CN110479231A - A kind of preparation method for the catalyst adding hydrogen for alpha, beta-unsaturated aldehyde selection - Google Patents
A kind of preparation method for the catalyst adding hydrogen for alpha, beta-unsaturated aldehyde selection Download PDFInfo
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- CN110479231A CN110479231A CN201910837310.1A CN201910837310A CN110479231A CN 110479231 A CN110479231 A CN 110479231A CN 201910837310 A CN201910837310 A CN 201910837310A CN 110479231 A CN110479231 A CN 110479231A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 13
- 239000001257 hydrogen Substances 0.000 title claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000012530 fluid Substances 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 20
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims abstract description 19
- 238000000975 co-precipitation Methods 0.000 claims abstract description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 235000019441 ethanol Nutrition 0.000 claims description 36
- 229960004756 ethanol Drugs 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 235000003642 hunger Nutrition 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- FTWGTNVTSDGLFG-UHFFFAOYSA-N nitric acid zirconium Chemical compound [Zr].O[N+]([O-])=O FTWGTNVTSDGLFG-UHFFFAOYSA-N 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 10
- 150000001299 aldehydes Chemical class 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 description 8
- 239000013049 sediment Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229940043350 citral Drugs 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229930016911 cinnamic acid Natural products 0.000 description 2
- 235000013985 cinnamic acid Nutrition 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000352 supercritical drying Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000003834 hydroxide co-precipitation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- NEBDODHTONKHGR-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O NEBDODHTONKHGR-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002119 pyrolysis Fourier transform infrared spectroscopy Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 239000002023 wood Substances 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to one kind to be used for α, beta-unsaturated aldehyde selective hydrogenation prepares α, and the preparation method of the catalyst of beta unsaturated alcohol and the catalyst being prepared by this method and the catalyst are by α, beta-unsaturated aldehyde selective hydrogenation synthesizes α, the application in beta unsaturated alcohol.Preparation method according to the present invention includes: that (1) prepares zirconium source solution A；(2) aqueous slkali B is prepared；(3) solution A and solution B co-precipitation；(4) filter, wash, alcohol wash, supercritical fluid drying, then roast.Zirconium dioxide prepared in accordance with the method for the present invention activity and unsaturated alcohol selectivity with higher in alpha, beta-unsaturated aldehyde selective hydrogenation.Catalyst preparation process is simple, cheap, easy to use, activity and selectivity with higher, α, and beta-unsaturated aldehyde conversion ratio and α, beta unsaturated alcohol are selectively all larger than 90%.
Description
Technical field
The present invention relates to a kind of systems of catalyst that alpha, beta unsaturated alcohol is prepared for alpha, beta-unsaturated aldehyde selective hydrogenation
Preparation Method and the catalyst being prepared by this method and the catalyst are by α, beta-unsaturated aldehyde selective hydrogenation
Synthesize the application in alpha, beta unsaturated alcohol.
Background technique
Alcohols fine chemicals, especially α, beta unsaturated alcohol, functionalization alcohols have good biocompatibility and ten
Divide extensive purposes, has a wide range of applications in organic synthesis, be fragrance, drug and other fine chemical product production processes
In important source material and reaction intermediate.Wherein the domestic and international market demand of prenol is very big, and the country there is no on a large scale
Production, most of to need to produce from external import or as intermediate, market has openings is very big.With the increasing of people's health care consciousness
By force, the dosage of vitamin is consequently increased, and wherein the demand of mesosome prenol is also increasingly increased sharply, and yield cannot fully meet state
The demand of interior growing prenol is required every year from external import.
Industrial production unsaturated alcohol is carried out by the homogeneous metering reaction in the presence of organic solvent at present, process flow
Long, solvent and reaction reagent consumption are big, and product separation is cumbersome and process generates a large amount of wastes, constitute to environment quite big
Harm, do not meet the requirement of sustainable economic development.The selective reduction of C=O key is realized using efficient heterogeneous catalysis technology
Meet the requirement of current Green Sustainable, but C=C key and C=O key due to there is conjugation in molecule, selectivity of product
It is difficult to control.Traditional noble metal catalyst is expensive, and is conducive to the hydrogen that adds of C=C key, therefore develop novel non-noble metal and urge
Agent or metal oxide catalyst, study α, and beta-conjugated unsaturated aldehyde selective hydrogenation has important application value.
