CN105854877A - Preparation method of platinum tin silicon dioxide catalyst for hydrogenation production of ethyl alcohol using acetic acid - Google Patents
Preparation method of platinum tin silicon dioxide catalyst for hydrogenation production of ethyl alcohol using acetic acid Download PDFInfo
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- CN105854877A CN105854877A CN201610266337.6A CN201610266337A CN105854877A CN 105854877 A CN105854877 A CN 105854877A CN 201610266337 A CN201610266337 A CN 201610266337A CN 105854877 A CN105854877 A CN 105854877A
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- acetic acid
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 138
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- 235000019441 ethanol Nutrition 0.000 title abstract 7
- -1 platinum tin silicon dioxide Chemical compound 0.000 title abstract 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-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 43
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 43
- 238000003756 stirring Methods 0.000 claims abstract description 43
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 43
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 60
- 229910021529 ammonia Inorganic materials 0.000 claims description 26
- 230000032683 aging Effects 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052756 noble gas Inorganic materials 0.000 claims description 4
- XKUTVNLXHINPAP-UHFFFAOYSA-N azane platinum Chemical compound N.[Pt] XKUTVNLXHINPAP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000003570 air Substances 0.000 claims 1
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- 150000002835 noble gases Chemical class 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 36
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 229910052718 tin Inorganic materials 0.000 abstract description 10
- 229910002847 PtSn Inorganic materials 0.000 abstract description 9
- 230000003993 interaction Effects 0.000 abstract description 4
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 229960004756 ethanol Drugs 0.000 description 42
- 229910006854 SnOx Inorganic materials 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 22
- 239000000446 fuel Substances 0.000 description 14
- 239000008187 granular material Substances 0.000 description 14
- 229960000935 dehydrated alcohol Drugs 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000005660 chlorination reaction Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 238000001802 infusion Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 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
- 239000003921 oil Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 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
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 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
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- ZLRANBHTTCVNCE-UHFFFAOYSA-N 2-phenyl-3-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CN=C1C1=CC=CC=C1 ZLRANBHTTCVNCE-UHFFFAOYSA-N 0.000 description 1
- 235000011437 Amygdalus communis Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- 241000220304 Prunus dulcis Species 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 235000020224 almond Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- QPXZALHPZYRQIT-UHFFFAOYSA-N ethanol;methoxymethane Chemical compound CCO.COC QPXZALHPZYRQIT-UHFFFAOYSA-N 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000012262 fermentative production 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 239000011219 quaternary composite Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 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
- 239000007790 solid phase Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 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
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 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—
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a platinum tin silicon dioxide catalyst for hydrogenation production of ethyl alcohol using acetic acid. The preparation method comprises the following steps: dissolving tin-containing salt and ethyl orthosilicate in ethyl alcohol and dropwise adding deionized water while stirring, thereby acquiring a SnOx-SiO2 compound oxide; adding an ammonia solution, and then adding a platinammine-containing aqueous solution; grinding the acquired solid into powder and forming, thereby acquiring the platinum tin silicon dioxide catalyst for the hydrogenation production of ethyl alcohol using acetic acid. According to the invention, a sol-gel method and an ion exchange method are combined for modifying the loading mode of Pt and Sn, the dispersity of Pt and Sn and the interaction degree of Pt and Sn are promoted, the PtSn catalyst with excellent performance is acquired and the efficiency of hydrogenation production of ethyl alcohol using acetic acid is increased. Compared with the catalyst used in the existing technique of hydrogenation production of ethyl alcohol using acetic acid, the catalyst provided by the invention can realize high conversion of acetic acid under a mild reaction condition; the conversion rate of acetic acid can reach 99% or more; the selectivity of ethyl alcohol can reach 95%.
Description
Technical field
The invention belongs to chemical technology field, relate to hydrogenation catalyst, be a kind of height for acetic acid direct hydrogenation ethanol
Effect catalyst.
Background technology
Alcohol fuel is the traditional product appeared on the market 20 beginnings of the century, after be eliminated because of extensive, the low cost development of oil.
Since 20 century 70 mid-terms four times bigger " oil crisis ", promote fuel ethanol industry in world many countries
Developed rapidly.Alcohol fuel, as new cleaning fuel, has become as the emphasis of world today's Renewable Energy Development,
Along with various countries strengthen the dynamics of ethanol petrol application, the yield of world fuel ethanol rises year by year.Alcohol fuel is as gasoline
Additive, can be effectively improved octane number and the explosion-proof performance of gasoline.Ethanol has obvious ring as one cleaning fuel
Border benefit, the oxygen content of ethanol is high, adds in gasoline as oxygenation agent, gasoline can be helped to burn completely, reduces car tail
Carbon monoxide and the discharge of Hydrocarbon in gas, thus improve the quality of vehicle exhaust, to alleviate the pollution to air.
