CN107185532A - A kind of macroporous titanium dioxide assemble nanometer metallic catalyst, prepare and for ethanol phase catalytic reaction - Google Patents
A kind of macroporous titanium dioxide assemble nanometer metallic catalyst, prepare and for ethanol phase catalytic reaction Download PDFInfo
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- CN107185532A CN107185532A CN201710329214.7A CN201710329214A CN107185532A CN 107185532 A CN107185532 A CN 107185532A CN 201710329214 A CN201710329214 A CN 201710329214A CN 107185532 A CN107185532 A CN 107185532A
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- titanium dioxide
- liquid
- macroporous titanium
- macroporous
- ethanol
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 195
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 96
- 238000006555 catalytic reaction Methods 0.000 title abstract description 14
- 239000003863 metallic catalyst Substances 0.000 title abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 28
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 28
- 229910052709 silver Inorganic materials 0.000 claims abstract description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 229910052737 gold Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract 3
- 239000007788 liquid Substances 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 56
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 32
- 239000010931 gold Substances 0.000 claims description 23
- 230000001588 bifunctional effect Effects 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims description 9
- 238000005886 esterification reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 239000006193 liquid solution Substances 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910001961 silver nitrate Inorganic materials 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 150000001241 acetals Chemical class 0.000 description 30
- 239000003643 water by type Substances 0.000 description 15
- 239000000969 carrier Substances 0.000 description 12
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229920000151 polyglycol Polymers 0.000 description 6
- 239000010695 polyglycol Substances 0.000 description 6
- 229910002710 Au-Pd Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000010944 silver (metal) Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- -1 acetaldehyde, acetal Chemical class 0.000 description 3
- TYGDMAQFSSHPRP-UHFFFAOYSA-N acetaldehyde;acetic acid Chemical compound CC=O.CC(O)=O TYGDMAQFSSHPRP-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910006636 γ-AlOOH Inorganic materials 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000006280 diesel fuel additive Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
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- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
A kind of macroporous titanium dioxide assemble nanometer metallic catalyst, prepare and for ethanol phase catalytic reaction, belong to nano metal catalysis and technical field of fine.It is first titanium dioxide nanoparticle through ball mill ball milling, then with Ti (SO using titanium dioxide as raw material4)2Or TiO (SO4) material mixing, using polyethylene glycol as template, preparing hole wall using ultrasonic wave hydro-thermal method has the macroporous titanium dioxide carrier of meso-hole structure；Then using macroporous titanium dioxide as carrier, respectively by the catalytic active component such as Au, Pd, Ag and two-component metal Au Pd, Au Ag, Pd Ag, it is assembled under ul-trasonic irradiation in the hole of macroporous titanium dioxide, prepares nano metal/macroporous titanium dioxide catalyst.The present invention improves the conversion ratio and acetal of ethanol, the overall selectivity of ethyl acetate, therefore with important industrial application value.
Description
Technical field
The present invention relates to a kind of macroporous titanium dioxide assemble nanometer metallic catalyst, prepare and anti-for ethanol liquid-phase catalysis
Should, belong to nano metal catalysis and technical field of fine.
Background technology
Ethanol is important basic chemical industry raw material, and with the production capacity surplus of ethanol, exploitation has under the ethanol of high added value
Trip product has great importance.In numerous ethanol downstream product, (chemical name is 1,1- diethoxies for acetaldehyde, acetal
Base ethane) and ethyl acetate be to enjoy high added value ethanol downstream green chemical products of concern.Acetaldehyde be manufacture acetic acid,
The important source material of the multi-chemicals such as peracetic acid, acetic anhydride, ketenes, crotonaldehyde, n-butanol.Acetal is synthetic drug, perfume (or spice)
One important intermediate of material, is widely used to the fields such as medicine, cosmetics.Meanwhile, acetal is also an excellent performance
Diesel fuel additives, the Cetane number of diesel oil can not only be significantly improved, and be favorably improved the efficiency of combustion of diesel oil, reduced
Particulate and oxynitride discharge in tail gas, reduce the dirt to environment, therefore with very high industrial application value.Acetic acid second
Ester is a kind of excellent organic solvent and organic synthesis intermediate, widely should be had in fields such as spices, dyestuff, pharmacy and paint
With.
