CN104888778B - A kind of Cu/MgO catalyst of catalysis glucose hydrogenolysis and preparation method thereof - Google Patents
A kind of Cu/MgO catalyst of catalysis glucose hydrogenolysis and preparation method thereof Download PDFInfo
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- CN104888778B CN104888778B CN201510209248.3A CN201510209248A CN104888778B CN 104888778 B CN104888778 B CN 104888778B CN 201510209248 A CN201510209248 A CN 201510209248A CN 104888778 B CN104888778 B CN 104888778B
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Abstract
The invention discloses a kind of Cu/MgO catalyst of catalysis glucose hydrogenolysis and preparation method thereof, belongs to heterogeneous catalysis technology field.Under the conditions of anhydrous and oxygen-free, the liquid that Red copper oxide, 1,5 cyclo-octadiene, hexafluoroacetylacetonate reactive ketone are obtained is produced to the metastable metallorganic precursors hexafluoroacetylacetone cyclo-octadiene copper of air and hexafluoroacetylacetone copper through filtration, vacuum distillation, sublimation purification.With Magnesium acetate (Mg(OAc)2) tetrahydrate as raw material, the mixed solution of ethanol and deionized water is solvent, with solvent structure petal-shaped Mg (OH)2, calcine the alkaline mesoporous MgO carriers for obtaining Gao Bibiao.Two kinds of metallorganic precursors are supported on MgO carriers with mocvd method, copper-based catalysts Cu/MgO is prepared in Jing hydrogen reducings, for the hydrogenolysis of glucose.The present invention has operating procedure simple, and reaction condition is gentle, catalyst activity and good stability, and with good prospects for commercial application.
Description
Technical field
The invention belongs to heterogeneous catalysis technology field, is related to a kind of catalysis glucose hydrogenolysis high valuable chemicals
Cu/MgO catalyst and preparation method.
Background technology
With the worsening shortages of Fossil fuel, world population quantity is on the increase, at the same the mankind to the demand of the energy again
It is continuously increased so that the catalyst that Renewable resource (biomass) is converted into high valuable chemicals is had important by research and development
Meaning.Biomass source is extensively, cheap, wherein, glucose be distributed in nature it is most wide and most important a kind of single
Sugar, is a kind of polyhydroxy aldehyde, and the glucose being naturally occurring belongs to D configurations, predominantly pyrans formula structure present in aqueous solution
Type.At present, what the reaction great majority of glucose catalytic hydrogenolysiss production low-carbon polyol were adopted is all noble metal catalyst, is produced into
This height, and often need to add alkaline matter as accelerator, according to hydrogenolysis mechanism, under conditions of alkali-free, glucose can occur
Hydrogenation and isomerization reaction, production Sorbitol and Mannitol, and in the basic conditions, glucose can occur hydrogenolysis, production
Low-carbon polyol, such as 1,2-PD, glycerol, ethylene glycol etc., they are all important chemicals and Organic Chemicals, for example, 1,
2- Propylene Glycol is production unsaturated polyester (UP), the important source material of epoxy resin, is answered in the industries such as coating, medicine, cosmetics, chemical industry
With extensive.
Chinese patent, publication number：CN101781167A, introduces the side that glucose catalytic hydrogenolysiss prepare dihydroxylic alcohols and polyhydric alcohol
Method, which adopts the pH for adding alkaline matter to adjust solution to promote catalyst C-C bond fissions and prevent because producing organic acid
Deng by-product caused by catalyst loss.Reaction pressure needed for the technique is high and not high to the single selective of product.