Zirconium dioxide is due to good with chemical stability, the advantages that corrosion resistance is strong, and fusing point is high, has become green wood in recent years
The research hotspot in material field.Particularly interesting is that it has excellent catalytic properties, and zirconium dioxide has surface simultaneously
Acidic site and surface basic site also have good ion-exchange performance and redox property, therefore can not only be used for catalyst,
But also as catalyst carrier or auxiliary agent, more and more concerns are caused in catalytic field.
Chinese patent CN103523830A discloses a kind of preparation method, in three-necked flask or autoclave, zirconates is molten
Solution obtains acid solution of the pH less than 5, is heated to reflux, with roasting after ammonium hydroxide adjusting pH value of solution to 5~10, obtains high-specific surface area
Monoclinic phase zirconium dioxide.Chinese patent CN108190951A discloses another preparation ZrO2Method, with zirconates, precipitating
Agent, surfactant are raw material, by adjusting the ratio of alcohol and water in solution, prepare various grain sizes and crystalline substance using hydro-thermal method
The nano zirconium dioxide of type.The zirconium oxide that prior art preparation obtains is often the multiphase of four directions and monocline, is hardly resulted in
The tetragonal-phase zirconia of the high-specific surface area of purity is high, and preparation process uses surfactant more, it is difficult to it completely removes.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, it is an object of the present invention to provide one kind for by α, β-insatiable hunger
The ZrO of alpha, beta unsaturated alcohol is prepared with aldehyde selective hydrogenation2The preparation method of catalyst.Preparation method according to the present invention raw material
Cheap and easy to get, catalyst preparation process is simple, and reaction condition is mild, and catalyst has good activity.
Preparation method according to the present invention includes the following steps:
(1) zirconium source is dissolved in deionized water, uses 0.5~2h of magnetic stirrer at room temperature, being made into molar concentration is
The solution A of 0.01mol/L to 0.05mol/L.
(2) alkali is made into the aqueous solution B that mass percent concentration is 5~15%.
(3) under stirring, by solution A and solution B co-precipitation, pH value of solution=6~10 is controlled, 1~3h of stirring, In are continued
Aging 3h~5 day at 50~90 DEG C.
(4) after aging filter, wash, alcohol wash, supercritical fluid drying, be then put in Muffle furnace 300~600
DEG C roasting 3~6h.
Preferably, zirconium source described in step 1) is zirconium oxychloride, zirconium nitrate or zirconyl nitrate.
Preferably, alkali described in step 2) is sodium hydroxide, sodium carbonate, ammonium hydroxide or its mixed solution.
Preferably, supercritical fluid drying method described in step 4) carries out as follows: dehydrated alcohol is made overcritical Jie
Matter rises to 240~280 DEG C with the heating rate of 3~10 DEG C/min, in isothermal after 20~60min of constant temperature and pressure under 6~8.0MPa
Lower slow release ethyl alcohol fluid and in N2Air-blowing, which is swept down, to be cooled to room temperature, and opens reactor up to powder.
It is highly preferred that the zirconium source molar concentration of solution A is 0.02mol/L to 0.025mol/L in step 1).
It is another object of the present invention to provide a kind of ZrO prepared by the preparation method2Catalyst.
It is yet a further object of the present invention to provide a kind of ZrO that preparation method according to the present invention is prepared2Catalysis
Application of the agent in the reaction for preparing alpha, beta unsaturated alcohol by alpha, beta-unsaturated aldehyde selective hydrogenation.
It is yet a further object of the present invention to provide one kind to prepare α, β-unsaturation by alpha, beta-unsaturated aldehyde selective hydrogenation
The method of alcohol, which comprises three times with hydrogen purge reaction kettle, the air removed in reaction kettle will be anti-using alcohol as solvent
Answer object alpha, beta-unsaturated aldehyde and above-mentioned preparation ZrO2Catalyst is added in reaction kettle, and control reaction temperature is 70-180 DEG C, hydrogen
Pressure is 0.1~1MPa, is stirred to react 0.5~12h.
