CN105854877B - The preparation method of the platinum tin SiO 2 catalyst of ethyl alcohol is produced for acetic acid plus hydrogen - Google Patents
The preparation method of the platinum tin SiO 2 catalyst of ethyl alcohol is produced for acetic acid plus hydrogen Download PDFInfo
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- CN105854877B CN105854877B CN201610266337.6A CN201610266337A CN105854877B CN 105854877 B CN105854877 B CN 105854877B CN 201610266337 A CN201610266337 A CN 201610266337A CN 105854877 B CN105854877 B CN 105854877B
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 140
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 235000019441 ethanol Nutrition 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000001257 hydrogen Substances 0.000 title claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 45
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 42
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 42
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 42
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 229910052718 tin Inorganic materials 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 42
- 230000032683 aging Effects 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XKUTVNLXHINPAP-UHFFFAOYSA-N azane platinum Chemical compound N.[Pt] XKUTVNLXHINPAP-UHFFFAOYSA-N 0.000 claims description 2
- -1 platinum tin titanium dioxide Chemical compound 0.000 claims description 2
- 239000003570 air Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 11
- 229910002847 PtSn Inorganic materials 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 28
- 229910006854 SnOx Inorganic materials 0.000 description 26
- 241000370738 Chlorion Species 0.000 description 19
- 239000000446 fuel Substances 0.000 description 14
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 13
- 125000005909 ethyl alcohol group Chemical group 0.000 description 13
- 238000007873 sieving Methods 0.000 description 13
- 239000003643 water by type Substances 0.000 description 13
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 11
- 239000000908 ammonium hydroxide Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 9
- 238000003483 aging Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000005660 chlorination reaction Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 238000001802 infusion Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 244000144725 Amygdalus communis Species 0.000 description 1
- 235000011437 Amygdalus communis Nutrition 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000020224 almond Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011219 quaternary composite Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- B01J35/50—
Abstract
The present invention relates to the preparation methods for the platinum tin SiO 2 catalyst for adding hydrogen production ethyl alcohol for acetic acid；Stanniferous salt and ethyl orthosilicate are dissolved in ethyl alcohol, lower dropwise addition deionized water is stirred, obtains SnOx‑SiO2Composite oxides；It is added in ammonia spirit, the aqueous solution of platiniferous ammonia salt is then added；Obtained solid is ground into powdery, molding obtains the platinum tin SiO 2 catalyst of acetic acid preparation of ethanol by hydrogenating.Present invention combination sol-gal process and ion-exchange, improve Pt, Sn uploads mode, improves the dispersion degree of Pt, Sn and the Degree of interaction of the two, to obtain the PtSn catalyst of function admirable, improves the efficiency that acetic acid adds hydrogen production ethyl alcohol.Compared with existing acetic acid adds hydrogen to produce the catalyst used in ethanol, catalyst of the invention can realize the high conversion of acetic acid under more mild reaction condition, and acetic acid conversion ratio is up to 99% or more, and ethanol selectivity is up to 95%.
Description
Technical field
The invention belongs to chemical technology fields, are related to hydrogenation catalyst, be it is a kind of be used for acetic acid direct hydrogenation ethyl alcohol
Effective catalyst.
Background technology
Alcohol fuel is the traditional product to appear on the market early 20th century, after be eliminated because of the extensive of oil, low cost development.
Since the 1970s mid-term four times larger " oil crisises ", fuel ethanol industry is pushed to be able in world many countries
It rapidly develops.Alcohol fuel has become the emphasis of world today's Renewable Energy Development, with each as new cleaning fuel
State increases the dynamics of ethanol petrol application, and the yield of world fuel ethyl alcohol rises year by year.Alcohol fuel, can as gasoline additive
Effectively improve the octane number and explosion-proof performance of gasoline.Ethyl alcohol has apparent environmental benefit, ethyl alcohol as a kind of clean fuel
High oxygen content, be added in gasoline as oxygenation agent, can help gasoline completely burned, reduce carbon monoxide and carbon in vehicle exhaust
The discharge of hydrogen compound, so as to improve the quality of vehicle exhaust, to mitigate the pollution to air.As the country needs energy consumption
The continuous improvement asked, the country will also be substantially increased the potential demand of alcohol fuel, and alcohol fuel will have in the development of China
More wide foreground.In China, Fuel Alcohol Development industry meets the developing direction of National Security Strategy and regenerative resource,
It is technically ripe, securely and reliably, there is preferable economic benefit and social benefit.
