CN101711982B - Supported nano Au catalyst for preparing crotyl alcohol and preparation method thereof - Google Patents
Supported nano Au catalyst for preparing crotyl alcohol and preparation method thereof Download PDFInfo
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- CN101711982B CN101711982B CN2009101990474A CN200910199047A CN101711982B CN 101711982 B CN101711982 B CN 101711982B CN 2009101990474 A CN2009101990474 A CN 2009101990474A CN 200910199047 A CN200910199047 A CN 200910199047A CN 101711982 B CN101711982 B CN 101711982B
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Abstract
The invention belongs to the chemical technical field and particularly relates to a supported nano Au catalyst for preparing crotyl alcohol by crotonic aldehyde selective hydrogenation and a preparation method thereof. The catalyst is prepared by using mesoporous titanium dioxide microballoons having core-shell structures as the carrier and loading the active constituents, nano Au, to the titanium dioxide microballoons by the deposition-precipitation method. The catalyst has the characteristics that the active constituents are highly dispersed, and the mol ratio of the titanium dioxide to the active constituents is 23.0-305.7. Compared with the nano Au catalyst supported by the commercial titanium dioxide carrier P25, the Au/TiO2 microspherical catalyst shows higher selectivity of target products in the reaction of preparing crotyl alcohol by crotonic aldehyde selective hydrogenation, thereby having important industrial application value.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of crotonaldehyde that is used for and select load type nano gold catalyst of hydrogenation processed fructus crotonis alcohol and preparation method thereof.
Background technology
α, beta-unsaturated aldehyde select hydrogenation to generate α, and beta unsaturated alcohol is important source material and the reaction intermediate during spices, medicine and other fine chemical products are produced, and in organic synthesis, has a wide range of applications.Crotonyl alcohol is α, representative compound in the beta unsaturated alcohol.It is a kind of intermediate of very important organic synthesis, is usually used in making n-butanol, hutanal, thiofide, alcotate, tanning agent, herbicide and soil fumigant etc., can be used as the warning agent of flue gas in addition.Therefore, crotonaldehyde selects catalytic hydrogenation generation crotonyl alcohol process to have economic worth.
Usually mostly the method that obtains unsaturated alcohol is to adopt tetrahydro lithium aluminium, sodium borohydride or aluminium isopropoxide directly to reduce unsaturated aldehyde, though this method can obtain the α of high yield, beta unsaturated alcohol; But reducing agent costs an arm and a leg; Severe reaction conditions, product and reducing agent, separated from solvent difficulty, the post processing of product is loaded down with trivial details, and the three wastes of generation are many; The unsaturated alcohol of common every production 1kg will produce the refuse of 20-50kg, not meet the requirement of modern chemical industry.If adopt the method for catalysis of solid catalyst hydrogenation then can greatly reduce the generation of these refuses, product is easy to separate with catalyst.And adopt solvent to carry out hydrogenation reaction, and need only distill product simply with solvent or decompression distillation separates and get final product, say it is feasible from technological angle, the while also can greatly be reduced reaction cost.Therefore adopt catalysis of solid catalyst α, beta-unsaturated aldehyde is selected hydrogenation preparing α, and beta unsaturated alcohol can meet the requirement of atom economy and Green Chemistry.
Crotonaldehyde is multi-functional compound, has C=C key and C=O key in the molecule simultaneously.In hydrogenation process, with different butyraldehyde, crotonyl alcohol and the butanols of obtaining of hydrogenation position and hydrogenation degree.Existing work shows, on most metallic catalyst, and for typical α, beta-unsaturated aldehyde-crotonaldehyde-be more prone to hydrogenation to generate butyraldehyde, the selectivity of target product crotonyl alcohol is low.To α, the catalyst that beta unsaturated alcohol has a high selectivity concentrates on still that (Pt, Ru Pd) are main catalyst, though it is active and selectivity is very high, cost an arm and a leg, and are not suitable for large-scale industrial production with noble metal.Nearest research shows that nano catalyst has higher carbonyl hydrogen selectivity than precious metals pt, at α, has shown better catalytic performance in the reaction of beta-unsaturated aldehyde selection hydrogenation generation unsaturated alcohol.Simultaneously, because with respect to noble metal (Pt, Ru, Pd) catalyst, the relative low price of gold.Therefore, nano catalyst is expected at α, and beta-unsaturated aldehyde is selected hydrogenation preparing α, is applied in the beta unsaturated alcohol technology.
Summary of the invention
The objective of the invention is to propose the novel supported nano catalyst that crotonaldehyde is selected hydrogenation crotyl alcohol preparation that is used for of a kind of catalytic efficiency height, good reaction selectivity, and propose this Preparation of catalysts method.