Chinese patent, publication number：CN101921174A, introduces carbon nano-fiber load ruthenium catalyzing sorbitol hydrogenolysis and prepares 1,2-PD and EG
Method, the catalyst used by which be noble metal catalyst, it is expensive, NaOH need to be added to adjust solutionPH 11～
13, and the selectivity of the conversion ratio and product of Sorbitol is not high.B.C.Miranda et al. (Appl.Catal.B:
Environ., 2015,166-167,166-180) describe the bimetallic catalyst prepared by equi-volume impregnating for sweet
In the hydrogenolysis of oil, component is supported when make use of preparation catalyst and is distributed in carrier surface, the features such as utilization rate is high, system
Standby preferable into a kind of dispersion, specific surface area is big, activity preferably catalyst, but in the preparation process, the reduction temperature of catalyst
Degree is high, and precursor produces waste gas when decomposing, and causes environmental pollution.Chinese patent, publication number：CN102924233A, describes with altogether
Catalyst prepared by the sedimentation method is used for hydrogenolysis of glycerin and prepares in Propylene Glycol, and the preparation process of catalyst is more, and influence factor is complicated,
If operating condition control is improper, active component local concentration may be made too high, produce reunion.X.C.Wang et al. (Green
Chem., the method that the nickel catalytic cellulose hydrogenolysis of load changes into 1,2- alkane glycol, the work 2012,14,758-765) are described
In skill, less (the about 20m of specific surface area of catalyst prepared using coprecipitation2g-1), and the product kind of hydrogenolysis production
Class is more, and single selective is poor.
For the Catalyst Production high cost used by glucose hydrogenolysis, reaction solution need to often add alkaline matter as promotion
The problems such as agent and low production efficiency, we successfully have developed and prepare alkaline oxygenated magnesium-supported cuprio using MOCVD methods
Catalyst, preferably, specific surface area is larger for its dispersibility, and catalysis activity is high, is applied in glucose hydrogenolysis, need not add alkali
Property accelerator, and glucose can be converted completely, be 60%～72% to the selectivity of 1,2-PD.
The content of the invention
The invention provides a kind of Cu/MgO catalyst of catalysis glucose hydrogenolysis high valuable chemicals and preparation side
Method.
The present invention synthesizes petal-shaped Mg (OH) in Hydrothermal Synthesiss kettle with solvent-thermal method2, alkalescence is obtained Jing after calcining mesoporous
MgO carriers, remain Mg (OH)2Appearance structure and with larger specific surface area；Synthesize to sky under the conditions of anhydrous and oxygen-free
The metastable two kinds of metallorganic precursors hexafluoroacetylacetone of gas-cyclo-octadiene copper (I) and hexafluoroacetylacetone copper；Using gold
Category organic chemical vapor deposition (MOCVD), the method synthesized high-performance Cu/MgO catalysis materials of hydrogen reducing；And with Green Water be
Solvent, carries out glucose hydrogenolysis (concentration of glucose is 5-20wt%) in high-pressure hydrogenation reactor, and hydrogenolysis are adopted
Segmentation constant voltage operation, first paragraph reaction temperature 120-140 DEG C, reaction pressure 4-8MPa；Second segment reaction temperature 200-250 DEG C,
Reaction pressure 4-8MPa.The present invention is improve in the hydrogenolysis solution of the selectivity and glucose of 1,2- Propylene Glycol without extra
Add alkali as accelerator, operating procedure is simple, and environmental friendliness, catalysis activity are high, and the single selective of product is fine.
Technical scheme is as follows：
A kind of Cu/MgO catalyst and preparation method thereof of catalysis glucose hydrogenolysis, Magnesium acetate (Mg(OAc)2) tetrahydrate and goes ethanol
Ionized water is stirred reaction, solution is injected in stainless steel autoclave afterwards, reacts in being placed on 180 DEG C of baking oven；Take out
Autoclave is cooled to room temperature, reactant liquor is centrifuged, is washed, drying to obtain white solid powder magnesium hydroxide；Will
Magnesium hydroxide is calcined under the atmosphere of argon and oxygen obtains MgO carriers.Under the conditions of anhydrous and oxygen-free, will be oxidation sub-
Copper, 1,5- cyclo-octadiene, hexafluoroacetylacetone, tetrahydrofuran stirring reaction, the solution for obtaining is carried out vacuum distillation to remove
The pressed powder for obtaining is carried out sublimation purification by solvent afterwards, obtains metallorganic precursors hexafluoro second metastable to air
Acyl acetone-cyclo-octadiene copper (I) and hexafluoroacetylacetone copper；Both precursors for obtaining fully are mixed with carrier magnesium oxide respectively
Attach together in Shi Lanke bottles, carry out vapour deposition respectively under conditions of uniform temperature, vacuum.Take out post-depositional pressed powder
It is placed in reduction tube, is reduced under argon, the atmosphere of hydrogen and obtain catalysis material Cu/MgO, by itself and 5-20wt% Portugal
Grape sugar juice carries out hydrogenolysis, reaction pressure 4-8MPa, first paragraph reaction temperature 120- in being added to autoclave together
140 DEG C, second segment reaction temperature 200-250 DEG C, mixing speed 800r/min naturally cool to room temperature after having reacted.Filter anti-
Product after answering, and reclaim catalyst.Jointly product is characterized with liquid chromatograph with gas phase, calculate turning for glucose
The selectivity of rate and product.