In recent years, it has been found that some catalyst can make alcohol catalysis generate acetaldehyde, acetal, ethyl acetate etc..Such as
Peng Liu etc. are reported, using M/MgCuCr2O4(M=Cu, Ag, Pd, Pt, Au) catalyst, in ethanol/O2/ He mol ratio is
Under the reaction condition of 1/3/63 (ethanol is 1.5vol%), can make acetaldehyde selective oxidation generate acetaldehyde (Peng Liu,
Xiaochun Zhu,Shuibin Yang,Tao Li,Emiel J.M. Hensen.On the metal-support
synergy for selective gas phase ethanol oxidation over MgCuCr2O4 supported
metal nanoparticle catalysts.Journal of Catalysis,2015,331: 138-146).Chinese patent
CN 103130625A report that the load type metal chloride catalyst of preparation urges the gas phase media containing ethanol by being loaded with
The reactor of agent, can prepare acetaldehyde co-production acetal, under certain reaction condition, and the selectivity of acetal is higher than second
The selectivity of aldehyde.Xiaohui He etc. are reported, are raw material with ethanol, using two-step method, by Cu/SiO2With H-Y molecular sieves difference
It is placed in the double-deck reactor of series connection, makes ethanol successively experience selective dehydrogenation acetaldehyde and ethanol-acetaldehyde condensation reaction, and then
Obtain higher acetal yield (Xiaohui He, Haichao Liu.Efficient synthesis of 1,1-
diethoxyethane via sequential ethanol reactions on silica-supported copper
and H-Y zeolite catalysts.Catalysis Today,2014,233:133-139).But these catalytic reactions are big
All it is the gas-solid reaction carried out in fixed bed reactors, the concentration of alcohol of charging is general than relatively low, therefore during the course of the reaction
There is substantial amounts of inert gas to recycle, observable index is higher.Meanwhile, the reaction temperature also bad control of gas-solid catalytic reaction,
The selectivity for easily causing product acetaldehyde, acetal, ethyl acetate etc. declines.If prepared, some are new, available for liquid phase
The catalyst of alcohol catalysis conversion, then can avoid the circulation of a large amount of inert gases in gas-solid reaction, simultaneously as liquid phase is urged
The reaction temperature of change is easier control, and this is also very favorable to the selectivity for improving product.
Research shows, is that ethanol is being urged first in the catalytic process that ethanol is Material synthesis acetal (ethyl acetate)
Selective Oxidation, generation acetaldehyde (acetic acid) occur for agent surface；Then, the acetaldehyde (acetic acid) of generation is in the acid of catalyst
Occurs condensation (esterification) reaction with ethanol in the heart, so as to generate acetal (ethyl acetate).If by ethanol selective oxidation performance
Good metal active constituent, is assembled in the hole with acid macroporous oxide, it is possible to prepare the choosing both with ethanol
Select oxidation susceptibility has the bifunctional catalyst of condensation (esterification) performance again, so that the step of ethanol one generates acetal (acetic acid
Ethyl ester), develop new technology of the ethanol for Material synthesis acetal and ethyl acetate.
Recently, we can be quickly prepared with mesoporous SiO using ultrasonic technology2The meso-SiO of shell structurre2@
Fe3O4Microballoon (Hongfei Liu, Shengfu Ji, Hao Yang, Huan Zhang, Mi Tang. Ultrasonic-
assisted ultra-rapid synthesis of monodisperse meso-SiO2@Fe3O4 microspheres
with enhanced mesoporous structure.Ultrasonics Sonochemistry.2014, 21：505-
512)；Using ultrasonic technology can also in the γ-AlOOH holes of meso-hole structure assemble nanometer Pd catalytic active components, prepare
Go out the equally distributed Pd/ γ-AlOOH Fe of nano Pd particle particle3O4Catalyst (YANG Hao, JI ShengFu, LIU XueFei,
ZHANG DanNi&SHI Da.Magnetically recyclable Pd/γ-AlOOH@Fe3O4 catalysts and
their catalytic performance for the Heck coupling reaction.Science China
Chemistry,2014,57(6):866-872)。
Based on these research work basis, the present invention is first nanometer through ball mill ball milling for raw material with titanium dioxide (P25)
Titanium dioxide granule, then with Ti (SO4)2、TiO(SO4) etc. material mixing, using polyethylene glycol as template, using ultrasonic wave-
Hydro-thermal method, which prepares hole wall, has the macroporous titanium dioxide carrier of meso-hole structure.Due to the unique cavitation of ultrasonic wave, prepare
During solution formation the rupture of bubble moment, can high temperature, high pressure and the ultrafast cooling of a part can be formed inside hole
Environment, so as to prepare macroporous titanium dioxide.Then using macroporous titanium dioxide as carrier, respectively by single component metal
The catalytic active component such as Au, Pd, Ag and two-component metal Au-Pd, Au-Ag, Pd-Ag, macropore is assembled under ul-trasonic irradiation
In the hole of titanium dioxide, nano metal/macroporous titanium dioxide catalyst is prepared.
