CN102091624A - 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, and the 2-propane diols (1,2-PDO) be important chemical material, 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 1,2-dichloropropane hydrolysis and producing, but all have problems such as bigger environmental pollution and cost be higher.Because the quick rise of petrochemical material prices such as propylene, existing production method faces the pressure of production cost, presses for exploitation new raw material sources and synthetic route.
Ethylene glycol (EG) is another kind of important Organic Chemicals, is mainly used in to produce 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 an indirect material, but along with the decay day by day of petroleum resources, the energy and the Chemical Manufacture approach of exploring non-petroleum path seem even more important.In Chemical Manufacture and daily life, have very and use widely.At present, the main method of producing EG both at home and abroad is that epoxyethane water is legal, but the technological process of this method is long, equipment is many, energy consumption is high, thereby production cost is also high, also exist simultaneously equipment perishable with problem such as contaminated environment.
Biomass-based polyalcohol such as sorbierite and glycerine etc. are called the novel plateform molecules that synthesizes recyclable fuel and chemicals from now on.Adopt the catalytic hydrogenolysis method, biomass polyalcohol etc. is converted into 1, 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 remedies dihydroxylic alcohols output of dihydroxylic alcohols production, meet China's strategy of sustainable development.
In the relevant so far patent documentation of sorbierite hydrogenolysis produce diatomic alcohol, in the majority with exploitation supported precious metal catalyst system.For example, describe a kind of carbon nanofibers among the Chinese patent CN101347731A and carry the Ru catalyst, 220 ℃, under the 10MPa stagnation pressure, sorbierite conversion ratio 71.5%, dihydroxylic alcohols selectivity 50%.The Chinese patent CN101583583A of Germany's BASF AG application has prepared loading type Pd/C catalyst series, and in the presence of CaO, 230 ℃ and Hydrogen Vapor Pressure 25MPa react 10h down, sorbierite conversion ratio 100%, and the dihydroxylic alcohols selectivity is greater than 70%.Chinese patent CN1078662A has introduced the Ru/C catalyst that Sn mixes, and 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) selectivity wherein adopts the required reaction condition of fixed bed reactors all than the required reaction condition gentleness of tank reactor greater than 60%.Europe is applied to the sorbierite hydrogenolysis with the Pt/C catalyst among the EP0510238, 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 the influences in the elements such as antimony dopant, copper, iron, tin, ruthenium, lanthanum, cobalt, molybdenum, boron, phosphorus, rhenium have been investigated respectively to the sorbierite hydrogenolysis, with 95%Ni-4%Cu-1%Ru is example, be used for 25wt% sorbierite hydrogenolysis, 225 ℃, Hydrogen Vapor Pressure 11MPa is reaction 16h down, sorbitol concentration 0.91%, glycol concentration 2.79%, propane diols concentration 8.40%.But this Preparation of catalysts is had relatively high expectations to equipment, and energy consumption is big, and a large amount of skeleton nickel of using has also increased the cost of Preparation of Catalyst.CN1683293A has introduced from the living beings of corn and has transformed route, wherein adopt support type 5%Ru-50%Ni/G1-80 catalyst, with 25wt% concentration sorbierite is feedstock production C2～C4 dihydroxylic alcohols, at 230 ℃, Hydrogen Vapor Pressure 13MPa, regulating the pH value with NaOH is 13, and 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 is promoter with KOH, and at 220 ℃, 12.41MPa is reaction 4h down, sorbierite conversion ratio 55.7%, and ethylene glycol and propane diols selectivity 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, is 0.8% o'clock in the Ni load capacity, with Ca (OH)
2Be promoter, at 275 ℃, 13.8MPa is reaction 1h down, and the sorbierite conversion ratio is 95%, and the dihydroxylic alcohols selectivity is 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.(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 selectivity 13%.
The suitable sorbierite mass concentration that is applied to the sorbierite hydrogenolysis catalyst of existing patent report be 25% or below, for example, above-described Chinese patent CN1683293A, the material liquid sorbitol concentration is 25wt% among CN1078662A and the CN101199930A.Yet the sorbitol concentration that sugar alcohol hydrogenation makes is about 70%, and exploitation is applicable to that the catalyst of higher concentration sorbierite hydrogenolysis will provide easier industrialization route and high economic benefit undoubtedly under this background.
Summary of the invention
Purpose of the present invention is intended to provide a kind of Catalysts and its preparation method of polyalcohol hydrogenolysis produce diatomic alcohol, and this catalyst is applicable to that sorbierite or glycerine hydrogenolysis that concentration range is wide produce dihydroxylic alcohols, and catalyst can be repeatedly used, and the catalyst cost is low.