It is that raw material passes through fermentation, separation, denaturation that the production of 95% alcohol fuel of world wide at present, which is with sugarcane, grain etc.,
Etc. processes obtain.For this method since by-product is more, cost of material is high, and the problems such as threaten grain security and is made
About.And alcohol fuel its yield of China's fermentation method production cannot be satisfied the huge consumption demand of alcohol fuel, it is " poor in conjunction with China
The energy resource structure present situation of oil, few gas, coal relative abundance ", exploitation produce the variation route of alcohol fuel, portion using synthesis gas as raw material
Divide substitution using grain as the technique of raw material, can not only protect the grain security in China, but also can reduce to Imported oil Resource Dependence, increases
Strong Chinese energy safety.At present in synthesis legal system ethyl alcohol, the research of the direct synthesizing alcohol of synthesis gas is the most extensive, especially
Rhodium base supported catalyst shows preferable catalytic performance, and synthesis gas is also furtherd investigate through dimethyl ether ethyl alcohol route
And extensive use.In addition, the domestic serious superfluous and ethyl alcohol demand of acetic acid production capacity soars all the way, acetic acid hydrogenation ethyl alcohol is promoted to pass through
There is feasibility in Ji, therefore become new research hotspot through acetic acid hydrogenation ethyl alcohol technological development using synthesis gas as raw material.
Acetic acid is a kind of important industrial chemicals.Country's acetic acid plant is averaged the utilization of capacity less than 60% at present, acetic acid production capacity
Relative surplus causes acetic acid price to continue to decline, and the production of acetic acid performance of enterprises is sluggish, therefore need to urgently develop the production of acetic acid downstream
Product extend the industrial chain of acetic acid industry.And by acetic acid preparation of ethanol by hydrogenating, it is one of the good approach for solving acetic acid excess capacity.
There are mainly two types of approach for acetic acid hydrogenation ethyl alcohol：One is acetic acid direct hydrogenations to produce ethyl alcohol；Another kind is first will
Acid esterification, then add hydrogen to obtain ethyl alcohol under relatively mild conditions using Supported Cu catalyst.Although acetic acid is through being esterified road
The selectivity of diameter ethyl alcohol is usually compared with directed hydrogenation height, but its process route is long, equipment equipment investment is big.And directed hydrogenation
Process route is simple, low energy consumption, although the corrosion resistance to equipment has higher requirements, high with carbon resource utilization rate,
The advantages that green high-efficient, therefore have good application prospect.
The acetic acid hydrogenation catalyst reported both at home and abroad at present, the mainly loaded noble metal catalysts such as Pt, Pd, Ru, instead
Answer condition more harsh, and there are catalyst activities it is low, ethanol selectivity is poor the problems such as.United States Patent (USP) 29995 describes acetic acid
It is catalyzed oxygenation ethyl alcohol new process, which can carry out under gas phase or liquid-phase condition, and catalyst is solid phase, preferentially selects gas phase
Reaction.Catalyst is prepared using infusion process, and wherein active metal is Pt and Sn, and the mass ratio of Pt/Sn is 0.5-1.5, can also be added
Enter the third active metal, such as Pd, Ru etc., silica, activated carbon etc. may be selected in carrier.Reaction temperature is in 225-275 DEG C of model
In enclosing, acetic acid, H2Molar ratio is 0.5-20, reaction pressure 1-2.5MPa.The conversion ratio of raw acetic acid is up to 90% or so, second
The selectivity of alcohol is up to 90%-95%.The United States Patent (USP) US4517391 of BASF AG discloses a kind of quaternary composite oxides
CoO-CuO-Mn3O4-MoO3For acetic acid hydrogenation ethyl alcohol, in 250 DEG C, air speed 0.126h-1, 300bar Hydrogen Vapor Pressure under, second
Alcohol yield is up to 97%.CN86102420A prepares 2.5%Pd-5.l%Mo/ graphite catalysts using infusion process, in 249 DEG C, hydrogen
Atmospheric pressure 10.3bar, LHSV=0.35h-1Under conditions of, acetic acid conversion 58%, the overall selectivity of ethyl alcohol and ester in product
It is 82.7%.