Improving constantly energy resource consumption demand along with domestic, the domestic potential demand to alcohol fuel also will be substantially increased, fuel
Ethanol will have more wide prospect in the development of China.In China, Fuel Alcohol Development industry meets National Security Strategy
With the developing direction of regenerative resource, technically maturation, safe and reliable, has preferable economic benefit and social benefit.
The production of world wide 95% alcohol fuel at present is by fermentation, separation, degeneration with Caulis Sacchari sinensis, grain etc. for raw material
Obtain etc. process.The method is many due to by-product, and cost of material is high, and threatens the problems such as grain security and be subject to
Restriction.And its yield of the alcohol fuel of China's fermentative Production cannot meet the consumption demand that alcohol fuel is huge, in conjunction with me
The energy resource structure present situation of state's " gas, coal relative abundance oil-poor, few ", exploitation is with synthesis gas for raw material production alcohol fuel
Variation route, part replaces the technique with grain as raw material, both can protect the grain security of China, can reduce again import stone
Oil Resource Dependence, strengthens Chinese energy safety.At present in synthesis legal system ethanol, synthesis gas is directly synthesized the research of ethanol
For extensive, especially rhodium base supported catalyst shows preferable catalytic performance, and synthesis gas is through dimethyl ether ethanol
Route have also been obtained further investigation and extensively application.Additionally, domestic acetic acid production capacity is seriously superfluous and ethanol demand soars all the way,
Acetic acid hydrogenation ethanol is promoted to have feasibility economically, therefore with synthesis gas for raw material through acetic acid hydrogenation ethanol technology
It is developed into new study hotspot.
Acetic acid is a kind of important industrial chemicals.The current average utilization of capacity of domestic acetic acid plant less than 60%, acetic acid production capacity phase
To surplus, causing acetic acid price continuous decrease, the production of acetic acid performance of enterprises is low, therefore needs urgently to develop acetic acid downstream and produces
Product, extend the industrial chain of acetic acid industry.And by acetic acid preparation of ethanol by hydrogenating, be solve acetic acid production capacity surplus good approach it
One.
Acetic acid hydrogenation ethanol mainly has two kinds of approach: one is that acetic acid direct hydrogenation produces ethanol；Another kind is first by second
Esterification, then use Supported Cu catalyst to be hydrogenated with under relatively mild conditions to obtain ethanol.Although acetic acid is through esterification
The selectivity of path ethanol generally relatively directed hydrogenation is high, but its process route length, equipment equipment investment are big.And it is direct
Hydrogenation method process route is simple, energy consumption is low, although having higher requirements the corrosion resistance of equipment, but it has carbon resource
The advantages such as utilization rate height, green high-efficient, therefore have good application prospect.
The acetic acid hydrogenation catalyst of report the most both at home and abroad, mainly Pt, Pd, Ru even load type noble metal catalyst,
Reaction condition is the harshest, and there is the problems such as catalyst activity is low, ethanol selectivity is poor.United States Patent (USP) 29995 is introduced
Acetic acid catalysis oxygenation ethanol new technology, this technique can be carried out under gas phase or liquid-phase condition, catalyst is solid phase, preferentially
Selection gas phase is reacted.Catalyst uses infusion process to prepare, and wherein active metal is Pt and Sn, and the mass ratio of Pt/Sn is
0.5-1.5, also can add the third active metal, and such as Pd, Ru etc., carrier may select silicon dioxide, activated carbon etc..
Reaction temperature in the range of 225-275 DEG C, acetic acid, H2Mol ratio is 0.5-20, and reaction pressure is 1-2.5MPa.Raw material
The conversion ratio of acetic acid is up to about 90%, and the selectivity of ethanol is up to 90%-95%.The United States Patent (USP) of BASF AG
US4517391 discloses a kind of quaternary composite oxides CoO-CuO-Mn3O4-MoO3For acetic acid hydrogenation ethanol,
250 DEG C, air speed 0.126h-1, 300bar Hydrogen Vapor Pressure under, ethanol yield is up to 97%.CN86102420A uses
Infusion process prepares 2.5%Pd-5.l%Mo/ graphite catalyst, at 249 DEG C, Hydrogen Vapor Pressure 10.3bar, LHSV=0.35h-1's
Under the conditions of, acetic acid conversion is 58%, and in product, the overall selectivity of ethanol and ester is 82.7%.
Chinese patent CN102229520A uses infusion process to be prepared for 10%W-5%Re-2%Ru/ almond Pd/carbon catalyst,
250 DEG C, 10MPa, air speed 1h-1Under conditions of react 50h, acetic acid conversion be more than 99%, ethanol selectivity is 98.1%.
