CN106824149B - The preparation method of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon - Google Patents
The preparation method of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon Download PDFInfo
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- CN106824149B CN106824149B CN201710119948.2A CN201710119948A CN106824149B CN 106824149 B CN106824149 B CN 106824149B CN 201710119948 A CN201710119948 A CN 201710119948A CN 106824149 B CN106824149 B CN 106824149B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 67
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 63
- 150000001875 compounds Chemical class 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims abstract description 37
- 239000004793 Polystyrene Substances 0.000 claims abstract description 35
- 229920002223 polystyrene Polymers 0.000 claims abstract description 35
- 239000004005 microsphere Substances 0.000 claims abstract description 32
- 239000011148 porous material Substances 0.000 claims abstract description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 150000003608 titanium Chemical class 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 83
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 31
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 239000012153 distilled water Substances 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 11
- 239000006210 lotion Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000002191 fatty alcohols Chemical class 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 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
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 210000002421 cell wall Anatomy 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 239000011806 microball Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 231100000614 poison Toxicity 0.000 abstract description 5
- 230000007096 poisonous effect Effects 0.000 abstract description 5
- 239000002585 base Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 229920006389 polyphenyl polymer Polymers 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241001088180 Eremocosta titania Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Images
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or hydrogen sulfide
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
-
- 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
- B01D2257/308—Carbonoxysulfide COS
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a kind of compound hydrolytic catalyst of carbonyl sulfur of titanium silicon and preparation method thereof, belong to desulphurization catalyst technical field.The compound hydrolytic catalyst of carbonyl sulfur of titanium silicon is TiO2Base hydrolytic catalyst of carbonyl sulfur, wherein, the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon is using polystyrene microsphere as macropore template, with P123 for mesoporous template, using soluble titanium salt as catalyst carrier predecessor, using soluble silicon as reinforcing agent predecessor, using potassium oxalate coordination solution as active component predecessor.Compound hydrolytic catalyst of carbonyl sulfur of titanium silicon provided by the present invention and preparation method thereof is the TiO of the orderly pore structure with bigger serface2Base COS hydrolyst, and it is formed with the step pore structure of macropore, the combination of mesoporous and micropore, the catalyst both can improve COS hydrolysis reaction activity and titanium oxide anti-sulfur poisonous performance by bigger serface, there is suitable step duct to be conducive to reaction product smoothly to export again, further improve catalyst service life.
Description
Technical field
The present invention relates to desulphurization catalyst technical field more particularly to a kind of systems of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon
Preparation Method.
Background technique
In the coal raw material of industry gas of cos-containing, always there is micro O2In the presence of, and this micro existing O2Turn in COS
During change, hydrolysate can be made to aoxidize to form sulfate, so as to cause catalyst activity reduction.Titanium oxide is due to its uniqueness
Electronic structure and have oxygen migration ability, to show in micro O2Good anti-sulfur poisonous performance in atmosphere, therefore
A kind of excellent carrier as hydrolytic catalyst of carbonyl sulfur.But since titanium oxide has as carrier, specific surface area is small and machine
The low disadvantage of tool intensity, therefore limit the application of titania based hydrolytic reagent industrially.
Summary of the invention
In order to solve at least one aspect of the above-mentioned problems in the prior art and defect, the present invention provides one kind
The preparation method of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon.
It is an object of the present invention to provide a kind of compound hydrolytic catalyst of carbonyl sulfur of titanium silicon.
Another object of the present invention is to provide a kind of methods for preparing the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon.
According to an aspect of the present invention, the present invention provides a kind of compound hydrolytic catalyst of carbonyl sulfur of titanium silicon, wherein institute
Stating the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon is TiO2Base hydrolytic catalyst of carbonyl sulfur, wherein the compound carbonyl sulfur water of titanium silicon
Catalyst is solved using polystyrene microsphere as macropore template, with P123 for mesoporous template, using soluble titanium salt as catalyst carrier
Predecessor, using soluble silicon as reinforcing agent predecessor, using potassium oxalate coordination solution as active component predecessor.
Specifically, the soluble titanium salt includes any one of butyl titanate, titanium sulfate, titanium tetrachloride or their times
Meaning combination；
The soluble silicon includes any one of ethyl orthosilicate, potassium silicate, sodium metasilicate or their any combination.
Preferably, the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon is TiO2/SiO2Compound hydrolytic catalyst of carbonyl sulfur,
The compound hydrolytic catalyst of carbonyl sulfur of titanium silicon, which is negative, is loaded with the step pore titanium oxide base catalyst of potassium carbonate.