Supported non-noble metal catalysis material prepared according to the methods of the invention can be applicable to hydrogenation, dehydrogenation, oxidation, alkane
Base, it is cyclized, goes the aspects such as removal organic polluter, automobile exhaust pollution thing to embody excellent catalytic performance, and present invention behaviour
Make simple, environmental friendliness, with wide prospects for commercial application.Glucose hydrogen is used for by the metal supported catalyst of the present invention
Solution reaction, glucose converted completely, to the selectivity of 1,2-PD up to more than 70%, solves glucose hydroformylation product solution list
The problems such as one selectivity is not good.
Description of the drawings
The stereoscan photograph of Fig. 1 carrier MgO.
Transmission electron microscope photo of Fig. 2 (a) loadings for 5%Cu/MgO (I).
Transmission electron microscope photo of Fig. 2 (b) loadings for 5%Cu/MgO (II).
Transmission electron microscope photo of Fig. 2 (c) loadings for 15%Cu/MgO (I).
Transmission electron microscope photo of Fig. 2 (d) loadings for 15%Cu/MgO (II).
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with technical scheme and accompanying drawing.
Embodiment 1～3
Magnesium acetate (Mg(OAc)2) tetrahydrate is added separately to mixed solution (the volume ratio difference of the deionized water and dehydrated alcohol of 60ML
For：2:1,1:1,1:2) stirring reaction in, is then added separately to solution in stainless steel autoclave, is placed on 180 DEG C of baking ovens
It is middle to continue reaction, respectively reactant liquor is centrifuged afterwards, with the deionized water and absolute ethanol washing of corresponding proportion, most
After be put into baking oven in be dried, that is, obtain Mg (OH)2, it is placed in tube type resistance furnace, at 500 DEG C, the gas of argon and oxygen
Calcine under atmosphere, that is, obtain MgO carriers.Consider the pattern and yield of MgO, it is 1 to choose volume ratio:2 deionized water and anhydrous second
Alcohol is reacted.The stereoscan photograph of gained sample is shown in Fig. 1.
| Magnesium acetate (Mg(OAc)2) tetrahydrate/g | VDeionized water：VDehydrated alcohol | Magnesium hydroxide/g | |
| Example 1 | 1.29 | 2:1 | 0.009 |
| Example 2 | 1.29 | 1:1 | 0.032 |
| Example 3 | 1.29 | 1:2 | 0.100 |
Embodiment 4
By Cu2O is added in three neck round bottom flask, adds 1,5- cyclo-octadiene and THF stirrings anti-under the atmosphere of argon
Should, 1,1,1,5,5,5- hexafluoro -2 are injected within half an hour by constant pressure separatory funnel then, 4- pentanediones and THF continue stirring
Reaction, reaction filter unreacted Cu after terminating2The filtrate for obtaining is carried out vacuum distillation to remove solvent, afterwards to solid by O
Powder carries out sublimation purification, obtains corresponding metallorganic precursors hexafluoroacetylacetone-cyclo-octadiene copper (I), by thermogravimetric analysiss
Learn, the temperature that supports of monovalence copper precursors elects 100 DEG C as.
Embodiment 5
It is substantially the same manner as Example 4, only do not add 1,5- cyclo-octadiene, you can obtain corresponding metallorganic precursors six
Acetyl fluoride acetone copper.Learnt by thermogravimetric analysiss, the temperature that supports of bivalence copper precursors elects 60 DEG C as.
