption of cos, hydrolysis and anti-high concentration carbon dioxide ability at low temperatures.
Detailed description of the invention
Embodiment 1
Low temperature hydrolytic catalyst of carbonyl sulfur described in the present embodiment, it is with modification γ-FeOOH for active component, and wherein the content of each component is:
Modification γ-FeOOH, 80g;
Forming agent is the mixture that boehmite and kaolin form with mass ratio 1:1,7g;
Binding agent polyvinyl alcohol, 5g.
Described low temperature hydrolytic catalyst of carbonyl sulfur is adopted and is prepared with the following method:
(1) 199gFeCl is taken
24H
2o is water-soluble to be made into ferrous salt solution, adds mixture 2.75g that aluminum sulfate, zirconyl nitrate and titanium sulfate form using mass ratio 1:1:1 afterwards wherein as modifier, mixes and form transparent mixed liquor, reaction temperature 40 DEG C;
(2) drip in described transparent mixed liquor under stirring condition 500mL concentration be the NaOH of 4mol/L as precipitating reagent, stir and make it mix, regulate pH to be 7, through ageing 3h, centrifugal, washing, drying obtains described modification γ-FeOOH;
(3) take modification γ-FeOOH described in 80g, add binding agent described in forming agent described in 7g, 5g and 5g deionized water wherein, stir make it mix, through kneading, extrude slivering, 80 DEG C of dry 5h after obtain this hydrolytic catalyst of carbonyl sulfur.
Embodiment 2
Low temperature hydrolytic catalyst of carbonyl sulfur described in the present embodiment, it is with modification γ-FeOOH for active component, and wherein the content of each component is:
Modification γ-FeOOH, 80g;
Forming agent is the mixture that cement and kaolin form with mass ratio 1:1,5g;
Binding agent sesbania powder, 5g.
Described low temperature hydrolytic catalyst of carbonyl sulfur is adopted and is prepared with the following method:
(1) take 174g ferrous acetate water-soluble to be made into ferrous salt solution, add mixture that 4.68g zirconyl nitrate and titanium sulfate form using mass ratio 1:1 afterwards wherein as modifier, mix the transparent mixed liquor of formation, reaction temperature 50 DEG C;
(2) in described transparent mixed liquor, drip the NH of 80mL concentration 25wt% under stirring condition
3h
2o, as precipitating reagent, stirs and makes it mix, and regulates pH to be 6.8, and through ageing 3h, centrifugal, washing, drying obtains described modification γ-FeOOH;
(3) take modification γ-FeOOH described in 80g, add binding agent described in forming agent described in 5g, 5g and 5g deionized water wherein, stir make it mix, through kneading, extrude slivering, 80 DEG C of dry 5h after obtain this hydrolytic catalyst of carbonyl sulfur.
Embodiment 3
Low temperature hydrolytic catalyst of carbonyl sulfur described in the present embodiment, it is with modification γ-FeOOH for active component, and wherein the content of each component is:
Modification γ-FeOOH, 70g;
Forming agent is the mixture that bauxitic ore and kaolin form with mass ratio 1:1,10g;
Binding agent polyacrylamide, 6g.
Described low temperature hydrolytic catalyst of carbonyl sulfur is adopted and is prepared with the following method:
(1) 278gFeSO is taken
47H
2o is water-soluble to be made into ferrous salt solution, adds mixture that 1.39g zirconyl nitrate and aluminum sulfate form using mass ratio 1:1 afterwards wherein as modifier, mixes the transparent mixed liquor of formation, reaction temperature 50 DEG C;
(2) in described transparent mixed liquor, the NH that 364mL concentration is 2.75mol/L is dripped under stirring condition
4hCO
3as precipitating reagent, stir and make it mix, regulate pH to be 6.5, through ageing 3h, centrifugal, washing, drying obtains described modification γ-FeOOH;
(3) take modification γ-FeOOH described in 74g, add binding agent described in forming agent described in 10g, 6g and 10g deionized water wherein, stir make it mix, through kneading, extrude slivering, 120 DEG C of dry 2h after obtain this hydrolytic catalyst of carbonyl sulfur.
Embodiment 4
Low temperature hydrolytic catalyst of carbonyl sulfur described in the present embodiment, it is with modification γ-FeOOH for active component, and wherein the content of each component is:
Modification γ-FeOOH, 85g;
Forming agent is the mixture that cement and kaolin form with mass ratio 1:1,5g;
Binding agent polyvinyl alcohol, 1g.