Preferably, the step pore titanium oxide base catalyst has macropore, mesoporous and micropore,
Micropore on the step pore titanium oxide base catalyst is after the macropore and mesoporous formation, in the macropore
With the hole formed in mesoporous cell walls.
According to another aspect of the present invention, the present invention provides a kind of sides for preparing the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon
Method the described method comprises the following steps:
(1) soluble titanium salt, soluble silicon, polystyrene microsphere, mesoporous template P123, potassium oxalate, oxalic acid, dilute is provided
Hydrochloric acid, dehydrated alcohol, fatty alcohol polyoxyethylene ether and distilled water；
(2) it prepares the solution of titania precursor body, the solution for preparing silica solution, preparing mesoporous template, prepare polyphenyl second
Alkene microballoon macropore template and preparation active component predecessor potassium oxalate are coordinated solution；
(3) solution and the silica solution for mixing the titania precursor body are to obtain titanium silicon composite sol；
(4) solution of the titanium silicon composite sol and the mesoporous template is mixed to obtain a mixed solution；
(5) the polystyrene microsphere macropore template is immersed into the mixed solution and the mixed solution is made to insert institute
It states in polystyrene microsphere macropore template, to obtain once-combined body；
(6) active component predecessor potassium oxalate coordination solution spraying is added in the once-combined body and is made
The active component predecessor potassium oxalate coordination solution penetrates into the once-combined body, to obtain secondary complex；
(7) to roast the secondary complex by two sections of temperature-programmed calcination methods compound to obtain the titanium silicon with step hole
Hydrolytic catalyst of carbonyl sulfur.
Specifically, in step (2), the preparation active component predecessor potassium oxalate coordination solution step includes:
A1) fatty alcohol polyoxyethylene ether is added in the distilled water to obtain modified water；
A2) potassium oxalate and oxalic acid are added in the modified water to obtain the active component predecessor potassium oxalate
It is coordinated solution.
Further, in step (2), soluble titanium salt is is dissolved into institute by the solution for preparing titania precursor body
State the solution that the titania precursor body is obtained in dehydrated alcohol；
It is described prepare silica solution be soluble silicon is dissolved into dilute hydrochloric acid, dehydrated alcohol and distilled water it is molten to obtain silicon
Glue；
The solution for preparing mesoporous template is that mesoporous template P123 is dissolved into the dehydrated alcohol, to obtain
The solution of the mesoporous template；
It is described prepare polystyrene microsphere template be by polystyrene microsphere lotion is centrifuged and is dried with
Obtain the polystyrene microsphere macropore template.
Preferably, in step (2), the soluble silicon is ethyl orthosilicate, the ethyl orthosilicate, dilute hydrochloric acid, nothing
Water-ethanol, distilled water volume ratio be 4.17:0.38:9.23:1.30.
Further, the method also includes the once-combined body is placed on Buchner funnel after step (5)
It is filtered to remove mixed solution extra on the once-combined body surface face, later by the once-combined body scheduled
At a temperature of it is dry.
Specifically, in step (7), two sections of temperature-programmed calcination methods roast the secondary complex to be had
The compound hydrolytic catalyst of carbonyl sulfur sample of the titanium silicon in step hole the following steps are included:
B1 the secondary complex) is placed in progress first segment heating in temperature programming Muffle furnace, the first segment heating
Heating rate be 1 DEG C/min, rise to 450 DEG C by room temperature, and constant temperature 2h at this temperature, there is macropore and mesoporous to obtain
Secondary complex；
B2) by described there is macropore and mesoporous secondary complex to carry out second segment heating, the liter of the second segment heating
Warm rate is 5 DEG C/min, 600 DEG C is warming up to by 450 DEG C, and constant temperature 2h at this temperature, in the macropore and mesoporous hole
Micropore is re-formed on wall.
The preparation method of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon provided by the present invention at least has in following advantages
One:
(1) preparation method of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon provided by the present invention is to have by the way that size is controllable
Machine object microballoon is as macropore template, and using silica as reinforcing agent, preparation has the TiO of the orderly pore structure of bigger serface2Base
COS hydrolyst；
(2) preparation method of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon provided by the present invention realize catalyst both can be with
The anti-sulfur poisonous performance of COS hydrolysis reaction activity and titanium oxide is improved by big specific surface area, and there is suitable step hole
Road is conducive to the smooth export of reaction product, and it is living that catalyst can be made to show good COS hydrolysis under an oxygen-containing atmosphere
Property, the service life of catalyst is thus further improved, while also reducing TiO2The production cost of base COS hydrolyst,
To be more conducive to its extensive use industrially；
(3) preparation method of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon provided by the present invention by by carrier predecessor,
Mesoporous template and active component predecessor immerse in polystyrene microsphere macropore template by several times, are coordinated solution by potassium oxalate later
Decomposition forms micropore on macropore and mesoporous secondary complex, so as to form macropore, the ladder of mesoporous and micropore combination
Grade pore structure, and then avoid after carrier is made with the reduction in duct caused by impregnation method load active component.