Embodiment 6～7
Monovalence copper precursors and bivalence copper precursors are individually placed to into the side in two chemical vapor deposition unit Y-pieces, are carried
Body is placed on opposite side, respectively at 100 DEG C and 60 DEG C, vapour deposition is carried out under vacuum condition, you can obtain loading for 5wt%'s
Supported copper catalyst (embodiment 6).
Monovalence copper precursors and bivalence copper precursors are placed on carrier in agate mortar respectively and are ground so as to fully mixed, so
Afterwards mixture is respectively charged in Shi Lanke bottles, vapour deposition is carried out in the case where other conditions are identical, you can respectively obtain and support
Measure the supported copper catalyst (embodiment 7) for 5wt%.Supporting device and operating for embodiment 6,7 is compared, by carrier and precursor
Grinding is easier to support together, that is, obtain the supported copper catalyst that loading is 10wt%, 15wt%.Before monovalence copper
Body, catalyst obtained in bivalence copper precursors are respectively labeled as Cu/MgO (I), Cu/MgO (II).
Embodiment 8～9
The pressed powder for having supported is placed in reduction tube, at 200 DEG C, argon (flow is 20mL/min), hydrogen
(20mL/min) reductase 12 h (embodiment 8) under atmosphere, it is found that when gas flow is big, cause the precursor for supporting to be taken away by gas.
Therefore the flow of modulation hydrogen and argon and be all 10mL/min (embodiment 9), other conditions are constant, you can obtain what is reduced
The supported copper catalyst of different loadings.The transmission electron microscope photo of gained sample is shown in Fig. 2 (a)-(d).
Embodiment 10～12
Weigh glucose to be dissolved in deionized water, be made into the solution that 3 parts of mass concentrations are 5wt%, be separately added into
To in reactor, the supported copper catalyst that the good loading of prereduction is 5wt%, 10wt%, 15wt% is separately added into afterwards
Cu/MgO (I), capping kettle, using segmentation constant pressure heating operation, in 6Mpa, stirring reaction 2h under conditions of 140 DEG C, stirring
Speed is set to 800r/min, then reacts 3h under conditions of 220 DEG C.The product after reacting is filtered, gas phase and liquid phase is carried out
Chromatography, and reclaim catalyst.The conversion ratio for obtaining glucose is 100%.
Embodiment 13～15
Weigh glucose to be dissolved in deionized water, be made into the solution that 3 parts of mass concentrations are 5wt%, be separately added into
To in reactor, the supported copper catalyst that the good loading of prereduction is 5wt%, 10wt%, 15wt% is separately added into afterwards
Cu/MgO (II), capping kettle, using segmentation constant pressure heating operation, in 6Mpa, stirring reaction 2h under conditions of 140 DEG C is stirred
Mix speed and be set to 800r/min, then 3h is reacted under conditions of 220 DEG C.The product after reacting is filtered, gas phase and liquid is carried out
Analysis of hplc, and reclaim catalyst.The conversion ratio for obtaining glucose is 100%.
Embodiment 16
In order to compare the glucose hydrogenolysis performance of the catalyst prepared without method, weigh glucose and be dissolved in deionized water
In, the solution that mass concentration is 5wt% is made into, is added it in reactor, add the load prepared using co-precipitation afterwards
Type copper catalyst Cu/MgO, capping kettle, using segmentation constant pressure heating operation, in 6Mpa, stirring reaction under conditions of 140 DEG C
2h, mixing speed are set to 800r/min, then react 3h under conditions of 220 DEG C.The product after reacting is filtered, gas phase is carried out
And liquid-phase chromatographic analysis, and reclaim catalyst.The conversion ratio for obtaining glucose is 71.9%.