Preferably, according to described by α, beta-unsaturated aldehyde selective hydrogenation prepares α, the method for beta unsaturated alcohol, wherein using
The alcohol for making solvent is selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and tert-butyl alcohol etc..
Preferably, according to described by α, beta-unsaturated aldehyde selective hydrogenation prepares α, the method for beta unsaturated alcohol, wherein
ZrO2The molar ratio of catalyst and reactant alpha, beta-unsaturated aldehyde is 1:10~20.
Beneficial effect
Zirconium dioxide made from preparation method according to the present invention has in alpha, beta-unsaturated aldehyde selective hydrogenation
Higher activity and unsaturated alcohol selectivity.Catalyst preparation process is simple, cheap, easy to use, work with higher
Property and selectivity, α, beta-unsaturated aldehyde conversion ratio and α, beta unsaturated alcohol are selectively all larger than 90%.The present invention can be solved effectively
The generally existing synthesis technology of certainly domestic citral industry is complicated, the three wastes are more, raw material midbody environmental hazard greatly, material recycle and
The common technologies features such as catalyst choice is difficult, product yield is low, production cost is high break art wall for domestic citral product
Establish technical foundation in base.
Detailed description of the invention
Fig. 1 is ZrO prepared by embodiment 62The XRD curve graph of sample；
Fig. 2 is ZrO prepared by embodiment 62The Raman map of sample；
Fig. 3 is ZrO prepared by embodiment 62The N of sample2Adsorption-desorption isothermal curve figure；
Fig. 4 is ZrO prepared by embodiment 62Sample pore size distribution curve；
Fig. 5 is ZrO prepared by embodiment 62Pyridine adsorption IR spectra (Py-FTIR) figure of sample；
Fig. 6 is the ZrO obtained in comparative example 1 using usual drying method2The XRD diagram of sample.
Specific embodiment
Hereinafter, will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims used in term should not be construed as being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of the appropriate principle for defining term to carry out best interpretations, according to meaning corresponding with technical aspect of the invention and generally
Thought explains.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The range of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
The crucial precipitating being using zirconium source aqueous solution and aqueous slkali co-precipitation in preparation method according to the present invention
Mode.Since zirconium oxide has surface acid basic active position, especially zirconium surface, there are oxygen vacancies abundant, in catalyst
In effect it is more unique, unique interaction can be formed with the other components in catalyst, these characteristics cause it adding
Special catalytic activity is shown in hydrogen reaction process, it will be apparent that influence the reactivity and selectivity of catalyst.Zirconium oxide
Form difference cause the difference of Surface Texture and structure and surface nature, to influence its absorption to surface species.Cause
This is in many catalysis reaction, and the reactivity difference of various forms zirconium oxide is larger, this may be with various forms zirconium oxide table
The L acidic site and acid ion alkali ion in face are to related.It can especially be prepared by controlling preparation parameter using co-precipitation method
The formation condition that zirconium oxide presoma is controlled in journey obtains the tetragonal phase zirconium oxide of single form；And co-precipitation method has
Have the advantages that preparation process is simple, at low cost, preparation condition is easily controllable, synthesis cycle is short.
In addition in the step 4) of preparation method according to the present invention by the way of supercritical fluid drying: by anhydrous second
Alcohol rises to 240~280 DEG C as supercritical medium, with the heating rate of 3~10 DEG C/min, constant temperature and pressure 20 under 6~8.0MPa
After~60min under isothermal slow release ethyl alcohol fluid and in N2Air-blowing, which is swept down, to be cooled to room temperature, and opens reactor up to powder.
General common dry technology, as air drying, baking drying etc. are produced when removing solvent in the drying process
Raw surface tension and capillarity usually inevitably results in material reunion, and thus generation material foundation particle is thicker,
Specific surface sharply declines and hole largely reduces etc. as a result, this is for the acquisition of nano material and the system of high-ratio surface material
It is standby extremely disadvantageous.