Detailed description of the invention
These and or other aspects and advantage of the invention will become from description of preferred embodiments with reference to the accompanying drawing
It obtains obviously and is readily appreciated that, in which:
Fig. 1 a is the electron microscope of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon of embodiment according to the present invention one；
Fig. 1 b is the amplification electron microscope of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon shown in Fig. 1 a；
Fig. 2 is the process of the method for preparing the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon of embodiment according to the present invention one
Figure；
Fig. 3 is the embodiment of the present invention one to the carbonyl sulfide hydrolysis of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon of embodiment three
Curve comparison figure.
Specific embodiment
Below with reference to the embodiments and with reference to the accompanying drawing the technical solutions of the present invention will be further described.Illustrating
In book, the same or similar drawing reference numeral indicates the same or similar component.Following reference attached drawings are to embodiment of the present invention
Illustrate to be intended to explain present general inventive concept of the invention, and is not construed as to a kind of limitation of the invention.
Inventive concept of the invention is: by the controllable organic matter microballoon of size as macropore template, mesoporous template
Regulate and control the mesoporous TiO that micropore, the mesoporous step pore structure combined with macropore are prepared with micropore with active component predecessor2Base
COS hydrolyst has micropore abundant to realize catalyst both to provide reaction surface, while also having suitable step
Duct in favor of reaction product smooth export；Alternatively by the controllable organic matter microballoon of size as macropore template, it is situated between
Template regulation in hole is mesoporous, while the potassium oxalate for using decomposition temperature high is coordinated solution for predecessor, by potassium oxalate ligand compound
The decomposition of object carries out after macropore template and mesoporous template decomposition, makes to re-form on the macropore and mesoporous hole wall of formation micro-
Hole, to form the TiO of macropore, the step pore structure that mesoporous and micropore combines2Base COS hydrolyst, to realize catalyst
Both had micropore abundant to provide reaction surface, while also there is suitable macropore, mesoporous smooth in favor of reaction product
Export.
In addition, the present invention passes through the controllable organic matter microballoon of size as macropore template, using silica as benefit in other words
Strong agent preparation has the TiO of the orderly pore structure of bigger serface2Base COS hydrolyst, while with P123 for mesoporous template,
Using potassium oxalate coordination solution as active component predecessor, to realize the existing big specific surface area of catalyst to improve reactivity
And the smooth export for giving full play to the sulfur poisoning resistance of titanium oxide, and there is suitable step duct to be conducive to reaction product, by
This further improves the service life of catalyst, while also reducing TiO2The production cost of base COS hydrolyst, thus
Conducive to its extensive use industrially.It will be understood by those skilled in the art that compared to the side of impregnation method load active component
Method, the method for the embodiment of the present invention one being explained in detail below carrier can also be avoided to be made after with impregnation method load active component
Caused by duct reduction.
The compound hydrolytic catalyst of carbonyl sulfur of titanium silicon provided by the present invention is TiO2Base hydrolytic catalyst of carbonyl sulfur, the titanium silicon
Compound hydrolytic catalyst of carbonyl sulfur is using polystyrene microsphere as template, with P123 (i.e. polyethylene oxide-polypropylene oxide-polycyclic
Oxidative ethane triblock copolymer) it is mesoporous template, using soluble titanium salt as catalyst carrier predecessor, using soluble silicon as reinforcement
Agent predecessor, using potassium oxalate coordination solution as active component.In an example of the invention, polystyrene microsphere macropore template
It is obtained for example, by monodispersed polystyrene microsphere lotion, and soluble titanium salt includes butyl titanate, titanium sulfate, titanium tetrachloride
Any one of or their any combination；Soluble silicon include any one of ethyl orthosilicate, potassium silicate, sodium metasilicate or
Their any combination, this example are only a kind of illustrated examples, and those skilled in the art are not construed as to of the invention
A kind of limitation.
Embodiment one:
As seen in figure la and lb, the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon of the present embodiment is ordered into hole, bigger serface
TiO2/SiO2Compound COS hydrolyst, and there is macropore, mesoporous and micropore on the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon
Combined step pore structure, the catalyst pass through TiO2Antioxygen property and be conducive to reaction product smoothly derived step duct knot
The combination of structure, which embodies the catalyst under an oxygen-containing atmosphere, has high anti-sulfur poisonous performance.