Ultrasonic technology is employed in the present invention so that be assembled in Au in macroporous titanium dioxide hole, Pd, Ag, Au-Pd,
The metal active constituents such as Au-Ag, Pd-Ag, nanometer Au, Pd, Ag, Au-Pd, Au-Ag, Pd-Ag catalysis for foring high dispersive is lived
Property component, has extraordinary catalytic performance to ethanol liquid-phase selective oxidation；Meanwhile, the acid site tool on macroporous titanium dioxide surface
There is good catalyzing and condensing (esterification) performance, and then the Selective Oxidation of ethanol and catalyzing and condensing (esterification) reaction are coupling in
Together, acetal and ethyl acetate are gone out by ethanol one-step synthesis.Therefore nano metal/macroporous titanium dioxide that prepared by the present invention is urged
Agent, acetaldehyde (acetic acid) had both been generated to ethanol liquid-phase selective oxidation has good catalytic action, and the second to being generated in reaction
Aldehyde (acetic acid) and ethanol are further condensed (esterification) with good catalytic action, be it is a kind of have ethanol selective oxidation performance with
It is condensed the bifunctional catalyst of (esterification) performance.
Nano metal/macroporous titanium dioxide bifunctional catalyst prepared by the inventive method, can cause the step of ethanol one to urge
Change is converted into acetal and ethyl acetate, and technological process is simple, easy to operate, therefore with important commercial Application valency
Value.
The content of the invention
The step of ethanol one is catalytically conveted to the difunctional of acetal and ethyl acetate it is an object of the invention to provide a kind of
Catalyst and preparation method and application.
The present invention, first using cheap titanium dioxide as raw material, is first titanium dioxide nanoparticle through ball mill ball milling, so
Afterwards with Ti (SO4)2Or TiO (SO4) etc. material mixing it is uniform, then using polyethylene glycol as template, using ultrasonic wave-hydro-thermal legal system
There is the macroporous titanium dioxide carrier of meso-hole structure for hole wall is gone out.Then using macroporous titanium dioxide as carrier, respectively by one pack system
The catalytic active component such as metal Au, Pd, Ag and two-component metal Au-Pd, Au-Ag, Pd-Ag, is assembled under ul-trasonic irradiation
In macroporous titanium dioxide hole, prepare and acetal and ethyl acetate are catalytically conveted to the step of ethanol one there is fine catalytic performance
Nano metal/macroporous titanium dioxide bifunctional catalyst.
Above-mentioned nano metal/macroporous titanium dioxide the bifunctional catalyst of the present invention, is prepared using including following method：
(1) prepared by macroporous titanium dioxide carrier：Commercially available titanium dioxide (P25) is added to 0.5M~1.0M sulfuric acid solution
In, it is the solution with titanium dioxide nanoparticle through ball mill ball milling, is designated as A liquid, preferably wherein TiO2Mass content be
16.0%~24.0%；By commercially available Ti (SO4)2Or TiO (SO4) solution is made in solution in deionized water, is designated as B liquid, preferably its
Middle Ti (SO4)2Content be 19.2wt%~28.8%, TiO (SO4) content be 16.0wt%~27.2%；Will be commercially available
Polyethylene glycol (PEG-1500), which is dissolved in ethanol, is made solution, is designated as C liquid, the mass content of polyethylene glycol is preferably wherein
6.0%~10.0%.Under 30-60 DEG C of stirring condition, B liquid and C liquid are added in A liquid, after being sufficiently stirred for, 150W~
Under 200W ultrasonic powers, then mixed liquor is put into autoclave by ultrasonic 50min~60min, at 120 DEG C~150 DEG C, water
Thermal crystallisation 8~10 hours, natural cooling washs neutrality with deionized water and ethanol respectively, vacuum drying, finally in 400-
500 DEG C are calcined 4-8 hours (preferably 450 DEG C are calcined 6 hours), and the macroporous titanium dioxide that hole wall, which is as made, has meso-hole structure is carried
Body；Further preferred titanium dioxide, Ti (SO4)2Or TiO (SO4), the mass ratio of polyethylene glycol be 10：(5-16)：(1.5-
2.5)。
(2) prepared by nano metal/macroporous titanium dioxide bifunctional catalyst：Weigh a certain amount of gold chloride, palladium bichloride, nitre
One or both of sour silver is dissolved in deionized water, and metal front liquid solution is made；Metal front liquid solution is added to step
Suddenly (1) prepare the macroporous titanium dioxide aqueous solution in, after being sufficiently stirred for, under 100W~150W ultrasonic powers ultrasound 40min~
60min, makes metal component be assembled in the hole of macroporous titanium dioxide；It is dried in vacuo again, N2In 250 DEG C~300 DEG C roastings under atmosphere
Burn 6~8 hours, be obtained nano metal/macroporous titanium dioxide bifunctional catalyst；In catalyst can to different metal and
Its different metal content is adjusted, so as to obtain nano metal/macropore with monometallic or bimetallic catalytic active component
Titanium dioxide double function catalyst.No matter monometallic or bimetallic are urged in nano metal/macroporous titanium dioxide bifunctional catalyst
The mass content for changing active component preferred Au is 2.45wt%~3.79wt%, Pd mass content for 1.53wt%~
3.09wt%, Ag mass content are 2.06wt%~3.13wt%.
