CN104370692A - Polyol preparation method through glucose hydrogenolysis - Google Patents
Polyol preparation method through glucose hydrogenolysis Download PDFInfo
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- CN104370692A CN104370692A CN201310351505.8A CN201310351505A CN104370692A CN 104370692 A CN104370692 A CN 104370692A CN 201310351505 A CN201310351505 A CN 201310351505A CN 104370692 A CN104370692 A CN 104370692A
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- 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/74—Iron group metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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Abstract
The invention discloses a polyol preparation method through glucose hydrogenolysis. The preparation method comprises a step of carrying out glucose catalytic hydrogenolysis reactions in a high-pressure continuous flowing reactor in the presence of a catalyst so as to obtain the polyol products. The preparation method has the advantages of simple operation, low requirements on equipment, low production cost, and high production efficiency, and is suitable for being applied to industry.
Description
Technical field
The present invention relates to a kind of method that glucose hydrogenolysis prepares polyvalent alcohol.
Background technology
Current, utilize biomass (such as glucose) to carry out the document of hydrogenolysis conversion and patent has a lot, reaction is multistep usually, and glucose is first converted into sugar alcohol and then hydrogenolysis, makes technical process complicated.Such as, Chinese patent 200610068869.5 discloses " a kind of novel process of producing ethylene glycol, it comprise the preparation of DX value glucose syrup, hydrogenation, Sorbitol Solution USP refining, the hydrogenolysis of sorbyl alcohol, the refining of polyol blends and be separated." more such as: Chinese patent 200510008652.0 discloses a kind of method of being produced C2-4 dibasic alcohol and polyvalent alcohol by the cracking of sorbyl alcohol aqueous phase, and the sorbyl alcohol that the method uses can be obtained by glucose hydrogenation.In addition, in the process of some hydrogenolysis, also must add promotor, cause corrosion to equipment, production cost is high.And what the reaction great majority utilizing biomass (such as glucose) to carry out hydrogenolysis conversion adopted is noble metal catalyst, makes the catalyzer output investment ratio of this technique larger.The biomass material concentration used is lower, and economic benefit is not high.Such as: Chinese patent 200480026228.2 discloses the method for hydrogenolysis " a kind of glycogen material in the presence of a catalyst ", and the method is that " wherein glycogen material comprises one or more polyols, and described catalyzer comprises: (a) ruthenium or osmium; (b) organic phosphine; Wherein, hydrogenolysis is carried out existing under water and temperature are greater than the condition of 150 DEG C.”
Moreover existing biomass (such as glucose) are carried out hydrogenolysis conversion and are used batch still to carry out hydrogenolysis, and be difficult to carry out operate continuously, production efficiency is low.Such as, Chinese patent application 200710038143.1 discloses " a kind of sorbitol prepares the method for resin dibasic alcohol ", and the method carries out sorbitol hydrogenation catalyst in intermittent high-pressure reactor.
To sum up, in prior art, the method for glucose hydrogenolysis has that step is many, expensive catalyst or the defect such as production efficiency is low.These drawbacks limit glucose hydrogenolysis prepares application and the industrialization of low-carbon polyol.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method that glucose hydrogenolysis prepares polyvalent alcohol, and the method is simple to operate, little to equipment requirements, and cost is low, and production efficiency is high and be beneficial to industrial applications.
For solving above-mentioned first technical problem, a kind of glucose hydrogenolysis of the present invention prepares the method for polyvalent alcohol, comprises the steps:
Under catalyst action, adopt high pressure continuous flow to lead to reactor carry out glucose catalytic hydrogenolytic cleavage, obtain polyol blend product.
Described polyvalent alcohol is C
2-C
6polyol; This C
2-C
6polyol comprise sorbyl alcohol, Xylitol, erythritol, N.F,USP MANNITOL, glycerine, propylene glycol and/or ethylene glycol.Wherein Xylitol and erythritol selectivity are far below propylene glycol and ethylene glycol.The productive rate of glycerol and butyleneglycol falls between.Wherein propylene glycol has comparative advantage with the selectivity of 1,2-PD.BT, 5 hydroxymethyl furfural and 1,5-PD also have a small amount of generation, and molar selectivity is all no more than 2%.Traditional polyvalent alcohol raw materials multi-source is in fossil resources such as oil and natural gas.This reaction not only can utilize cerelose for raw material, can also use fermentation industry, as the industry etc. that brews alcoholic beverages, and the by product even waste material of the polyvalent alcohol be rich in, aldehyde, acid.Effectively can utilize biomass, and can greatly increase economic efficiency.In a word, the polyvalent alcohol of generation based on ethylene glycol, propylene glycol, butyleneglycol, sorbyl alcohol molar selectivity lower than 20%, BT, HMF and furfural molar selectivity less than 5%.
