CN104119207B - A kind of method that carbohydrate catalyzed conversion prepares ethylene glycol - Google Patents
A kind of method that carbohydrate catalyzed conversion prepares ethylene glycol Download PDFInfo
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Abstract
The invention provides a kind of method that carbohydrate catalyzed conversion prepares ethylene glycol.The method is with carbohydrate as reaction raw materials, with water as solvent, the catalyst constituted with both one or more in the simple substance of lanthanum or compound and 8,9,10 group 4 transition metal ferrum, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum is as composite catalyst, at 120 300 DEG C, through a step catalytic conversion process under the hydrothermal condition of Hydrogen Vapor Pressure 1 13MPa, it is achieved cellulose selectivity efficient, high, high yield prepare ethylene glycol.Compared with existing petroleum base ethylene glycol synthetic route, it is Renewable resource, Atom economy advantage high, eco-friendly that reaction provided by the present invention has raw material.Additionally, with other with biomass for compared with the technology of raw material polyhydric alcohol, this process has that catalyst amount is few, cyclicity good, to advantages such as consersion unit corrosivity are little.
Description
Technical field
The present invention relates to a kind of catalyzed conversion carbohydrate method to ethylene glycol, specifically carbohydrate exists
Prepare the process of ethylene glycol through catalyzed conversion under hydrothermal condition.
Background technology
Ethylene glycol is a kind of important energy liquid fuel, is also very important polyester synthesis raw material (poly-terephthaldehyde
Acid second diester (PET), PEN (PEN)), it is also possible to live as antifreezing agent, lubricant, plasticizer, surface
Property agent, is broad-spectrum Organic Chemicals.
At present, the commercial production of ethylene glycol obtains epoxy second after mainly using petroleum route, i.e. ethylene epoxidizing
Alkane, then hydration obtain ethylene glycol (document 1: Cui little Ming, Ethylene Glycol production development overview, chemical industry, 2007,25,
(4), 15-21. document 2:Process for preparing ethanediol by catalyzing epoxyethane
Hydration, Patent No.CN1463960-A;CN1204103-C).Synthetic method depends on non-renewable oil money
Source, and production process includes selective oxidation or epoxidation step, technical difficulty is big, and efficiency is low, and by-product is many, energy consumption high and
Seriously polluted.
The biomass with recyclability are utilized to prepare ethylene glycol, it is possible to reduce mankind's dependence to fossil energy material,
It is advantageously implemented environmental friendliness and sustainable economic development.The carbohydrates such as cellulose are the renewable of yield maximum on the earth
Resource, originates the abundantest, utilizes cost the cheapest.The carbohydrate preparing ethylene glycols such as cellulose are utilized to be possible not only to open up
New synthesis path, it is achieved obtained the product of high economic worth by cheap carbohydrate.It is additionally, since the parts such as cellulose
Carbohydrate can not be by human consumption, because of without impacting the grain security of the mankind.
At present, ethylene glycol (document 1:Direct is prepared by catalytic hydroconversion cellulose under hydrothermal condition
catalytic conversion of cellulose into ethylene glycol using nickel-promoted
Tungsten carbide catalysts, Angew.Chem.Int.Ed.2008,47,8510-8513；Document 2:
Transition metal-tungsten bimetallic catalysts for the conversion of
Cellulose into ethylene glycol, ChemSusChem2010,3,63-66；Document 3:CN102190562A, one
The method planting preparing ethanediol from polyhydroxy compounds).The composite catalyst that the method forms with tungsten-based catalyst and hydrogenation catalyst
Cellulose is carried out catalyzed conversion, thus obtains the ethylene glycol of 60-75%.
Method provided by the present invention is with carbohydrate as raw material, with water as reaction medium, at Lanthanum based catalysts and
8, under the binary catalyst effect that 9,10 group 4 transition metals are constituted, by single step reaction process, i.e. cellulose can be realized efficient
It is converted into ethylene glycol.The method is the most simple to operate, with low cost, and catalyst amount is few, and cyclicity is good, to consersion unit
Corrosivity is little.
Summary of the invention
It is an object of the invention to provide a kind of quick, method of efficient catalytic conversion carbohydrate to ethylene glycol, relatively
Conventional process the method is simple to operate, with low cost, environmental friendliness, and catalyst amount is few, and cyclicity is good, etc. feature.