The present invention is applied to ethanol liquid phase using the nano metal/macroporous titanium dioxide bifunctional catalyst prepared and selects oxygen
Change coupling and catalyzing condensation (esterification) to react, acetal and ethyl acetate by ethanol one-step synthesis.Catalytic reaction is stirred in autoclave
Carried out in reactor, liquid ethanol is raw material, add nano metal/macroporous titanium dioxide bifunctional catalyst, added and only adsorb
The 3A molecular sieves of water, are then charged with O2, it is 90 DEG C~160 DEG C in reaction temperature, the reaction time is under conditions of 12~18 hours
Reacted, obtain acetal and ethyl acetate.As a result nano metal/macroporous titanium dioxide the bifunctional catalyst prepared is shown
With good ethanol conversion and acetal, the selectivity of ethyl acetate, and the active component of catalyst is not lost in, and has
Good stability.In addition, the 3A molecular sieves for only adsorbing water are added in reaction system, so can adsorption reaction in time
The water produced in journey, therefore, substantially increases conversion ratio and acetal, the overall selectivity of ethyl acetate of ethanol.
Nano metal prepared by the present invention/macroporous titanium dioxide catalyst has following remarkable advantage：
(1) in the preparation process of macroporous titanium dioxide carrier, as a result of the integrated processes of ultrasonic wave-hydro-thermal, profit
With the microenvironment of the localized hyperthermia of ultrasonic wave, high pressure and ultrafast cooling, can prepare hole wall has mesoporous macropore titanium dioxide
There is provided with acid, carrier that is easily assembling catalytic active component for titanium.
(2) prepare nano metal/macroporous titanium dioxide catalyst in, catalytic active component Au, Pd, Ag, Au-Pd,
Au-Ag, Pd-Ag etc. are assembled in carrier macroporous titanium dioxide hole, therefore the good dispersion of catalytic active component, and this is not only
The activity of catalyst is improved, and the aggregation and loss of catalytic active component in course of reaction can be avoided, greatly improves and urges
The hole wall on the surface that the stability of agent, wherein carrier are is the large pore material with meso-hole structure.
(3) nano metal/macroporous titanium dioxide catalyst prepared, can be anti-by ethanol selective oxidation and condensation, esterification
It should be coupled, the step of ethanol one is catalytically conveted to acetal and ethyl acetate, with good conversion ratio and selectivity, and
And the 3A molecular sieves for only adsorbing water are added in reaction system, the water that can be produced during adsorption reaction in time is carried significantly
The conversion ratio and acetal, the overall selectivity of ethyl acetate of high ethanol, therefore with important industrial application value.
Embodiment
With reference to embodiment, the invention will be further described, but the invention is not limited in this.
Embodiment 1
(1) weigh 16.0g titanium dioxide to be dissolved in 84.0g 0.5M sulfuric acid solutions, TiO is made2Mass content is
16.0wt% solution, through ball mill ball milling 12h, is designated as A1 liquid；Weigh 24.0g Ti (SO4)2Solution is in 76.0g deionized waters
In, Ti (SO are made4)2Content is 24.0wt% solution, is designated as B1 liquid；3.0g polyethylene glycol (PEG-1500) is weighed to be dissolved in
In 47.0g ethanol, the polyglycol solution that polyethylene glycol mass content is 6.0% is made, C1 liquid is designated as.In 40 DEG C of stirring bars
Under part, B1 liquid and C1 liquid are added in A1 liquid, after being sufficiently stirred for, under 150W ultrasonic powers, ultrasonic 50min then will be mixed
Close liquid to be put into autoclave, at 120 DEG C, hydrothermal crystallizing 10 hours, natural cooling is washed with deionized water and ethanol respectively
Neutrality, is dried in vacuo at 50 DEG C 8 hours, is finally calcined 6 hours at 400 DEG C, is that obtained hole wall has the big of meso-hole structure
Porous titanium dioxide carrier, is designated as TiZ1 carriers.
(2) 6.8g HAuCl is weighed4, it is dissolved in 93.2g deionized waters, the Au that Au mass contents are 3.94wt% is made
Solution.TiZ1 carriers made from 10.0g are weighed, 10.0g Au solution is added, after being sufficiently stirred for, under 100W ultrasonic powers, surpassed
Sound 50min, makes metal Au components be assembled in the hole of macroporous titanium dioxide.After drying, it is dried in vacuo 8 hours at 50 DEG C,
N2Lower 250 DEG C of atmosphere is calcined 8 hours, is obtained 3.79wt%Au/ macroporous titanium dioxide catalyst.