Chinese patent CN102311311A, CN102149661A and CN102304018A describe and Pt and Sn are passed through total immersion
The method of stain is supported on SiO2、CaSiO3, graphite, SiO2-A12O3On composite oxide carrier, 250 DEG C, 22bar,
GHSV is 2500h-1Under conditions of, acetic acid conversion 70～85%, ethanol selectivity is more than 93%.Chinese patent
It is the first metal that CN102149662A discloses with 10%Co, the Pd of 1%, Pt, Cr, Mo, Sn, W, Zn, Ir,
Re, Cu, Ru, Rh one therein is second component auxiliary agent, and carrier is SiO2、CaSiO3、A12O3、TiO2、ZrO2、
One in carbon, in the range of 225-275 DEG C, acetic acid conversion is 18～70%, and ethanol selectivity is more than 90%.
Result disclosed above shows, PtSn catalyst shows preferable catalytic performance in acetic acid is hydrogenated with, therefore before application
Scape is wide.But prepared by current PtSn catalyst many employings infusion process, the active component dispersion of gained catalyst is relatively low,
Interaction between active component and carrier is more weak, causes that catalyst activity and selectivity is relatively low, less stable and anti-
Answer condition the harshest.The present invention combines sol-gal process and ion exchange, utilizes sol-gal process to realize Sn at oxygen
SiClx is uniformly distributed, utilizes ion exchange to improve Pt at SnOx-SiO2Dispersion on complex carrier, and thus add
The strong degree that contacts with each other therebetween, thus solve the problems referred to above targetedly.
Summary of the invention
It is an object of the invention to provide and a kind of stable can realize acetic acid Efficient Conversion at gentle reaction condition and generate ethanol
It is easily achieved the catalyst for acetic acid preparation of ethanol by hydrogenating of industrialized production simultaneously.
The preparation method of the platinum stannum SiO 2 catalyst for acetic acid preparation of ethanol through hydrogenation that the present invention proposes, concrete steps
As follows:
(1) ratio that stanniferous salt and tetraethyl orthosilicate are 0.3～1.7:100 in mass ratio is dissolved in ethanol, under stirring
Dropping deionized water, after it forms vitreosol, with the pH to 3.0～5.0 of ammonia spirit regulation colloidal sol, then in room
Temperature is lower to be stood；Formed after gel until colloidal sol, heat up aging, be washed out, be dried, roasting, obtain SnOx-SiO2Multiple
Close oxide；
(2) SnO that will obtainx-SiO2Composite oxides add pH=9.0～12.0 ammonia spirit in, then press Pt and
SnOx-SiO2The mass ratio of composite oxides is the aqueous solution of the ratio addition platiniferous ammonia salt of 0.5～3:100, stirs 6-24h；
(3) filtering, be dried after a large amount of deionized water wash, by gained solid abrasive powdering, molding i.e. obtains platinum stannum
SiO 2 catalyst.
In the present invention, the mol ratio of Pt Yu Sn of platinum stannum SiO 2 catalyst is 0.6～1.2.
Preparation SnO in the present invention, mentioned by step (1)x-SiO2The chlorination that Sn salt is Sn used by composite oxides
Thing and hydrate thereof.
In the present invention, the temperature that gel mentioned by step (1) is aging is 50-70 DEG C, and ageing time is 10-48h.
In the present invention, the baking temperature of the gel mentioned by step (1) is 95-120 DEG C, and drying time is 5-10h.
SnO in the present invention, mentioned by step (1)x-SiO2Composite oxides use calcination atmosphere can be air and
Nitrogen, the noble gas such as argon, sintering temperature is 400-600 DEG C, and roasting time is 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 hydrate.
In the present invention, the drying mode preparing platinum stannum SiO 2 catalyst mentioned by step (3) be vacuum, air,
Being dried under nitrogen or other noble gas atmosphere, baking temperature is 60-200 DEG C, and drying time is 5-48h.
The PtSn catalyst utilizing the present invention to design synthesis is a kind of novel PtSn catalyst.Prepare with traditional method
PtSn catalyst is compared, and its novelty shows that microstructure has higher Pt, Sn dispersion and the two is more close
Interact.Therefore, it is applied to the reaction of acetic acid preparation of ethanol by hydrogenating, under gentle reaction condition, shows the highest
Activity and selectivity, acetic acid conversion ratio can reach more than 99%, and ethanol selectivity is up to 95%.Catalyst stability
Good, after reaction 320h, catalyst activity is held essentially constant with ethanol selectivity.The PtSn of the designed synthesis of the present invention
Catalyst is the acetic acid hydrogenation catalyst of a kind of excellent performance, is suitable for industrialization, contributes to solving acetic acid production capacity surplus
Problem.
Accompanying drawing explanation
Fig. 1 illustrates activity and ethanol, ethyl acetate, the selectivity of acetaldehyde of PtSn catalyst in the present invention.
Fig. 2 illustrates active component Pt of catalyst in the present invention, Sn in the dispersibility of catalyst surface, granule average particle
Footpath is about 1.4nm.
