CN102091624B - Catalyst for preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol and preparation method thereof - Google Patents
Catalyst for preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol and a preparation method thereof, and relates to a catalyst. The catalyst consists of nickel, an aid and a carrier in a mass ratio of (10-40):(0-5):100. The preparation method comprises the following steps of: dissolving quantitative metal nickel salt and aid salt in water, adding into the carrier, and stirring in a hot-water bath; preparing a precipitator into aqueous solution; adding metered precipitator solution into metal salt-carrier mixed solution with stirring, stirring and standing; and performing suction filtration to obtain a solid, washing until washing liquor is neutral, eluting and dehydrating to obtain a catalyst precursor, drying, and performing pre-reduction-activation treatment for 1 to 6 hours in the atmosphere of low-hydrogen mixed gas to obtain the black powdery solid catalyst. The catalyst is suitable for preparing the dihydric alcohol through hydrogenolysis of sorbic alcohol or glycerol in a wide concentration range, can be repeatedly used and is low in cost.
Description
Technical field
The present invention relates to a kind of catalyst, especially with the Catalysts and its preparation method of polyalcohol catalytic hydrogenolysis produce diatomic alcohol.
Background technology
1,2-PD (1, be 2-PDO) important industrial chemicals, be widely used in chemical industry, food, medicine and cosmetics industry.Existing 1, the 2-PDO production method generally adopts expoxy propane hydration method, also can utilize the hydrolysis of 1,2-dichloropropane and produce, but all having the problems such as larger environmental pollution and high expensive.Due to the quick rise of the petrochemical material prices such as propylene, existing production method faces the pressure of production cost, in the urgent need to developing new raw material sources and synthetic route.
Ethylene glycol (EG) is another kind of important Organic Chemicals, mainly for the production of polyester, anti-icing fluid, adhesive, paint solvent, Everlube, nonionic surface active agent, explosive and plasticizer etc., especially polyester.At present, the ethylene glycol industrial production mainly adopts the legal petroleum path of epoxyethane water, and ethene is direct material, and naphtha is indirect material, but along with the decay increasingly of petroleum resources, the energy and the Chemical Manufacture approach of exploring Non oil-based route seem even more important.Have in Chemical Manufacture and daily life very widely and use.At present, the main method of producing EG both at home and abroad is that epoxyethane water is legal, but the technological process of the method is long, equipment is many, energy consumption is high, thereby production cost is also high, also exist simultaneously equipment perishable with the problem such as contaminated environment.
Biomass-based polyalcohol such as sorbierite and glycerine etc. are called the Novel platform molecule that synthesizes from now on recyclable fuel and chemicals.Adopt catalytic hydrogenolysis, biomass polyalcohol etc. is converted into 1, the dihydroxylic alcohols such as 2-PDO and EG, both can increase industrial chain, increase economic efficiency, also developing of relevant biomass energy chemical industry will be promoted, and expand the new way and the shortage that makes up dihydroxylic alcohols output of dihydroxylic alcohols production, meet China's strategy of sustainable development.
In the relevant patent documentation of hydrogenolysis of sorbitol produce diatomic alcohol, in the majority with exploitation supported precious metal catalyst system so far.For example, describe a kind of carbon nanofibers in Chinese patent CN101347731A and carry the Ru catalyst, 220 ℃, under the 10MPa stagnation pressure, sorbierite conversion ratio 71.5%, dihydroxylic alcohols selective 50%.The Chinese patent CN101583583A of Germany's BASF AG application has prepared loading type Pd/C catalyst series, under CaO exists, reacts 10h under 230 ℃ and Hydrogen Vapor Pressure 25MPa, and sorbierite conversion ratio 100%, dihydroxylic alcohols are selectively greater than 70%.Chinese patent CN1078662A has introduced the Ru/C catalyst of Sn doping, it is characterized in that being applied to respectively tank reactor and fixed bed reactors, 225～270 ℃ of reaction temperatures, and reaction pressure 10～19MPa is with Ca (OH)
2Be promoter, the sorbierite conversion ratio is greater than 80%, and dihydroxylic alcohols (EG+PDO) wherein adopts the required reaction condition of fixed bed reactors all gentle than the required reaction condition of tank reactor selectively greater than 60%.In the EP0510238 of Europe, the Pt/C catalyst is applied to hydrogenolysis of sorbitol reaction, in the intermittence tank reactor, with Ca (OH)
2Be promoter, react 2h under 250 ℃ and Hydrogen Vapor Pressure 13MPa (before heating up) condition, the dihydroxylic alcohols yield is 60%; In fixed bed reactors, reaction temperature can suitably be reduced to 225 ℃, and the dihydroxylic alcohols yield maintains 60%.