Preferably, described high pressure continuous flow leads to reactor is fixed-bed reactor or rotating packed-bed reactor.
Preferably, in fixed-bed reactor, by D/W continuously across fixing beds generation hydrogenolysis.Preferably, in fixed-bed reactor, react for trickle bed pattern, make D/W through beds by the effect of gravity, product also departs from beds by gravity; Preferably, silica wool etc. is used to be fixed by solid catalyst; The batch still reaction that this method uses compared to traditional biomass hydrogenation has better continuity and operability.
Preferably, temperature of reaction 120-280 DEG C, reaction pressure is 1-100MPa, and hydrogen gas space velocity is 0.43kg(hkgcat)
-1, D/W liquid air speed is 0.1-2.4kg(minkgcat)
-1.
More preferably, temperature of reaction 150-220 DEG C, reaction pressure is 1-20MPa, and hydrogen gas space velocity is 0.43kg(hkgcat)
-1, D/W liquid air speed is 0.1-1.0kg(minkgcat)
-1.
Most preferably, temperature of reaction 200-210 DEG C, reaction pressure is 3-10MPa, and hydrogen gas space velocity is 0.43kg(hkgcat)
-1, D/W liquid air speed is 0.1-0.5kg(minkgcat)
-1.
Preferably, in rotating packed-bed reactor, D/W is continuously across the beds generation hydrogenolysis rotated.In rotating bed reaction, due to raw material enter reactor after become more tiny drop by rotating, thus to increase with the contact effect of beds, and departed from catalyzer by centrifugal force, considerably increase mass-transfer efficiency.Supergravity reactor makes the residence time of reacting have the minimizing of the order of magnitude in operational process, but the ratio that gas phase (hydrogen) is dissolved in the liquid phase of reaction simultaneously considerably increases, thus the carrying out of the hydrogenation chain-breaking reaction promoted; And by adjustment hypergravity level, the selection of one section of best results can be there is between the residence time and rate of mass transfer; Supergravity reactor can select vertical and horizontal two kinds.
Preferably, temperature of reaction 120-280 DEG C, reaction pressure is 1-100MPa, and hypergravity level is 2-300g, and hydrogen gas space velocity is 0.43kg(hkgcat)
-1, D/W liquid air speed is 0.1-2.4kg(minkgcat)
-1.Can take higher temperature of reaction when material concentration is lower in the present invention, can react more than 120 DEG C, preferential temperature is between 180 DEG C-240 DEG C.When glucose solution mass concentration is 2%, temperature of reaction can more than 210 DEG C, and with this understanding, the kind of by product and mol ratio all will reduce, and the ratio of butyleneglycol will increase.Under higher glucose concentrations, butyleneglycol is mainly 1,2-butyleneglycol.Under comparatively low glucose concentrations, three kinds of butyleneglycols all have generation, and 1,3 butylene glycol and 1,2-butyleneglycol more.Any suitable reaction pressure can be selected, between the preferred 0.5-20MPa of pressure of the present invention.
More preferably, temperature of reaction 150-220 DEG C, reaction pressure is 1-20MPa, and hypergravity level is 20-250g, and hydrogen gas space velocity is 0.43kg(hkgcat)
-1, D/W liquid air speed is 0.05-2.4kg(minkgcat)
-1.
Most preferably, temperature of reaction 200-210 DEG C, reaction pressure is 3-10MPa, and hypergravity level is 150-200g, and hydrogen gas space velocity is 0.43kg(hkgcat)
-1, D/W liquid air speed is 0.05-1kg(minkgcat)
-1.
