CN108236955A - A kind of preparation method of Hydrogenation of Dimethyl Oxalate synthesizing alcohol catalyst and thus obtained catalyst and its application - Google Patents
A kind of preparation method of Hydrogenation of Dimethyl Oxalate synthesizing alcohol catalyst and thus obtained catalyst and its application Download PDFInfo
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- CN108236955A CN108236955A CN201611217916.8A CN201611217916A CN108236955A CN 108236955 A CN108236955 A CN 108236955A CN 201611217916 A CN201611217916 A CN 201611217916A CN 108236955 A CN108236955 A CN 108236955A
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
The present invention relates to a kind of method for preparing prepared by dimethyl oxalate plus hydrogen ethyl alcohol catalyst, catalytic active component and optional catalyst aid, the catalyst which includes carrier and load thereon include：(A) element of Cu, Fe, Ni, Co, Ag and Au are selected from as catalytic active component for 1 50 weight % based on the element, (B) element of periodic table of elements third major element, transition elements and lanthanide series is selected from as catalyst aid for 0 10 weight % based on the element, and (C) carrier, catalyst of the present invention prepare and use CO by using the hydrothermal synthesis method that urea is assisted2Supercritical drying, the catalyst so prepared can not only obtain high ethano selectivity, but also can obtain high dimethyl oxalate conversion ratio when for prepared by dimethyl oxalate plus hydrogen ethyl alcohol.The invention further relates to the purposes of the catalyst being prepared by the method for the present invention and the catalyst in prepared by dimethyl oxalate plus hydrogen ethyl alcohol.
Description
Technical field
The present invention relates to a kind of preparation method of the catalyst for Hydrogenation of Dimethyl Oxalate synthesizing alcohol, the present invention also relates to
And the application of catalyst and the catalyst obtained by this method.
Background technology
Ethyl alcohol is commonly called as alcohol, is a kind of important industrial chemicals.It acts not only as synthesizing a series of small molecule chemical industry
The raw material and potential liquid fuel resource of product and polymer, by the extensive concern of countries in the world.At present, ethyl alcohol is given birth to
Production is mainly by following two approach：(1) grain ferments；(2) ethylene hydration that cracking of oil obtains.Ethylene hydration method is not only serious
The petroleum resources of increasingly depleted are relied on, and require equipment material high, unsuitable large-scale production ethyl alcohol.Although existing market
On most of ethyl alcohol be that the route to be fermented by grain is made, but prepare that fuel-grade ethanol is expensive and high energy consumption.Last century
The eighties, Kenji and William etc. propose a kind of by synthetic route of the synthesis gas through oxalate diester ethyl alcohol.The route
Synthesis gas is prepared by non-oil resource first, then by CO oxidative coupling synthesizing dimethyl oxalates, dimethyl oxalate is further catalyzed
It is hydrogenated to ethyl alcohol.One synthetic route of carbon not only has the advantages that environmentally protective, reaction condition is mild, Atom economy is high,
And there is important strategic importance to the interdependency of petroleum resources for adjustment world energy sources structure, improvement.Wherein, oxalic acid two
The exploitation of methyl ester hydrogenation synthesizing alcohol reacting middle catalyst is to realize the industrialized key of the route.
Research shows that Hydrogenation of Dimethyl Oxalate reaction is typical cascade reaction：First in Hydrogenation of Dimethyl Oxalate generation
Between product ethanol acid methyl esters, methyl glycollate repeated hydrogenation generation ethylene glycol, ethylene glycol deep hydrogenation generation ethyl alcohol.U.S. ARCO is public
Department has studied oxalate gas-phase catalytic hydrogenation process, wherein catalyst first on the basis of CO catalytic coupling synthesis of oxalate
Copper zinc chrome or copper chromium are used as active component, with Al2O3Or SiO2Deng for carrier, in 200-230 DEG C of temperature and pressure 1.07-
Under the conditions of 3.39MPa etc., the ethylene glycol yield of 11.7%-18.9% is obtained.1986, ARCO companies of the U.S. applied for grass first
Acid esters Hydrogenation ethylene glycol patent US4112245, wherein using Cu-Cr catalyst, the receipts of ethylene glycol under the pressure of 3.0MPa
Rate reaches 97.2%.