In addition, non-precious metal catalyst system, particularly nickel-base catalyst also receive increasing concern.Chinese patent CN101199930A has described a kind of skeletal nickel catalyst, one or more impacts on the hydrogenolysis of sorbitol reaction in the elements such as antimony dopant, copper, iron, tin, ruthenium, lanthanum, cobalt, molybdenum, boron, phosphorus, rhenium have been investigated respectively, take 95%Ni-4%Cu-1%Ru as example, be used for the reaction of 25wt% hydrogenolysis of sorbitol, 225 ℃, react 16h under Hydrogen Vapor Pressure 11MPa, sorbitol concentration 0.91%, glycol concentration 2.79%, propane diols concentration 8.40%.But the preparation of this catalyst is higher to equipment requirement, and energy consumption is large, and a large amount of skeleton nickel of using has also increased the cost of catalyst preparation.CN1683293A has introduced the biomass conversion route from corn, wherein adopt support type 5%Ru-50%Ni/G1-80 catalyst, prepare C2～C4 dihydroxylic alcohols take 25wt% concentration sorbierite as raw material, at 230 ℃, Hydrogen Vapor Pressure 13MPa, regulate the pH value as 13 take NaOH, product each key component concentration after fractionation is respectively: sorbierite, 1.21%; Propane diols, 8.91%; Ethylene glycol, 3.77%; Glycerine, 4.00%; Butanediol, 1.94%.WO03035582A1 has prepared the support type Ni/C catalyst that Re modifies, and take KOH as promoter, at 220 ℃, reacts 4h under 12.41MPa, sorbierite conversion ratio 55.7%, and ethylene glycol and propane diols selectively are respectively 15% and 31%.Du pont company is in the patent EP0072629 of application in 1984, and adopting the sial composite oxides is carrier, when the Ni load capacity is 0.8%, with Ca (OH)
2Be promoter, at 275 ℃, react 1h under 13.8MPa, the sorbierite conversion ratio is 95%, and dihydroxylic alcohols is selectively greater than 70%.This catalyst is equally applicable to the hydrogenolysis of xylitol, but needs to improve the Ni load capacity to keep reaction conversion ratio in higher level.(the Industrial﹠amp such as Saxena; Engineering Chemistry Research, 2005,44,1466-1473) developed support type 22.06%Ni-7.10%Mo-110%Cu/ diatomite catalyst, be applied to the sucrose hydrogenolysis, under the operating condition of 150 ℃ and reaction pressure 5.0MPa, after 135 minutes, sucrose inversion rate 88%, selective glycerol 28%, glycol selectivity 22%, propane diols selective 13%.
The applicable sorbierite mass concentration that is applied to catalyst for sorbitol hydrogenolysis of existing patent report be 25% or below, for example, above-described Chinese patent CN1683293A, CN1078662A and CN101199930A Central Plains feed liquid sorbitol concentration are 25wt%.Yet the sorbitol concentration that sugar alcohol hydrogenation makes is in 70% left and right, and the catalyst that exploitation is applicable to the higher concentration hydrogenolysis of sorbitol under this background will provide easier industrialization route and higher economic benefit undoubtedly.
Summary of the invention
Purpose of the present invention is intended to provide a kind of Catalysts and its preparation method of preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol, and this catalyst is applicable to the wide sorbierite of concentration range or hydrogenolysis of glycerin is produced dihydroxylic alcohols, and catalyst can be repeatedly used, and the catalyst cost is low.
The catalyst of preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol of the present invention consist of nickel, auxiliary agent and carrier, in catalyst, each component mass ratio is nickel: auxiliary agent: carrier=(10～40): (0～5): 100.
Described auxiliary agent can be at least a in calcium, iron, copper, cerium, barium, titanium, zinc, magnesium, rhenium, manganese, boron, tin, ruthenium, Rhodium, palladium, iridium and zirconium etc., preferred cerium, iron or barium etc.Described carrier can be any in active carbon, titanium dioxide, zirconium dioxide, silica, magnesia, aluminium oxide, kaolin and diatomite etc., preferred kaolin or aluminium oxide etc.Nickel in the catalyst of described preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol and auxiliary agent derive from its respective metal salt, and described slaine can be acetate, chlorate or nitrate etc., preferably nitrate etc.
