CN104370692B - Polyol preparation method through glucose hydrogenolysis - Google Patents
Polyol preparation method through glucose hydrogenolysis Download PDFInfo
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- CN104370692B CN104370692B CN201310351505.8A CN201310351505A CN104370692B CN 104370692 B CN104370692 B CN 104370692B CN 201310351505 A CN201310351505 A CN 201310351505A CN 104370692 B CN104370692 B CN 104370692B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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 polyhydric alcohol.
Background technology
Currently, using biomass（Such as glucose）Carry out the document of hydrogenolysis conversion and patent has a lot, generally react
For multistep, glucose be first converted into sugar alcohol then again hydrogenolysis so that technological process is complicated.For example, Chinese patent
200610068869.5 disclose that " a kind of new technology producing ethylene glycol, it is anti-that it includes the preparation of DX value glucose syrup, hydrogenation
Answer, the refined, the hydrogenolysis of Sorbitol, polyol blends of sorbitol solution refines and separate." more for example：Chinese patent
200510008652.0 disclose a kind of method cracking production C2-4 dihydroxylic alcohols and polyhydric alcohol by Sorbitol aqueous phase, and the method makes
Sorbitol can be obtained by glucose hydrogenation.In addition, accelerator must also be added during some hydrogenolysis, right
Equipment causes to corrode, and production cost is high.And, using biomass（Such as glucose）The reaction great majority carrying out hydrogenolysis conversion are adopted
It is noble metal catalyst, make the catalyst output investment ratio of this technique larger.The biomass material concentration using is relatively low, economic effect
Benefit is not high.For example：Chinese patent 200480026228.2 discloses the method for hydrogenolysis " a kind of glycogen material in the presence of a catalyst ",
The method is that " wherein glycogen material comprises one or more polyol, and described catalyst comprises：（a）Ruthenium or osmium；With（b）
Organic phosphine；Wherein, hydrogenolysis is carried out existing under conditions of water and temperature are more than 150 DEG C.”
Furthermore, existing biomass（Such as glucose）Carry out hydrogenolysis conversion and carry out hydrogenolysis using batch still it is difficult to carry out even
Continuous operation, production efficiency is low.For example, Chinese patent application 200710038143.1 discloses that " prepared by one kind glucitol
The method of resin dihydroxylic alcohols ", the method is to carry out glucitol 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 production efficiency is low lacks
Fall into.These drawbacks limit glucose hydrogenolysis prepares application and the industrialization of low-carbon polyol.
Content of the invention
The technical problem to be solved in the present invention is a kind of method providing glucose hydrogenolysis to prepare polyhydric alcohol, and the method operates
Simply, little to equipment requirements, low cost, production efficiency is high and is beneficial to industrial applications.
For solving above-mentioned first technical problem, the method that a kind of present invention glucose hydrogenolysis prepares polyhydric alcohol, including such as
Lower step：
Under catalyst action, reactor is led to using high pressure continuous flow and carry out glucose catalytic hydrogenolytic cleavage, obtain mixing many
First alcohol product.
Described polyhydric alcohol is C2-C6Polyol；This C2-C6Polyol include Sorbitol, xylose
Alcohol, erythritol, Mannitol, glycerol, propylene glycol and/or ethylene glycol.Wherein xylitol and erythritol selectivity are far below third
Glycol and ethylene glycol.The yield of glycerol and butanediol falls between.Wherein propylene glycol is with the selection of 1,2-PD
Property has comparative advantage.BT, 5 hydroxymethyl furfural and 1,5-PD also have a small amount of generation, and molar selectivity is equal
Less than 2%.Coming from the fossil resources such as oil and natural gas traditional polyols preparation raw material more.This reaction not only can profit
It is raw material with cerelose, fermentation industry, the industry that such as brews alcoholic beverages etc. can also be used, the polyhydric alcohol being rich in, aldehyde, sour by-product are very
To waste material.Can effectively utilizes biomass, and be greatly improved economic benefit.In a word, the polyhydric alcohol of generation with ethylene glycol, the third two
Based on alcohol, butanediol, Sorbitol molar selectivity be less than 20%, BT, HMF and furfural molar selectivity 5% with
Under.
Preferably, described high pressure continuous flow leads to reactor is fixed bed reactors or rotating packed-bed reactor.