As shown in Fig. 2, preparing the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon it illustrates embodiment according to the present invention one
Method flow chart.Method includes the following steps:
(1) soluble titanium salt, soluble silicon, polystyrene microsphere, mesoporous template P123, potassium oxalate, oxalic acid, dilute is provided
Hydrochloric acid, dehydrated alcohol, fatty alcohol polyoxyethylene ether and distilled water, wherein polystyrene microsphere selection in this example is monodispersed
Polystyrene microsphere lotion, distilled water can select deionized water to substitute, certainly it will be appreciated by those skilled in the art that, polyphenyl second
Alkene microballoon can also use other any suitable forms, and distilled water can also be carried out accordingly using other suitable solvent
Substitution；
(2) soluble titanium salt (such as butyl titanate) is added in dehydrated alcohol to obtain titania precursor liquid, it can
Dissolubility silicon (such as ethyl orthosilicate), dilute hydrochloric acid, dehydrated alcohol and distilled water are mixed according to a certain percentage to obtain silica solution,
Mesoporous template P123 is dissolved in the solution that mesoporous template is obtained in dehydrated alcohol, and will for example monodispersed polyphenyl second
Alkene microballoon lotion is dried after being centrifuged 6 hours at 30 DEG C to obtain polystyrene microsphere macropore template and preparation active component
Predecessor potassium oxalate is coordinated solution；
(3) solution of titania precursor body is mixed with silica solution, and is stirred evenly with blender, it is compound to obtain titanium silicon
Colloidal sol；
(4) the titanium silicon composite sol of preparation is mixed with the solution of mesoporous template, and is stirred evenly with blender to obtain
Obtain a mixed solution；
(5) polystyrene microsphere macropore template is immersed into above-mentioned mixed solution and keeps mixed solution filling polystyrene micro-
In ball macropore template, to obtain once-combined body, the once-combined body is placed on Buchner funnel filters to remove later
Mixed solution extra on the once-combined body surface face is removed, later dries the once-combined body at a predetermined temperature；
(6) active component predecessor potassium oxalate coordination solution spraying is added in dry once-combined body and makes to live
Property component predecessor potassium oxalate coordination solution penetrate into once-combined body, it is then that this is secondary to obtain secondary complex
Complex is dry at 30 DEG C；
(7) step hole is formed using two sections of temperature-programmed calcination methods: the secondary complex after drying is placed in temperature programming
First segment heating is carried out in Muffle furnace, the heating rate of first segment heating is 1 DEG C/min, rises to 450 DEG C by room temperature, and herein
At a temperature of constant temperature 2h, form macropore and mesoporous；Second segment heating is carried out later, the heating rate of second segment heating is 5 DEG C/min,
Be warming up to 600 DEG C by 450 DEG C, and constant temperature 2h at this temperature, decompose active component predecessor, in the macropore formed and
Re-form micropore on mesoporous hole wall, thus avoid after carrier is made with impregnation method load active component at duct
Reduction.Macropore will be formed with later, mesoporous and micropore step pore catalyst is naturally cooling to room temperature and takes out, obtain load have
K2CO3The step pore catalyst sample (i.e. titania-based catalyst sample) of (potassium carbonate).
It is high as active component predecessor potassium oxalate coordination its decomposition temperature of solution in step (2), it can be in big casement
Compound is carried out after plate and mesoporous template decomposition again to decompose to form micropore, at the same potassium oxalate coordination solution can with macropore
Template and mesoporous template decompose and do not generate sediment when reacting, and are not plugged up and reduce so that being formed by micropore
The reactivity of hydrolytic catalyst of carbonyl sulfur.Specifically, preparation active component predecessor potassium oxalate coordination solution step includes:
A1) fatty alcohol polyoxyethylene ether is added in distilled water, modified water is made；
A2) potassium oxalate and oxalic acid are added to together in the modified water, and stirring is uniformly mixed it as active component
Predecessor potassium oxalate is coordinated solution.
The chemical substance material that the embodiment of the present invention one uses are as follows: butyl titanate, ethyl orthosilicate, monodispersed polyphenyl second
Alkene microballoon lotion, potassium oxalate, oxalic acid, dilute hydrochloric acid, dehydrated alcohol, fatty alcohol polyoxyethylene ether and distilled water；
(1) solution of titania precursor body is prepared
Measure butyl titanate 37.25mL ± 0.01mL, dehydrated alcohol 50mL ± 0.001mL, the metatitanic acid that will be measured later
Butyl ester and dehydrated alcohol are placed in a beaker, and the titanium solution for obtaining that concentration is 2mol/L to being completely dissolved, i.e. oxygen are stirred with blender
Change the solution of titanium precursors.