The preparation method of the catalyst of described preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol comprises the following steps:
1) press the catalyst quality ratio, nickel: auxiliary agent A: carrier=(10～40): (0～5): 100, take quantitative nickel salts and builder salts water-soluble, be configured to the solution that concentration is 0.1mol/L～saturated solution, then add in carrier, stir, continue to stir in hot bath;
2) precipitating reagent is configured to the aqueous solution, concentration is 0.5～4.0mol/L;
3) stir the lower precipitant solution that adds metering in slaine-carrier mixed liquor, continue stirring 1～3h, standing;
4) with step 3) the gained mixture obtains solid through suction filtration, with deionized water wash be neutrality to washing lotion after, then with absolute ethyl alcohol drip washing dehydration, obtain catalyst precursor;
5) catalyst precursor is dry, except anhydrating and absolute ethyl alcohol;
6) with dried catalyst precursor under 400～800 ℃, prereduction activation process 1～6h under low hydrogen mixture gas atmosphere gets black powder shape solid catalyst.
In step 1) in, the temperature of described hot bath can be 70～90 ℃, and the time of continuing in described hot bath to stir can be 0.5～2h.
In step 2) in, described precipitating reagent can be soluble carbonate salt, urea or alkali metal hydroxide etc., preferred carbonate etc.; The mol ratio of described precipitating reagent and slaine-carrier mixed liquor can be 1～1.2; Described concentration is preferably 1.0～2.0mol/L.
In step 5) in, the temperature of described drying can be 80～120 ℃, and the dry time can be 2～12h.
In step 6) in, described low hydrogen gaseous mixture can be and contains 5%H
2H
2-N
2Gaseous mixture or contain 5%H
2H
2-Ar gaseous mixture etc.
The activity rating of catalyst carries out in tank reactor.Sorbierite or glycerine water solution, base agent and the catalyst fines of metering are joined in autoclave, use in High Purity Nitrogen or hydrogen exchange still after the envelope still to pass into hydrogen to reaction pressure after air, be heated to reaction temperature and start stirring reaction.The hydrogenolysis condition is: 180～240 ℃ of reaction temperatures, reaction pressure 4.0～7.0MPa, stir speed (S.S.) 500～1000r/min.After reaction was completed, the liquids and gases product adopted respectively liquid chromatogram and gas-chromatography TCD to detect and analyzes.Wherein base agent comprises wherein a kind of of alkali metal hydroxide, alkaline earth metal hydroxide, alkali carbonate, alkaline earth oxide, preferably calcium hydroxide or calcium oxide.
The present invention is with base metal, nickel particularly, be carried on carrier cheap and easy to get, prepared catalyst is applicable to sorbierite or the glycerine water solution hydrogenolysis is produced dihydroxylic alcohols, be particularly useful for sorbitol aqueous solution hydrogenolysis produce diatomic alcohol, when this catalyst is used for the hydrogenolysis of polyatomic alcohol water solution, 200～240 ℃ of reaction temperatures and reaction pressure 5.0～7.0MPa than making the polyalcohol conversion ratio reach 88%～100% under temperate condition, liquid phase principal product 1,2-PD and ethylene glycol overall selectivity reach 50%～65%.The catalyst cost is low, can reuse, and having good should have prospect.
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1: take the 7.0g nickel nitrate and be dissolved in 80mL water, join in the 500mL flask, in 70～90 ℃ of water-baths, under mechanical agitation, add 7.0g kaolin, stirred 30 minutes.Take 3.0g sodium carbonate and be dissolved in 30mL water, it is slowly splashed in above-mentioned nickel nitrate-kaolin suspension, dropwise rear continuation and stir 1～3h, then add the 150mL deionized water, stir 1h.Use the deionized water filtering and washing, with the absolute ethyl alcohol dehydration, obtain the blue-green precursor at last; Precursor is placed in vacuum drying chamber vacuum drying under 110 ℃ of conditions spends the night, dried precursor is with 5% H
2-N
2Gaseous mixture obtains the black catalyst fines at 500 ℃ of lower activating pretreatment 1h, and catalyst consists of 20%Ni/ kaolin.Change kind of carrier, according to this method difference Kaolinite Preparation of Catalyst 20%Ni/SiO
2, 20%Ni/Al
2O
3, 20%Ni/C and 20%Ni/ diatomite.