Fig. 3 illustrates the TPR figure of catalyst in the present invention, uses catalyst prepared by the present invention, and its reduction temperature is more normal
The reduction temperature of catalyst prepared by rule infusion process is high, shows have between catalyst activity component Pt in the present invention, Sn
There is stronger interaction.
Detailed description of the invention
Below by embodiment and comparative example, the present invention is further elaborated, but the present invention is not made any limit by them
System.
Embodiment 1:Pt1Sn1/SiO2-1# catalyst
0.393g SnCl2It is dissolved in 50.2mL dehydrated alcohol, adds 70.766g tetraethyl orthosilicate, drip 50.1mL while stirring
Deionized water, regulation sol pH to 3.0, treat that water droplet stands after adding at room temperature, after it becomes gel in
70 DEG C aging 10 hours, washing, removes chloride ion, and in baking oven, 110 DEG C were dried after 8 hours, were placed on 500 DEG C
Muffle kiln roasting 5 hours, obtains SnOx/SiO2Complex carrier, is fully ground carrier, obtains pulverulent solids.
By 4g SnOx/SiO2In the ammonia spirit that complex carrier powder adds, stirring is lower adds 4mL chlorination four ammonium conjunction platinum water
Solution (0.01gPt/mL), continues stirring 10 hours, and dropping ammonia is to keep pH=11.0 in good time, then filters, washes
Remove chloride ion, be dried 5 hours at 200 DEG C.By catalyst powder tabletting, crush, sieve, obtain 40～60 mesh granules,
It is designated as 1# catalyst.
Embodiment 2:Pt0.5Sn0.5/SiO2-2# catalyst
0.212g SnCl2It is dissolved in 30.8mL dehydrated alcohol, adds 70.766g tetraethyl orthosilicate, drip 30.2mL while stirring
Deionized water, regulation sol pH to 4.2, treat that water droplet stands after adding at room temperature, after it becomes gel in
70 DEG C aging 10 hours, washing, removes chloride ion, and in baking oven, 95 DEG C were dried after 10 hours, were placed on 600 DEG C
Muffle kiln roasting 2 hours, obtains SnOx/SiO2Complex carrier, is fully ground carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder adds in ammonia spirit, and it is water-soluble that stirring lower addition 2mL chlorination four ammonium closes platinum
Liquid (0.01gPt/mL), continues stirring 24 hours, and dropping ammonia is to keep pH=9.0 in good time, then filters, washes away chlorine
Ion, is dried 10 hours at 110 DEG C.By catalyst powder tabletting, crush, sieve, obtain 40～60 mesh granules, note
For 2# catalyst.
Embodiment 3:Pt2Sn1/SiO2-3# catalyst
0.393g SnCl2It is dissolved in 75.2mL dehydrated alcohol, adds 70.766g tetraethyl orthosilicate, drip 61.2mL while stirring
Deionized water, regulation sol pH to 5.0, treat that water droplet stands after adding at room temperature, after it becomes gel in
Aging 48 hours of 50 DEG C of water-baths, washing, remove chloride ion, after baking oven is dried 5 hours at 120 DEG C, be placed on
400 DEG C of Muffle kiln roastings 10 hours, obtain SnOx/SiO2Complex carrier, is fully ground carrier, obtains powder solid
Body.
By 4g SnOx/SiO2Complex carrier powder adds in ammonia spirit, and it is water-soluble that stirring lower addition 8mL chlorination four ammonium closes platinum
Liquid (0.01gPt/mL), continuous stirring 6 hours, dropping ammonia is to keep pH=12.0 in good time, then filters, washes away chlorine
Ion, is dried 48 hours at 60 DEG C.By catalyst powder tabletting, crush, sieve, obtain 40～60 mesh granules, note
For 3# catalyst.
Embodiment 4:Pt1Sn1/SiO2-4# catalyst
0.393g SnCl4It is dissolved in 50.2mL dehydrated alcohol, adds 70.766g tetraethyl orthosilicate, drip 40.5mL while stirring
Deionized water, regulation sol pH to 5.0, treat that water droplet is placed after adding at room temperature, after it becomes gel in
Aging 24 hours of 60 DEG C of water-baths, washing, remove chloride ion, after being dried 5 hours at 105 DEG C, be placed on 500 DEG C of horses
Not kiln roasting 4 hours, obtain SnOx/SiO2Complex carrier, is fully ground carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder adds in ammonia spirit, and stirring is lower adds 4mL chlorination four ammonium conjunction platinum water
Solution (0.01gPt/mL), continuous stirring 10 hours, dropping ammonia is to keep pH=10.6 in good time, then filters, washes
Remove chloride ion, be dried 5 hours at 200 DEG C.By catalyst powder tabletting, crush, sieve, obtain 40～60 mesh granules,
Carry out activity rating, be designated as 4# catalyst.