Preferably, D/W makees solvent with water, do not add any soda acid promotor, and glucose weight percent is in the solution 1-40%, and more preferably, glucose weight percent is in the solution 1-20%.This reaction process is gas-liquid-solid phase reaction, raw materials of glucose is dissolved in the water, relative to dimethyl sulfoxide (DMSO), valerolactone equal solvent is cost-saving and have high-dissolvability, and mass concentration is selected below 40%, can avoid glucose feed problem such as coking in reactor.In addition, do not add any basic-type accelerator, drop to minimum to the damage of equipment yet, not easily retain in pipeline.Hydrogen and the continuously feeding of raw materials of glucose solution, glucose feed is pumped in reactor by phase autoclave.
Preferably, described catalyzer is 20-40 object solid particulate.
Preferably, one or more comprising in Mo, W, Ru, Co, Al, Zr, Ni of described catalyzer are the activeconstituents of catalyzer, and comprising gac, silicon-dioxide or aluminium sesquioxide is carrier.
More preferably, one or more comprising in Ru, Ni, Co of described catalyzer are activeconstituents, activeconstituents load weight is in the catalyst than being 0.5%-40%, and one or more comprising Mo, W, Al, Zr are auxiliary agent, and auxiliary agent load weight is in the catalyst than being 5%-40%.
Preferably, the preparation method of described catalyzer, comprises the steps:
1) using the salts solution of above-mentioned promoter metal to use iso volumetric impregnation method to be immersed on carrier, through vacuumizing drying, 100-150 DEG C of drying and 300-500 DEG C of calcining, then reducing at 300-500 DEG C;
2) using the salts solution of above-mentioned activity component metal to use iso volumetric impregnation method to be immersed on carrier, through vacuumizing drying, 100-150 DEG C of drying and 300-500 DEG C of calcining, then reducing at 300-500 DEG C; Reduction temperature is preferably between 350 DEG C-500 DEG C, and under this temperature of reaction, transition metal can be reduced or be partially reduced, and generates the complex compound of oxide compound and hydrogen, and this kind of substance advantageous is in hydrogenation deoxidation;
Preferably, step 1) or 2) in step, if carrier is gac, then calcines and carry out in nitrogen.
Preferably, step 1) or 2) in step, if when carrier is silicon-dioxide, carbon process is carried out to carrier and makes its loaded metal carbide.
Preferably, step 1) or 2) in, described salt is nitrate or ammonium salt
Preferably, if not containing carbon in catalyzer, then use carbon compound to carry out pre-treatment to catalyzer in steeping process.Product collection rate can be made to improve and the content of ethylene glycol has the lifting of certain amplitude through pretreated catalyzer.Wherein Ni element is conducive to generating sorbyl alcohol, is add a small amount of precious metal in the catalyzer of main component, effectively can not changes the selectivity of product at Ni.There is the trend generating more aldehydes in Mo element.
The present invention has following beneficial effect:
Method of the present invention is simple to operate, little to equipment requirements, and cost is low, and production efficiency is high and be beneficial to industrial applications.
Embodiment
Embodiment 1
Ni/AC method for preparing catalyst
Get in the water-soluble solution of Nickelous nitrate hexahydrate, on activity carbon carrier, use iso volumetric impregnation method to flood according to the amount of the mass loading rate 10% of Ni, activity carbon carrier is in advance at N
2in 200 DEG C purge two hours.Put into vacuum-drying 1h after dipping, then put into 100 DEG C of air drying 10h, then N at 400 DEG C
22h is calcined in atmosphere.
Embodiment 2
Ni/W/AC method for preparing catalyst
In embodiment 1 before Ni dipping, use the W(ammonium metawolframate of iso volumetric impregnation method impregnating effect load factor 15%, Aladdin company), put into vacuum-drying 1h after dipping, then put into 120 DEG C of air drying 10h, then N at 300 DEG C
22h is calcined in atmosphere.Other are with embodiment 1.
Embodiment 3
Ni/Al/SiO
2method for preparing catalyst
Silica supports is 200 DEG C of calcining 2h in atmosphere, then use the Al of iso volumetric impregnation method dipping 10% on silica supports
2o
3, put into vacuum-drying 1h after dipping, then put into 120 DEG C of air drying 10h, then at 400 DEG C, calcine 2h in air atmosphere.Then use the Ni of iso volumetric impregnation method dipping 10%, put into vacuum-drying 1h after dipping, then put into 130 DEG C of air drying 10h, then at 500 DEG C, calcine 2h in air atmosphere.