Chinese patent CN102229520A is prepared for 10%W-5%Re-2%Ru/ almond Pd/carbon catalysts using infusion process,
250 DEG C, 10MPa, air speed 1h-1Under conditions of react 50h, acetic acid conversion is more than 99%, ethanol selectivity 98.1%.China
Patent CN102311311A, CN102149661A and CN102304018A, which are described, loads Pt and Sn by the method for co-impregnation
In SiO2、CaSiO3, graphite, SiO2-A12O3On composite oxide carrier, 250 DEG C, 22bar, GHSV 2500h-1Condition
Under, acetic acid conversion 70~85%, ethanol selectivity is more than 93%.Chinese patent CN102149662A is disclosed is with 10%Co
First metal, 1% Pd, Pt, Cr, Mo, Sn, W, Zn, Ir, Re, Cu, Ru, Rh one such are the second component auxiliary agent, carrier
For SiO2、CaSiO3、A12O3、TiO2、ZrO2, one kind in carbon, within the scope of 225-275 DEG C, acetic acid conversion is 18~
70%, ethanol selectivity is 90% or more.
It is disclosed above the results show that PtSn catalyst shows preferable catalytic performance in acetic acid adds hydrogen, therefore apply
It has a extensive future.But current PtSn catalyst mostly uses infusion process preparation, and the active component dispersion degree of gained catalyst is relatively low, living
Interaction between property component and carrier is weaker, leads to that catalyst activity and selectivity is relatively low, stability is poor and reaction condition
It is more harsh.Present invention combination sol-gal process and ion-exchange realize Sn in silica uniformly using sol-gal process
Distribution improves Pt in SnO using ion-exchangex-SiO2Dispersion degree on complex carrier, and thus strengthen between the two
Contact with each other degree, to targetedly solve the above problem.
Invention content
It can realize that acetic acid Efficient Conversion generates second in mild reaction condition the object of the present invention is to provide a kind of stabilization
Alcohol is easily industrialized the catalyst for acetic acid preparation of ethanol by hydrogenating of production simultaneously.
The preparation method of platinum tin SiO 2 catalyst proposed by the present invention for acetic acid preparation of ethanol through hydrogenation is specific to walk
It is rapid as follows：
(1) it is 0.3~1.7 in mass ratio by stanniferous salt and ethyl orthosilicate：100 ratio is dissolved in ethyl alcohol, under stirring
Deionized water is added dropwise, after it forms vitreosol, the pH to 3.0~5.0 of colloidal sol is adjusted with ammonia spirit, then at room temperature
It stands；After colloidal sol forms gel, heat up aging, is washed out, dries, roasts, obtains SnOx-SiO2Composite oxides；
(2) SnO that will be obtainedx-SiO2Composite oxides be added pH=9.0~12.0 ammonia spirit in, then press Pt with
SnOx-SiO2The mass ratio of composite oxides is 0.5~3：The aqueous solution of platiniferous ammonia salt is added in 100 ratio, stirs 6-24h；
(3) it filters, it is dry after a large amount of deionized water washings, obtained solid is ground into powdery, molding obtains platinum tin two
Silicon oxide catalyst.
In the present invention, the molar ratio of the Pt and Sn of platinum tin SiO 2 catalyst are 0.6~1.2.
In the present invention, the preparation SnO mentioned by step (1)x-SiO2The chloride that Sn salt used in composite oxides is Sn
And its hydrate.
In the present invention, the temperature of the gel aging mentioned by step (1) is 50-70 DEG C, ageing time 10-48h.
In the present invention, the drying temperature of the gel mentioned by step (1) is 95-120 DEG C, drying time 5-10h.
In the present invention, the SnO mentioned by step (1)x-SiO2The calcination atmosphere that composite oxides use can for air and
Nitrogen, the inert gases such as argon gas, calcination temperature are 400-600 DEG C, roasting time 2-10h.
In the present invention, the platinum ammonia salt mentioned by step (2) is Pt (NH3)4Cl2、Pt(NH3)4(NO3)2、Pt(NH3)4(OH)2
And its hydrate.
In the present invention, the drying mode for preparing platinum tin SiO 2 catalyst mentioned by step (3) be vacuum, air,
Dry under nitrogen or other inert gas atmosphere, drying temperature is 60-200 DEG C, drying time 5-48h.