(2) silica solution is prepared
The accurate ethyl orthosilicate for measuring 11.8mL ± 0.01mL, and according to ethyl orthosilicate: dilute hydrochloric acid: dehydrated alcohol:
The volume ratio of distilled water is that 4.17:0.38:9.23:1.30 measures corresponding dilute hydrochloric acid, dehydrated alcohol and distilled water, and is mixed
It closes, stirring makes its substantially uniformity to obtain silica solution.
(3) solution of titania precursor body produced above is mixed with silica solution, is stirred evenly with blender, obtains titanium
Silicon composite sol；
(4) solution of mesoporous template is prepared
The mesoporous template P123 of 15.00g ± 0.001g is accurately weighed, and the weighed mesoporous template P123 of institute is dissolved in
In 30mL ± 0.01mL dehydrated alcohol, the solution of mesoporous template is obtained；
(5) titanium silicon composite sol produced as described above is mixed with the solution of mesoporous template, is stirred evenly with blender
Obtain mixed solution；
(6) it takes 650mL ± 0.01mL monodisperse polystyrene microsphere lotion to be centrifuged 6 hours, will be centrifuged later resulting solid
Compound is dried to obtain polystyrene microsphere macropore template at 30 DEG C；
(7) polystyrene microsphere macropore template is immersed in above-mentioned mixed solution, and mixed solution is made to be filled into polyphenyl
Once-combined body is formed in ethylene microballoon macropore template, the once-combined body is taken out later, is filtered on a buchner funnel,
It is then that the once-combined body is dry at 30 DEG C to remove the liquid of once-combined body excess surface；
(8) preparation active component predecessor potassium oxalate is coordinated solution
The fatty alcohol polyoxyethylene ether of 0.49g ± 0.001g is accurately weighed into the distilled water of 100mL ± 0.01mL, is made
Modified water；The K of 1.95g ± 0.001g is accurately weighed later2C2O4The H of (potassium oxalate) and 0.48g ± 0.001g2C2O4(oxalic acid) one
It rises and is added in the modified water that volume is 7.5mL ± 0.01mL, and stirring makes its uniformly mixed potassium oxalate that becomes be coordinated solution；
(9) potassium oxalate coordination solution spraying is added in once-combined body, and penetrates into potassium oxalate coordination solution
It is then that secondary complex is dry at 30 DEG C to obtain secondary complex in once-combined body；
(10) step hole is formed using two sections of temperature-programmed calcination methods: the secondary complex after drying is placed in temperature programming
In Muffle furnace, first segment heating rate is set as 1 DEG C/min, rises to 450 DEG C by room temperature, and constant temperature 2h at this temperature, is formed
Macropore and mesoporous；Second segment heating rate is set as 5 DEG C/min, is warming up to 600 DEG C by 450 DEG C, and constant temperature 2h at this temperature,
Active component predecessor is decomposed, micropore is re-formed on the macropore and mesopore orbit wall formed, is naturally cooling to later
Room temperature is simultaneously taken out, and load K is obtained2CO3Step pore catalyst sample (i.e. titania-based catalyst sample).
Embodiment two:
The chemical substance material that the embodiment of the present invention two uses are as follows: butyl titanate, ethyl orthosilicate, monodisperse polystyrene
Microballoon lotion, dilute hydrochloric acid, dehydrated alcohol and distilled water；
(1) solution of titania precursor body is prepared
Measure butyl titanate 37.25mL ± 0.01mL, dehydrated alcohol 50mL ± 0.001mL, the metatitanic acid that will be measured later
Butyl ester and dehydrated alcohol are placed in a beaker, and the titanium solution for obtaining that concentration is 2mol/L to being completely dissolved, i.e. oxygen are stirred with blender
Change the solution of titanium precursors.
(2) silica solution is prepared
The accurate ethyl orthosilicate for measuring 11.8mL ± 0.01mL, and according to ethyl orthosilicate: dilute hydrochloric acid: dehydrated alcohol:
The volume ratio of distilled water is that 4.17:0.38:9.23:1.30 measures corresponding dilute hydrochloric acid, dehydrated alcohol and distilled water, and is mixed
It closes, stirring makes its substantially uniformity to obtain silica solution.