The load type nano gold catalyst that is used for crotonaldehyde selection hydrogenation processed fructus crotonis alcohol provided by the invention is a kind of golden mesoporous TiO 2 microspherical catalyst that contains, and it is a carrier with the mesoporous TiO 2 microballoon with nucleocapsid structure, and nm of gold is an active component.The mol ratio of carrier and active component is 23.0～305.7.The characteristics of this catalyst are the active component high degree of dispersion, have effectively improved the catalytic performance of nano catalyst.It is different from the nano catalyst of commercial titanium dioxide P25 load, so the present invention is referred to as to contain golden mesoporous TiO 2 microspherical catalyst, is designated as Au/TiO
2
Catalyst provided by the invention, its Jin Yuan are gold chloride (HAuCl
44H
2O), precipitating reagent is urea (CO (NH
2)
2), catalyst adopts the preparation of the deposition-precipitation method.Concrete steps are: the mesoporous TiO that at room temperature 1.0～1.3g is had nucleocapsid structure
2The HAuCl of microsphere supported adding 60～70mL
44H
2In the mixed solution of O and urea, the following slow heated solution of stirring is to 353K and keep 2～12h, gets catalyst precursor; Then the catalyst precursor that makes is promptly made through pervaporation, oven dry, reduction activation step and contain golden mesoporous TiO 2 microspherical catalyst.
Among the above-mentioned preparation method, HAuCl
44H
2The molar concentration of O is 0.06～0.8M, urea and HAuCl
44H
2The mol ratio of O is 80～120.In the said reduction activation step, reduction activation atmosphere is 5% H
2/ Ar gas is specially: at H
2In/Ar the gas, with the oven dry after the catalyst precursor with 1～3Kmin
-1Heating rate be heated to 573～773K, and keep 2～4h.
The used mesoporous TiO 2 of the present invention is microsphere supported to be the homogeneous precipitation method preparation, this method by people such as Guo Changwen in reported first in 2003 (Guo Changwen etc. regular mesopore TiO
2Synthetic and the application in the cyclopentene oxidation reaction [J] of the precipitation from homogeneous solution of microballoon. SCI, 2003,6:1097～1099).According to catalyst provided by the invention, the active component gold with the form high degree of dispersion of metallic state on carrier.Fig. 1 and Fig. 2 are respectively the microsphere supported and Au/TiO of typical mesoporous TiO 2
2The transmission electron microscope photo of catalyst.
Activity of such catalysts provided by the invention can be used following method test:
Intermittently investigate catalyst performance in the tank reactor at the 0.22L stainless steel.Crotonaldehyde, a certain amount of heptane, catalyst are put into still.Autoclave sealing back is with hydrogen exchange 3 times, to remove the air in the still.Constant hydrogen presses off the beginning reaction after being heated to reaction temperature behind the preliminary filling hydrogen, and reaction temperature is 50～150 ℃, and more excellent 80～120 ℃, hydrogen pressure 0.5～5MPa, more excellent 1～2MPa begins during reaction to stir, and stir speed (S.S.) is greater than 1000 rev/mins.Take out response sample at interval with gas chromatographic analysis crotonyl alcohol content, crotonaldehyde content and other possible product content wherein with certain hour in the course of reaction.Show that catalyst of the present invention is used for crotonaldehyde and selects hydrogenation crotyl alcohol preparation, catalytic efficiency is high, good reaction selectivity.
Description of drawings
Fig. 1 is the microsphere supported transmission electron microscope photo of mesoporous TiO 2.
Fig. 2 is Au/TiO
2The transmission electron microscope photo of catalyst.
The specific embodiment
Further describe the present invention through specific embodiment below:
Embodiment 1: at room temperature with 1.0g TiO
2Carrier adds 60mL HAuCl
44H
2In the mixed solution of O (0.08M) and urea (8M), the following slow heated solution of stirring is to 353K and keep 4h; After with the presoma that makes stir evaporation, 393K dries by the fire 24h; The back is at H
2In/Ar the gas, with 1Kmin
-1Heating rate be heated to 673K, and keep 3h.Be designated as the 1# catalyst.
Embodiment 2: at room temperature with 1.0g TiO
2Carrier adds 60mLHAuCl
44H
2In the mixed solution of O (0.17M) and urea (17M), the following slow heated solution of stirring is to 353K and keep 4h; Surplus with real row 1.Be designated as the 2# catalyst.
Embodiment 3: at room temperature with 1.0g TiO
2Carrier adds 60mL HAuCl
44H
2In the mixed solution of O (0.42M) and urea (42M), the following slow heated solution of stirring is to 353K and keep 4h; Surplus with real row 1.Be designated as the 3# catalyst.