The test of catalyst activity is carried out in the 100mL autoclave, and at first adding the 20mL mass concentration in the autoclave is 30% sorbitol aqueous solution, then drops in the catalyst of pure sorbitol quality 4% and 1.6% Ca (OH)
2, be charged to the required pressure of reaction for several times with the high-purity hydrogen gas washing, hydrogenation reaction 8h under 240 ℃, 7.0MPa, after reaction was completed, the liquids and gases product adopted respectively liquid chromatogram and gas-chromatography TCD to detect and analyzes.Liquid product mainly comprises glycerine, ethylene glycol, 1,2-PD and 1,2-butanediol, also may comprise a small amount of lactic acid, pentanediol, ethanol and methyl alcohol.Gas-phase product comprises methane and carbon dioxide.The results are shown in Table 1.
Embodiment 2～5: the preparation method changes kind of carrier with embodiment 1, respectively Kaolinite Preparation of Catalyst 20%Ni/SiO
2, 20%Ni/Al
2O
3, 20%Ni/C and 20%Ni/ diatomite.The evaluation of catalyst the results are shown in Table 1 with embodiment 1.
Catalyst formulation and the reaction result of table 1.30% concentration sorbitol aqueous solution hydrogenolysis produce diatomic alcohol
Embodiment 6～10
In employing embodiment 1, method prepares the 20%Ni/ kaolin catalyst.The test of catalyst activity is carried out in the 100mL autoclave, at first adding the 20mL mass concentration in the autoclave is 30% sorbitol aqueous solution, then drop in the catalyst of pure sorbitol quality 4% and 1.6% alkaline accelerator, be charged to the required pressure of reaction for several times with the high-purity hydrogen gas washing, hydrogenation reaction 8h under 240 ℃, 7.0MPa, after reaction was completed, the liquids and gases product adopted respectively liquid chromatogram and gas-chromatography TCD to detect and analyzes.Change the kind of promoter, investigate it to the impact of reaction, the results are shown in table 2.
The impact of table 2. promoter kind on the reaction of sorbitol aqueous solution hydrogenolysis produce diatomic alcohol
Embodiment 11～18: take respectively 7.0g nickel nitrate and 0.11g cerous nitrate and be dissolved in 80mL water and mix, join in the 500mL flask, in 70～90 ℃ of water-baths, under mechanical agitation, add 7.0g kaolin, stirred 30 minutes.Take 3.0g sodium carbonate and be dissolved in 30mL water, it is slowly splashed in above-mentioned nickel nitrate-cerous nitrate-kaolin suspension, dropwise rear continuation and stir 1～3h, then add the 150mL deionized water, stir 1h.Use the deionized water filtering and washing, with the absolute ethyl alcohol dehydration, obtain the blue-green precursor at last; Precursor is placed in vacuum drying chamber vacuum drying under 110 ℃ of conditions spends the night, dried precursor is with 5% H
2-N
2Gaseous mixture obtains the black catalyst fines at 500 ℃ of lower activating pretreatment 1h, and catalyst consists of 20%Ni-0.5%Ce/ kaolin.The consumption of change cerous nitrate method is according to this prepared respectively the different catalyst 20%Ni-1%Ce/ kaolin that form, 20%Ni-2%Ce/ kaolin; Change the kind of auxiliary agent, prepare catalyst 20%Ni-2%Fe/ kaolin according to said method, 20%Ni-2%Sn/ kaolin, 20%Ni-2%Ru/ kaolin, 20%Ni-2%Cu/ kaolin and 20%Ni-2%Ba/ kaolin.The evaluation of catalyst the results are shown in Table 3 with embodiment 1.
Embodiment 19: prepare the 20%Ni-0.5%Ce/ kaolin catalyst according to the method in embodiment 11.The test of catalyst activity is carried out in the 100mL autoclave, and at first adding the 20g mass concentration in the autoclave is 10% sorbitol aqueous solution, then drops in the catalyst of pure sorbitol quality 4% and 1.6% Ca (OH)
2, be charged to the required pressure of reaction for several times with the high-purity hydrogen gas washing, hydrogenation reaction 8h under 240 ℃, 7.0MPa, after reaction was completed, the liquids and gases product adopted respectively liquid chromatogram and gas-chromatography TCD to detect and analyzes.The results are shown in Table 4.