Although Cu-Cr catalyst is a kind of efficient catalyst, but since Cr is very big to human body and environmental pollution damage,
Therefore the research without Cr catalyst is increasingly becoming the research tendency of Hydrogenation of Dimethyl Oxalate catalyst.
Ube Industries Ltd. beginning of the eighties, to Chrome-free copper-based catalysts in preparing ethylene glycol by using dimethyl oxalate plus hydrogen reaction
Using having carried out numerous studies.Wherein clear 57-122946, clear 57-123127, clear 57-180432 and clear 57-122941 are reported
Catalyst based on copper has investigated carrier (Al2O3、SiO2、La2O3Deng), auxiliary agent (K, Si, Ag, Mo, Ba etc.) and preparation side
The influence to catalytic activity and selectivity such as method.UCC companies of the U.S. have also applied for US4628U8, US4649226, US4628U9 system
The copper silicon systems catalyst patent of row dimethyl oxalate gas phase hydrogenation preparing ethylene glycol.The copper silicon systems catalyst is prepared using infusion process,
And be associated with the relationship between carrier physical parameter and catalyst activity, it is proposed that the method for Vehicle element, about 220 DEG C,
95% ethylene glycol yield is obtained under 3MPa.Chinese Fudan University reports one kind in patent CN101455976 and is respectively adopted
Magnesium, manganese or aluminium are supported on catalyst on mesopore molecular sieve for the copper of additive modification, temperature be 210 DEG C, pressure 3MPa, hydrogen
Ester ratio is 180, air speed 0.1-1Under the conditions of, dimethyl oxalate conversion ratio reaches 100%, glycol selectivity and reaches 96%.
At present, in existing Hydrogenation of Dimethyl Oxalate technical solution, principal product is methyl glycollate or ethylene glycol.Although
The research of current prepared by dimethyl oxalate plus hydrogen methyl glycollate and ethylene glycol catalyst has been achieved with certain progress, but into
Research in terms of catalyst needed for one step deep hydrogenation ethyl alcohol is also seldom.In the technical solution of prepared by dimethyl oxalate plus hydrogen ethyl alcohol
In, copper-based catalysts because its activity it is high, it is cheap, be easy to get and while preparing simply is widely adopted.Chinese Academy of Sciences coalification institute and multiple
The research institutions such as the denier university also research in terms of prepared by dimethyl oxalate plus hydrogen ethyl alcohol catalyst is engaged in, due to caltalyst
The differences such as system, reaction condition, evaluating apparatus, analysis means, the levels of catalysts difference of report is larger, and comparativity is not very strong.
It is well known that prepared by dimethyl oxalate plus hydrogen ethyl alcohol is strong exothermal reaction.For exothermic catalytic reaction, with reacting
The progress of journey, the inactivation of reaction heat certainty accelerator activator constantly released influence the stability of catalyst.Copper-based catalysts,
Since the fusing point of its main active component-copper is relatively low, the easy-sintering in prepared by dimethyl oxalate plus hydrogen ethanol synthesis limits this
The large-scale application of route.
Invention content
In view of the above-mentioned condition of the prior art, the present inventor is in prepared by dimethyl oxalate plus hydrogen ethyl alcohol catalyst side
Face has carried out extensive and in-depth study, to find a kind of preparation of new prepared by dimethyl oxalate plus hydrogen ethyl alcohol catalyst
Method, the catalyst prepared by this method can not only obtain the height of ethyl alcohol when for prepared by dimethyl oxalate plus hydrogen ethyl alcohol
Selectivity, but also the high conversion of dimethyl oxalate can be obtained, especially obtain the highly selective of ethyl alcohol.Human hair of the present invention
It is existing, when preparing prepared by dimethyl oxalate plus hydrogen ethyl alcohol catalyst, if prepared simultaneously using the hydrothermal synthesis method that urea is assisted
And use CO in drying2Supercritical drying, the catalyst so prepared is when for prepared by dimethyl oxalate plus hydrogen ethyl alcohol, not only
The highly selective of ethyl alcohol can be obtained, but also the high conversion of dimethyl oxalate can be obtained, especially obtains the Gao Xuan of ethyl alcohol
Selecting property.The present invention is based on aforementioned discovery and is achieved.