(3) in 100ml autoclave stirred reactors, 0.3mol ethanol is added, the 3.79wt% of preparation is then added
Au/ macroporous titanium dioxide catalyst 0.3g, add dried 3A molecular sieve 3g, are filled with O2To 1.5MPa, then at 90 DEG C
Lower reaction 18 hours.After the completion of reaction, determined by chromatography, the conversion ratio of ethanol is 58.6%, the selectivity of acetal
For 72.5%, the selectivity of ethyl acetate is 21.6%, and the overall selectivity of acetal and ethyl acetate is 94.1%.
Embodiment 2
(1) weigh 20.0g titanium dioxide to be dissolved in 80.0g 0.8M sulfuric acid solutions, TiO is made2Mass content is
20.0wt% solution, through ball mill ball milling 12h, is designated as A2 liquid；Weigh 16.0g TiO (SO4) solution is in 84.0g deionized waters
In, TiO (SO are made4) content be 16.0wt% solution, be designated as B2 liquid；4.0g polyethylene glycol (PEG-1500) is weighed to be dissolved in
In 46.0g ethanol, the polyglycol solution that polyethylene glycol mass content is 8.0% is made, C2 liquid is designated as.In 40 DEG C of stirring bars
Under part, B2 liquid and C2 liquid are added in A2 liquid, after being sufficiently stirred for, under 120W ultrasonic powers, ultrasonic 60min then will be mixed
Close liquid to be put into autoclave, at 130 DEG C, hydrothermal crystallizing 9 hours, natural cooling is washed with deionized water and ethanol respectively
Neutrality, is dried in vacuo at 50 DEG C 8 hours, is finally calcined 8 hours at 500 DEG C, is that obtained hole wall has the big of meso-hole structure
Porous titanium dioxide carrier, is designated as TiZ2 carriers.
(2) 5.3g PdCl is weighed2, it is dissolved in 94.7g deionized waters, the Pd that Pd mass contents are 3.19wt% is made molten
Liquid.TiZ2 carriers made from 10.0g are weighed, 10.0g Pd solution is added, after being sufficiently stirred for, under 120W ultrasonic powers, ultrasound
40min, makes metal Pd component be assembled in the hole of macroporous titanium dioxide.After drying, it is dried in vacuo 8 hours at 50 DEG C, in N2
Lower 300 DEG C of atmosphere is calcined 7 hours, is obtained 3.09wt%Pd/ macroporous titanium dioxide catalyst.
(3) in 100ml autoclave stirred reactors, 0.35mol ethanol is added, the 3.09wt% of preparation is then added
Pd/ macroporous titanium dioxide catalyst 0.3g, add dried 3A molecular sieve 4g, are filled with O2To 1.5MPa, then at 120 DEG C
Lower reaction 14 hours.After the completion of reaction, determined by chromatography, the conversion ratio of ethanol is 56.9%, the selectivity of acetal
For 71.7%, the selectivity of ethyl acetate is 20.8%, and the overall selectivity of acetal and ethyl acetate is 92.5%.
Embodiment 3
(1) weigh 24.0g titanium dioxide to be dissolved in 76.0g 1.0M sulfuric acid solutions, TiO is made2Mass content is
24.0wt% solution, through ball mill ball milling 12h, is designated as A3 liquid；Weigh 28.8g Ti (SO4)2Solution is in 71.2g deionized waters
In, Ti (SO are made4)2Content is 28.8wt% solution, is designated as B3 liquid；5.0g polyethylene glycol (PEG-1500) is weighed to be dissolved in
In 45.0g ethanol, the polyglycol solution that polyethylene glycol mass content is 10.0% is made, C3 liquid is designated as.In 40 DEG C of stirring bars
Under part, B3 liquid and C3 liquid are added in A3 liquid, after being sufficiently stirred for, under 200W ultrasonic powers, ultrasonic 60min then will be mixed
Close liquid to be put into autoclave, at 150 DEG C, hydrothermal crystallizing 8 hours, natural cooling is washed with deionized water and ethanol respectively
Neutrality, is dried in vacuo at 50 DEG C 8 hours, is finally calcined 6 hours at 450 DEG C, is that obtained hole wall has the big of meso-hole structure
Porous titanium dioxide carrier, is designated as TiZ3 carriers.