Embodiment 4
The Ni/W/AC method for preparing catalyst that Ru promotes, on the basis of embodiment 2, adds the Ru of 0.5%.
Embodiment 5
The Ni/Al/SiO that Ru promotes
2method for preparing catalyst, on the basis of embodiment 3, adds the Ru of 0.5%.
Embodiment 6
Ru/W/AC method for preparing catalyst:
Use iso volumetric impregnation method to flood ammonium metatungstate solution according on the amount activity carbon carrier after treatment of W mass loading rate 15%, put into vacuum-drying 1h after dipping, then put into 120 DEG C of air drying 10h, then N at 400 DEG C
22h is calcined in atmosphere; Then on activity carbon carrier, use iso volumetric impregnation method to flood ruthenium trichloride solution according to the amount of Ru mass loading rate 4%, put into vacuum-drying 1h after dipping, then put into 140 DEG C of air drying 10h, then N at 400 DEG C
22h is calcined in atmosphere.
Embodiment 7
Ru/Al/SiO
2the preparation method of catalyzer:
Silica supports is 200 DEG C of calcining 2h in atmosphere, then use the Al of iso volumetric impregnation method dipping 10% on silica supports
2o
3, put into vacuum-drying 1h after dipping, then put into 150 DEG C of air drying 10h, then at 350 DEG C, calcine 2h in air atmosphere.Then with the Ru of iso volumetric impregnation method dipping 4%, put into vacuum-drying 1h after dipping, then put into 120 DEG C of air drying 10h, then at 450 DEG C, calcine 2h in air atmosphere.
Embodiment 8
Ru/Mo/W/SiO
2method for preparing catalyst:
Silica supports is 200 DEG C of calcining 2h in atmosphere, then the W of iso volumetric impregnation method impregnating effect mark 10% is used on silica supports, put into vacuum-drying 1h after dipping, then put into 120 DEG C of air drying 10h, then at 400 DEG C, calcine 2h in air atmosphere.Then use iso volumetric impregnation method by ammonium molybdate solution according to 10% amount be impregnated in this presoma, put into vacuum-drying 1h after dipping, then put into 120 DEG C of air drying 10h, then at 400 DEG C, calcine 2h in air atmosphere.Then use the Ru of iso volumetric impregnation method impregnating effect mark 1% on silica supports, put into vacuum-drying 1h after dipping, then put into 120 DEG C of air drying 10h, then at 400 DEG C, calcine 2h in air atmosphere.
Embodiment 9
Ru/Mo/SiO
2method for preparing catalyst
Silica supports is 200 DEG C of calcining 2h in atmosphere, then iso volumetric impregnation method is used to be impregnated in presoma by ammonium molybdate solution according to the amount of massfraction 10% on silica supports, vacuum-drying 1h is put into after dipping, then put into 120 DEG C of air drying 10h, then at 400 DEG C, calcine 2h in air atmosphere.Then use the Ru of iso volumetric impregnation method dipping 1% on silica supports, put into vacuum-drying 1h after dipping, then put into 120 DEG C of air drying 10h, then at 400 DEG C, calcine 2h in air atmosphere.
Embodiment 10
Ru/Zr/AC method for preparing catalyst:
According to iso volumetric impregnation zirconyl nitrate solution on the amount activity carbon carrier after treatment of zirconium dioxide mass loading rate 10%, put into vacuum-drying 1h after dipping, then put into 120 DEG C of air drying 10h, then N at 400 DEG C
22h is calcined in atmosphere.Then according to amount iso volumetric impregnation ruthenium trichloride solution on activity carbon carrier of Ru mass loading rate 1%, put into vacuum-drying 1h after dipping, then put into 120 DEG C of air drying 10h, then N at 400 DEG C
22h is calcined in atmosphere.