Preferably, in fixed bed reactors, be there is hydrogen continuously across fixing beds in D/W
Solution reaction.Preferably, in fixed bed reactors, react for trickle bed pattern, D/W is made by the effect of gravity
Through beds, product departs from beds also by gravity；Preferably, using silica wool etc., solid catalyst is entered
Row is fixed；The method has better seriality and operability compared to the batch still reaction that traditional biomass hydrogenation uses.
Preferably, reaction temperature 120-280 DEG C, reaction pressure is 1-100MPa, and hydrogen gas space velocity is 0.43kg（h·
kgcat）-1, D/W liquid air speed is 0.1-2.4kg（min·kgcat）-1.
It is highly preferred that reaction temperature 150-220 DEG C, reaction pressure is 1-20MPa, and hydrogen gas space velocity is 0.43kg（h·
kgcat）-1, D/W liquid air speed is 0.1-1.0kg（min·kgcat）-1.
Most preferably, reaction temperature 200-210 DEG C, reaction pressure is 3-10MPa, and hydrogen gas space velocity is 0.43kg（h·
kgcat）-1, D/W liquid air speed is 0.1-0.5kg（min·kgcat）-1.
Preferably, in rotating packed-bed reactor, D/W occurs continuously across the beds of rotation
Hydrogenolysis.In rotating bed reaction, due to raw material enter reactor after by rotation become more tiny drop, thus with urge
The contact effect of agent bed increases, and is departed from catalyst by centrifugal force, considerably increases mass-transfer efficiency.Hypergravity is anti-
Answer device so that there is the minimizing of the order of magnitude time of staying of reaction in running, but gas phase simultaneously（Hydrogen）It is dissolved into reaction
Liquid phase in ratio considerably increase, thus promote hydrogenation chain-breaking reaction carrying out；And by adjusting hypergravity level,
Can there is the selection of one section of best results between the time of staying and mass transfer rate；Supergravity reactor can from vertical and
Horizontal two kinds.
Preferably, reaction temperature 120-280 DEG C, reaction pressure is 1-100MPa, and hypergravity level is 2-300g, and hydrogen is empty
Speed is 0.43kg（h·kgcat）-1, D/W liquid air speed is 0.1-2.4kg（min·kgcat）-1.This
Somewhat higher reaction temperature can be taken when material concentration is relatively low in bright, can react more than 120 DEG C, preferential temperature exists
Between 180 DEG C -240 DEG C.When glucose solution mass concentration is 2%, reaction temperature can be more than 210 DEG C, and at this
Under part, the species of by-product and mol ratio all will reduce, and the ratio of butanediol will increase.Under higher glucose concentrations, fourth two
Alcohol is mainly 1,2- butanediol.Under compared with low glucose concentrations, three kinds of butanediols all have generation, and 1,3 butylene glycol and 1,2- fourth
Glycol is more.Any suitable reaction pressure can be selected, for pressure of the present invention between preferred 0.5-20MPa.
It is highly preferred that reaction temperature 150-220 DEG C, reaction pressure is 1-20MPa, and hypergravity level is 20-250g, hydrogen
Air speed is 0.43kg（h·kgcat）-1, D/W liquid air speed is 0.05-2.4kg（min·kgcat）-1.
Most preferably, reaction temperature 200-210 DEG C, reaction pressure is 3-10MPa, and hypergravity level is 150-200g, hydrogen
Gas air speed is 0.43kg（h·kgcat）-1, D/W liquid air speed is 0.05-1kg（min·kgcat）-1.
Preferably, D/W is to make solvent with water, be added without any soda acid accelerator, and glucose is in the solution
Percentage by weight is 1-40%, it is highly preferred that glucose percentage by weight in the solution is 1-20%.This course of reaction is gas
Liquid solid phase reaction, raw materials of glucose is dissolved in the water, and with respect to dimethyl sulfoxide, valerolactone equal solvent is cost-effective and has
High-dissolvability, mass concentration selects, below 40%, to avoid glucose feed the problems such as coking in reactor.In addition, not
Add any alkaline accelerator, the damage to equipment is also preferably minimized, and is difficult to retain in pipeline.Hydrogen and raw materials of glucose
Solution continuous feed, glucose feed is pumped in reactor by phase autoclave.
Preferably, described catalyst is the solid particle of 20-40 mesh.
Preferably, described catalyst includes the activity that one or more of Mo, W, Ru, Co, Al, Zr, Ni are catalyst
Composition, is carrier including activated carbon, silicon dioxide or aluminium sesquioxide.