Supercritical Drying Technology is the drying carried out under the conditions of dried medium critical-temperature and critical pressure, avoids gas
Liquid two-phase coexistent eliminates the effect of surface tension, and wet gel is completed under the premise of maintaining skeleton structure and is turned to aeroge
Become, controls the reunion of gel particles in drying process, collapsing for gel structure with shrinkage phenomenon.This method can be to avoid
The contraction and fragmentation of material in the drying process prevent primary nanoparticle to keep the original structure of material and state
Reunion and coalescence, obtain even particle size distribution, macropore volume, the superfine powder of high-ratio surface.
The present invention uses the ZrO of supercritical drying preparation2And distribution small with specific surface area and Kong Rong great, partial size is equal
Even, crystal phase composition purity is high and the advantages of favorable repeatability shows in the reaction of unsaturated aldehyde selective hydrogenation unsaturated alcohol
Excellent performance out has important application value.And the powder particle of usual drying method preparation is used, reunite between particle existing
As than more serious, and the shape of particle for forming powder is irregular, and granular size is uneven, and particle diameter is about 0.05~0.1 μm.
The specific surface area and pore volume of particle can be increased by illustrating supercritical fluid drying not only, but also reunion can be effectively prevented
The generation of body, drastically decreases particle size.
Following embodiment is enumerated only as the example of embodiment of the present invention, does not constitute any limit to the present invention
System, it will be appreciated by those skilled in the art that modification in the range of without departing from essence and design of the invention each falls within the present invention
Protection scope.Unless stated otherwise, reagent and instrument used in the following embodiment are commercially available product.
Embodiment 1
By 0.1 mole of ZrOCl2It is dissolved in 500mL deionized water, 28% ammonium hydroxide is diluted one times, by ZrOCl2Solution
With ammonium hydroxide at 60 DEG C co-precipitation, control pH ≈ 9, sediment 60 DEG C aging 4 hours in mother liquor.The process obtains heavy
Starch uses supercritical fluid drying after filtering, washing, ethanol washing to no Cl- ion, and dehydrated alcohol makees supercritical medium,
Rise to 260 DEG C with the heating rate of 3 DEG C/min, under 8.0MPa after constant temperature and pressure 30min under isothermal slow release ethyl alcohol fluid
And be cooled to room temperature in the case where N2 air-blowing is swept, ZrO is obtained in 350 DEG C of roasting 3h2-(1)。
Hydrogenation reaction carries out in 50mL stainless steel cauldron, 0.1g ZrO2(1) catalyst, 0.1g cinnamic acid, 20mL
The tert-butyl alcohol (solvent), 150 DEG C of reaction temperature, nitrogen pressure 0.1MPa, speed of agitator 600r/min, reaction time 2h.Reaction is lived
Property the results are shown in Table 1.
Embodiment 2
0.1 molar nitric acid oxygen zirconium is dissolved in 500mL deionized water, 28% ammonium hydroxide is diluted one times, by Nitric Acid Oxidation
Zirconium solution and the ammonium hydroxide co-precipitation at 70 DEG C control pH ≈ 10, sediment 60 DEG C aging 4 hours in mother liquor.The process
Obtained sediment uses supercritical fluid drying after filtering, washing, ethanol washing to no Cl- ion, and dehydrated alcohol surpasses
Critical medium rises to 250 DEG C with the heating rate of 4 DEG C/min, under 7.0MPa after constant temperature and pressure 20min under isothermal slow release
Ethyl alcohol fluid and in N2Air-blowing, which is swept down, to be cooled to room temperature, and obtains ZrO in 350 DEG C of roasting 3h2-(2)。
Hydrogenation reaction carries out in 50mL stainless steel cauldron, 0.05g ZrO2(2) catalyst, 0.1g methacrolein,
15mL ethyl alcohol (solvent), 130 DEG C of reaction temperature, nitrogen pressure 0.1MPa, speed of agitator 600r/min, reaction time 1h.Reaction
Activity Results are shown in Table 1.