For achieving the above object, the technical scheme that the present invention takes is: with carbohydrate as reaction raw materials, at airtight height
Carrying out catalytic hydrogenation reaction in water in pressure reactor, the catalyst used is composite catalyst, including catalyst A and catalysis
Agent B, the active component of catalyst A is one or two or more kinds in the simple substance of lanthanum or compound, and the active component of catalyst B is
8th, 9, the transition metal iron of 10 races, cobalt, nickel, ruthenium, rhodium, palladium, iridium, one or two or more kinds in platinum, under reactor stirs
Reaction；Filling hydrogen in reactor, reaction temperature >=120 DEG C before reaction, the response time was no less than 5 minutes；
In use, in system the mass content (in terms of lanthanoid metal) of catalyst A at 0.001%-10%, catalyst B
Metal active composition and active component (in terms of the lanthanoid metal weight) weight ratio of catalyst A between 0.01-200 times of scope.
In reactor during room temperature initial hydrogen pressure more preferably be 1-12MPa, more preferably reaction temperature be 120-300
DEG C, the response time is 0.5h-5h；More preferably before reaction, in reactor, the initial pressure of filling hydrogen is 3-7MPa；Reaction temperature
For 200-280 DEG C, the response time is 0.5h-3h.
Catalyst A is unsupported catalyst, can be the one in the oxide of lanthanum, hydroxide, salt or two kinds with
On, the mass content (in terms of lanthanoid metal) in whole system is at 0.001%-10%；Catalyst A can also be supported catalyst
Agent, active component is supported on carrier, described carrier be activated carbon, aluminium oxide, silicon oxide, carborundum, zirconium oxide, zinc oxide,
One or two or more kinds complex carrier of titanium dioxide, the activity component metal (in terms of lanthanoid metal) content on catalyst exists
0.01%-50wt%。
Catalyst B is unsupported catalyst, using active component as the framework metal catalyst of catalyst backbone.Catalysis
Agent B can also be loaded catalyst, and active component is supported on carrier, described carrier be activated carbon, aluminium oxide, silicon oxide,
One or two or more kinds complex carrier of carborundum, zirconium oxide, zinc oxide, titanium dioxide；Activity component metal is on catalyst
Content at 0.05%-50wt%.
Composite catalyst can be single loaded catalyst, will in the simple substance of catalyst A lanthanum or compound one
Kind or more than two kinds as carrier, catalyst B activity component is supported on the catalyst A of carrier, activity component metal B
Content on catalyst is at 1-50wt%；
Or the active component mutual load of catalyst A and catalyst B is on the same vector, described carrier is activated carbon, oxygen
Change aluminum, silicon oxide, carborundum, zirconium oxide, zinc oxide, one or two or more kinds complex carrier of titanium dioxide；Active component gold
Belong to B content on catalyst at 0.05%-50wt%, the activity component metal A content on catalyst at 0.05%-40wt%.
The consumption of reaction raw materials cellulose and water is partly or completely all liquid with reaction mass under reaction condition can be at this
Under the conditions of be stirred, reactant can be made to be heated evenly, it is to avoid local temperature is too high to be caused raw material to burn phenomenon to occur.
Carbohydrate be cellulose, starch, hemicellulose, Jerusalem artichoke, sucrose, glucose, mannose, fructose, levan,
One or two or more kinds in xylose, arabinose, soluble oligomeric xylose.
The simple substance of lanthanum or compound be lanthanoid metal, halogen (fluorine, chlorine, bromine, iodine) change lanthanum, lanthanum hydroxide, Lanthanum (III) nitrate, lanthanum sulfate,
In lanthanum carbonate, basic carbonate lanthanum, halogen (fluorine, chlorine, bromine, iodine) acid lanthanum, high halogen (fluorine, chlorine, bromine, iodine) acid lanthanum, lanthanum oxalate, lanthanum orthophosphate
One or two or more kinds.
In system, the preferred weight concentration of catalyst A is at 0.01%-1%；The metal active composition of described catalyst B and catalysis
The active component (calculating with lanthanoid metal weight) of agent A preferred weight ratio in use is between 0.1-100 times of scope.