PtSn catalyst using present invention design synthesis is a kind of novel PtSn catalyst.It is prepared with conventional method
PtSn catalyst is compared, and novelty shows that microstructure has higher Pt, Sn dispersion degree and the two relatively closely mutual
Effect.Therefore, be applied to the reaction of acetic acid preparation of ethanol by hydrogenating, under mild reaction conditions, show very high activity and
Selectivity, acetic acid conversion ratio can reach 99% or more, and ethanol selectivity is up to 95%.Catalyst stability is good, reacts 320h
Afterwards, catalyst activity is held essentially constant with ethanol selectivity.The designed PtSn catalyst synthesized of the invention is a kind of performance
Excellent acetic acid hydrogenation catalyst, is suitable for industrializing, and helps to solve the problems, such as acetic acid excess capacity.
Description of the drawings
Fig. 1 illustrates the activity of PtSn catalyst and the selectivity of ethyl alcohol, ethyl acetate, acetaldehyde in the present invention.
Fig. 2 illustrates dispersibility of active component Pt, Sn in catalyst surface of catalyst in the present invention, and particle is averaged grain
Diameter is about 1.4nm.
Fig. 3 illustrates the TPR figures of catalyst in the present invention, and using the catalyst of the invention prepared, reduction temperature is more normal
The reduction temperature for advising catalyst prepared by infusion process is high, show to have between catalyst activity component Pt, Sn in the present invention compared with
Strong interaction.
Specific implementation mode
Below by embodiment and comparative example, the present invention is further elaborated, but they the present invention is not made it is any
Limitation.
Embodiment 1：Pt1Sn1/SiO2- 1# catalyst
0.393g SnCl250.2mL absolute ethyl alcohols are dissolved in, 70.766g ethyl orthosilicates are added, are added dropwise while stirring
50.1mL deionized waters, adjust sol pH to 3.0, stood at room temperature after water is added dropwise, after it becomes gel in
70 DEG C of agings 10 hours, washing remove chlorion, in baking oven after 110 DEG C of dryings 8 hours, place it in 500 DEG C of Muffle furnaces and roast
It burns 5 hours, obtains SnOx/SiO2Carrier is fully ground by complex carrier, obtains pulverulent solids.
By 4g SnOx/SiO2In the ammonia spirit that complex carrier powder is added, it is added with stirring four ammonium of 4mL chlorinations and closes platinum water
Solution (0.01gPt/mL), continue stirring 10 hours, in due course be added dropwise ammonium hydroxide to keep pH=11.0, then filter, wash away chlorine from
Son, it is 5 hours dry at 200 DEG C.By catalyst powder tabletting, broken, sieving, 40~60 mesh particles are obtained, 1# catalyst is denoted as.
Embodiment 2：Pt0.5Sn0.5/SiO2- 2# catalyst
0.212g SnCl230.8mL absolute ethyl alcohols are dissolved in, 70.766g ethyl orthosilicates are added, are added dropwise while stirring
30.2mL deionized waters, adjust sol pH to 4.2, stood at room temperature after water is added dropwise, after it becomes gel in
70 DEG C of agings 10 hours, washing remove chlorion, in baking oven after 95 DEG C of dryings 10 hours, place it in 600 DEG C of Muffle furnaces and roast
It burns 2 hours, obtains SnOx/SiO2Carrier is fully ground by complex carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder is added in ammonia spirit, and it is water-soluble to be added with stirring four ammonium of 2mL chlorinations conjunction platinum
Liquid (0.01gPt/mL), continues stirring 24 hours, and ammonium hydroxide is added dropwise in due course to keep pH=9.0, then filters, washes away chlorion,
It is 10 hours dry at 110 DEG C.By catalyst powder tabletting, broken, sieving, 40~60 mesh particles are obtained, 2# catalyst is denoted as.
Embodiment 3：Pt2Sn1/SiO2- 3# catalyst
0.393g SnCl275.2mL absolute ethyl alcohols are dissolved in, 70.766g ethyl orthosilicates are added, are added dropwise while stirring
61.2mL deionized waters, adjust sol pH to 5.0, stood at room temperature after water is added dropwise, after it becomes gel in
50 DEG C of water-bath agings 48 hours, washing remove chlorion, after 5 hours dry at 120 DEG C in baking oven, place it in 400 DEG C of Muffles
Kiln roasting 10 hours, obtains SnOx/SiO2Carrier is fully ground by complex carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder is added in ammonia spirit, and it is water-soluble to be added with stirring four ammonium of 8mL chlorinations conjunction platinum
Liquid (0.01gPt/mL) continuously stirs 6 hours, and ammonium hydroxide is added dropwise in due course to keep pH=12.0, then filters, washes away chlorion,
It is 48 hours dry at 60 DEG C.By catalyst powder tabletting, broken, sieving, 40~60 mesh particles are obtained, 3# catalyst is denoted as.