(2) 5.1g Ag (NO are weighed3) be dissolved in 94.9g deionized waters, the Ag that Ag mass contents are 3.24wt% is made
Solution.TiZ3 carriers made from 10.0g are weighed, 10.0g Ag solution is added, after being sufficiently stirred for, under 100W ultrasonic powers, surpassed
Sound 50min, makes metal Ag components be assembled in the hole of macroporous titanium dioxide.After drying, it is dried in vacuo 8 hours at 50 DEG C,
N2Lower 280 DEG C of atmosphere is calcined 6 hours, is obtained 3.13wt%Ag/ macroporous titanium dioxide catalyst.
(3) in 100ml autoclave stirred reactors, 0.3mol ethanol is added, the 3.13wt%Ag/ of preparation is then added
Macroporous titanium dioxide catalyst 0.4g, adds dried 3A molecular sieve 3g, is filled with O2To 1.8MPa, then at 150 DEG C
Reaction 12 hours.After the completion of reaction, determined by chromatography, the conversion ratio of ethanol is 52.8%, and the selectivity of acetal is
67.3%, the selectivity of ethyl acetate is 22.9%, and the overall selectivity of acetal and ethyl acetate is 90.2%.
Embodiment 4
(1) weigh 18.4g titanium dioxide to be dissolved in 81.6g 0.7M sulfuric acid solutions, TiO is made2Mass content is
18.4wt% solution, through ball mill ball milling 12h, is designated as A4 liquid；Weigh 27.2g TiO (SO4) solution is in 72.8g deionized waters
In, TiO (SO are made4) content be 27.2wt% solution, be designated as B4 liquid；4.5g polyethylene glycol (PEG-1500) is weighed to be dissolved in
In 45.5g ethanol, the polyglycol solution that polyethylene glycol mass content is 9.0% is made, C4 liquid is designated as.In 40 DEG C of stirring bars
Under part, B4 liquid and C4 liquid are added in A4 liquid, after being sufficiently stirred for, under 150W ultrasonic powers, ultrasonic 55min then will be mixed
Close liquid to be put into autoclave, at 130 DEG C, hydrothermal crystallizing 8 hours, natural cooling is washed with deionized water and ethanol respectively
Neutrality, is dried in vacuo at 50 DEG C 8 hours, is finally calcined 7 hours at 500 DEG C, is that obtained hole wall has the big of meso-hole structure
Porous titanium dioxide carrier, is designated as TiZ4 carriers.
(2) 5.1g HAuCl is weighed4, it is dissolved in 94.9g deionized waters, the Au that Au mass contents are 2.96wt% is made
Solution.Weigh 2.7g PdCl2, it is dissolved in 97.3g deionized waters, the Pd solution that Pd mass contents are 1.59wt% is made.Claim
TiZ4 carriers made from 10.0g are taken, 10.0g Au solution is added, adds 10.0g Pd solution, after being sufficiently stirred for,
Under 150W ultrasonic powers, ultrasonic 60min makes metal Au components and Pd components be assembled in the hole of macroporous titanium dioxide.After drying,
It is dried in vacuo 8 hours at 50 DEG C, in N2Lower 300 DEG C of atmosphere is calcined 6 hours, is obtained 2.83wt%Au-1.52wt%
Pd/ macroporous titanium dioxide catalyst.
(3) in 100ml autoclave stirred reactors, 0.35mol ethanol is added, the 2.83wt% of preparation is then added
Au-1.52wt%Pd/ macroporous titanium dioxide catalyst 0.3g adds dried 3A molecular sieve 4g, is filled with O2To 1.5MPa,
Then reacted 14 hours at 120 DEG C.After the completion of reaction, determined by chromatography, the conversion ratio of ethanol is 65.6%, second contracting
The selectivity of aldehyde is 74.2%, and the selectivity of ethyl acetate is 22.3%, and the overall selectivity of acetal and ethyl acetate is
96.5%.
Embodiment 5
(1) weigh 17.6g titanium dioxide to be dissolved in 82.4g 0.6M sulfuric acid solutions, TiO is made2Mass content is
17.6wt% solution, through ball mill ball milling 12h, is designated as A5 liquid；Weigh 24.0g TiO (SO4) solution is in 76.0g deionized waters
In, TiO (SO are made4) content be 24.0wt% solution, be designated as B5 liquid；4.2g polyethylene glycol (PEG-1500) is weighed to be dissolved in
In 46.0g ethanol, the polyglycol solution that polyethylene glycol mass content is 8.4% is made, C5 liquid is designated as.In 40 DEG C of stirring bars
Under part, B5 liquid and C5 liquid are added in A5 liquid, after being sufficiently stirred for, under 180W ultrasonic powers, ultrasonic 55min then will be mixed
Close liquid to be put into autoclave, at 120 DEG C, hydrothermal crystallizing 10 hours, natural cooling is washed with deionized water and ethanol respectively
Neutrality, is dried in vacuo at 50 DEG C 8 hours, is finally calcined 8 hours at 450 DEG C, is that obtained hole wall has the big of meso-hole structure
Porous titanium dioxide carrier, is designated as TiZ5 carriers.