Embodiment 5:Pt1.5Sn1/SiO2-5# catalyst
0.787g SnCl4·5H2O is dissolved in 75.2mL dehydrated alcohol, adds 70.766g tetraethyl orthosilicate, drips while stirring
61.2mL deionized water, regulation sol pH, to 4.0, is treated water droplet to add under complete rear chamber temperature and is placed, treat that it becomes gel
After in aging 10 hours of 70 DEG C of water-baths, ethanol washes away chloride ion, is dried after 5 hours, is placed on 600 DEG C at 105 DEG C
In tube furnace, roasting 4 hours under nitrogen atmosphere, obtain SnOx/SiO2Complex carrier, is fully ground carrier, obtains powder
Shape solid.
By 4g SnOx/SiO2Complex carrier powder adds in ammonia spirit, and stirring is lower adds 6mL tetraethanolammonium hydroxide conjunction platinum water
Solution (0.01gPt/ml), continuous stirring 6 hours, dropping ammonia is to keep pH=12.0 in good time, then filters, washes away
Chloride ion, is dried 10 hours in baking oven at 105 DEG C.By catalyst powder tabletting, crush, sieve, obtain 40～60 mesh
Granule, is designated as 5# catalyst.
Embodiment 6:Pt3Sn3/SiO2-6# catalyst
1.203g SnCl2·2H2O is dissolved in 75.2mL dehydrated alcohol, adds 70.766g tetraethyl orthosilicate, drips while stirring
40.9mL deionized water, regulation sol pH, to 3.0, is treated water droplet to add under complete rear chamber temperature and is placed, treat that it becomes gel
After in aging 24 hours of 70 DEG C of water-baths, ethanol washes away chloride ion, is dried after 10 hours, is placed on 400 DEG C at 95 DEG C
Under tube furnace argon gas atmosphere, roasting 10 hours, obtain SnOx/SiO2Complex carrier, is fully ground carrier, obtains powder
Solid.
By 4g SnOx/SiO2Complex carrier powder adds in ammonia spirit, and stirring is lower adds 4mL chlorination four ammonium conjunction platinum water
Solution (0.03g Pt/mL), continuous stirring 6 hours, dropping ammonia is to keep pH=12.0 in good time, then filters, washes
Remove chloride ion, be dried 5 hours at 200 DEG C.By catalyst powder tabletting, crush, sieve, obtain 40～60 mesh granules,
It is designated as 6# catalyst.
Embodiment 7:Pt1Sn1/SiO2-7# catalyst
0.393g SnCl2It is dissolved in 60.6mL dehydrated alcohol, adds 70.766g tetraethyl orthosilicate, drip 60.6mL while stirring
Deionized water, regulation sol pH, to 5.0, is treated water droplet to add under complete rear chamber temperature and is placed, in 70 DEG C after it becomes gel
Aging 10 hours of water-bath, washing, remove chloride ion, after being dried 5 hours at 105 DEG C, be placed on 400 DEG C of Muffles
Kiln roasting 10 hours, obtains SnOx/SiO2Complex carrier, is fully ground carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder adds in ammonia spirit, and it is water-soluble that stirring lower addition 4mL hydrogen-oxygen four ammonium closes platinum
Liquid (0.01gPt/mL), continues stirring 6 hours, and dropping ammonia is to keep pH=12.0 in good time, then filters, washes away chlorine
Ion, is vacuum dried 5 hours at 120 DEG C.By catalyst powder tabletting, crush, sieve, obtain 40～60 mesh granules,
It is designated as 7# catalyst.
Embodiment 8:Pt1Sn1/SiO2-8# catalyst
0.393g SnCl2It is dissolved in 105.2mL dehydrated alcohol, adds 70.766g tetraethyl orthosilicate, drip 70.2mL while stirring
Deionized water, regulation sol pH, to 3.0, is treated water droplet to add under complete rear chamber temperature and is placed, in 70 DEG C after it becomes gel
Aging 48 hours of water-bath, ethanol washes away chloride ion, after being dried 5 hours, is placed in 600 DEG C of Muffle furnaces at 120 DEG C
Roasting 4 hours, obtains SnOx/SiO2Complex carrier, is fully ground carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder adds in ammonia spirit, and it is water-soluble that stirring lower addition 4mL chlorination four ammonium closes platinum
Liquid (0.01gPt/mL), continuous stirring 12 hours, dropping ammonia is to keep pH=10.0 in good time, then filters, washes away
Chloride ion, is dried 8 hours under 150 DEG C of pipe type stove nitrogen atmospheres.By catalyst powder tabletting, crush, sieve,
To 40～60 mesh granules, it is designated as 8# catalyst.