Embodiment 11
Ru/Co/AC method for preparing catalyst:
Use iso volumetric impregnation method to flood cobalt nitrate solution according on the amount activity carbon carrier after treatment of tricobalt tetroxide mass loading rate 10%, put into vacuum-drying 1h after dipping, then put into 120 DEG C of air drying 10h, then N at 400 DEG C
22h is calcined in atmosphere.Then on activity carbon carrier, use iso volumetric impregnation method to flood ruthenium trichloride solution according to the amount of Ru mass loading rate 1%, put into vacuum-drying 1h after dipping, then put into 120 DEG C of air drying 10h, then N at 400 DEG C
22h is calcined in atmosphere.
Embodiment 12
The pretreated Ru/W/SiO of carbon
2
Silica supports is 200 DEG C of calcining 2h in atmosphere, then the W of iso volumetric impregnation method dipping 10% is used on silica supports, put into vacuum-drying 1h after dipping, then put into 120 DEG C of air drying 10h, then at 400 DEG C, calcine 2h in air atmosphere.Then 120 DEG C of pre-treatment 2h in n-decane, calcine 2h in air atmosphere at 400 DEG C.Then use the Ru of iso volumetric impregnation method impregnating effect mark 4%, put into vacuum-drying 1h after dipping, then put into 120 DEG C of air drying 10h, then at 400 DEG C, calcine 2h in air atmosphere.
Embodiment 13
The pretreated Ru/Mo/SiO of carbon
2,
Changed by W in embodiment 12 and be Mo, other are with embodiment 11.
Embodiment 14
The pretreated Ru/Zr/SiO of carbon
2,
Changed by W in embodiment 12 and be Zr, other are with embodiment 11.
Embodiment 15-16 describes the impact of reaction conditions in different reactor
Embodiment 15
Evaluating catalyst reaction conditions in fixed-bed reactor:
Fixed bed reaction, catalyzer 0.5g, reaction pressure 4MPa, WHSV=0.3h
-1, H
2/ C
6h
12o
6=64.3:1 (molar ratio), carries out reduction 10h under pure hydrogen atmosphere at liquid phase quality concentration 10%, 500 DEG C by 205 DEG C.
Reaction evaluating is as shown in table 1 below:
Evaluating catalyst reaction conditions in embodiment 16 rotary drill reactor: rotating bed reaction, catalyzer 1.0g, reaction pressure 4MPa, WHSV=0.3h
-1, H
2/ C
6h
12o
6=64.3:1 (molar ratio), 205 DEG C, liquid concentration 10%, carries out reduction 10h under pure hydrogen atmosphere at 500 DEG C.Hypergravity level is 2-300g.
Note (1): the horizontal 200g of hypergravity
Note (2): the horizontal 2g of hypergravity
Note (3): the horizontal 300g of hypergravity
Embodiment 17 low concentration glucose raw material
Fixed bed reaction, catalyzer 1.0g, reaction pressure 4MPa, WHSV=0.03h
-1, H
2/ C
6h
12o
6=320:1 (molar ratio), 205 DEG C, liquid concentration 2%, carries out reduction 10h under pure hydrogen atmosphere at 500 DEG C.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give exhaustive to all embodiments.Every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (10)
1. glucose hydrogenolysis prepares a method for polyvalent alcohol, it is characterized in that, comprises the steps:
Under catalyst action, adopt high pressure continuous flow to lead to reactor carry out glucose one step catalytic hydrogenolytic cleavage, directly obtain polyol blend product.
2. glucose hydrogenolysis according to claim 1 prepares the method for polyvalent alcohol, it is characterized in that: preferably, and described polyvalent alcohol comprises ethylene glycol, propylene glycol and butyleneglycol; And sorbitol content is lower than 20% in product, the content of hydroxymethylfurfural and furfural is lower than 5%.
3. glucose hydrogenolysis according to claim 1 prepares the method for polyvalent alcohol, it is characterized in that: preferably, and it is fixed-bed reactor or rotating packed-bed reactor that described high pressure continuous flow leads to reactor.
4. glucose hydrogenolysis according to claim 3 prepares the method for polyvalent alcohol, it is characterized in that: preferably, in fixed-bed reactor, by D/W continuously across fixing beds generation hydrogenolysis.