The present invention has the following advantages:
1. with the maximum cellulose family carbohydrate of yield in nature biotechnology matter as raw material, its wide material sources, and
Exist with low cost, do not strive with people grain strive ground advantage.And, relative to existing ethylene glycol industrial production uses ethylene
For raw material, course of reaction provided by the present invention does not consume fossil resource, has the reproducible advantage of raw material resources, meets and can hold
Twice laid, increasing peasant income are had great importance by the requirement of supervention exhibition.
2., under this composite catalyst effect, the selectivity of ethylene glycol is good, simultaneously should during catalyst amount few, circulation
Property is good.
3. present alkalescence due to Lanthanum based catalysts in aqueous, thus life-time service be little to reaction unit corrosivity,
Can be greatly saved equipment investment, prospects for commercial application is good.
Below by specific embodiment, the present invention is described in detail, but these embodiments are not to present disclosure
It is construed as limiting.
Detailed description of the invention
Embodiment 1
Prepared by Lanthanum based catalysts: the unsupported catalysts such as the oxide of lanthanum, hydroxide, salt are the business directly bought
Medicine, medicine purity level is analytical pure.In loaded catalyst, active component is supported on carrier, and described carrier is for living
One or two or more kinds complex carrier of property charcoal, aluminium oxide, silicon oxide, carborundum, zirconium oxide, zinc oxide, titanium dioxide, by lanthanum
Slaine (anion can be one or two or more kinds in nitrate anion, chloride ion or bromide ion) aqueous solution pass through incipient impregnation
Method loads on carrier, is dried overnight at 120 DEG C, calcines 4h afterwards at 700 DEG C under N2 atmosphere.
Embodiment 2
Prepared by catalytic hydrogenation: by activated carbon, aluminium oxide, silicon oxide, carborundum, zirconium oxide, zinc oxide, titanium dioxide
Titanium one or two or more kinds as carrier, by chloroplatinic acid, Palladous chloride., ruthenic chloride, radium chloride, iridium chloride, nickel nitrate, ferric nitrate,
The aqueous solution of cobalt nitrate is loaded on carrier respectively by equi-volume impregnating, is dried overnight at 120 DEG C.
More than load the catalyst of the noble metals such as ruthenium, rhodium, palladium, iridium, platinum before use, need to reduce at 250 DEG C with hydrogen
2h, at 1%O2/N2(V/V) it is passivated 4h under atmosphere；The non-noble metal catalyst such as nickel-loaded, ferrum, cobalt before use, need to use hydrogen
Reductase 12 h at 450 DEG C, at 1%O2/N2(V/V) it is passivated 4h under atmosphere.
Embodiment 3
Prepared by lanthana supported nickel catalyst: weigh 1.5g La2O3,0.8g Ni (NO3) 2 6H2O, and nickel nitrate is molten
In 20ml water, then being joined by La2O3 and dissolve completely in nickel nitrate solution, under 25 DEG C of water bath condition, stirring 12h is to the most molten
Liquid evaporation is completely.8h, in N2 atmosphere, roasting 2h at 500 DEG C it is dried, then in H2 atmosphere, at 500 DEG C also in 120 DEG C of baking ovens
Former 5h.
Embodiment 4
The preparation of loaded catalyst altogether: use repeatedly equi-volume impregnating, weigh 1.5g activated carbon, 0.4g La (NO3)
3 6H2O, 0.8g Ni (NO3) 2 6H2O, first by soluble in water for La (NO3) 3 6H2O, then it is molten to pour activated carbon into Lanthanum (III) nitrate
In liquid, put in 120 DEG C of baking ovens and be dried overnight, roasting 4h at N2 atmosphere 700 DEG C, more roasting catalyst be impregnated in Ni
(NO3) in 2 6H2O solution, left at room temperature 12h, put in 120 DEG C of baking ovens and be dried overnight, roasting at lower 700 DEG C of N2 atmosphere
4h, finally reduction 4h at 700 DEG C.
Embodiment 5
Catalyzed conversion is tested: by 0.25g carbohydrate, composite catalyst and the 25ml water of certain mass join 75ml
In reactor, after then passing to six gases of hydrogen exchange, it is flushed with hydrogen gas to 5MPa, is warmed up to uniform temperature, react 30-
240min.After reaction terminates, it is down to room temperature, takes the supernatant fluid after being centrifuged, high performance liquid chromatography is analyzed detection.Product is received
Target product ethylene glycol, propylene glycol and hexahydroxylic alcohols (including sorbitol, mannitol) are only calculated by rate.