Embodiment 3
By 0.1 mole of ZrOCl2It is dissolved in 400mL deionized water, 28% ammonium hydroxide is diluted one times, by ZrOCl2Solution
With ammonium hydroxide at 35 DEG C co-precipitation, control pH ≈ 7, sediment 35 DEG C aging 5 days in mother liquor.The precipitating that the process obtains
Object uses supercritical fluid drying after filtering, washing, ethanol washing to no Cl- ion, and dehydrated alcohol makees supercritical medium, with
The heating rate of 5 DEG C/min rises to 260 DEG C, and slow release ethyl alcohol fluid is simultaneously under isothermal after constant temperature and pressure 30min under 6.0MPa
In N2Air-blowing, which is swept down, to be cooled to room temperature, and obtains ZrO in 350 DEG C of roasting 3h2-(3)。
Hydrogenation reaction carries out in 50mL stainless steel cauldron, 0.15g ZrO2(3) catalyst, 0.2g isoamyl olefine aldehydr,
15mL isopropanol (solvent), 140 DEG C of reaction temperature, nitrogen pressure 0.1MPa, speed of agitator 600r/min, reaction time 3h.Instead
Activity is answered to the results are shown in Table 1.
Embodiment 4
By 0.1 mole of ZrOCl2It is dissolved in 400mL deionized water, 28% ammonium hydroxide is diluted one times, by ZrOCl2Solution
With ammonium hydroxide at 40 DEG C co-precipitation, control pH ≈ 8, sediment 40 DEG C aging 5 days in mother liquor.The precipitating that the process obtains
Object is through filtering, washing, ethanol washing to no Cl-Supercritical fluid drying is used after ion, dehydrated alcohol makees supercritical medium, with
The heating rate of 5 DEG C/min rises to 270 DEG C, and slow release ethyl alcohol fluid is simultaneously under isothermal after constant temperature and pressure 40min under 6.0MPa
In N2Air-blowing, which is swept down, to be cooled to room temperature, and obtains ZrO in 350 DEG C of roasting 3h2-(4)。
Hydrogenation reaction carries out in 50mL stainless steel cauldron, 0.1g ZrO2(4) catalyst, 0.1g furfural, 15mL is just
Propyl alcohol (solvent), 100 DEG C of reaction temperature, Hydrogen Vapor Pressure 0.1MPa, speed of agitator 600r/min, reaction time 2h.Reactivity
It the results are shown in Table 1.
Embodiment 5
By 0.1 mole of ZrOCl2It is dissolved in 400mL deionized water, the Na with 10% (wt)2CO3Solution co-precipitation,
Control pH=9, the aging 3h at 70 DEG C.The sediment that this method obtains is through filtering, washing, ethanol washing without Cl-After ion, nothing
Water-ethanol is replaced, and is then placed in autoclave, and dehydrated alcohol makees extraction solvent, rises to 260 with the heating rate of 8 DEG C/min
DEG C, after stablizing 0.5h under the conditions of the Ethanol supercritical of 8.0MPa, slow release fluid, while logical N2Air cooling is to room temperature, in 550
DEG C obtained zirconium oxide of roasting 3h is denoted as ZrO2-(5)。
Hydrogenation reaction carries out in 50mL stainless steel cauldron, 0.1g ZrO2(5) catalyst, 0.1g citral, 15mL
N-butanol (solvent), 170 DEG C of reaction temperature, Hydrogen Vapor Pressure 0.1MPa, speed of agitator 600r/min, reaction time 5h.Reaction is lived
Property the results are shown in Table 1.
Embodiment 6
0.1 molar nitric acid zirconium is dissolved in 400mL deionized water, the Na with 10% (wt)2CO3Solution co-precipitation,
Control pH=10, the aging 4h at 70 DEG C.The sediment that this method obtains is through filtering, washing, ethanol washing without Cl-After ion,
Dehydrated alcohol is replaced, and is then placed in autoclave, and dehydrated alcohol makees extraction solvent, is risen to the heating rate of 5 DEG C/min
265 DEG C, after stablizing 0.5h under the conditions of the Ethanol supercritical of 7.5MPa, slow release fluid, while logical N2Air cooling to room temperature, in
The zirconium oxide that 550 DEG C of roasting 3h are obtained is denoted as ZrO2-(6)。
By Wide angle X-ray diffraction analyze it is found that roast after sample 2 θ be 30.3 ° and 35.0 ° there is diffraction maximum, table
It is now pure t-ZrO2Crystal phase；It is analyzed by Raman it is found that 455,470 and 645cm occurs in the sample after roasting-1Equal t-
ZrO2Eigen vibration peak, show ZrO2Sample maintains pure tetragonal phase；Pass through low temperature N2Adsorption-desorption isothermal curve point
Analysis it is found that sample adsorption-desorption isothermal curve be IUPAC classification in IV type thermoisopleth, belong to typical mesoporous material, press
The mesoporous distribution that desorption curve is calculated more is concentrated according to BJH model；Sample is in 1480cm after roasting-1There is apparent L
Sour characteristic peak, in 1540cm-1Weaker B acid characteristic peak, t-ZrO can be observed in place2Catalyst surface is primarily present Lewis acidity
Position.