5. glucose hydrogenolysis according to claim 4 prepares the method for polyvalent alcohol, it is characterized in that: preferably, temperature of reaction 120-280 DEG C, and reaction pressure is 1-100MPa, and hydrogen gas space velocity is 0.43kg(hkgcat)
-1, D/W liquid air speed is 0.1-2.4kg(minkgcat)
-1;
More preferably, temperature of reaction 150-220 DEG C, reaction pressure is 1-20MPa, and hydrogen gas space velocity is 0.43kg(hkgcat)
-1, D/W liquid air speed is 0.1-1.0kg(minkgcat)
-1;
Most preferably, temperature of reaction 200-210 DEG C, reaction pressure is 3-10MPa, and hydrogen gas space velocity is 0.43kg(hkgcat)
-1, D/W liquid air speed is 0.1-0.5kg(minkgcat)
-1.
6. glucose hydrogenolysis according to claim 3 prepares the method for polyvalent alcohol, it is characterized in that: preferably, in rotating packed-bed reactor, by D/W continuously across the beds generation hydrogenolysis rotated.
7. glucose hydrogenolysis according to claim 6 prepares the method for polyvalent alcohol, it is characterized in that: preferably, temperature of reaction 120-280 DEG C, and reaction pressure is 1-100MPa, and hypergravity level is 2-300g, and hydrogen gas space velocity is 0.43kg(hkgcat)
-1, D/W liquid air speed is 0.1-2.4kg(minkgcat)
-1;
More preferably, temperature of reaction 150-220 DEG C, reaction pressure is 1-20MPa, and hypergravity level is 20-250g, and hydrogen gas space velocity is 0.43kg(hkgcat)
-1, D/W liquid air speed is 0.05-2.4kg(minkgcat)
-1;
Most preferably, temperature of reaction 200-210 DEG C, reaction pressure is 3-10MPa, and hypergravity level is 150-200g, and hydrogen gas space velocity is 0.43kg(hkgcat)
-1, D/W liquid air speed is 0.05-1kg(minkgcat)
-1.
8. the glucose hydrogenolysis according to claim 4 or 6 prepares the method for polyvalent alcohol, it is characterized in that: preferably, and described D/W is that the water not adding any soda acid promotor makees solvent, and glucose weight percent is in the solution 1-40%; More preferably, glucose weight percent is in the solution 1-20%;
Preferably, described catalyzer is 20-40 object solid particulate;
Preferably, described catalyzer comprise one or more in Mo, W, Ru, Co, Al, Zr, Ni be the activeconstituents of catalyzer; Comprising gac, silicon-dioxide or aluminium sesquioxide is carrier;
More preferably, one or more comprising in Ru, Ni, Co of described catalyzer are activeconstituents, activeconstituents load weight is in the catalyst than being 0.5%-40%, and one or more comprising Mo, W, Al, Zr are auxiliary agent, and auxiliary agent load weight is in the catalyst than being 5%-40%.
9. glucose hydrogenolysis according to claim 8 prepares the method for polyvalent alcohol, it is characterized in that, preferably, the preparation method of described catalyzer, comprises the steps:
1) using the salts solution of above-mentioned promoter metal to use iso volumetric impregnation method to be immersed on carrier, through vacuumizing drying, 100-150 DEG C of drying and 300-500 DEG C of calcining, then reducing at 300-500 DEG C;
2) using the salts solution of above-mentioned activity component metal to use iso volumetric impregnation method to be immersed on carrier, through vacuumizing drying, 100-150 DEG C of drying and 300-500 DEG C of calcining, then reducing at 300-500 DEG C; Reduction temperature is preferably between 350 DEG C-500 DEG C, and under this temperature of reaction, transition metal can be reduced or be partially reduced, and generates the complex compound of oxide compound and hydrogen, and this kind of substance advantageous is in hydrogenation deoxidation.
10. glucose hydrogenolysis according to claim 9 prepares the method for polyvalent alcohol, it is characterized in that:
Preferably, step 1) or 2) in step, if carrier is gac, then calcines and carry out in nitrogen;
Preferably, step 1) or 2) in step, if when carrier is silicon-dioxide, carbon process is carried out to carrier and makes its loaded metal carbide;
Preferably, step 1) or 2) in, described salt is nitrate or ammonium salt;
Preferably, if not containing carbon in catalyzer, then use carbon compound to carry out pre-treatment to catalyzer in steeping process.
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