Embodiment 6
The catalyzed conversion Comparative result of microcrystalline Cellulose under different catalysts, wherein catalyst include single-metal reforming catalyst and
Composite catalyst.In composite catalyst, catalyst A is lanthanum hydroxide, and catalyst B is different metal hydrogenation catalyst, reacts bar
Part is with embodiment 5.
The result that in table one different catalysts, cellulose catalytic converts
(catalyst A mass is 0.1g；Catalyst B mass is 0.15g；Reaction temperature is 245 DEG C, and the response time is
30min)
As shown in Table 1, composite catalyst has facilitation to the generation of ethylene glycol, before and after contrast adds lanthanum hydroxide
Ethylene glycol and the change of hexahydroxylic alcohols yield, it can be seen that the existence of lanthanum hydroxide promotes the yield of ethylene glycol to significantly improve, hexahydroxylic alcohols
Yield substantially reduces.
Embodiment 7
In composite catalyst, catalyst A is containing lanthanum compound, and catalyst B is Ni/AC.Reaction condition is with embodiment 5, respectively
Plant the catalyzed conversion result (table two) of cellulose on composite catalyst.
The impact that cellulose catalytic is converted by the presoma of the different lanthanum of table two
(catalyst A mass is 0.1g；Catalyst B mass is 0.15g；Reaction temperature is 245 DEG C, and the response time is
30min)
As shown in Table 2, use the different lanthanum compound that contains as catalyst, within the 30min time, add lanthana and hydrogen
Ethylene glycol yield obtained by lanthana is far above the compound of other lanthanums, but now cellulose converts the most completely.
Embodiment 8
In composite catalyst, catalyst A is lanthanum hydroxide, and catalyst B is Ni/AC.Reaction condition is with embodiment 5, compound
Catalyst system and catalyzing catalyzed conversion result (table three) on different carbohydrates.
Table three composite catalyst catalyzed conversion result on different carbohydrates
(catalyst A mass is 0.005g；Catalyst B mass is 0.15g；Reaction temperature is 245 DEG C, and the response time is
120min)
As shown in Table 3, this composite catalyst has different selectivitys on different carbohydrates, to C2 and C3 alcohol
Selectivity be better than C6 alcohol and C4 alcohol, illustrate that this composite catalyst has certain scission of link effect, and make with cellulose former
The yield of the ethylene glycol that material obtains is higher than other carbohydrates.
Embodiment 9
The impact in response time.Catalyst A is La (OH) 3, and catalyst B is 10%Ni/AC, fiber under the differential responses time
Element catalyzed conversion result (table four).In addition to response time difference, reaction condition is with embodiment 5.
Cellulose catalytic conversion results on composite catalyst under the table four differential responses time
(catalyst A mass is 0.1g；Catalyst B mass is 0.15g；Reaction temperature is 245 DEG C)
As shown in Table 4, in the range of certain time, this composite catalyst system all has preferable ethylene glycol yield.Time preferably
Between be 1h-2.5h.
Embodiment 10
The impact of reaction temperature.Catalyst A is La (OH) 3, and catalyst B is 10%Ni/AC, fiber at a temperature of differential responses
Element catalyzed conversion result (table five), reaction condition is with embodiment 5.
Cellulose catalytic conversion results on composite catalyst at a temperature of table five differential responses
(catalyst A mass is 0.1g；Catalyst B mass is 0.15g；Response time is 110min)
As shown in Table 5, in certain temperature range, this composite catalyst system all has preferable ethylene glycol yield.Preferably temperature
Degree is for 230-260 DEG C.
Embodiment 11
Catalyst A consumption affects.Catalyst A is La (OH) 3, and catalyst B is under 10%Ni/AC, A catalyst different amounts
Cellulose catalytic conversion results (table six), reaction condition is with embodiment 5.