Therefore, it is an object of the present invention to provide a kind of sides for preparing prepared by dimethyl oxalate plus hydrogen ethyl alcohol catalyst
Method.This method prepares catalyst and in drying using CO using the hydrothermal synthesis method that urea is assisted2Supercritical drying, such as
The catalyst that this is prepared can not only obtain the highly selective of ethyl alcohol when for prepared by dimethyl oxalate plus hydrogen ethyl alcohol, but also
The high conversion of dimethyl oxalate can be obtained, especially obtains the highly selective of ethyl alcohol.
It is a further object to provide the prepared by dimethyl oxalate plus hydrogen ethyl alcohol being prepared by the method for the present invention with urging
Agent.The catalyst can not only obtain the highly selective of ethyl alcohol, but also can when for prepared by dimethyl oxalate plus hydrogen ethyl alcohol
The high conversion of dimethyl oxalate is obtained, especially obtains the highly selective of ethyl alcohol.
Final object of the present invention is to provide the catalyst being prepared by the method for the present invention in Hydrogenation of Dimethyl Oxalate
As the purposes of catalyst in ethyl alcohol processed.The catalyst can not only obtain second when for prepared by dimethyl oxalate plus hydrogen ethyl alcohol
Alcohol it is highly selective, but also the high conversion of dimethyl oxalate can be obtained, especially obtain the highly selective of ethyl alcohol.
Realizing the technical solution of above-mentioned purpose of the present invention can be summarized as follows：
1. a kind of method for preparing prepared by dimethyl oxalate plus hydrogen ethyl alcohol catalyst, which is loaded catalyst,
Comprising carrier and the catalytic active component being carried on carrier and optional catalyst aid, the total weight based on the catalyst should
Catalyst includes：
(A) it is based on the element one or more element conducts in Cu, Fe, Ni, Co, Ag and Au of 1-50 weight %
Catalytic active component,
(B) periodic table of elements is selected from for the one or more of catalytic active component that are different from of 0-10 weight % based on the element
Element in third major element, transition elements and lanthanide series as catalyst aid and
(C) carrier,
It is characterized in that the catalyst is prepared by a method comprising the following steps：
(1) soluble metallic salt of catalytic active component and the soluble-salt of optional catalyst aid are provided in deionized water
In aqueous solution；
(2) urea is added into the aqueous solution that step (1) obtains as precipitating reagent, carrier is added after stirring evenly, obtains
To a mixture, the wherein additive amount of urea should cause the quality that urea includes water with the aqueous solution provided in step (1)
Than being 1:100-10:100；
(3) by the mixture obtained in step (2) in hydrothermal reaction kettle in 100-200 DEG C of hydrothermal synthesis；
(4) hydrothermal product obtained in step (3) is filtered, washing, then CO2Supercritical drying；And
(5) by step (4) through CO2The product roasting of supercritical drying, obtains catalyst.
2. according to the method for the 1st, wherein the total weight based on the catalyst, which includes：
(A) based on the element for 5-30 weight % catalytic active component and
(B) it is based on the element the catalyst aid of 1-5 weight %；And
(C) carrier of 65-94 weight %.
3. according to the method for the 1st or 2, wherein catalytic active component is one or more members in Cu, Ag and Fe
The combination of element, especially Cu or Cu and Ag and/or catalyst aid are one or more members in B, Al, La, Ce and Zn
Element, one or more elements and/or carrier especially in B, La and Ce are selected from carbon nanotube, graphene, activity
Charcoal, SiO2、Al2O3、ZrO2, one or more in SBA-15, MCM-41, MCM-48, HMS, ZnO and ZSM-5, preferably carbon
Nanotube, graphene, SiO2、Al2O3、ZrO2With it is one or more in ZSM-5, on condition that：When catalyst aid is Al, carry
Body is not Al2O3, when catalyst aid is Zr, carrier is not ZrO2。
4. according to the method for any one of 1-3, wherein the soluble metallic salt of catalytic active component is nitrate, vinegar
Hydrochlorate, chlorate, their hydrate or the soluble-salt of its any mixture and/or catalyst aid are nitrate, acetic acid
Salt, chlorate, their hydrate or its any mixture.