Embodiment 4：Pt1Sn1/SiO2- 4# catalyst
0.393g SnCl450.2mL absolute ethyl alcohols are dissolved in, 70.766g ethyl orthosilicates are added, are added dropwise while stirring
40.5mL deionized waters, adjust sol pH to 5.0, placed at room temperature after water is added dropwise, after it becomes gel in
60 DEG C of water-bath agings 24 hours, washing remove chlorion, after 5 hours dry at 105 DEG C, place it in 500 DEG C of Muffle furnaces and roast
It burns 4 hours, obtains SnOx/SiO2Carrier is fully ground by complex carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder is added in ammonia spirit, and it is water-soluble to be added with stirring four ammonium of 4mL chlorinations conjunction platinum
Liquid (0.01gPt/mL) continuously stirs 10 hours, and ammonium hydroxide is added dropwise in due course to keep pH=10.6, then filters, washes away chlorion,
It is 5 hours dry at 200 DEG C.By catalyst powder tabletting, broken, sieving, 40~60 mesh particles are obtained, carry out activity rating, note
For 4# catalyst.
Embodiment 5：Pt1.5Sn1/SiO2- 5# catalyst
0.787g SnCl4·5H2O is dissolved in 75.2mL absolute ethyl alcohols, and 70.766g ethyl orthosilicates are added, drip while stirring
Add 61.2mL deionized waters, adjust sol pH to 4.0, after water is added dropwise room temperature decentralization set, after it becomes gel in
70 DEG C of water-bath agings 10 hours, ethyl alcohol wash away chlorion, after 5 hours dry at 105 DEG C, place it in nitrogen in 600 DEG C of tube furnaces
It is roasted 4 hours under gas atmosphere, obtains SnOx/SiO2Carrier is fully ground by complex carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder is added in ammonia spirit, is added with stirring 6mL tetraethanolammonium hydroxides and closes platinum water
Solution (0.01gPt/ml) continuously stirs 6 hours, in due course be added dropwise ammonium hydroxide to keep pH=12.0, then filter, wash away chlorine from
Son, it is 10 hours dry in baking oven at 105 DEG C.By catalyst powder tabletting, broken, sieving, 40~60 mesh particles are obtained, 5# is denoted as
Catalyst.
Embodiment 6：Pt3Sn3/SiO2- 6# catalyst
1.203g SnCl2·2H2O is dissolved in 75.2mL absolute ethyl alcohols, and 70.766g ethyl orthosilicates are added, drip while stirring
Add 40.9mL deionized waters, adjust sol pH to 3.0, after water is added dropwise room temperature decentralization set, after it becomes gel in
70 DEG C of water-bath agings 24 hours, ethyl alcohol wash away chlorion, after 10 hours dry at 95 DEG C, place it in 400 DEG C of tube furnace argon gas
It is roasted 10 hours under atmosphere, obtains SnOx/SiO2Carrier is fully ground by complex carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder is added in ammonia spirit, and it is water-soluble to be added with stirring four ammonium of 4mL chlorinations conjunction platinum
Liquid (0.03g Pt/mL), continuously stirs 6 hours, and ammonium hydroxide is added dropwise in due course to keep pH=12.0, then filters, washes away chlorion,
It is 5 hours dry at 200 DEG C.By catalyst powder tabletting, broken, sieving, 40~60 mesh particles are obtained, 6# catalyst is denoted as.