It is highly preferred that it is active component that described catalyst includes one or more of Ru, Ni, Co, active component is being urged
For 0.5%-40%, one or more including Mo, W, Al, Zr are auxiliary agent to load weight in agent ratio, and auxiliary agent is in the catalyst
Load weight than for 5%-40%.
Preferably, the preparation method of described catalyst, comprises the steps：
1）Saline solution using above-mentioned promoter metal is immersed on carrier using iso volumetric impregnation method, is dried through evacuation,
100-150 DEG C of drying and 300-500 DEG C of calcining, then reduce at 300-500 DEG C；
2）Saline solution using above-mentioned activity component metal is immersed on carrier using iso volumetric impregnation method, does through evacuation
Dry, 100-150 DEG C of drying and 300-500 DEG C calcining, then at 300-500 DEG C reduce；Preferably 350 DEG C -500 of reduction temperature
Between DEG C, under this reaction temperature, transition metal can be reduced or be partially reduced, and generates the complexation of oxide and hydrogen
Thing, this kind of substance advantageous are in hydrogenation deoxidation；
Preferably, step 1）Or 2）In step, if carrier is activated carbon, calcines and carry out in nitrogen.
Preferably, step 1）Or 2）In step, if carrier is silicon dioxide, carrier is carried out with carbon process makes it load
Metal carbides.
Preferably, step 1）Or 2）In, described salt is nitrate or ammonium salt
Preferably, if not containing carbon in catalyst, using carbon compound, catalyst is entered in dipping process
Row pretreatment.Product collection rate can be made to improve through the catalyst of pretreatment and the content of ethylene glycol has carrying of certain amplitude
Rise.Wherein Ni element is conducive to generating Sorbitol, adds a small amount of noble metal in Ni is for the catalyst of main component, can not
Effectively change the selectivity of product.There is the trend generating more aldehydes in Mo element.
The present invention has the advantages that：
The method of the present invention is simple to operate, little to equipment requirements, low cost, and production efficiency is high and is beneficial to industrial applications.
Specific embodiment
Embodiment 1
Ni/AC method for preparing catalyst
Nickelous nitrate hexahydrate is taken to be dissolved in aqueous solution, the amount according to the mass loading rate 10% of Ni makes on activity carbon carrier
With iso volumetric impregnation method dipping, activity carbon carrier is in advance in N2In 200 DEG C purging two hours.Dipping puts into vacuum drying after finishing
1h, is then placed in 100 DEG C of air drying 10h, then N at 400 DEG C22h is calcined in atmosphere.
Embodiment 2
Ni/W/AC method for preparing catalyst
In embodiment 1 before Ni dipping, using the W of iso volumetric impregnation method impregnating effect load factor 15%（Ammonium metatungstate, I
Ding company）, dipping is put into after finishing and is vacuum dried 1h, is then placed in 120 DEG C of air drying 10h, then N at 300 DEG C2Gas
2h is calcined in atmosphere.Other are with embodiment 1.
Embodiment 3
Ni/Al/SiO2Method for preparing catalyst
Silica supports 200 DEG C of calcining 2h in atmosphere, are then soaked using iso volumetric impregnation method on silica supports
The Al of stain 10%2O3, dipping is put into after finishing and is vacuum dried 1h, is then placed in 120 DEG C of air drying 10h, then at 400 DEG C
2h is calcined in air atmosphere.Then using the Ni of iso volumetric impregnation method dipping 10%, dipping puts into vacuum drying 1h after finishing, then
Put into 130 DEG C of air drying 10h, then in air atmosphere at 500 DEG C, calcine 2h.
Embodiment 4
The Ni/W/AC method for preparing catalyst that Ru promotes, on the basis of embodiment 2, adds 0.5% Ru.
Embodiment 5
The Ni/Al/SiO that Ru promotes2Method for preparing catalyst, on the basis of embodiment 3, adds 0.5% Ru.
Embodiment 6
Ru/W/AC method for preparing catalyst：
Impregnate metatungstic acid according on the amount activity carbon carrier after treatment of W mass loading rate 15% using iso volumetric impregnation method
Ammonium salt solution, dipping puts into vacuum drying 1h after finishing, be then placed in 120 DEG C of air drying 10h, then N at 400 DEG C2Gas
2h is calcined in atmosphere；Then according to the amount of Ru mass loading rate 4% impregnates ruthenium trichloride using iso volumetric impregnation method on activity carbon carrier
Solution, dipping puts into vacuum drying 1h after finishing, be then placed in 140 DEG C of air drying 10h, then N at 400 DEG C2Atmosphere
Middle calcining 2h.