(3) solution of titania precursor body produced above is mixed with silica solution, is stirred evenly with blender, obtains titanium
Silicon composite sol；
(4) solution of mesoporous template is prepared
The mesoporous template P123 of 15.00g ± 0.001g is accurately weighed, and the weighed mesoporous template P123 of institute is dissolved in
In 30mL ± 0.01mL dehydrated alcohol, the solution of mesoporous template is obtained；
(5) titanium silicon composite sol produced as described above is mixed with the solution of mesoporous template, is stirred evenly with blender
Obtain mixed solution；
(6) it takes 650mL ± 0.01mL monodisperse polystyrene microsphere lotion to be centrifuged 6 hours, will be centrifuged later resulting solid
Compound is dried to obtain polystyrene microsphere macropore template at 30 DEG C；
(7) polystyrene microsphere macropore template is immersed in above-mentioned mixed solution, and mixed solution is made to be filled into polyphenyl
Once-combined body is formed in ethylene microballoon macropore template, the once-combined body is taken out later, is filtered on a buchner funnel,
It is then that the once-combined body is dry at 30 DEG C to remove the liquid of once-combined body excess surface；
(8) hole is formed using roasting method: the once-combined body after drying is placed in temperature programming Muffle furnace, first segment liter
Warm rate is set as 1 DEG C/min, rises to 450 DEG C by room temperature, and constant temperature 2h at this temperature, forms macropore and mesoporous, later from
It is so cooled to room temperature and takes out, that is, obtain the titania-based catalyst sample of embodiment two.
Embodiment three:
The chemical substance material that the embodiment of the present invention three uses are as follows: butyl titanate, ethyl orthosilicate, monodisperse polystyrene
Microballoon lotion, potassium carbonate, dilute hydrochloric acid, dehydrated alcohol and distilled water；
(1) solution of titania precursor body is prepared
Measure butyl titanate 37.25mL ± 0.01mL, dehydrated alcohol 50mL ± 0.001mL, the metatitanic acid that will be measured later
Butyl ester and dehydrated alcohol are placed in a beaker, and the titanium solution for obtaining that concentration is 2mol/L to being completely dissolved, i.e. oxygen are stirred with blender
Change the solution of titanium precursors.
(2) silica solution is prepared
The accurate ethyl orthosilicate for measuring 11.8mL ± 0.01mL, and according to ethyl orthosilicate: dilute hydrochloric acid: dehydrated alcohol:
The volume ratio of distilled water is that 4.17:0.38:9.23:1.30 measures corresponding dilute hydrochloric acid, dehydrated alcohol and distilled water, and is mixed
It closes, stirring makes its substantially uniformity to obtain silica solution.
(3) solution of titania precursor body produced above is mixed with silica solution, is stirred evenly with blender, obtains titanium
Silicon composite sol；
(4) solution of mesoporous template is prepared
The mesoporous template P123 of 15.00g ± 0.001g is accurately weighed, and the weighed mesoporous template P123 of institute is dissolved in
In 30mL ± 0.01mL dehydrated alcohol, the solution of mesoporous template is obtained；
(5) titanium silicon composite sol produced as described above is mixed with the solution of mesoporous template, is stirred evenly with blender
Obtain mixed solution；
(6) it takes 650mL ± 0.01mL monodisperse polystyrene microsphere lotion to be centrifuged 6 hours, will be centrifuged later resulting solid
Compound is dried to obtain polystyrene microsphere macropore template at 30 DEG C；
(7) polystyrene microsphere macropore template is immersed in above-mentioned mixed solution, and mixed solution is made to be filled into polyphenyl
Once-combined body is formed in ethylene microballoon macropore template, the once-combined body is taken out later, is filtered on a buchner funnel,
It is then that the once-combined body is dry at 30 DEG C to remove the liquid of once-combined body excess surface；
(8) using high-temperature roasting method removal macropore and mesoporous template
Once-combined body after drying is placed in temperature programming Muffle furnace, heating rate is set as 1 DEG C/min, by room temperature
450 DEG C are warming up to, and keeps the temperature 2h at this temperature, is taken out after being naturally cooling to room temperature later, required ordered big hole and Jie are obtained
The material in hole.
(9) alkali steeping
Accurately weigh the K of 1.5744g2CO3, it is added in the distilled water that volume is 7.35mL, stirring, which is uniformly mixed it, to be become
Solution of potassium carbonate；Ordered Macroporous Materials 10g produced above is weighed later to be impregnated in configured solution of potassium carbonate, is placed in
In vacuum oven, taken out after being impregnated under conditions of 30 DEG C of temperature, pressure -0.1kPa for 24 hours.
(10) sample after alkali steeping is placed in high temperature furnace, makes 10 DEG C/min of heating rate, N2Flow 50mL/min,
And 500 DEG C are risen to by room temperature, constant temperature 1h is naturally cooling to room temperature later, obtains load K2CO3Ordered big hole and mesoporous catalysis
Agent sample completely cuts off air later and saves, for use.