Embodiment 7：Pt1Sn1/SiO2- 7# catalyst
0.393g SnCl260.6mL absolute ethyl alcohols are dissolved in, 70.766g ethyl orthosilicates are added, are added dropwise while stirring
60.6mL deionized waters adjust sol pH to 5.0, and room temperature is transferred and set after water is added dropwise, in 70 after it becomes gel
DEG C water-bath aging 10 hours, washing go chlorion to place it in 400 DEG C of Muffle furnaces and roast after being dried 5 hours at 105 DEG C
It burns 10 hours, obtains SnOx/SiO2Carrier is fully ground by complex carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder is added in ammonia spirit, and it is water-soluble to be added with stirring four ammonium of 4mL hydrogen-oxygens conjunction platinum
Liquid (0.01gPt/mL), continues stirring 6 hours, and ammonium hydroxide is added dropwise in due course to keep pH=12.0, then filters, washes away chlorion,
It is dried in vacuo 5 hours at 120 DEG C.By catalyst powder tabletting, broken, sieving, 40~60 mesh particles are obtained, are denoted as 7# catalysis
Agent.
Embodiment 8：Pt1Sn1/SiO2- 8# catalyst
0.393g SnCl2105.2mL absolute ethyl alcohols are dissolved in, 70.766g ethyl orthosilicates are added, are added dropwise while stirring
70.2mL deionized waters adjust sol pH to 3.0, and room temperature is transferred and set after water is added dropwise, in 70 after it becomes gel
DEG C water-bath aging 48 hours, ethyl alcohol wash away chlorion, after 5 hours dry at 120 DEG C, place it in 600 DEG C of Muffle kiln roastings 4
Hour, obtain SnOx/SiO2Carrier is fully ground by complex carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder is added in ammonia spirit, and it is water-soluble to be added with stirring four ammonium of 4mL chlorinations conjunction platinum
Liquid (0.01gPt/mL) continuously stirs 12 hours, and ammonium hydroxide is added dropwise in due course to keep pH=10.0, then filters, washes away chlorion,
It is 8 hours dry under 150 DEG C of pipe type stove nitrogen atmospheres.By catalyst powder tabletting, broken, sieving, 40~60 mesh particles are obtained,
It is denoted as 8# catalyst.
Embodiment 9：Pt1Sn1/SiO2- 9# catalyst
0.393g SnCl285.2mL absolute ethyl alcohols are dissolved in, 70.766g ethyl orthosilicates are added, are added dropwise while stirring
51.2mL deionized waters adjust sol pH to 5.0, and room temperature is transferred and set after water is added dropwise, in 50 after it becomes gel
DEG C water-bath aging 48 hours, washing remove chlorion, after 10 hours dry at 95 DEG C, place it in 500 DEG C of Muffle kiln roastings
4 hours, obtain SnOx/SiO2Carrier is fully ground by complex carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder is added in ammonia spirit, and it is water-soluble to be added with stirring four ammonium of 4mL chlorinations conjunction platinum
Liquid (0.01gPt/mL) continuously stirs 6 hours, and ammonium hydroxide is added dropwise in due course to keep pH=12.0, then filters, washes away chlorion,
It is 10 hours dry under argon gas atmosphere in 105 DEG C of pipe type stoves.By catalyst powder tabletting, broken, sieving, 40~60 mesh are obtained
Grain, is denoted as 9# catalyst.
Embodiment 10：Pt1Sn1/SiO2- 10# catalyst
0.393g SnCl280.2mL absolute ethyl alcohols are dissolved in, 70.766g ethyl orthosilicates are added, are added dropwise while stirring
71.2mL deionized waters adjust sol pH to 3.0, and room temperature is transferred and set after water is added dropwise, in 70 after it becomes gel
DEG C water-bath aging 10 hours, washing remove chlorion, after 5 hours dry at 120 DEG C, place it in 600 DEG C of Muffle kiln roastings
2 hours, obtain SnOx/SiO2Carrier is fully ground by complex carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder is added in ammonia spirit, and four ammonium of 4mL nitric acid, which is added, after stirring is lower closes platinum water
Solution (0.01gPt/mL) continuously stirs 24 hours, in due course be added dropwise ammonium hydroxide to keep pH=10.0, then filter, wash away chlorine from
Son, it is 5 hours dry at 200 DEG C.By catalyst powder tabletting, broken, sieving, 40~60 mesh particles are obtained, are denoted as 10# catalysis
Agent.