5. according to the method for any one of 1-4, wherein in step (2), the additive amount of urea should cause urea and step
Suddenly the mass ratio that the aqueous solution provided in (1) includes water is 1:100-8:100, preferably 1:100-6:100.
6. according to the method for any one of 1-5, wherein in step (3), by the mixture obtained in step (2) in
Hydrothermal synthesis is carried out at 100-180 DEG C；And/or the hydrothermal synthesis time is 4-72 hours, preferably 10-48h；And/or the hydro-thermal is closed
It is carried out under into the speed of agitator in 1-10rpm, preferably 1-5rpm.
7. according to the method for any one of 1-6, wherein in step (4), CO2Supercritical drying in the following way into
Row：Hydrothermal synthesis solid after washing is placed in enclosed high pressure kettle, and be continually fed into supercritical CO2, in 40-60 DEG C and 10-
20MPa is dry preferably under the conditions of 40-45 DEG C and 10-12MPa；And/or CO2Supercritical drying carries out 10-48h, preferably 24-
48h。
8. according to the method for any one of 1-7, the roasting wherein in step (5) carries out at 350-550 DEG C.
9. pass through catalyst made from the method according to any one of 1-8.
10. by catalyst made from the method according to any one of 1-8 in prepared by dimethyl oxalate plus hydrogen ethyl alcohol
Purposes.
11. according to the purposes of the 10th, wherein in the reaction of prepared by dimethyl oxalate plus hydrogen ethyl alcohol, DMO/H2Molar ratio is
50-300, pressure are 1-5MPa (gauge pressure), and reaction temperature is 150-350 DEG C and liquid hourly space velocity (LHSV) is 0.1-6.4h-1；It is preferred that DMO/
H2Molar ratio is 100-200, and reaction pressure is 2-4MPa (gauge pressure), and reaction temperature is 200-300 DEG C and liquid hourly space velocity (LHSV) is 0.4-
3.2h-1。
For these and other purposes, features and advantages of the present invention after the hereafter consideration present invention is combined, it is common to be readily able to
Technical staff understands.
Specific embodiment
According to an aspect of the invention, there is provided a kind of side for preparing prepared by dimethyl oxalate plus hydrogen ethyl alcohol catalyst
Method, the catalyst are loaded catalyst, are helped comprising carrier and the catalytic active component being carried on carrier and optional catalysis
Agent, the total weight based on the catalyst, the catalyst include：
(A) it is based on the element one or more element conducts in Cu, Fe, Ni, Co, Ag and Au of 1-50 weight %
Catalytic active component,
(B) periodic table of elements is selected from for the one or more of catalytic active component that are different from of 0-10 weight % based on the element
Element in third major element, transition elements and lanthanide series as catalyst aid and
(C) carrier,
It is characterized in that the catalyst is prepared by a method comprising the following steps：
(1) soluble metallic salt of catalytic active component and the soluble-salt of optional catalyst aid are provided in deionized water
In aqueous solution；
(2) urea is added into the aqueous solution that step (1) obtains as precipitating reagent, carrier is added after stirring evenly, obtains
To a mixture, the wherein additive amount of urea should cause the quality that urea includes water with the aqueous solution provided in step (1)
Than being 1:100-10:100；
(3) by the mixture obtained in step (2) in hydrothermal reaction kettle in 100-200 DEG C of hydrothermal synthesis；
(4) hydrothermal product obtained in step (3) is filtered, washing, then CO2Supercritical drying；And
(5) by step (4) through CO2The product roasting of supercritical drying, obtains catalyst.