Embodiment 9:Pt1Sn1/SiO2-9# catalyst
0.393g SnCl2It is dissolved in 85.2mL dehydrated alcohol, adds 70.766g tetraethyl orthosilicate, drip 51.2mL while stirring
Deionized water, regulation sol pH, to 5.0, is treated water droplet to add under complete rear chamber temperature and is placed, in 50 DEG C after it becomes gel
Aging 48 hours of water-bath, washing, remove chloride ion, after being dried 10 hours at 95 DEG C, be placed on 500 DEG C of Muffle furnaces
Middle roasting 4 hours, obtains SnOx/SiO2Complex carrier, is fully ground carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder adds in ammonia spirit, and it is water-soluble that stirring lower addition 4mL chlorination four ammonium closes platinum
Liquid (0.01gPt/mL), continuous stirring 6 hours, dropping ammonia is to keep pH=12.0 in good time, then filters, washes away chlorine
Ion, is dried 10 hours under argon gas atmosphere in 105 DEG C of pipe type stoves.By catalyst powder tabletting, crush, sieve,
To 40～60 mesh granules, it is designated as 9# catalyst.
Embodiment 10:Pt1Sn1/SiO2-10# catalyst
0.393g SnCl2It is dissolved in 80.2mL dehydrated alcohol, adds 70.766g tetraethyl orthosilicate, drip 71.2mL while stirring
Deionized water, regulation sol pH, to 3.0, is treated water droplet to add under complete rear chamber temperature and is placed, in 70 DEG C after it becomes gel
Aging 10 hours of water-bath, washing, remove chloride ion, after being dried 5 hours at 120 DEG C, be placed on 600 DEG C of Muffle furnaces
Middle roasting 2 hours, obtains SnOx/SiO2Complex carrier, is fully ground carrier, obtains pulverulent solids.
By 4g SnOx/SiO2Complex carrier powder adds in ammonia spirit, adds 4mL nitric acid four ammonium and close platinum water after stirring is lower
Solution (0.01gPt/mL), continuous stirring 24 hours, dropping ammonia is to keep pH=10.0 in good time, then filters, washes
Remove chloride ion, be dried 5 hours at 200 DEG C.By catalyst powder tabletting, crush, sieve, obtain 40～60 mesh granules,
It is designated as 10# catalyst.
Embodiment 11:
Evaluate platinum stannum silicon dioxide catalytic performance in acetic acid preparation of ethanol by hydrogenating reacts with fixed bed reactors, wherein, urge
The loadings of agent is 2mL.First use pure H2Temperature programmed reduction is carried out under reaction pressure, little in 300 DEG C of reduction 4
It is down to reaction temperature time after, is then pumped into acetic acid and starts reaction.With the reacted liquid of chromatographic, calculate vinegar
The conversion ratio of acid and the selectivity of ethanol.As shown in Table 1, wherein reaction temperature is 260 DEG C to catalyst activity evaluation result,
Reaction pressure is 2.6MPa, and hydracid mol ratio is 20.
Embodiment 12:
Investigate the reduction temperature impact on the catalytic performance of catalyst prepared by embodiment 1.Reducing condition is under reaction pressure
400 DEG C are reduced 4 hours, the catalyst performance evaluation condition in actual conditions such as embodiment 11, and catalyst activity evaluation is tied
Fruit is as shown in Table 1.
Embodiment 13:
Investigate the catalyst life of embodiment 1 preparation, the catalyst performance evaluation condition in actual conditions such as embodiment 11.
As it is shown in figure 1, through reaction in 300 hours, the conversion ratio of acetic acid and selectivity were still maintained at reaction level just, show
Catalyst has good stability.
Embodiment 14:
TEM is used to characterize the granular size of active component in the catalyst of embodiment 1 preparation.As in figure 2 it is shown, live
The mean diameter of property component particles is 1.4nm, shows that active component has good dispersibility at catalyst surface.
Embodiment 15:
Temperature programmed reduction (TPR) is used to investigate Pt, Sn component in the catalyst of embodiment 1, embodiment 3 preparation
Interact, and contrast with the catalyst of comparative example 1 preparation.As it is shown on figure 3, embodiment 1, embodiment
Catalyst reduction temperature prepared by 3 is high compared with the catalyst reduction temperature prepared by comparative example 1, and the above two are described
Pt, Sn component has stronger interaction.
Comparative example 1:Pt1Sn1/SiO2-11# catalyst
0.393g SnCl2It is dissolved in 85.2mL dehydrated alcohol, adds 70.766g tetraethyl orthosilicate, drip 51.2mL while stirring
Deionized water, regulation sol pH, to 5.0, is treated water droplet to add under complete rear chamber temperature and is placed, in 70 DEG C after it becomes gel
Aging 10 hours of water-bath, washing, remove chloride ion, after being dried 5 hours at 200 DEG C, be placed on 500 DEG C of Muffle furnaces
Middle roasting 4 hours, obtains SnOx/SiO2Complex carrier, is fully ground powder process powder by carrier.