Embodiment 11：
With catalytic performance of the fixed bed reactors evaluation platinum tin silica in the reaction of acetic acid preparation of ethanol by hydrogenating, wherein
The loadings of catalyst are 2mL.First with pure H2Temperature programmed reduction is carried out under reaction pressure, is dropped after being restored 4 hours in 300 DEG C
To reaction temperature, it is then pumped into acetic acid and starts to react.Liquid after being reacted with chromatographic calculates the conversion ratio of acetic acid
With the selectivity of ethyl alcohol.Catalyst activity evaluation result is as shown in Table 1, and wherein reaction temperature is 260 DEG C, and reaction pressure is
2.6MPa, hydracid molar ratio are 20.
Embodiment 12：
The influence of the catalytic performance for the catalyst that investigation reduction temperature prepares embodiment 1.Reducing condition is reaction pressure
Lower 400 DEG C restore 4 hours, the catalyst performance evaluation condition in actual conditions such as embodiment 11, catalyst activity evaluation result
As shown in Table 1.
Embodiment 13：
Investigate catalyst life prepared by embodiment 1, the catalyst performance evaluation condition in actual conditions such as embodiment 11.
As shown in Figure 1, being reacted by 300 hours, the conversion ratio and selectivity of acetic acid are still maintained at the first level of reaction, show catalyst
With good stability.
Embodiment 14：
The granular size of active component in the catalyst of the preparation of embodiment 1 is characterized using TEM.As shown in Fig. 2, activearm
It is 1.4nm to divide the average grain diameter of particle, shows that active component has good dispersibility in catalyst surface.
Embodiment 15：
Pt, Sn component is mutual in the catalyst prepared using temperature programmed reduction (TPR) investigation embodiment 1, embodiment 3
Effect, and compared with catalyst prepared by comparative example 1.As shown in figure 3, urging prepared by embodiment 1, embodiment 3
Agent reduction temperature is high compared with the catalyst reduction temperature prepared by comparative example 1, illustrate the above two Pt, Sn component have compared with
Strong interaction.
Comparative example 1：Pt1Sn1/SiO2- 11# catalyst
0.393g SnCl285.2mL absolute ethyl alcohols are dissolved in, 70.766g ethyl orthosilicates are added, are added dropwise while stirring
51.2mL deionized waters adjust sol pH to 5.0, and room temperature is transferred and set after water is added dropwise, in 70 after it becomes gel
DEG C water-bath aging 10 hours, washing remove chlorion, after 5 hours dry at 200 DEG C, place it in 500 DEG C of Muffle kiln roastings
4 hours, obtain SnOx/SiO2It is powdered to be fully ground system by complex carrier for carrier.
Pt is uploaded using equi-volume impregnating, to 4g SnOx/SiO22mL platinum nitrate aqueous solutions are added dropwise in complex carrier powder
(0.02g Pt/mL) stands 2 hours after stirring evenly, 80 DEG C of backspins be evaporated it is dry, then be placed in 105 DEG C of baking ovens in re-dry 12
Hour, in 500 DEG C of Muffle kiln roastings 4 hours.By the tabletting of gained catalyst powder, broken, sieving, 40~60 mesh are obtained
Grain, is denoted as 11# catalyst.
Comparative example 2：Pt1Sn1/SiO2- 12# catalyst
70.766g ethyl orthosilicates are dissolved in 85.2mL absolute ethyl alcohols, and 51.2mL deionized waters are added dropwise while stirring, adjust molten
Glue pH value is to 5.0, and room temperature is transferred and set after water is added dropwise, in 70 DEG C of water-bath agings 24 hours, 200 DEG C after it becomes gel
After lower drying 5 hours, 500 DEG C of Muffle kiln roastings are placed it in 4 hours, obtain SiO2Carrier.Carrier is fully ground powder processed
After last shape, it is added dropwise contains SnCl thereto2The ethanol solution of 0.393g, then dry, roasting, obtains SnOx/SiO2Complex carrier.
By 4g SnOx/SiO2Complex carrier powder is added in ammonia spirit, and it is water-soluble to be added with stirring four ammonium of 4mL chlorinations conjunction platinum
Liquid (0.01gPt/mL) continuously stirs 24 hours, and ammonium hydroxide is added dropwise in due course to keep pH=10.0, then filters, washes away chlorion,
It is 5 hours dry at 200 DEG C.By catalyst powder tabletting, broken, sieving, 40~60 mesh particles are obtained, 12# catalyst is denoted as.