Claims (2)
1. it is a kind of catalysis glucose hydrogenolysis Cu/MgO catalyst preparation method, it is characterised in that：
Petal-shaped Mg (OH) is synthesized in Hydrothermal Synthesiss kettle with solvent-thermal method2, alkaline mesoporous MgO carriers are obtained Jing after calcining；In nothing
Synthesize under water oxygen free condition two kinds of metallorganic precursors hexafluoroacetylacetones-cyclo-octadiene copper (I) metastable to air and
Hexafluoroacetylacetone copper；Using the method synthesized high-performance Cu/MgO catalysis materials of metal organic chemical vapor deposition, hydrogen reducing
Material；With water as solvent, glucose hydrogenolysis are carried out in high-pressure hydrogenation reactor, concentration of glucose is 5-20wt%；
Hydrogenolysis are using segmentation constant voltage operation：
First paragraph reaction temperature 120-140 DEG C, reaction pressure 4-8MPa；
Second segment reaction temperature 200-250 DEG C, reaction pressure 4-8Mpa.
2. preparation method according to claim 1, it is characterised in that：
(1) Magnesium acetate (Mg(OAc)2) tetrahydrate, ethanol and deionized water are stirred into reaction, the solution injection stainless steel autoclave for obtaining
In, react in being placed on 180 DEG C of baking oven；Take out autoclave and be cooled to room temperature, reactant liquor is centrifuged, washs, is done
It is dry to obtain white solid powder magnesium hydroxide；
(2) magnesium hydroxide is calcined under the atmosphere of argon and oxygen and had both been obtained MgO carriers；
(3) under the conditions of anhydrous and oxygen-free, will be the stirring of Red copper oxide, 1,5- cyclo-octadiene, hexafluoroacetylacetone and tetrahydrofuran anti-
Should, the solution for obtaining is carried out into vacuum distillation to remove solvent, the pressed powder for obtaining is carried out into sublimation purification afterwards, obtain right
The metastable metallorganic precursors hexafluoroacetylacetone of air-cyclo-octadiene copper (I) and hexafluoroacetylacetone copper；
(4) two kinds of precursors that step (3) is obtained are sufficiently mixed with MgO carriers respectively, carry out vapour deposition；Take out post-depositional
Pressed powder is placed in reduction tube, is reduced and obtain catalysis material Cu/MgO under argon, the atmosphere of hydrogen；
(5) catalysis material Cu/MgO and 5-20wt% glucose solutions are added to into segmentation constant pressure hydrogenolysis in autoclave anti-
Should, room temperature is naturally cooled to after having reacted；The product after reacting is filtered, and reclaims catalyst.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD295096A5 (en) * | 1990-06-13 | 1991-10-24 | Deutsches Hydrierwerk Rodleben,De | PROCESS FOR PREPARING A CATALYST FOR GLUCOSE HYDROGENATION |
| CN102153446A (en) * | 2011-03-10 | 2011-08-17 | 江苏大学 | Cu/MgO catalyst, preparation method thereof and method for catalyzing glycerin hydrogenolysis |
| CN103240102A (en) * | 2013-05-15 | 2013-08-14 | 常州工学院 | Preparation method of copper-metallic oxide and method for preparing 1, 2-propylene glycol by hydrogenating glycerol |
-
2015
- 2015-04-27 CN CN201510209248.3A patent/CN104888778B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD295096A5 (en) * | 1990-06-13 | 1991-10-24 | Deutsches Hydrierwerk Rodleben,De | PROCESS FOR PREPARING A CATALYST FOR GLUCOSE HYDROGENATION |
| CN102153446A (en) * | 2011-03-10 | 2011-08-17 | 江苏大学 | Cu/MgO catalyst, preparation method thereof and method for catalyzing glycerin hydrogenolysis |
| CN103240102A (en) * | 2013-05-15 | 2013-08-14 | 常州工学院 | Preparation method of copper-metallic oxide and method for preparing 1, 2-propylene glycol by hydrogenating glycerol |
Non-Patent Citations (2)
| Title |
|---|
| Cu/Mg0催化剂CO加氢低温甲醇合成研究;张建利等;《煤炭转化》;20130131;第36卷(第1期);第93-96页 * |
| Hydrogenolysis of biomass-derived sorbitol to glycols and glycerol over Ni-MgO catalysts;Xinguo Chen et al.;《Catalysis Communications》;20130521;第39卷;第86-89页 * |
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