It, can be to each implementation after the compound carbonyl hydrolyst of titanium silicon that embodiment one is prepared to embodiment three
The compound carbonyl hydrolyst sample of titanium silicon of example is detected, analyzed and is characterized, the detection, analysis and characterization alumina catalyzation
The method of agent are as follows:
A1 carries out the specific surface area of catalyst analysis to the embodiment of the present invention one to embodiment three with n2 absorption apparatus.This point
The results are shown in Table 1 for analysis, and embodiment two is only added with macropore and mesoporous template and not to be coordinated solution using potassium oxalate to be roasted
The titanium-based support samples that method obtains, embodiment three are to impregnate K by using dipping method on the basis of example 22CO3Titanium
Base hydrolytic catalyst of carbonyl sulfur sample.Referring to following tables 1.
1 the embodiment of the present invention one of table to embodiment three texture parameter comparison table
As shown in Table 1, the specific surface area of the titanium-based support samples of embodiment two is 137.3m2/ g, total pore volume are
0.4219mL/g, Micropore volume 0.05367mL/g；The specific surface area of the titanium-based hydrolytic catalyst of carbonyl sulfur sample of embodiment three
For 112.3m2/ g, total pore volume 0.3672mL/g, Micropore volume 0.04591mL/g.It compares, the embodiment of the present invention one
The specific surface area of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon is 147.1m2/ g, total pore volume 0.4589mL/g, Micropore volume are
0.05961mL/g.It can thus be seen that the specific surface area of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon of the embodiment of the present invention one
Maximum, and micropore rich in and have and can be conducive to macropore and mesoporous derived from reactant.
A2 carries out catalytic performance test under oxygen atmosphere with micro- trans- chromatogram arrangement.As shown in figure 3, being in relative humidity
14.3%, 1.6 ten thousand h of air speed-1, COS concentration is 800mg/m3, O2Concentration is 2%, and hydrolysis temperature be 70 DEG C under conditions of to carbonyl
Base sulphur is removed, and the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon of the embodiment of the present invention one is up to 99% to cos conversion rate
More than, and 12h or more can be continued.And the hydrolytic catalyst of carbonyl sulfur of embodiment two and embodiment three conversion ratio and it is lasting when
Between on be not so good as the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon of embodiment one, and since the catalyst sample of embodiment two does not have
Active component, only carrier, therefore embodiment one and embodiment three are lower than to the conversion ratio of carbonyl sulfur.
It, can be to avoid in carrier system by above-mentioned analysis it is found that the method for embodiment one is compared to the method for embodiment three
With the reduction in duct caused by impregnation method load active component after.
When storing to the prepared compound hydrolytic catalyst of carbonyl sulfur of titanium silicon, needing will be prepared ordered porous
The compound carbonyl sulfur catalyst storage of titanium silicon in the glass container of amber transparent, and it is closed be protected from light storage, and be placed in shady and cool, dry
Dry, clean environment, while moisture-proof, sun-proof, anti-acid-alkali salt also being wanted to corrode, preferably storage temperature is 20 DEG C, relative humidity≤
10%.
The preparation method of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon provided by the present invention at least has in following advantages
One:
(1) preparation method of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon provided by the present invention is to have by the way that size is controllable
Machine object microballoon is as macropore template, and using silica as reinforcing agent, preparation has the TiO of the orderly pore structure of bigger serface2Base
COS hydrolyst；
(2) preparation method of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon provided by the present invention realize catalyst both can be with
The anti-sulfur poisonous performance of COS hydrolysis reaction activity and titanium oxide is improved by big specific surface area, and there is suitable step hole
Road is conducive to the smooth export of reaction product, and catalyst can be made to show good COS hydrolysis under an oxygen-containing atmosphere
Thus activity further improves the service life of catalyst, while also reducing TiO2Base COS hydrolyst is produced into
This, to be more conducive to its extensive use industrially；
(3) preparation method of the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon provided by the present invention by by carrier predecessor,
Mesoporous template and active component predecessor immerse in polystyrene microsphere macropore template by several times, are coordinated solution by potassium oxalate later
Decomposition forms micropore on macropore and mesoporous secondary complex, so as to form macropore, the ladder of mesoporous and micropore combination
Grade pore structure, and then avoid after carrier is made with the reduction in duct caused by impregnation method load active component.
Although some embodiments of this present general inventive concept have been shown and have illustrated, those of ordinary skill in the art will be managed
Solution can make a change these embodiments in the case where the principle and spirit without departing substantially from this present general inventive concept, of the invention
Range is limited with claim and their equivalent.