Embodiment 7
Ru/Al/SiO2The preparation method of catalyst：
Silica supports 200 DEG C of calcining 2h in atmosphere, are then soaked using iso volumetric impregnation method on silica supports
The Al of stain 10%2O3, dipping is put into after finishing and is vacuum dried 1h, is then placed in 150 DEG C of air drying 10h, then at 350 DEG C
2h is calcined in air atmosphere.Then use the Ru of iso volumetric impregnation method dipping 4%, dipping puts into vacuum drying 1h after finishing, be then placed in
120 DEG C of air drying 10h, then calcine 2h in air atmosphere at 450 DEG C.
Embodiment 8
Ru/Mo/W/SiO2Method for preparing catalyst：
Silica supports 200 DEG C of calcining 2h in atmosphere, are then soaked using iso volumetric impregnation method on silica supports
The W of stain mass fraction 10%, dipping puts into vacuum drying 1h after finishing, be then placed in 120 DEG C of air drying 10h, Ran Hou
2h is calcined in air atmosphere at 400 DEG C.Then using iso volumetric impregnation method, ammonium molybdate solution is impregnated into this forerunner according to 10% amount
In body, dipping puts into vacuum drying 1h after finishing, be then placed in 120 DEG C of air drying 10h, then air gas at 400 DEG C
2h is calcined in atmosphere.Then on silica supports using the Ru of iso volumetric impregnation method impregnating effect fraction 1%, dipping is put after finishing
Enter to be vacuum dried 1h, be then placed in 120 DEG C of air drying 10h, then in air atmosphere at 400 DEG C, calcine 2h.
Embodiment 9
Ru/Mo/SiO2Method for preparing catalyst
Silica supports 200 DEG C of calcining 2h in atmosphere, then on silica supports will using iso volumetric impregnation method
Ammonium molybdate solution is impregnated in presoma according to the amount of mass fraction 10%, and dipping puts into vacuum drying 1h after finishing, be then placed in
120 DEG C of air drying 10h, then calcine 2h in air atmosphere at 400 DEG C.Then on silica supports using etc. hold
The Ru of impregnation 1%, dipping puts into vacuum drying 1h after finishing, be then placed in 120 DEG C of air drying 10h, Ran Hou
2h is calcined in air atmosphere at 400 DEG C.
Embodiment 10
Ru/Zr/AC method for preparing catalyst：
Molten according to iso volumetric impregnation zirconyl nitrate on the amount activity carbon carrier after treatment of zirconium dioxide mass loading rate 10%
Liquid, dipping puts into vacuum drying 1h after finishing, be then placed in 120 DEG C of air drying 10h, then N at 400 DEG C2In atmosphere
Calcining 2h.Then according to the amount of Ru mass loading rate 1% iso volumetric impregnation solution of ruthenium trichloride on activity carbon carrier, dipping finishes
After put into vacuum drying 1h, be then placed in 120 DEG C of air drying 10h, then N at 400 DEG C22h is calcined in atmosphere.
Embodiment 11
Ru/Co/AC method for preparing catalyst：
According on the amount activity carbon carrier after treatment of Cobalto-cobaltic oxide mass loading rate 10% using the leaching of iso volumetric impregnation method
Stain cobalt nitrate solution, dipping puts into vacuum drying 1h after finishing, be then placed in 120 DEG C of air drying 10h, then at 400 DEG C
Lower N22h is calcined in atmosphere.Then according to the amount of Ru mass loading rate 1% impregnates three using iso volumetric impregnation method on activity carbon carrier
Chlorination ruthenium solution, dipping puts into vacuum drying 1h after finishing, be then placed in 120 DEG C of air drying 10h, then at 400 DEG C
N22h is calcined in atmosphere.
Embodiment 12
The Ru/W/SiO of carbon pretreatment2
Silica supports 200 DEG C of calcining 2h in atmosphere, are then soaked using iso volumetric impregnation method on silica supports
The W of stain 10%, dipping puts into vacuum drying 1h after finishing, be then placed in 120 DEG C of air drying 10h, then empty at 400 DEG C
2h is calcined in gas atmosphere.Then 120 DEG C of pretreatment 2h in n-decane, calcine 2h in air atmosphere at 400 DEG C.Then use
The Ru of iso volumetric impregnation method impregnating effect fraction 4%, dipping puts into vacuum drying 1h after finishing, be then placed in 120 DEG C of air dryings
10h, then calcines 2h in air atmosphere at 400 DEG C.