Embodiment 4: at room temperature with 1.0gTiO
2Carrier adds 60mLHAuCl
44H
2In the mixed solution of O (0.85M) and urea (85M), the following slow heated solution of stirring is to 353K and keep 4h; Surplus with real row 1.Be designated as the 4# catalyst.
Comparative example: at room temperature 1.0g P25 carrier is added 60mLHAuCl
44H
2In the mixed solution of O (0.42M) and urea (42M), the following slow heated solution of stirring is to 353K and keep 4h; Surplus with real row 1.Be designated as the 5# catalyst.
The test of crotonaldehyde hydrogenation activity: catalyst amount is 1.0 grams, 1 milliliter of pure crotonaldehyde, and 49 milliliters of heptane, reaction temperature 393K, Hydrogen Vapor Pressure 2.0MPa, 1000 rev/mins of stir speed (S.S.)s, the hydrogenation result is shown in table two.
The physicochemical properties of table one, catalyst
Crotonaldehyde hydrogenation result on table two, the catalyst
aThe pairing selectivity of the highest yield of crotonyl alcohol
bThe conversion ratio of 2h crotonaldehyde
Claims (3)
1. the preparation method of the load type nano gold catalyst of processed fructus crotonis alcohol usefulness; It is characterized in that adopting the deposition-precipitation method; With the gold chloride is Jin Yuan, is precipitating reagent with urea, and its concrete steps are following: the mesoporous TiO 2 micro-sphere material that at room temperature 1.0～1.3g is had a nucleocapsid structure adds in the mixed solution of 60～70mL gold chloride and urea; The said mixed solution of the following heating of stirring is to 353K and keep 2～12h; Get catalyst precursor, the catalyst precursor that makes through pervaporation, oven dry, reduction activation step, is promptly made required catalyst; This catalyst is a carrier with the mesoporous TiO 2 micro-sphere material with nucleocapsid structure, is active component with the nm of gold, and the mol ratio of carrier and active component is 23.0～305.7.
2. preparation method according to claim 1, the molar concentration that it is characterized in that gold chloride is 0.06～0.8M.
3. preparation method according to claim 1, the mol ratio that it is characterized in that used urea and gold chloride is 80～120.
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| CN2009101990474A CN101711982B (en) | 2009-11-19 | 2009-11-19 | Supported nano Au catalyst for preparing crotyl alcohol and preparation method thereof |
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| CN2009101990474A CN101711982B (en) | 2009-11-19 | 2009-11-19 | Supported nano Au catalyst for preparing crotyl alcohol and preparation method thereof |
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| CN101711982B true CN101711982B (en) | 2012-05-30 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI395729B (en) * | 2011-01-14 | 2013-05-11 | China Petrochemical Dev Corp | A method for producing a dihydric alcohol compound |
| WO2015198204A1 (en) * | 2014-06-23 | 2015-12-30 | Sabic Global Technologies B.V. | Benzene production from ethanol over gold/titanium dioxide catalysts |
| CN104353456B (en) * | 2014-11-14 | 2016-08-24 | 上海应用技术学院 | A kind of nano titania catalyst of gold-supported and its preparation method and application |
| CN110627617A (en) * | 2019-08-27 | 2019-12-31 | 浙江工业大学 | Application of carbon nano tube embedded metal particle catalyst in reaction of synthesizing crotyl alcohol by selective catalytic hydrogenation of crotonaldehyde |
| CN111454126B (en) * | 2020-05-20 | 2023-06-02 | 浙江师范大学 | Nano rod-like CeO 2 Application of nanocrystalline catalyst in gas-solid phase crotonaldehyde selective hydrogenation catalytic reaction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101015790A (en) * | 2007-03-08 | 2007-08-15 | 复旦大学 | Titanium dioxide microsphere photocatalyst capable of degrading organic pollutant and its prodn. method |
| CN101157677A (en) * | 2007-09-27 | 2008-04-09 | 复旦大学 | Method for catalytic preparation of delta-valerolactone by using supported nano-gold catalyst |
-
2009
- 2009-11-19 CN CN2009101990474A patent/CN101711982B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101015790A (en) * | 2007-03-08 | 2007-08-15 | 复旦大学 | Titanium dioxide microsphere photocatalyst capable of degrading organic pollutant and its prodn. method |
| CN101157677A (en) * | 2007-09-27 | 2008-04-09 | 复旦大学 | Method for catalytic preparation of delta-valerolactone by using supported nano-gold catalyst |
Non-Patent Citations (2)
| Title |
|---|
| Zhenfeng Bian et al.In situ encapsulation of Au nanoparticles in mesoporous core–shell TiO2 microspheres with enhanced activity and durability.《Chem. Commun.》.2009, * |
| 杨秋芸等.Au/TiO2催化剂制备条件对巴豆醛选择加氢的影响.《物理化学学报》.2009,第25卷(第09期),1853-1860. * |
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