The catalyst of polyalcohol hydrogenolysis produce diatomic alcohol of the present invention consist of nickel, auxiliary agent and carrier, each component mass ratio is a nickel in the catalyst: 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 the 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 the diatomite etc., preferred kaolin or aluminium oxide etc.Nickel in the catalyst of described polyalcohol hydrogenolysis produce diatomic 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 of catalysts method of described polyalcohol hydrogenolysis produce diatomic alcohol may further comprise the steps:
1) press the catalyst quality ratio, nickel: auxiliary agent A: carrier=(10～40): (0～5): 100, it is water-soluble to take by weighing quantitative nickel salts and builder salts, be configured to the solution that concentration is 0.1mol/L～saturated solution, add then in the carrier, stir, in hot bath, continue to stir;
2) precipitating reagent is configured to the aqueous solution, concentration is 0.5～4.0mol/L;
3) stirring adds the precipitant solution of measuring down in slaine-carrier mixed liquor, continues stirring 1～3h, leaves standstill;
4) step 3) gained mixture is obtained solid through suction filtration, after spending deionised water to washing lotion and being neutrality, with absolute ethyl alcohol drip washing dehydration, obtain catalyst precursor again;
5), remove and anhydrate and absolute ethyl alcohol with the catalyst precursor drying;
6) with dried catalyst precursor under 400～800 ℃, prereduction activation processing 1～6h under low hydrogen mixture gas atmosphere, black powder shape solid catalyst.
In step 1), the temperature of described hot bath can be 70～90 ℃, and the time of continuing in the described hot bath to stir can be 0.5～2h.
In step 2) in, described precipitating reagent can be soluble carbon hydrochlorate, 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), the temperature of described drying can be 80～120 ℃, and the dry time can be 2～12h.
In step 6), 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 of such catalysts evaluation is carried out in tank reactor.Sorbierite or glycerine water solution, base agent and the catalyst fines of metering are joined in the autoclave, use behind the envelope still to feed hydrogen in high purity nitrogen or the hydrogen exchange still behind the air, be heated to reaction temperature and start stirring reaction to reaction pressure.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 finished, the liquids and gases product adopted liquid chromatogram and gas-chromatography TCD check and analysis respectively.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 the carrier cheap and easy to get, prepared catalyst is applicable to that sorbierite or glycerine water solution hydrogenolysis produce 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 the temperate condition, liquid phase principal product 1,2-propane diols 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 by weighing the 7.0g nickel nitrate and be dissolved in the 80mL water, join in the 500mL flask, in 70～90 ℃ of water-baths, under the mechanical agitation, add 7.0g kaolin, stirred 30 minutes.Take by weighing 3.0g sodium carbonate and be dissolved in the 30mL water, it is slowly splashed in above-mentioned nickel nitrate-kaolin suspension, dropwise the back and continue to stir 1～3h, add the 150mL deionized water again, stir 1h.Use the deionized water filtering and washing, with the absolute ethyl alcohol dehydration, obtain the blue-green precursor at last; Place vacuum drying chamber vacuum drying under 110 ℃ of conditions to spend the night precursor, dried precursor is with 5% H
2-N
2Gaseous mixture is handled 1h 500 ℃ of following pre-activated and is obtained the black catalyst fines, and catalyst consists of 20%Ni/ kaolin.Change kind of carrier, method prepares catalyst 20%Ni/SiO respectively according to this
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 autoclave is 30% sorbitol aqueous solution, drops into then 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 finished, the liquids and gases product adopted liquid chromatogram and gas-chromatography TCD check and analysis respectively.Liquid product mainly comprises glycerine, ethylene glycol, 1,2-propane diols and 1, and the 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, prepares catalyst 20%Ni/SiO respectively
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.
The catalyst formulation and the reaction result of table 1.30% concentration sorbitol aqueous solution hydrogenolysis produce diatomic alcohol
Embodiment 6～10
Method prepares the 20%Ni/ kaolin catalyst among the employing embodiment 1.The test of catalyst activity is carried out in the 100mL autoclave, at first adding the 20mL mass concentration in 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 finished, the liquids and gases product adopted liquid chromatogram and gas-chromatography TCD check and analysis respectively.Change the kind of promoter, investigate its influence, the results are shown in table 2 reaction.