Embodiment 13
The Ru/Mo/SiO of carbon pretreatment2,
W in embodiment 12 is changed and is Mo, other are with embodiment 11.
Embodiment 14
The Ru/Zr/SiO of carbon pretreatment2,
W in embodiment 12 is changed and is Zr, other are with embodiment 11.
Embodiment 15-16 describes the impact of reaction condition in different reactor
Embodiment 15
Evaluating catalyst reaction condition in fixed bed reactors：
Fixed bed reaction, catalyst 0.5g, reaction pressure 4MPa, WHSV=0.3h-1,H2/C6H12O6=64.3:1(molar
Ratio), 205 DEG C, liquid phase quality concentration 10%, carry out under pure hydrogen atmosphere at 500 DEG C reducing 10h.
Reaction evaluating is as shown in table 1 below：
Evaluating catalyst reaction condition in embodiment 16 rotary drill reactor：Rotating bed reaction, catalyst 1.0g, reaction
Pressure 4MPa, WHSV=0.3h-1,H2/C6H12O6=64.3:1 (molar ratio), 205 DEG C, liquid concentration 10% is pure at 500 DEG C
Carry out under hydrogen atmosphere reducing 10h.Hypergravity level is 2-300g.
Note is (1)：The horizontal 200g of hypergravity
Note is (2)：The horizontal 2g of hypergravity
Note is (3)：The horizontal 300g of hypergravity
Embodiment 17 low concentration glucose raw material
Fixed bed reaction, catalyst 1.0g, reaction pressure 4MPa, WHSV=0.03h-1,H2/C6H12O6=320:1(molar
Ratio), 205 DEG C, liquid concentration 2%, carry out under pure hydrogen atmosphere at 500 DEG C reducing 10h.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not right
The restriction of embodiments of the present invention.For those of ordinary skill in the field, also may be used on the basis of the above description
To make other changes in different forms.Here all of embodiment cannot be exhaustive.Every belong to this
Obvious change that bright technical scheme is extended out or change the row still in protection scope of the present invention.
Claims (13)
1. a kind of glucose hydrogenolysis prepares the method for polyhydric alcohol it is characterised in that comprising the steps：
Under catalyst action, reactor is led to using high pressure continuous flow and carry out glucose one step catalytic hydrogenolytic cleavage, directly obtain mixed
Close polyol product；
It is active component that described catalyst includes one or more of Ru, Co, active component load weight in the catalyst
Than for 0.5%-40%；
One or more including Mo, W, Zr are auxiliary agent, and auxiliary agent load weight in the catalyst ratio is for 5%-40%；
It is carrier containing activated carbon, silicon dioxide or aluminium sesquioxide；
Described polyhydric alcohol includes ethylene glycol, propylene glycol and butanediol；And sorbitol content is less than 20% in product, methylol bran
The content of aldehyde and furfural is less than 5%；
It is fixed bed reactors or rotating packed-bed reactor that described high pressure continuous flow leads to reactor；
Reaction temperature 120-280 DEG C, reaction pressure is 1-100MPa, and hydrogen gas space velocity is 0.43kg (h kgcat)-1, glucose
Aqueous liquid air speed is 0.1-2.4kg (min kgcat)-1.
2. glucose hydrogenolysis according to claim 1 prepare polyhydric alcohol method it is characterised in that：In fixed bed reactors
In, be there are hydrogenolysis continuously across fixing beds in D/W.
3. glucose hydrogenolysis according to claim 1 prepare polyhydric alcohol method it is characterised in that：
Reaction temperature 150-220 DEG C, reaction pressure is 1-20MPa, and hydrogen gas space velocity is 0.43kg (h kgcat)-1, glucose
Aqueous liquid air speed is 0.1-1.0kg (min kgcat)-1.
4. glucose hydrogenolysis according to claim 1 prepare polyhydric alcohol method it is characterised in that：
Reaction temperature 200-210 DEG C, reaction pressure is 3-10MPa, and hydrogen gas space velocity is 0.43kg (h kgcat)-1, glucose
Aqueous liquid air speed is 0.1-0.5kg (min kgcat)-1.