Cellulose catalytic conversion results on composite catalyst under table six A catalyst different amounts
(catalyst B mass is 0.15g；Reaction temperature is 245 DEG C, and the response time is 110min)
As shown in Table 6, when catalyst A amount reduces to 1mg, remain to obtain preferable ethylene glycol yield, this catalytic body is described
Cording has higher activity, and in system, the preferable weight concentration of catalyst A is at 0.01-0.5%.
Embodiment 12
The circulative examination of catalyst 10%Ni/La2O3.Catalyst B activity component is supported on the catalyst as carrier
On A, examining or check the cyclicity (table seven) of this composite catalyst, reaction condition is with embodiment 5.
Table seven 10%Ni/La2O3 recycles examination result
(catalyst quality is 0.15g, and reaction temperature is 245 DEG C, and the response time is 150min)
| Cycle-index | Ethylene glycol yield % | Propylene glycol yield % | Hexahydroxylic alcohols yield % |
| For the first time | 42.6 | 13.2 | 2.0 |
| For the second time | 45.7 | 13.3 | 2.5 |
| For the third time | 46.5 | 13.8 | 6.1 |
| 4th time | 45.0 | 13.3 | 5.9 |
| 5th time | 38.0 | 12.1 | 6.3 |
As shown in Table 7, first five of catalyst 10%Ni/La2O3 time circulation all can obtain higher ethylene glycol yield, and this is multiple
Closing catalyst preferably cycle-index is 5 times.
It is ethylene glycol that binary composite catalyst system in the present invention can realize carbohydrate Efficient Conversion.The method is not
The most simple to operate, with low cost, and also it is few to there is catalyst amount, and cyclicity is good, to advantages such as consersion unit corrosivity are little.
Claims (9)
1. the method that a carbohydrate catalyzed conversion prepares ethylene glycol, it is characterised in that: it is with carbohydrate for reaction
Raw material, in enclosed high pressure reactor, carries out catalytic hydrogenation reaction in water, and the catalyst used is composite catalyst, bag
Include catalyst A and catalyst B；The active component of catalyst A is one or two or more kinds in the simple substance of lanthanum or compound, catalysis
The active component of agent B is the 8th, 9, the transition metal iron of 10 races, cobalt, nickel, ruthenium, rhodium, palladium, iridium, one or two or more kinds in platinum；
React on stirring in enclosed high pressure reactor to carry out；Filling hydrogen in reactor before reaction, reaction temperature >=120 DEG C, during reaction
Between no less than 5 minutes；
Described composite catalyst is single loaded catalyst, will one in the simple substance of catalyst A lanthanum or compound or
As carrier, catalyst B activity component is supported on the catalyst A of carrier for more than two kinds；Or catalyst A and catalyst
The active component mutual load of B is on the same vector；
In use, the mass content of catalyst A in reaction system, in terms of lanthanoid metal, between 0.001%-10%, urge
The metal active composition of agent B and the active component of catalyst A, in terms of lanthanoid metal weight, weight ratio is 0.01-200 times of scope
Between.
The most in accordance with the method for claim 1, it is characterised in that: filling hydrogen in the front reactor of reaction, hydrogen during room temperature
Initial pressure is 1-12MPa；Reaction temperature >=120 DEG C, temperature upper limit does not occur thermal decomposition to be as the criterion with product.
The most in accordance with the method for claim 1, it is characterised in that: reaction temperature is 200-280 DEG C, hydrogen in reactor under room temperature
The initial pressure 3-7MPa of gas, the response time is 0.5h-3h.
The most in accordance with the method for claim 1, it is characterised in that:
Described catalyst A is unsupported catalyst, can be one or two or more kinds in the simple substance of lanthanum or compound, whole
Mass content in individual reaction system, in terms of lanthanoid metal, at 0.001%-10%；
Or, described catalyst A is loaded catalyst, and active component is supported on carrier, and described carrier is activated carbon, oxidation
A kind of carrier of aluminum, silicon oxide, carborundum, zirconium oxide, zinc oxide, titanium dioxide or the complex carrier of more than two kinds, active component
Metal, in terms of lanthanoid metal, the content on catalyst is at 0.01%-50wt%.
The most in accordance with the method for claim 1, it is characterised in that:
Described catalyst B is unsupported catalyst, using metal active constituent as the framework metal catalyst of catalyst backbone；
Or, described catalyst B is loaded catalyst, and active component is supported on carrier, and described carrier is activated carbon, oxidation
A kind of carrier of aluminum, silicon oxide, carborundum, zirconium oxide, zinc oxide, titanium dioxide or the complex carrier of more than two kinds；Active component
Metal content on catalyst is at 0.05%-50wt%.