The impact on the reaction of 30wt% sorbitol aqueous solution hydrogenolysis produce diatomic alcohol of the different auxiliary agents of table 3. and content
Embodiment 20: according to method in embodiment 19, changing the sorbierite mass concentration is 50%, the results are shown in Table 4.
Embodiment 21: prepare the 20%Ni-0.5%Ce/ kaolin catalyst according to the method in embodiment 11.The test of catalyst activity is carried out in the 300mL autoclave, and at first adding the 100g mass concentration in the autoclave is 30% sorbitol aqueous solution, then drops in the catalyst of pure sorbitol quality 4% and 1.6% Ca (OH)
2, be charged to the required pressure of reaction for several times with the high-purity hydrogen gas washing, hydrogenation reaction 8h under 240 ℃, 7.0MPa, after reaction was completed, the liquids and gases product adopted respectively liquid chromatogram and gas-chromatography TCD to detect and analyzes.The results are shown in Table 4.
Embodiment 22: prepare the 20%Ni-0.5%Ce/ kaolin catalyst according to the method in embodiment 11.The test of catalyst activity is carried out in the 600mL autoclave, and at first adding the 200g mass concentration in the autoclave is 30% sorbitol aqueous solution, then drops in the catalyst of pure sorbitol quality 5% and 1.6% Ca (OH)
2, be charged to the required pressure of reaction for several times with the high-purity hydrogen gas washing, hydrogenation reaction 24h under 240 ℃, 7.0MPa, after reaction was completed, the liquids and gases product adopted respectively liquid chromatogram and gas-chromatography TCD to detect and analyzes.The results are shown in Table 4.
The reaction result of sorbitol aqueous solution hydrogenolysis produce diatomic alcohol under the various reaction conditions of table 4.
Embodiment 23: prepare 20%Ni-0.5%Ce/Al according to the method in embodiment 11
2O
3Catalyst.The test of catalyst activity is carried out in the 100mL autoclave, and at first adding the 20mL mass concentration in the autoclave is 30% sorbitol aqueous solution, then drops in the catalyst of pure sorbitol quality 4% and 1.6% Ca (OH)
2, be charged to the required pressure of reaction for several times with the high-purity hydrogen gas washing, hydrogenation reaction 12h under 240 ℃, 7.0MPa, after reaction was completed, the liquids and gases product adopted respectively liquid chromatogram and gas-chromatography TCD to detect and analyzes.The results are shown in table 5.
Embodiment 24～26: with the catalyst recovery in embodiment 23, after the operations such as centrifugal, washing, oven dry, carry out activity rating according to method in embodiment 23.The results are shown in table 5.
Table 5. catalyst is reused result
Embodiment 27: prepare the 20%Ni-0.5%Ce/ kaolin catalyst according to the method in embodiment 11.The test of catalyst activity is carried out in the 100mL autoclave, and at first adding the 20mL mass concentration in the autoclave is 20% glycerine water solution, then drops in the catalyst of pure glycerin quality 5% and 2.5% Ca (OH)
2, be charged to the required pressure of reaction for several times with the high-purity hydrogen gas washing, hydrogenation reaction 12h under 220 ℃, 5.0MPa, after reaction was completed, the liquids and gases product adopted respectively liquid chromatogram and gas-chromatography TCD to detect and analyzes.Glycerol conversion yield 88%, glycol selectivity 14.8%, 1,2-PD selective 65.1%.
Claims (9)
1. the catalyst of a preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol, is characterized in that it consists of nickel, auxiliary agent and carrier, and in catalyst, each component mass ratio is nickel: auxiliary agent: carrier=(10～40): (0～5): 100;
Described auxiliary agent is at least a in calcium, iron, copper, cerium, barium, titanium, zinc, magnesium, rhenium, manganese, boron, tin, ruthenium, Rhodium, palladium, iridium, zirconium;
Described carrier is any in active carbon, titanium dioxide, zirconium dioxide, silica, magnesia, aluminium oxide, kaolin, diatomite;
The catalyst of described a kind of preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol is prepared by following methods:
1) press the catalyst quality ratio, nickel: auxiliary agent: carrier=(10～40): (0～5): 100, take quantitative nickel salts and builder salts water-soluble, be configured to the solution that concentration is 0.1mol/L～saturated solution, then add in carrier, stir, continue to stir in hot bath;
2) precipitating reagent is configured to the aqueous solution, concentration is 0.5～4.0mol/L;
3) stir the lower precipitant solution that adds metering in slaine-carrier mixed liquor, continue stirring 1～3h, standing;
4) step 3) gained mixture is obtained solid through suction filtration, with deionized water wash be neutrality to washing lotion after, then with absolute ethyl alcohol drip washing dehydration, obtain catalyst precursor;
5) catalyst precursor is dry, except anhydrating and absolute ethyl alcohol;
6) with dried catalyst precursor under 400～800 ℃, prereduction activation process 1～6h under low hydrogen mixture gas atmosphere gets black powder shape solid catalyst.