Table 2. promoter kind is to the influence of sorbitol aqueous solution hydrogenolysis produce diatomic alcohol reaction
Embodiment 11～18: take by weighing 7.0g nickel nitrate and 0.11g cerous nitrate respectively and be dissolved in the 80mL water and mix, join in the 500mL flask, in 70～90 ℃ of water-baths, under the mechanical agitation, add 7.0g kaolin, stirred 30 minutes.Take by weighing 3.0g sodium carbonate and be dissolved in the 30mL water, it is slowly splashed in above-mentioned nickel nitrate-cerous nitrate-kaolin suspension, dropwise the back and continue to stir 1～3h, add the 150mL deionized water again, stir 1h.Use the deionized water filtering and washing, with the absolute ethyl alcohol dehydration, obtain the blue-green precursor at last; Place vacuum drying chamber vacuum drying under 110 ℃ of conditions to spend the night precursor, dried precursor is with 5% H
2-N
2Gaseous mixture is handled 1h 500 ℃ of following pre-activated and is obtained the black catalyst fines, and catalyst consists of 20%Ni-0.5%Ce/ kaolin.The consumption of change cerous nitrate method is according to this prepared the different catalyst 20%Ni-1%Ce/ kaolin of forming, 20%Ni-2%Ce/ kaolin respectively; Change the kind of auxiliary agent, go out catalyst 20%Ni-2%Fe/ kaolin according to method for preparing, 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 among the embodiment 11.The test of catalyst activity is carried out in the 100mL autoclave, at first adds the 20g mass concentration and be 10% sorbitol aqueous solution in autoclave, drops into then 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 finished, the liquids and gases product adopted liquid chromatogram and gas-chromatography TCD check and analysis respectively.The results are shown in Table 4.
Different auxiliary agents of table 3. and content are to the influence of 30wt% sorbitol aqueous solution hydrogenolysis produce diatomic alcohol reaction
Embodiment 20: according to method among the 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 among the embodiment 11.The test of catalyst activity is carried out in the 300mL autoclave, at first adds the 100g mass concentration and be 30% sorbitol aqueous solution in autoclave, drops into then 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 finished, the liquids and gases product adopted liquid chromatogram and gas-chromatography TCD check and analysis respectively.The results are shown in Table 4.
Embodiment 22: prepare the 20%Ni-0.5%Ce/ kaolin catalyst according to the method among the embodiment 11.The test of catalyst activity is carried out in the 600mL autoclave, at first adds the 200g mass concentration and be 30% sorbitol aqueous solution in autoclave, drops into then 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 finished, the liquids and gases product adopted liquid chromatogram and gas-chromatography TCD check and analysis respectively.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 among the embodiment 11
2O
3Catalyst.The test of catalyst activity is carried out in the 100mL autoclave, at first adds the 20mL mass concentration and be 30% sorbitol aqueous solution in autoclave, drops into then 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 finished, the liquids and gases product adopted liquid chromatogram and gas-chromatography TCD check and analysis respectively.The results are shown in table 5.
Embodiment 24～26: with the catalyst recovery among the embodiment 23, after operations such as centrifugal, washing, oven dry, carry out activity rating according to method among the embodiment 23.The results are shown in table 5.
Table 5. catalyst is reused the result
Embodiment 27: prepare the 20%Ni-0.5%Ce/ kaolin catalyst according to the method among the embodiment 11.The test of catalyst activity is carried out in the 100mL autoclave, at first adds the 20mL mass concentration and be 20% glycerine water solution in autoclave, drops into then 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 finished, the liquids and gases product adopted liquid chromatogram and gas-chromatography TCD check and analysis respectively.Glycerol conversion yield 88%, glycol selectivity 14.8%, 1,2-propane diols selectivity 65.1%.
Claims (10)
1. the catalyst of a polyalcohol hydrogenolysis produce diatomic alcohol is characterized in that it consists of nickel, auxiliary agent and carrier, and each component mass ratio is a nickel in the catalyst: auxiliary agent: carrier=(10～40): (0～5): 100.
2. the catalyst of a kind of polyalcohol hydrogenolysis produce diatomic alcohol as claimed in claim 1, it is characterized in that described auxiliary agent is at least a in calcium, iron, copper, cerium, barium, titanium, zinc, magnesium, rhenium, manganese, boron, tin, ruthenium, Rhodium, palladium, iridium, the zirconium, preferred cerium, iron or barium.
3. the catalyst of a kind of polyalcohol hydrogenolysis produce diatomic alcohol as claimed in claim 1, it is characterized in that described carrier is any in active carbon, titanium dioxide, zirconium dioxide, silica, magnesia, aluminium oxide, kaolin, the diatomite, preferred kaolin or aluminium oxide.