Claims (7)
1. a kind of method for preparing the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon, the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon are
TiO2Base hydrolytic catalyst of carbonyl sulfur, wherein the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon is using polystyrene microsphere as macropore
Template, with P123 for mesoporous template, using soluble titanium salt as catalyst carrier predecessor, using soluble silicon as reinforcing agent forerunner
Object, using potassium oxalate coordination solution as active component predecessor,
It the described method comprises the following steps:
(1) soluble titanium salt, soluble silicon, polystyrene microsphere, mesoporous template P123, potassium oxalate, oxalic acid, dilute salt are provided
Acid, dehydrated alcohol, fatty alcohol polyoxyethylene ether and distilled water；
(2) soluble titanium salt is added to the solution that titania precursor body is prepared in dehydrated alcohol；Soluble silicon is dissolved into
Silica solution is prepared in dilute hydrochloric acid, dehydrated alcohol and distilled water；Mesoporous template P123 is dissolved in dehydrated alcohol to prepare
The solution of mesoporous template；It is big to prepare polystyrene microsphere by the way that polystyrene microsphere lotion is centrifuged and is dried
Hole template；And modified water is made and by potassium oxalate and oxalic acid one by the way that fatty alcohol polyoxyethylene ether to be added in distilled water
It rises and is added in the modified water, and stirring is uniformly mixed it to prepare active component predecessor potassium oxalate coordination solution；
(3) solution and the silica solution for mixing the titania precursor body are to obtain titanium silicon composite sol；
(4) solution of the titanium silicon composite sol and the mesoporous template is mixed to obtain a mixed solution；
(5) the polystyrene microsphere macropore template is immersed into the mixed solution and keeps the mixed solution filling described poly-
In phenylethylene micro ball macropore template, to obtain once-combined body；
(6) active component predecessor potassium oxalate coordination solution spraying is added in the once-combined body and is made described
Active component predecessor potassium oxalate coordination solution penetrates into the once-combined body, to obtain secondary complex；
(7) the secondary complex is roasted by two sections of temperature-programmed calcination methods to obtain the compound carbonyl of titanium silicon with step hole
Sulfide hydrolysis.
2. the method according to claim 1 for preparing the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon, which is characterized in that
The solubility titanium salt includes any one of butyl titanate, titanium sulfate, titanium tetrachloride or their any combination；
The soluble silicon includes any one of ethyl orthosilicate, potassium silicate, sodium metasilicate or their any combination.
3. the method according to claim 2 for preparing the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon, which is characterized in that
The compound hydrolytic catalyst of carbonyl sulfur of titanium silicon is TiO2/SiO2Compound hydrolytic catalyst of carbonyl sulfur,
The compound hydrolytic catalyst of carbonyl sulfur of titanium silicon, which is negative, is loaded with the step pore titanium oxide base catalyst of potassium carbonate.
4. the method according to claim 1 for preparing the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon, which is characterized in that
In step (2), the soluble silicon is ethyl orthosilicate, the ethyl orthosilicate, dilute hydrochloric acid, dehydrated alcohol, distillation
The volume ratio of water is 4.17:0.38:9.23:1.30.
5. the method according to claim 4 for preparing the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon, which is characterized in that
The method also includes the once-combined body is placed on Buchner funnel after step (5) to filter to remove
Extra mixed solution, later dries the once-combined body at a predetermined temperature on the once-combined body surface face.
6. the method according to claim 5 for preparing the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon, which is characterized in that
In step (7), two sections of temperature-programmed calcination methods roast the secondary complex to obtain the titanium with step hole
The compound hydrolytic catalyst of carbonyl sulfur sample of silicon the following steps are included:
B1 the secondary complex) is placed in progress first segment heating in temperature programming Muffle furnace, the liter of the first segment heating
Warm rate is 1 DEG C/min, rises to 450 DEG C by room temperature, and constant temperature 2h at this temperature, has macropore and mesoporous two to obtain
Secondary complex；
B2) by described there is macropore and mesoporous secondary complex to carry out second segment heating, the heating speed of the second segment heating
Rate is 5 DEG C/min, 600 DEG C is warming up to by 450 DEG C, and constant temperature 2h at this temperature, on the macropore and mesoporous hole wall
Re-form micropore.
7. the method according to claim 3 for preparing the compound hydrolytic catalyst of carbonyl sulfur of titanium silicon, which is characterized in that
The step pore titanium oxide base catalyst has macropore, mesoporous and micropore,
Micropore on the step pore titanium oxide base catalyst is after the macropore and mesoporous formation, in the macropore and Jie
The hole formed in the cell walls in hole.
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| CN104117374A (en) * | 2014-07-30 | 2014-10-29 | 沈阳三聚凯特催化剂有限公司 | Copper-zinc-aluminum based carbonyl sulfide hydrolysis catalyst and preparation method thereof |
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