Catalyst of the present invention is loaded catalyst, described comprising catalytic active component, optional catalyst aid and carrier
Catalytic active component and optional catalyst aid are carried on carrier.As catalytic active component, it is usually one or more
Element in Cu, Fe, Ni, Co, Ag and Au, especially preferably one or more elements in Cu, Ag and Fe, Cu
And/or Ag.Catalytic active component can be present in as simple substance in catalyst, can also be deposited as the form of compound such as oxide
It is in catalyst, then is present in catalyst as a mixture of both.Based on the element, catalyst of the present invention is usual
The catalytic active component of the catalytic active component of 1-50 weight %, preferably 5-30 weight % is included, the total weight based on catalyst.
Catalyst aid is the optional components of catalyst of the present invention, and can include can not also include, and preferably comprise.Catalysis helps
Ethanol selectivity and dimethyl oxalate conversion ratio when the presence of agent can further improve prepared by dimethyl oxalate plus hydrogen ethyl alcohol, especially
It is the selectivity for further improving ethyl alcohol.As catalyst aid, it is usually one or more different from catalytic active component
The element in periodic table of elements third major element, transition elements and lanthanide series.Third major element include B, Al,
Ga and In.When third major element is as catalyst aid, preferably B and/or Al.Transition elements refers to d in the periodic table of elements
A series of metallic elements in area, this region has the element of ten races altogether including 3-12, but does not include the inner transition element in f areas,
Do not include lanthanide series and actinides namely.As transition elements can be mentioned that Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
W, Mn, Tc, Re, Ru, Os, Rh, Ir, Pd, Pt, Zn, Cd and Hg.When transition metal is as catalyst aid, be preferably selected from Mo,
It is one or more in Mn, Pd and Zn, particularly preferred Zn and/or Mn.As lanthanide series can be mentioned that La, Ce, Pr, Nd, Pm,
Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.When lanthanide series is as catalyst aid, be preferably selected from La, Ce, Pr and
It is one or more in Tb, particularly preferred La and/or Ce.Catalyst aid can be present in as simple substance in catalyst, can also make
Form for compound such as oxide is present in catalyst, then is present in catalyst as a mixture of both.
Based on the element, catalyst of the present invention generally comprises the catalyst aid of the catalyst aid of 0-10 weight %, preferably 1-5 weight %, base
In the total weight of catalyst.
Catalyst of the present invention is loaded catalyst, and catalytic active component and optional catalyst aid are carried on carrier.
As carrier, it can be any carrier suitable for Hydrogenation of Dimethyl Oxalate synthesizing alcohol catalyst.Carrier is preferably one kind
It is or a variety of selected from carbon nanotube, graphene, activated carbon, SiO2、Al2O3、ZrO2, SBA-15 (mesopore molecular sieve), MCM-41 (be situated between
Porous molecular sieve), MCM-48 (mesopore molecular sieve), HMS (hollow mesoporous silicon oxide), the carrier in ZnO and ZSM-5, more preferably
To be one or more selected from carbon nanotube, graphene, SiO2、Al2O3、ZrO2It is especially a kind of and more with the carrier in ZSM-5
Kind is selected from carbon nanotube, graphene, SiO2With the carrier in ZSM-5, on condition that：When catalyst aid is Al, carrier is not
Al2O3, when catalyst aid is Zr, carrier is not ZrO2.Catalyst of the present invention generally comprises the carrier of 40-99 weight %, preferably
The carrier of 65-94 weight %, the total weight based on catalyst.