Hydrogenation reaction carries out in 50mL stainless steel cauldron, 0.1g ZrO2(6) catalyst, 0.1g cinnamic acid, 15mL
Methanol (solvent), 110 DEG C of reaction temperature, nitrogen pressure 0.1MPa, speed of agitator 600r/min, reaction time 0.5h.Reaction is lived
Property the results are shown in Table 1.
Embodiment 7
By 0.4 mole of ZrOCl2It is dissolved in 170mL deionized water, 45 milliliter 28% of ammonium hydroxide is diluted to 150 milliliters,
Co-precipitation is carried out under water bath condition, controls pH value of solution 9.5 or so, obtained 100 DEG C of ageing 60h of white precipitate are cooling
To room temperature, through filtering, washing, ethanol washing to no Cl-Afterwards, dehydrated alcohol is replaced, and is then placed in autoclave, anhydrous
Ethyl alcohol makees extraction solvent, rises to 260 DEG C with the heating rate of 6 DEG C/min, stablizes 0.6h under the conditions of the Ethanol supercritical of 7.9MPa
Afterwards, slow release fluid, while logical N2Air cooling obtains ZrO in 500 DEG C of roasting 3h to room temperature2-(7)。
Hydrogenation reaction carries out in 50mL stainless steel cauldron, 0.1g ZrO2(7) catalyst, 0.1g citral, 15mL
Methanol (solvent), 160 DEG C of reaction temperature, Hydrogen Vapor Pressure 0.1MPa, speed of agitator 600r/min, reaction time 5h.Reactivity
It the results are shown in Table 1.
Embodiment 8
By 0.4 mole of ZrOCl2It is dissolved in 170mL deionized water, 45 milliliter 28% of ammonium hydroxide is diluted to 150 milliliters,
It is co-precipitated under water bath condition, controls pH value of solution 9.5 or so, obtained 100 DEG C of ageing 60h of white precipitate are cooled to room
Wen Hou, through filtering, washing, ethanol washing to no Cl-Afterwards, dehydrated alcohol is replaced, and is then placed in autoclave, dehydrated alcohol
Make extraction solvent, rises to 260 DEG C with the heating rate of 3 DEG C/min, after stablizing 0.5h under the conditions of the Ethanol supercritical of 8.0MPa, delay
On The Drug Release fluid, while logical N2Air cooling obtains ZrO in 500 DEG C of roasting 3h to room temperature2-(8)。
Hydrogenation reaction carries out in 50mL stainless steel cauldron, 0.1g ZrO2(8) catalyst, 0.2g isoamyl olefine aldehydr,
15mL isopropanol (solvent), 140 DEG C of reaction temperature, Hydrogen Vapor Pressure 0.1MPa, speed of agitator 600r/min, reaction time 1h.Instead
Activity is answered to the results are shown in Table 1.
1 alpha, beta-unsaturated aldehyde selective hydrogenation catalytic activity of table
Comparative example 1
With common coprecipitation, ZrO is prepared using conventional drying methods2Catalyst methacrolein is to isobutene alcohol.