(2) 4.4g HAuCl is weighed4, it is dissolved in 95.6g deionized waters, the Au that Au mass contents are 2.56wt% is made
Solution.Weigh 3.4g Ag (NO3) be dissolved in 96.6g deionized waters, the Ag solution that Ag mass contents are 2.15wt% is made.Claim
TiZ5 carriers made from 10.0g are taken, 10.0g Au solution is added, adds 10.0g Ag solution, after being sufficiently stirred for,
Under 150W ultrasonic powers, ultrasonic 50min makes metal Au components and Ag components be assembled in the hole of macroporous titanium dioxide.After drying,
It is dried in vacuo 8 hours at 50 DEG C, in N2Lower 300 DEG C of atmosphere is calcined 7 hours, is obtained 2.45wt%Au-2.06wt%
Ag/ macroporous titanium dioxide catalyst.
(3) in 100ml autoclave stirred reactors, 0.3mol ethanol is added, the 2.45wt% of preparation is then added
Au-2.06wt%Ag/ macroporous titanium dioxide catalyst 0.35g adds dried 3A molecular sieve 3g, is filled with O2Arrive
1.8MPa, then reacts 12 hours at 160 DEG C.After the completion of reaction, determined by chromatography, the conversion ratio of ethanol is
63.8%, the selectivity of acetal is 71.6%, and the selectivity of ethyl acetate is 23.7%, total choosing of acetal and ethyl acetate
Selecting property is 95.3%.
Embodiment 6
(1) weigh 22.3g titanium dioxide to be dissolved in 77.7g 0.9M sulfuric acid solutions, TiO is made2Mass content is
22.3wt% solution, through ball mill ball milling 12h, is designated as A6 liquid；Weigh 19.2g Ti (SO4)2Solution is in 80.8g deionized waters
In, Ti (SO are made4)2Content is 19.2wt% solution, is designated as B6 liquid；4.6g polyethylene glycol (PEG-1500) is weighed to be dissolved in
In 45.4g ethanol, the polyglycol solution that polyethylene glycol mass content is 9.2% is made, C6 liquid is designated as.In 40 DEG C of stirring bars
Under part, B6 liquid and C6 liquid are added in A6 liquid, after being sufficiently stirred for, under 200W ultrasonic powers, ultrasonic 50min then will be mixed
Close liquid to be put into autoclave, at 130 DEG C, hydrothermal crystallizing 10 hours, natural cooling is washed with deionized water and ethanol respectively
Neutrality, is dried in vacuo at 50 DEG C 8 hours, is finally calcined 6 hours at 450 DEG C, is that obtained hole wall has the big of meso-hole structure
Porous titanium dioxide carrier, is designated as TiZ6 carriers.
(2) 3.5g PdCl is weighed2, it is dissolved in 96.5g deionized waters, the Pd that Pd mass contents are 3.5wt% is made molten
Liquid.Weigh 4.2g Ag (NO3) be dissolved in 95.8g deionized waters, the Ag solution that Ag mass contents are 4.2wt% is made.Weigh
TiZ6 carriers made from 10.0g, add 10.0g Pd solution, add 10.0g Ag solution, after being sufficiently stirred for, super in 150W
Under acoustical power, ultrasonic 55min makes metal Pd component and Ag components be assembled in the hole of macroporous titanium dioxide.After drying, at 50 DEG C
Lower vacuum drying 8 hours, in N2Lower 300 DEG C of atmosphere is calcined 8 hours, is obtained 2.03wt%Pd-2.57wt%Ag/ big
Porous titanium dioxide catalyst.
(3) in 100ml autoclave stirred reactors, 0.35mol ethanol is added, the 2.03wt% of preparation is then added
Pd-2.57wt%Ag/ macroporous titanium dioxide catalyst 0.4g, add dried 3A molecular sieve 5g, are filled with O2Arrive
1.5MPa, then reacts 15 hours at 130 DEG C.After the completion of reaction, determined by chromatography, the conversion ratio of ethanol is
62.5%, the selectivity of acetal is 70.2%, and the selectivity of ethyl acetate is 24.4%, total choosing of acetal and ethyl acetate
Selecting property is 94.6%.