2. the catalyst of a kind of preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol as claimed in claim 1, is characterized in that described auxiliary agent is cerium, iron or barium.
3. the catalyst of a kind of preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol as claimed in claim 1, is characterized in that described carrier is kaolin or aluminium oxide.
4. the catalyst of a kind of preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol as claimed in claim 1, is characterized in that in step 1), and the temperature of described hot bath is 70～90 ℃, and the time of continuing in described hot bath to stir is 0.5～2h.
5. the catalyst of a kind of preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol as claimed in claim 1, is characterized in that in step 2) in, described precipitating reagent is soluble carbonate salt, urea or alkali metal hydroxide.
6. the catalyst of a kind of preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol as claimed in claim 5, is characterized in that in step 2) in, described precipitating reagent is soluble carbonate salt.
7. the catalyst of a kind of preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol as claimed in claim 1, is characterized in that in step 2) in, described concentration is 1.0～2.0mol/L.
8. the catalyst of a kind of preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol as claimed in claim 1, is characterized in that in step 5), and the temperature of described drying is 80～120 ℃, and the dry time is 2～12h.
9. the catalyst of a kind of preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol as claimed in claim 1, is characterized in that in step 6), and described low hydrogen gaseous mixture is for containing 5%H
2H
2-N
2Gaseous mixture or contain 5%H
2H
2-Ar gaseous mixture.
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| CN102824915B (en) * | 2012-07-14 | 2017-11-03 | 辽宁石油化工大学 | A kind of catalyst of C5, C6 sugar alcohol mixtures hydrogenolysis low-carbon dihydric alcohol and preparation method thereof |
| CN103170337B (en) * | 2013-02-27 | 2015-01-14 | 厦门大学 | Catalyst for producing ethanol and preparation method thereof |
| CN104119207B (en) * | 2013-04-26 | 2016-08-10 | 中国科学院大连化学物理研究所 | A kind of method that carbohydrate catalyzed conversion prepares ethylene glycol |
| CN104399468B (en) * | 2014-11-24 | 2017-03-29 | 南京工业大学 | A kind of nickel-base catalyst and its preparation method and application |
| CN104557452B (en) * | 2015-01-04 | 2017-02-22 | 南京工业大学 | Method for catalyzing glycerinum one-step hydrogenolysis reaction through nickel-based catalyst |
| CN105413694B (en) * | 2015-12-04 | 2017-11-10 | 大连理工大学 | It is a kind of to be used to be catalyzed catalyst of hydrogenation of petroleum resin and its preparation method and application |
| CN106311264B (en) * | 2016-07-26 | 2018-12-11 | 厦门大学 | A kind of silicon dioxide carried nickel tungsten catalyst and the preparation method and application thereof |
| CN107029765A (en) * | 2017-04-07 | 2017-08-11 | 厦门大学 | A kind of method of the phosphide catalyst of hydrogenolysis of glycyl alcohol monohydric alcohol |
| CN107020102B (en) * | 2017-04-26 | 2019-05-31 | 浙江大学 | A kind of nickel-chrome acid Mg catalyst and preparation method thereof and the application in ethyl alcohol is prepared in glycerol |
| CN114054031B (en) * | 2021-11-03 | 2023-08-11 | 中国石油大学(华东) | Catalyst for producing glycollic acid by catalytic oxidation of polyalcohol and preparation method thereof |
| CN115650164A (en) * | 2022-11-03 | 2023-01-31 | 海南巨澜新能源有限公司 | Hydrogen production fuel based on water reaction and combustion process thereof |
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