Equi-volume impregnating is used to upload Pt, to 4g SnOx/SiO2Complex carrier powder drips 2mL platinum nitrate aqueous solution
(0.02g Pt/mL), stands 2 hours after stirring, and 80 DEG C of backspins are evaporated dry, then inserts in 105 DEG C of baking ovens again
It is dried 12 hours, in 500 DEG C of Muffle kiln roastings 4 hours.By gained catalyst powder tabletting, crush, sieve,
Obtain 40～60 mesh granules, be designated as 11# catalyst.
Comparative example 2:Pt1Sn1/SiO2-12# catalyst
70.766g tetraethyl orthosilicate is dissolved in 85.2mL dehydrated alcohol, while stirring dropping 51.2mL deionized water, regulation
Sol pH, to 5.0, is treated water droplet to add under complete rear chamber temperature and is placed, aging 24 little in 70 DEG C of water-baths after it becomes gel
Time, after being dried 5 hours at 200 DEG C, it is placed on 500 DEG C of Muffle kiln roastings 4 hours, obtains SiO2Carrier.Will
After carrier is fully ground powder process powder, dropping is containing SnCl wherein2The ethanol solution of 0.393g, then dry, roasting,
Obtain SnOx/SiO2Complex carrier.
By 4g SnOx/SiO2Complex carrier powder adds in ammonia spirit, and stirring is lower adds 4mL chlorination four ammonium conjunction platinum water
Solution (0.01gPt/mL), continuous stirring 24 hours, dropping ammonia is to keep pH=10.0 in good time, then filters, washes
Remove chloride ion, be dried 5 hours at 200 DEG C.By catalyst powder tabletting, crush, sieve, obtain 40～60 mesh granules,
It is designated as 12# catalyst.
Comparative example 3:Pt1Sn1/SiO2-13# catalyst
70.766g tetraethyl orthosilicate is dissolved in 85.2mL dehydrated alcohol, while stirring dropping 51.2mL deionized water, regulation
Sol pH is to 5.0, and after stirring 1 hour, ambient temperatare is put, in aging 24 hours of 70 DEG C of water-baths after it becomes gel,
After being dried 5 hours at 200 DEG C, it is placed on 500 DEG C of Muffle kiln roastings 4 hours, obtains SiO2Carrier.By carrier
After being fully ground powder process powder, dropping is containing Sn (C wherein2O4)2The aqueous solution of nitric acid of 0.360g, is then dried, roasts
Burn, obtain SnOx/SiO2Composite oxides.
Equi-volume impregnating is used to upload Pt, to 4g SnOx/SiO2Complex carrier powder drips the water-soluble of 2mL platinum nitrate
Liquid (0.02gPt/mL), stands 2 hours after stirring, and 80 DEG C of backspins are evaporated dry, then inserts in 105 DEG C of baking ovens again
It is dried 12 hours, in 500 DEG C of Muffle kiln roastings 4 hours.By gained catalyst powder tabletting, crush, sieve,
Obtain 40～60 mesh granules, be designated as 13# catalyst.
Table one PtSn/SiO2The evaluation result of catalyst
aReduction temperature is 400 DEG C.
Present invention disclosure and a kind of preparation side being hydrogenated with the platinum stannum SiO 2 catalyst producing ethanol for acetic acid proposed
Method, those skilled in the art can suitably change the links such as condition route realize by using for reference present disclosure, although the present invention
Method and technology of preparing be described by preferred embodiment, person skilled substantially can be without departing from this
In bright content, spirit and scope, methods and techniques described herein route is modified or reconfigures, realize final
Technology of preparing.Special needs to be pointed out is, all similar replacements and change are aobvious for a person skilled in the art
And be clear to, they are considered as being included in present invention spirit, scope and content.
Claims (8)
1. the preparation method of the platinum stannum SiO 2 catalyst of ethanol is produced for acetic acid hydrogenation；It is characterized in that step is as follows:
(1) ratio that stanniferous salt and tetraethyl orthosilicate are 0.3～1.7:100 in mass ratio being dissolved in ethanol, the lower dropping of stirring is gone
Ionized water, after it forms vitreosol, with the pH to 3.0～5.0 of ammonia spirit regulation colloidal sol, stands the most at room temperature；
Formed after gel until colloidal sol, heat up aging, be washed out, be dried, roasting, obtain SnOx-SiO2Composite oxides；
(2) SnO that will obtainx-SiO2Composite oxides add pH=9.0～12.0 ammonia spirit in, then press Pt and
SnOx-SiO2The mass ratio of composite oxides is the aqueous solution of the ratio addition platiniferous ammonia salt of 0.5～3:100, stirs 6-24h；
(3) filtering, be dried after a large amount of deionized water wash, by gained solid abrasive powdering, molding i.e. obtains platinum stannum titanium dioxide
Si catalyst.