Described low temperature hydrolytic catalyst of carbonyl sulfur is adopted and is prepared with the following method:
(1) 278gFeSO is taken
47H
2o is water-soluble to be made into ferrous salt solution, adds 2.78g titanium sulfate afterwards wherein as modifier, mixes and form transparent mixed liquor, reaction temperature 50 DEG C;
(2) drip in described transparent mixed liquor under stirring condition 500mL concentration be the urea of 2mol/L as precipitating reagent, stir and make it mix, regulate pH to be 8, through ageing 3h, centrifugal, washing, drying obtains described modification γ-FeOOH;
(3) take modification γ-FeOOH described in 85g, add binding agent described in forming agent described in 5g, 1g and 5g deionized water wherein, stir make it mix, through kneading, extrude slivering, 100 DEG C of dry 4h after obtain this hydrolytic catalyst of carbonyl sulfur.
Embodiment 5
Low temperature hydrolytic catalyst of carbonyl sulfur described in the present embodiment, it is with modification γ-FeOOH for active component, and wherein the content of each component is:
Modification γ-FeOOH, 85g;
Forming agent is the mixture that cement, boehmite, kaolin and natural bauxite form with mass ratio 1:1:1:1,10g;
Binding agent is the mixture that polyvinyl alcohol, polyacrylamide and sesbania powder form with mass ratio 1:1:1,4g.
Described low temperature hydrolytic catalyst of carbonyl sulfur is adopted and is prepared with the following method:
(1) 199gFeCl is taken
24H
2o is water-soluble to be made into ferrous salt solution, adds mixture that 0.988g aluminum sulfate and titanium sulfate form using mass ratio 1:1 afterwards wherein as modifier, mixes the transparent mixed liquor of formation, reaction temperature 50 DEG C;
(2) drip in described transparent mixed liquor under stirring condition 500mL concentration be the NaOH of 4mol/L as precipitating reagent, stir and make it mix, regulate pH to be 8, through ageing 3h, centrifugal, washing, drying obtains described modification γ-FeOOH;
(3) take modification γ-FeOOH described in 85g, add binding agent described in forming agent described in 10g, 4g and 5g deionized water wherein, stir make it mix, through kneading, extrude slivering, 80 DEG C of dry 5h after obtain this hydrolytic catalyst of carbonyl sulfur.
Embodiment 6
Low temperature hydrolytic catalyst of carbonyl sulfur described in the present embodiment, it is with modification γ-FeOOH for active component, and wherein the content of each component is:
Modification γ-FeOOH, 90g;
Forming agent is the mixture that boehmite, kaolin and natural bauxite form with mass ratio 1:1:1,2g;
Binding agent is the mixture that polyvinyl alcohol and sesbania powder form with mass ratio 1:1,3g;
Described low temperature hydrolytic catalyst of carbonyl sulfur is adopted and is prepared with the following method:
(1) 278gFeSO is taken
47H
2o is water-soluble to be made into ferrous salt solution, adds 1.96g zirconyl nitrate afterwards wherein as modifier, mixes and form transparent mixed liquor, reaction temperature 50 DEG C;
(2) drip in described transparent mixed liquor under stirring condition 500mL concentration be the methenamine of 2mol/L as precipitating reagent, stir and make it mix, regulate pH to be 7.5, through ageing 3h, centrifugal, washing, drying obtains described modification γ-FeOOH;
(3) take modification γ-FeOOH described in 90g, add binding agent described in forming agent described in 2g, 3g and 2g deionized water wherein, stir make it mix, through kneading, extrude slivering, 80 DEG C of dry 5h after obtain this hydrolytic catalyst of carbonyl sulfur.
Comparative example 1
This comparative example adopts prior art to prepare a kind of nano α-FeOOH catalyst, and its concrete preparation process is as follows:
(1) homogeneous precipitation method is adopted to prepare alpha-feooh particle: to take a certain amount of ferric sulfate hydrate and mix with urea, be placed in there-necked flask, add certain density diluted acid again, strong agitation, make it to dissolve, then slowly be warming up to 363K, constant temperature, utilizes pH meter track record solution ph, until reading change being no more than ± 0.2 time stop reaction, product, through repeatedly washing to neutral, filtration drying, obtains the alpha-feooh particle that particle diameter is 30-80nm;
(2) preparation of nano α-FeOOH catalyst: with nano α-FeOOH particle for active component, add the components such as other carriers a certain amount of, by its Homogeneous phase mixing, then compression molding on hydraulic press, broken, be sieved into 40-60 order, roasting 2h obtains nano α-FeOOH catalyst at a certain temperature.。
Comparative example 2
This comparative example adopts prior art to prepare a kind of normal-temperature natural-gas sulphur adsorbent, and it adopts following steps to prepare:
(1) adopt soluble ferric iron salt and carbonate generation coprecipitation reaction, generate active γ-FeOOH;
(2) in the suspension of γ-FeOOH, to add in Ti, Cu, Co, Ni, Zn, Ca, Mg, Ba, Mo, Mn the soluble salt solutions homogeneous precipitation in urea liquid of one or more, obtain their oxide;
(3) mixed precipitation is squeezed into required shape, then drying and moulding, cures through 400-700 DEG C, obtain the sulfur absorbent with perovskite structure composite metal oxide active component.