The most in accordance with the method for claim 1, it is characterised in that: catalyst B activity component is supported on urging as carrier
Time in agent A, active component B metal content on catalyst is at 1%-50wt%；
The active component mutual load of catalyst A and catalyst B on the same vector time, described carrier be activated carbon, aluminium oxide,
One or two or more kinds complex carrier of silicon oxide, carborundum, zirconium oxide, zinc oxide, titanium dioxide；Activity component metal B in
Content on catalyst at 0.05%-50wt%, the activity component metal A content on catalyst at 0.05%-40wt%.
The most in accordance with the method for claim 1, it is characterised in that: the consumption of reaction raw materials and water is with reactant under reaction condition
Material is partly or completely all liquid；
Described carbohydrate be cellulose, starch, hemicellulose, Jerusalem artichoke, sucrose, glucose, mannose, fructose, levan,
One or two or more kinds in xylose, arabinose, soluble oligomeric xylose.
8. according to the method described in claim 1 or 4, it is characterised in that:
The simple substance of lanthanum or compound are lanthanoid metal, lanthanum fluoride, lanthanum chloride, lanthanum bromide, lanthanum iodite, lanthanum hydroxide, Lanthanum (III) nitrate, sulphuric acid
Lanthanum, lanthanum carbonate, basic carbonate lanthanum, fluoric acid lanthanum, chloric acid lanthanum, lanthanum bromate, lanthanum iodate, high fluoric acid lanthanum, ytterbium perchlorate, hyperbromic acid lanthanum,
One or two or more kinds in periodic acid lanthanum, lanthanum oxalate, lanthanum orthophosphate.
The most in accordance with the method for claim 1, it is characterised in that: in system, the weight concentration of catalyst A is at 0.01%-1%；
The metal active composition of described catalyst B and the active component of catalyst A, calculate with lanthanoid metal weight, in use
Weight ratio is between 0.01-100 times of scope.
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| CN106694009B (en) | 2015-11-12 | 2019-12-13 | 中国科学院大连化学物理研究所 | Method for preparing low-carbon dihydric alcohol by using alloy catalyst for catalyzing carbohydrate |
| CN108367274A (en) * | 2015-12-17 | 2018-08-03 | 国际壳牌研究有限公司 | hydrogenation or hydrogenolysis method |
| CN111054342B (en) * | 2018-10-16 | 2023-06-06 | 中国石油化工股份有限公司 | Catalyst for preparing glycol from carbohydrate and preparation method thereof |
| CN112713273B (en) * | 2020-12-18 | 2022-04-26 | 浙江金鹰瓦力新能源科技有限公司 | Preparation method of battery zinc cathode material |
| CN115779913B (en) * | 2021-09-10 | 2024-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing glycol from glucose, and preparation method and application thereof |
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| CN102203034A (en) * | 2008-08-27 | 2011-09-28 | 维仁特能源系统公司 | Synthesis of liquid fuels from biomass |
| CN101870638A (en) * | 2009-04-21 | 2010-10-27 | 北京金骄生物质化工有限公司 | Method for preparing ethylene alcohol by plant straws |
| CN102858728A (en) * | 2009-12-30 | 2013-01-02 | 维仁特公司 | Improved catalysts for hydrodeoxygenation of polyols |
| CN102858453A (en) * | 2010-02-23 | 2013-01-02 | 巴特尔纪念研究院 | Catalysts and processes for the hydrogenolysis of glycerol and other organic compounds for producing polyols and propylene glycol |
| CN101781166A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Preparation method of dihydric alcohol |
| CN101781167A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Method for synthesizing dihydric alcohol and polyhydric alcohol |
| CN101781171A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Preparation method of dihydric alcohol |
| CN101781168A (en) * | 2010-03-18 | 2010-07-21 | 西安近代化学研究所 | Method for synthesizing dihydric alcohol and polyhydric alcohol |
| CN102091624A (en) * | 2010-12-01 | 2011-06-15 | 厦门大学 | Catalyst for preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol and preparation method thereof |
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