2. the method for claim 1, is characterized in that described step (1) prepares SnOx-SiO2Sn used by composite oxides
Salt is chloride and the hydrate thereof of Sn.
3. the method for claim 1, is characterized in that the temperature that the gel of described step (1) is aging is 50-70 DEG C, aging
Time is 10-48h.
4. the method for claim 1, is characterized in that the baking temperature of the gel of described step (1) is 95-120 DEG C, dry
The dry time is 5-10h.
5. the method for claim 1, is characterized in that the SnO of described step (1)x-SiO2The roasting that composite oxides use
Atmosphere is air, nitrogen, argon or other noble gases；Sintering temperature is 400-600 DEG C, and roasting time is 2-10h.
6. the method for claim 1, is characterized in that the platinum ammonia salt of described step (2) is Pt (NH3)4Cl2、Pt(NH3)4(NO3)2
Or Pt (NH3)4(OH)2And their hydrate.
7. the method for claim 1, is characterized in that described step (3) prepares the dry side of platinum stannum SiO 2 catalyst
Formula is to be dried under vacuum, air, nitrogen or other noble gas atmosphere, and baking temperature is 60-200 DEG C, and drying time is 5-48h.
8. the method for claim 1, is characterized in that the mol ratio of Pt with Sn of described platinum stannum SiO 2 catalyst is
0.6～1.2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108404961A (en) * | 2018-03-27 | 2018-08-17 | 天津大学 | The nitrogenous hollow silica ball load platinum-tin catalyst of acetic acid preparation of ethanol by hydrogenating and preparation |
| CN114059097A (en) * | 2021-11-22 | 2022-02-18 | 吉林大学 | Preparation method of nitrogen reduction synthetic ammonia catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8501652B2 (en) * | 2008-07-31 | 2013-08-06 | Celanese International Corporation | Catalysts for making ethanol from acetic acid |
| CN103433039A (en) * | 2013-09-11 | 2013-12-11 | 神华集团有限责任公司 | Preparation method of acetic ester hydrogenation catalyst |
| CN103691450A (en) * | 2014-01-06 | 2014-04-02 | 神华集团有限责任公司 | Catalyst for preparing ethanol through acetic acid hydrogenation and preparation method thereof |
| CN103787827A (en) * | 2012-10-31 | 2014-05-14 | 中国石油化工股份有限公司 | Method for preparing alcohol by carboxylic acid selective hydrogenation |
| CN104275194A (en) * | 2014-10-10 | 2015-01-14 | 上海华谊（集团）公司 | Catalyst used in preparation of alcohol from acetic acid by hydrogenation and preparation method of catalyst |
-
2016
- 2016-04-25 CN CN201610266337.6A patent/CN105854877B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8501652B2 (en) * | 2008-07-31 | 2013-08-06 | Celanese International Corporation | Catalysts for making ethanol from acetic acid |
| CN103787827A (en) * | 2012-10-31 | 2014-05-14 | 中国石油化工股份有限公司 | Method for preparing alcohol by carboxylic acid selective hydrogenation |
| CN103433039A (en) * | 2013-09-11 | 2013-12-11 | 神华集团有限责任公司 | Preparation method of acetic ester hydrogenation catalyst |
| CN103691450A (en) * | 2014-01-06 | 2014-04-02 | 神华集团有限责任公司 | Catalyst for preparing ethanol through acetic acid hydrogenation and preparation method thereof |
| CN104275194A (en) * | 2014-10-10 | 2015-01-14 | 上海华谊（集团）公司 | Catalyst used in preparation of alcohol from acetic acid by hydrogenation and preparation method of catalyst |
Non-Patent Citations (1)
| Title |
|---|
| F. ORELLANA ET AL.: "SELECTIVE HYDRODECHLORINATION OF 1,2-DICHLOROETHANE OVER Pd-Sn/SiO2 CATALYSTS", 《J. CHIL. CHEM. SOC.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108404961A (en) * | 2018-03-27 | 2018-08-17 | 天津大学 | The nitrogenous hollow silica ball load platinum-tin catalyst of acetic acid preparation of ethanol by hydrogenating and preparation |
| CN108404961B (en) * | 2018-03-27 | 2019-11-19 | 天津大学 | The nitrogenous hollow silica ball load platinum-tin catalyst of acetic acid preparation of ethanol by hydrogenating and preparation |
| CN114059097A (en) * | 2021-11-22 | 2022-02-18 | 吉林大学 | Preparation method of nitrogen reduction synthetic ammonia catalyst |
| CN114059097B (en) * | 2021-11-22 | 2023-09-15 | 吉林大学 | Preparation method of nitrogen reduction synthetic ammonia catalyst |
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