5. glucose hydrogenolysis according to claim 1 prepare polyhydric alcohol method it is characterised in that：Anti- in RPB
Answer in device, D/W is occurred hydrogenolysis continuously across the beds of rotation.
6. glucose hydrogenolysis according to claim 5 prepare polyhydric alcohol method it is characterised in that：Reaction temperature 120-
280 DEG C, reaction pressure is 1-100MPa, and hypergravity level is 2-300g, and hydrogen gas space velocity is 0.43kg (h kgcat)-1, Portugal
Grape sugar aqueous solution liquid air speed is 0.1-2.4kg (min kgcat)-1.
7. glucose hydrogenolysis according to claim 5 prepare polyhydric alcohol method it is characterised in that：
Reaction temperature 150-220 DEG C, reaction pressure is 1-20MPa, and hypergravity level is 20-250g, and hydrogen gas space velocity is
0.43kg·(h·kgcat)-1.
8. glucose hydrogenolysis according to claim 5 prepare polyhydric alcohol method it is characterised in that：
Reaction temperature 200-210 DEG C, reaction pressure is 3-10MPa, and hypergravity level is 150-200g, and hydrogen gas space velocity is
0.43kg·(h·kgcat)-1.
9. the glucose hydrogenolysis according to claim 2 or 5 prepare polyhydric alcohol method it is characterised in that：Described glucose
Aqueous solution is to make solvent to be not added with the water of any soda acid accelerator, and glucose percentage by weight in the solution is 1-40%.
10. glucose hydrogenolysis according to claim 9 prepare polyhydric alcohol method it is characterised in that：Glucose is in solution
In percentage by weight be 1-20%.
11. glucose hydrogenolysis according to claim 1 prepare polyhydric alcohol method it is characterised in that：
Described catalyst is the solid particle of 20-40 mesh.
12. glucose hydrogenolysis according to claim 1 prepare the method for polyhydric alcohol it is characterised in that described catalyst
Preparation method, comprises the steps：
1) it is immersed on carrier using iso volumetric impregnation method using the saline solution of above-mentioned promoter metal, be dried through evacuation, 100-
150 DEG C of dryings and 300-500 DEG C of calcining, then reduce at 300-500 DEG C；
2) it is immersed on carrier using iso volumetric impregnation method using the saline solution of above-mentioned activity component metal, be dried through evacuation,
100-150 DEG C of drying and 300-500 DEG C of calcining, then reduce at 300-500 DEG C.
13. glucose hydrogenolysis according to claim 12 prepare polyhydric alcohol method it is characterised in that：
Step 1) or 2) in step, if carrier is activated carbon, calcines and carry out in nitrogen；
Step 1) or 2) in step, if carrier is silicon dioxide, carrier is carried out with carbon process making its carried metal carbide；
Step 1) or 2) in, described salt is nitrate or ammonium salt；
If not containing carbon in catalyst, in dipping process, using carbon compound, pretreatment is carried out to catalyst.
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| CN104961625A (en) * | 2015-04-27 | 2015-10-07 | 大连理工大学 | Method for synthesizing 1,2-propylene glycol using glucose |
| US11123712B2 (en) | 2016-07-26 | 2021-09-21 | Research Triangle Institute | Catalysts utilizing carbon dioxide for the epoxidation of olefins |
| CN107473934B (en) * | 2017-08-29 | 2020-04-07 | 中国科学技术大学 | Preparation method of sorbitol |
| CN109776259B (en) * | 2017-11-11 | 2021-12-31 | 华东理工大学 | Method for preparing cycloparaffin and polyalcohol by full utilization of primary biomass in one-pot method |
| CN109364948A (en) * | 2018-12-06 | 2019-02-22 | 浙江工业大学 | A kind of ruthenium nickel/active carbon is total to loaded catalyst and its preparation and application |
| CN110465296B (en) * | 2019-08-05 | 2022-02-08 | 中海油天津化工研究设计院有限公司 | Nickel-based glucose hydrogenation catalyst and preparation method thereof |
| CN110483239B (en) * | 2019-08-26 | 2021-04-06 | 同济大学 | Preparation method of propylene glycol |
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| CN101045674A (en) * | 2007-03-16 | 2007-10-03 | 东华大学 | Method for preparing resin dihydric alcohol by glucose alcohol |
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