Comparative example 3
This comparative example provides a kind of hydrolytic catalyst of carbonyl sulfur, and it is with non-modified γ-FeOOH for active component, and wherein the content of each component is:
γ-FeOOH，75g；
Forming agent is the mixture that calcium sulfate and calcium carbonate form with mass ratio 1:1,10g;
Binding agent cement, 5g;
Above-mentioned low temperature hydrolytic catalyst of carbonyl sulfur is adopted and is prepared with the following method::
(1) 278gFeSO is taken
47H
2o is water-soluble, adds the NaOH solution that 500mL concentration is 4mol/L, control pH=8, temperature 40 DEG C, reacts after 3.5 hours, after filtration, and obtained γ-FeOOH after 85 DEG C of dry 210min;
(2) take the above-mentioned γ of 75g-FeOOH, add the above-mentioned forming agent of 10g, the above-mentioned binding agent of 5g and 10g deionized water wherein, stir make it mix, through kneading, extrude slivering, 80 DEG C of dry 5h after obtain this hydrolytic catalyst of carbonyl sulfur.
Test case 1
Be A-H by the hydrolytic catalyst of carbonyl sulfur number consecutively prepared in embodiment 1-6 and comparative example 1-3, be hydrolyzed at COS and carry out activity rating to above-mentioned hydrolytic catalyst of carbonyl sulfur in evaluating apparatus, be specially: above-mentioned hydrolytic catalyst of carbonyl sulfur sample is respectively taken 2mL, bottom extra heavy pipe during measurement, sample being placed in the U-shaped sample cell that silica wool is housed, sample cell is placed in heating furnace, connects pipeline.
Unstripped gas forms: COS, 100mgS/m
3; CO, 8%; H
2, 40%; CO
2, 27%; N
2for Balance Air;
Catalytic reaction condition is: air speed: 1000h
-1, pressure: normal pressure, temperature: 30-80 DEG C;
Adopt the content of gas chromatography (Agilent 7890A detector FPD) determinator import and export COS, the conversion ratio by calculating COS under the cryogenic conditions of 30-80 DEG C characterizes the activity of above-mentioned hydrolytic catalyst of carbonyl sulfur sample A-G, and measurement result is in table 1.
Wherein, the computing formula of COS conversion ratio is as follows:
Under table 1-Different hypothermia condition, the hydrolyzation catalysis of above-mentioned hydrolytic catalyst of carbonyl sulfur sample A-H is active
As can be seen from Table 1, low temperature hydrolytic catalyst of carbonyl sulfur temperature hydrolytic catalyst of carbonyl sulfur sample A-G of the present invention, the optimum addition that its raw materials comprises modification γ-FeOOH(wherein modifier is 1%-5%), forming agent, binding agent and water, thus low temperature hydrolytic catalyst of carbonyl sulfur of the present invention can under the cryogenic conditions of 30-80 DEG C, CO in unstripped gas
2when concentration is higher, also show very strong catalytic activity, and along with the rising of temperature, the conversion ratio of cos increases, and shows that the catalytic activity of described low temperature hydrolytic catalyst of carbonyl sulfur raises along with temperature and strengthens in low temperature range; But, adopt in prior art based on rare-earth hydroxide La (OH)
3the hydrolytic catalyst of carbonyl sulfur prepared and pure γ-FeOOH be the hydrolytic catalyst of carbonyl sulfur of active component under 30-80 DEG C of condition, CO in unstripped gas
2when concentration is higher, then show relatively low catalytic activity.