Claims (8)
1. the preparation method of a kind of nano metal/macroporous titanium dioxide bifunctional catalyst, it is characterised in that including following method
Step：
(1) prepared by macroporous titanium dioxide carrier：In the sulfuric acid solution that titanium dioxide is added to 0.5M~1.0M, through ball mill ball milling
For the solution with titanium dioxide nanoparticle, A liquid is designated as；By Ti (SO4)2Or TiO (SO4) solution be made in deionized water it is molten
Liquid, is designated as B liquid；Polyethylene glycol is dissolved in ethanol solution is made, be designated as C liquid；Under 30-60 DEG C of stirring condition, by B liquid and
C liquid is added in A liquid, after being sufficiently stirred for, under 150W~200W ultrasonic powers, ultrasonic 50min~60min, then will mixing
Liquid is put into autoclave, at 120 DEG C~150 DEG C, hydrothermal crystallizing 8~10 hours, natural cooling, respectively with deionized water and second
Alcohol washing is dried in vacuo to neutrality, is finally calcined at 400-500 DEG C 4-8 hours, and hole wall, which is as made, has the big of meso-hole structure
Porous titanium dioxide carrier；
(2) prepared by nano metal/macroporous titanium dioxide bifunctional catalyst：Weigh a certain amount of gold chloride, palladium bichloride, silver nitrate
One or both of be dissolved in deionized water, metal front liquid solution is made；Metal front liquid solution is added to step (1)
In the macroporous titanium dioxide aqueous solution of preparation, after being sufficiently stirred for, ultrasound 40min~60min under 100W~150W ultrasonic powers,
Metal component is set to be assembled in the hole of macroporous titanium dioxide；In vacuum drying, N2Under atmosphere 6~8 are calcined at 250 DEG C~300 DEG C
Hour, it is obtained nano metal/macroporous titanium dioxide bifunctional catalyst, catalytic active component is monometallic or double gold
Category.
2. according to a kind of preparation method of nano metal/macroporous titanium dioxide bifunctional catalyst described in claim 1, it is special
Levy and be, step (1) is calcined 6 hours at 450 DEG C.
3. according to a kind of preparation method of nano metal/macroporous titanium dioxide bifunctional catalyst described in claim 1, it is special
Levy and be, TiO in step (1) A liquid2Mass content be 16.0%~24.0%；Ti (SO in B liquid4)2Content be
19.2wt%~28.8%, TiO (SO4) content be 16.0wt%~27.2%；The mass content of polyethylene glycol is in C liquid
6.0%~10.0%.
4. according to a kind of preparation method of nano metal/macroporous titanium dioxide bifunctional catalyst described in claim 1, it is special
Levy and be, step (1) B liquid, C liquid, A liquid mixing titanium dioxide, Ti (SO4)2Or TiO (SO4), the mass ratio of polyethylene glycol be 10：
(5-16)：(1.5-2.5).
5. according to a kind of preparation method of nano metal/macroporous titanium dioxide bifunctional catalyst described in claim 1, it is special
Levy and be, in nano metal/macroporous titanium dioxide bifunctional catalyst no matter Au in monometallic or bimetallic catalytic active component
Mass content be 2.45wt%~3.79wt%, Pd mass content is 1.53wt%~3.09wt%, Ag mass content
For 2.06wt%~3.13wt%.
6. the nano metal prepared according to any one of claim 1-5 method/macroporous titanium dioxide bifunctional catalyst.
7. the nano metal prepared according to any one of claim 1-5 method/macroporous titanium dioxide bifunctional catalyst
Using for the condensation of ethanol liquid-phase selective oxidation coupling and catalyzing and esterification, by ethanol one-step synthesis acetal and acetic acid second
Ester.
8. according to the application of claim 7, reaction is carried out in autoclave stirred reactor, and liquid ethanol is raw material, adds nanometer
Metal/macroporous titanium dioxide bifunctional catalyst, adds the 3A molecular sieves for only adsorbing water, is then charged with O2, it is in reaction temperature
90 DEG C~160 DEG C, the reaction time is to be reacted under conditions of 12~18 hours, obtains acetal and ethyl acetate.
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| CN108355716A (en) * | 2018-02-09 | 2018-08-03 | 北京化工大学 | A kind of Cu-BTC assemble nanometers metallic catalyst prepares and is used for CO2Formylation reaction |
| CN108355716B (en) * | 2018-02-09 | 2020-09-04 | 北京化工大学 | Cu-BTC assembled nano metal catalyst, preparation and application in CO2By formylation |
| CN108355652A (en) * | 2018-03-01 | 2018-08-03 | 河南师范大学 | A kind of preparation method for the gold-palladium nanocatalyst in CO oxidation reactions |
| CN108355652B (en) * | 2018-03-01 | 2021-10-29 | 河南师范大学 | Preparation method of gold-palladium nano catalyst for CO oxidation reaction |
| CN113185389A (en) * | 2021-05-10 | 2021-07-30 | 北京化工大学 | Method and catalyst for preparing acetal by efficiently photocatalysis ethanol |
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| CN107185532B (en) | 2020-05-19 |
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