Prepare ZrO2Catalyst: by 0.4 mole of ZrOCl2It is dissolved in 160mL deionized water, by 45 milliliter 28% of ammonium hydroxide
120 milliliters are diluted to, by ZrOCl2Solution is added dropwise in ammonia spirit, controls pH value of solution 9.5 or so, obtained white precipitate
90 DEG C of ageing 60h, after being cooled to room temperature, are filtered, are washed to no Cl-Afterwards, it is placed in baking oven in 80 DEG C of baking 3h, then at 110 DEG C
Lower baking for 24 hours, is subsequently placed in Muffle furnace, roasts 3h at 500 DEG C, obtains the ZrO that common coprecipitation method obtains2Catalyst,
It is denoted as ZrO2- R (Fig. 6).
Hydrogenation reaction carries out in 50mL stainless steel cauldron, 0.1g ZrO2- R catalyst, 0.1g methacrolein, 15mL
Isopropanol (solvent), 150 DEG C of reaction temperature, Hydrogen Vapor Pressure 0.05MPa, speed of agitator 600r/min, reaction time 4h.Isobutene
The conversion ratio of aldehyde is 45%, and selectivity is 38%, the ZrO obtained with supercritical fluid drying2Catalyst is compared, the comparative example
Method obtain catalyst dispersion it is bad, particle is larger, activity it is poor.
Claims (10)
1. a kind of for preparing the ZrO of alpha, beta unsaturated alcohol by alpha, beta-unsaturated aldehyde selective hydrogenation2The preparation method of catalyst,
Include the following steps:
(1) zirconium source is dissolved in deionized water, uses 0.5~2h of magnetic stirrer at room temperature, being made into molar concentration is
The solution A of 0.01mol/L to 0.05mol/L；
(2) alkali is made into the aqueous solution B that mass percent concentration is 5~15%；
(3) under stirring, by solution A and solution B co-precipitation, pH value of solution=6~10 is controlled, 1~3h of stirring is continued, 50~
Aging 3h~5 day at 90 DEG C；
(4) after aging filter, wash, alcohol wash, supercritical fluid drying, be then put in Muffle furnace 300~600 DEG C roast
Burn 3~6h.
2. preparation method according to claim 1, which is characterized in that zirconium source described in step 1) is zirconium oxychloride, nitric acid
Zirconium or zirconyl nitrate.
3. preparation method according to claim 1, which is characterized in that alkali described in step 2) be sodium hydroxide, sodium carbonate,
Ammonium hydroxide or its mixed solution.
4. preparation method according to claim 1, which is characterized in that supercritical fluid drying method described in step 4) is such as
Lower progress: using dehydrated alcohol as supercritical medium, rising to 240~280 DEG C with the heating rate of 3~10 DEG C/min, 6~
Under 8.0MPa after 20~60min of constant temperature and pressure under isothermal slow release ethyl alcohol fluid and in N2Air-blowing, which is swept down, to be cooled to room temperature,
Reactor is opened up to powder.
5. preparation method according to claim 1, which is characterized in that the zirconium source molar concentration of solution A is in step 1)
0.02mol/L to 0.025mol/L.
6. a kind of ZrO that preparation method as claimed in any of claims 1 to 5 is prepared2Catalyst.
7. a kind of ZrO according to claim 62Catalyst is preparing α, β-insatiable hunger by alpha, beta-unsaturated aldehyde selective hydrogenation
With the application in the reaction of alcohol.
8. a kind of by α, beta-unsaturated aldehyde selective hydrogenation prepares α, the method for beta unsaturated alcohol, which comprises use hydrogen
Purge reaction kettle three times, the air removed in reaction kettle is wanted using alcohol as solvent by reactant α, beta-unsaturated aldehyde and according to right
ZrO described in asking 62Catalyst is added in reaction kettle, and control reaction temperature is 70-180 DEG C, and Hydrogen Vapor Pressure is 0.1~1MPa, stirs
Mix 0.5~12h of reaction.
9. according to claim 8 by α, beta-unsaturated aldehyde selective hydrogenation prepares α, and the method for beta unsaturated alcohol is special
Sign is that the alcohol as solvent is selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and the tert-butyl alcohol.
10. according to claim 8 by α, beta-unsaturated aldehyde selective hydrogenation prepares α, and the method for beta unsaturated alcohol is special
Sign is, the ZrO2The molar ratio of catalyst and reactant alpha, beta-unsaturated aldehyde is 1:10~20.
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