Test case 2
Hydrolytic catalyst of carbonyl sulfur A-H is hydrolyzed activity rating in evaluating apparatus at COS, and described COS is hydrolyzed evaluating apparatus with test case 1.Actual conditions is
Unstripped gas forms: COS, 100mgS/m
3; CO, 8%; H
2, 40%; N
2for Balance Air;
Catalytic reaction condition is: air speed: 1000h
-1, pressure: normal pressure, temperature: 50 DEG C;
Test the conversion ratio reacted when starting rear 1h, 5h, 10h, 15h respectively, result is as shown in the table:
The hydrolyzation catalysis showing 2-50 DEG C of above-mentioned hydrolytic catalyst of carbonyl sulfur sample A-H is active
| Sample number into spectrum | A | B | C | D | E | F | G | H |
| 1h(%) | 95.6 | 94.8 | 93.1 | 93.2 | 94.5 | 86.3 | 85.6 | 79.6 |
| 5h(%) | 95.2 | 94.1 | 92.3 | 92.4 | 93.9 | 80.1 | 81.0 | 76.9 |
| 10h(%) | 93.3 | 92.1 | 90.7 | 90.2 | 91.6 | 75.6 | 77.1 | 74.9 |
| 15h(%) | 91.6 | 90.1 | 89.7 | 89.2 | 88.6 | 60.6 | 63.5 | 65.8 |
As can be seen from Table 2, low temperature hydrolytic catalyst of carbonyl sulfur temperature hydrolytic catalyst of carbonyl sulfur sample A-G of the present invention, the conversion ratio fall of reacting when starting rear 1h, 5h, 10h, 15h is very little, and its conversion ratio decrease speed of catalyst in comparative example will be far longer than the catalyst in the present invention, this proves that the catalyst in comparative example easily inactivation occurs after long-term use, and the catalyst in the application increases significantly compared to comparative example service life.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. a low temperature hydrolytic catalyst of carbonyl sulfur, is characterized in that, with modification γ-FeOOH for active component, and described low temperature hydrolytic catalyst of carbonyl sulfur comprises following component:
Modification γ-FeOOH, 70-90 weight portion;
Forming agent, 2-10 weight portion;
Binding agent, 1-6 weight portion;
Described modification γ-FeOOH adopts and prepares with the following method:
(1) in the solution of ferrous salt, the mixture of aluminum soluble salt, zirconates or titanium salt one or more is added as modifier, the mol ratio controlling described modifier and ferrous salt is 0.005-0.1, mix the transparent mixed liquor of rear formation, reaction temperature 40-60 DEG C;
(2) in described transparent mixed liquor, drip precipitating reagent under stirring condition, the mol ratio controlling described precipitating reagent and described ferrous salt is 0.5-1, mixes and regulates pH to be 6.5-8, and through ageing, centrifugal, washing, drying obtains described modification γ-FeOOH.
2. low temperature hydrolytic catalyst of carbonyl sulfur according to claim 1, is characterized in that, described ferrous salt is FeCl
24H
2o, FeSO
47H
2the mixture of one or more of O or ferrous acetate.
3. low temperature hydrolytic catalyst of carbonyl sulfur according to claim 1 and 2, is characterized in that, described aluminum soluble salt is selected from one or several the mixing in aluminum sulfate, aluminium chloride or aluminum nitrate; Solubility zirconates is selected from one or several the mixing in zirconyl nitrate, zirconium oxychloride or zirconium oxysulfate; Solubility titanium salt is selected from one or several the mixing in titanium sulfate, titanium tetrachloride, butyl titanate.
4., according to the arbitrary described low temperature hydrolytic catalyst of carbonyl sulfur of claim 1-3, it is characterized in that, described precipitating reagent is NaOH, NaHCO
3, NH
3h
2the mixture of one or more in O, urea or methenamine.
5., according to the arbitrary described low temperature hydrolytic catalyst of carbonyl sulfur of claim 1-4, it is characterized in that, the consumption of described modifier and the mol ratio of ferrous salt are 0.005-0.09.
6., according to the arbitrary described low temperature hydrolytic catalyst of carbonyl sulfur of claim 1-5, it is characterized in that, the molar ratio of described ferrous salt and precipitating reagent is 0.5-1.
7. according to the arbitrary described low temperature hydrolytic catalyst of carbonyl sulfur of claim 1-6, it is characterized in that, described forming agent is one or several mixing in cement, boehmite, kaolin or natural bauxite.
8., according to the arbitrary described low temperature hydrolytic catalyst of carbonyl sulfur of claim 1-7, it is characterized in that, described binding agent is the mixture of one or more in polyvinyl alcohol, polyacrylamide, sesbania powder.
9. the preparation method according to the arbitrary described low temperature hydrolytic catalyst of carbonyl sulfur of claim 1-8, its concrete steps are: in the described modification γ-FeOOH of above-mentioned weight portion, add the described forming agent of above-mentioned weight portion and described binding agent successively, add the deionized water of 2-10 weight portion afterwards, mix, after kneading, shaping, drying, obtain described low temperature hydrolytic catalyst of carbonyl sulfur.
10. the preparation method of low temperature hydrolytic catalyst of carbonyl sulfur according to claim 9, is characterized in that, the temperature of described drying process is 80-110 DEG C, and the dry time is 2-5h.
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| CN105056719B (en) * | 2015-07-30 | 2017-10-10 | 福州大学化肥催化剂国家工程研究中心 | The preparation method and desulfurizing agent obtained by this method of a kind of FeOOH low-temp desulfurization agent |
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