Comparative example 3：Pt1Sn1/SiO2- 13# catalyst
70.766g ethyl orthosilicates are dissolved in 85.2mL absolute ethyl alcohols, and 51.2mL deionized waters are added dropwise while stirring, adjust molten
Glue pH value is to 5.0, and room temperature is transferred and set after stirring 1 hour, after it becomes gel at 70 DEG C of water-bath agings 24 hours, 200 DEG C
After dry 5 hours, 500 DEG C of Muffle kiln roastings are placed it in 4 hours, obtain SiO2Carrier.Carrier is fully ground powder processed
After shape, it is added dropwise contains Sn (C thereto2O4)2The aqueous solution of nitric acid of 0.360g, then dry, roasting, obtains SnOx/SiO2Composite oxygen
Compound.
Pt is uploaded using equi-volume impregnating, to 4g SnOx/SiO2The water-soluble of 2mL platinum nitrates is added dropwise in complex carrier powder
Liquid (0.02gPt/mL) stands 2 hours after stirring evenly, 80 DEG C of backspins be evaporated it is dry, then be placed in 105 DEG C of baking ovens in re-dry 12
Hour, in 500 DEG C of Muffle kiln roastings 4 hours.By the tabletting of gained catalyst powder, broken, sieving, 40~60 mesh are obtained
Grain, is denoted as 13# catalyst.
One PtSn/SiO of table2The evaluation result of catalyst
aReduction temperature is 400 DEG C.
A kind of preparation for platinum tin SiO 2 catalyst for adding hydrogen to produce ethyl alcohol for acetic acid that the present invention is disclosed and proposed
Method, those skilled in the art can be by using for reference present disclosure, and the appropriate links such as condition route that change are realized, although the present invention
Method and technology of preparing are described by preferred embodiment, and related technical personnel can obviously not depart from the present invention
Hold, methods and techniques described herein route is modified or is reconfigured in spirit and scope, to realize final preparation
Technology.In particular, it should be pointed out that all similar replacements and change are apparent to those skilled in the art,
They are considered as being included in spirit of that invention, range and content.
Claims (7)
1. adding the preparation method of the platinum tin SiO 2 catalyst of hydrogen production ethyl alcohol for acetic acid；It is characterized in that steps are as follows：
(1) it is 0.3~1.7 in mass ratio by stanniferous salt and ethyl orthosilicate：100 ratio is dissolved in ethyl alcohol, stirs lower be added dropwise
Deionized water adjusts the pH to 3.0~5.0 of colloidal sol with ammonia spirit after it forms vitreosol, then quiet at room temperature
It sets；After colloidal sol forms gel, heat up aging, is washed out, dries, roasts, obtains SnOx-SiO2Composite oxides；
(2) SnO that will be obtainedx-SiO2Composite oxides be added pH=9.0~12.0 ammonia spirit in, then press Pt with
SnOx-SiO2The mass ratio of composite oxides is 0.5~3：The aqueous solution of platiniferous ammonia salt is added in 100 ratio, stirs 6-24h；
(3) it filters, it is dry after a large amount of deionized water washings, obtained solid is ground into powdery, molding obtains platinum tin titanium dioxide
Si catalyst；
The molar ratio of the Pt and Sn of the platinum tin SiO 2 catalyst are 0.6~1.2.
2. the method as described in claim 1, it is characterized in that the step (1) prepares SnOx-SiO2Used in composite oxides
Sn salt is the chloride and its hydrate of Sn.
3. the method as described in claim 1, it is characterized in that the temperature of the gel aging of the step (1) is 50-70 DEG C, always
The change time is 10-48h.
4. the method as described in claim 1, it is characterized in that the drying temperature of the gel of the step (1) is 95-120 DEG C,
Drying time is 5-10h.
5. the method as described in claim 1, it is characterized in that the SnO of the step (1)x-SiO2The roasting that composite oxides use
Burning atmosphere is air, nitrogen, argon gas or other inert gases；Calcination temperature is 400-600 DEG C, roasting time 2-10h.
6. the method as described in claim 1, it is characterized in that the platinum ammonia salt of the step (2) is Pt (NH3)4Cl2、Pt(NH3)4
(NO3)2Or Pt (NH3)4(OH)2And its their hydrate.
7. the method as described in claim 1, it is characterized in that the step (3) prepares the drying of platinum tin SiO 2 catalyst
Mode is dry under vacuum, air, nitrogen or other inert gas atmosphere, and drying temperature is 60-200 DEG C, drying time 5-
48h。
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