4. the catalyst of a kind of polyalcohol hydrogenolysis produce diatomic alcohol as claimed in claim 1, it is characterized in that nickel and auxiliary agent in the catalyst of described polyalcohol hydrogenolysis produce diatomic alcohol derive from its respective metal salt, described slaine is acetate, chlorate or nitrate, preferably nitrate.
5. the Preparation of catalysts method of a kind of polyalcohol hydrogenolysis produce diatomic alcohol as claimed in claim 1 is characterized in that may further comprise the steps:
1) press the catalyst quality ratio, nickel: auxiliary agent A: carrier=(10～40): (0～5): 100, it is water-soluble to take by weighing quantitative nickel salts and builder salts, be configured to the solution that concentration is 0.1mol/L～saturated solution, add then in the carrier, stir, in hot bath, continue to stir;
2) precipitating reagent is configured to the aqueous solution, concentration is 0.5～4.0mol/L;
3) stirring adds the precipitant solution of measuring down in slaine-carrier mixed liquor, continues stirring 1～3h, leaves standstill;
4) step 3) gained mixture is obtained solid through suction filtration, after spending deionised water to washing lotion and being neutrality, with absolute ethyl alcohol drip washing dehydration, obtain catalyst precursor again;
5), remove and anhydrate and absolute ethyl alcohol with the catalyst precursor drying;
6) with dried catalyst precursor under 400～800 ℃, prereduction activation processing 1～6h under low hydrogen mixture gas atmosphere, black powder shape solid catalyst.
6. the Preparation of catalysts method of a kind of polyalcohol hydrogenolysis produce diatomic alcohol as claimed in claim 5 is characterized in that in step 1), and the temperature of described hot bath is 70～90 ℃, and the time of continuing in the described hot bath to stir is 0.5～2h.
7. the Preparation of catalysts method of a kind of polyalcohol hydrogenolysis produce diatomic alcohol as claimed in claim 5 is characterized in that in step 2) in, described precipitating reagent is soluble carbon hydrochlorate, urea or alkali metal hydroxide, preferred carbonate.
8. as the Preparation of catalysts method of claim 5 or 7 described a kind of polyalcohol hydrogenolysis produce diatomic alcohols, it is characterized in that in step 2) in, the mol ratio of described precipitating reagent and slaine-carrier mixed liquor is 1～1.2; Described concentration is 1.0～2.0mol/L.
9. the Preparation of catalysts method of a kind of polyalcohol hydrogenolysis produce diatomic alcohol as claimed in claim 5 is characterized in that in step 5), and the temperature of described drying is 80～120 ℃, and the dry time is 2～12h.
10. the Preparation of catalysts method of a kind of polyalcohol hydrogenolysis produce diatomic alcohol as claimed in claim 5 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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| CN102824915A (en) * | 2012-07-14 | 2012-12-19 | 辽宁石油化工大学 | Catalyst for preparing lower-carbon glycols through hydrogenolysis of C5 and C6 sugar alcohol mixture and preparation method of catalyst |
| 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 |
| CN103170337A (en) * | 2013-02-27 | 2013-06-26 | 厦门大学 | Catalyst for producing ethanol and preparation method thereof |
| CN104119207A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Method for preparation of ethylene glycol by catalytic conversion of carbohydrate |
| 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 | Nickel-based catalyst and preparation method and application thereof |
| CN104399468A (en) * | 2014-11-24 | 2015-03-11 | 南京工业大学 | Nickel-based catalyst and preparation method and application thereof |
| CN104557452A (en) * | 2015-01-04 | 2015-04-29 | 南京工业大学 | Method for catalyzing one-step hydrogenolysis reaction of glycerol by using nickel-based catalyst |
| CN105413694A (en) * | 2015-12-04 | 2016-03-23 | 大连理工大学 | Catalyst for catalyzing hydrogenation of petroleum resin as well as preparation method and application thereof |
| 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 |
| CN106311264A (en) * | 2016-07-26 | 2017-01-11 | 厦门大学 | Silica supported nickel tungsten catalyst and preparation method and application thereof |
| 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 |
| CN107020102A (en) * | 2017-04-26 | 2017-08-08 | 浙江大学 | Sour Mg catalyst of a kind of nickel chromium triangle and preparation method thereof and the application in glycerine prepares ethanol |
| 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 |
| CN114054031A (en) * | 2021-11-03 | 2022-02-18 | 中国石油大学(华东) | Catalyst for producing glycollic acid by catalytic oxidation of polyol and preparation method thereof |
| 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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