Catalyst of the present invention is prepared and in drying by using the hydrothermal synthesis method that urea is assisted using CO2It is super to face
Boundary is dried, and the catalyst so prepared can not only obtain the high selection of ethyl alcohol when for prepared by dimethyl oxalate plus hydrogen ethyl alcohol
Property, but also the high conversion of dimethyl oxalate can be obtained, especially obtain the highly selective of ethyl alcohol.For this purpose, usually pass through packet
The method of following steps is included to prepare catalyst of the present invention：
(1) soluble metallic salt of catalytic active component and the soluble-salt of optional catalyst aid are provided in deionized water
In aqueous solution；
(2) urea is added into the aqueous solution that step (1) obtains as precipitating reagent, carrier is added after stirring evenly, obtains
To a mixture, the wherein additive amount of urea should cause the quality that urea includes water with the aqueous solution provided in step (1)
Than being 1:100-10:100；
(3) by the mixture obtained in step (2) in hydrothermal reaction kettle in 100-200 DEG C of hydrothermal synthesis；
(4) hydrothermal product obtained in step (3) is filtered, washing, then CO2Supercritical drying；And
(5) by step (4) through CO2The product roasting of supercritical drying, obtains catalyst.
In step (1), the soluble metallic salt of catalytic active component and the soluble-salt of optional catalyst aid are provided
Aqueous solution in deionized water.If catalyst includes catalyst aid, catalytic active component can be prepared respectively thus
Soluble metallic salt aqueous solution in deionized water and catalyst aid soluble-salt aqueous solution in deionized water, so
Both is merged afterwards.It alternatively, can also be by the soluble metallic salt of catalytic active component and optional catalyst aid
Soluble-salt add in deionized water in, prepare obtain catalytic active component soluble metallic salt and optional catalyst aid can
The aqueous solution of soluble in deionized water.The soluble metallic salt of catalytic active component and the soluble-salt of catalyst aid are respectively
Dosage it is corresponding with the catalytic active component in catalyst to be prepared and catalyst aid.The solubility of catalytic active component
The concentration of the aqueous solution of the soluble-salt of metal salt and optional catalyst aid in deionized water is not particularly limited, usually
Can be 5-50 weight %, preferably 15-30 weight %.The soluble metallic salt of catalytic active component can be nitrate, acetic acid
Salt, chlorate, their hydrate, acid or its any mixture, preferably nitrate, acetate and their hydrate.It urges
Change auxiliary agent soluble-salt can be nitrate, acetate, chlorate, their hydrate, acid or its any mixture, preferably
For nitrate, acetate and their hydrate.
Urea is added in step (2), in the aqueous solution obtained to step (1) as precipitating reagent, is added again after stirring evenly
Enter carrier, obtain a mixture, the wherein additive amount of urea should cause urea to include water with the aqueous solution provided in step (1)
The mass ratio of amount is 1:100-10:100.The purpose of addition urea is in the aqueous solution obtained in step (1)：Urea can with
Generation ammonia and CO are decomposed in water-heat process afterwards2, ammonia can precipitate reactant, and atmospheric carbon dioxide in the reaction system may be used
To play the role of pore-creating.Although the soluble-salt of the soluble metallic salt of catalytic active component and catalyst aid can be precipitated
Reagent there are many selecting, for example ammonium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate etc. can be used, but it is laggard to add urea
Row hydrothermal synthesis can so that precipitation is uniform to prepare catalyst of the present invention, and avoid introducing foreign ion such as sodium ion, and
Washing difficulty is reduced, in addition urea decomposes the pore-creating effect of the carbon dioxide generated so that catalytic carrier has higher specific surface
Product, is conducive to catalytic active component and catalyst aid is uniformly distributed.The additive amount of urea should cause urea with being provided in step (1)
Aqueous solution include water mass ratio be 1:100-10:100, preferably 1:100-8:100, more preferably 1:100-6:
100.Urea both can in itself be added as urea, can also be used as the aqueous solution addition of urea in deionized water.Addition urine
After element, it usually needs stir evenly gained mixture.The stirring usually carries out 30-120min.After stirring evenly, mixed to gained
It closes in object and adds in carrier, obtain a mixture.Advantageously, which is also required to stir evenly, then carries out hydro-thermal process.
In step (3), by the mixture obtained in step (2) in 100-200 DEG C of hydrothermal synthesis in hydrothermal reaction kettle,
It is preferred that it is carried out at 100-180 DEG C.The hydrothermal synthesis time is usually 4-72h, preferably 10-48h.Advantageously, it is closed in hydro-thermal
It into the process, carries out under the speed of agitator of 1-10rpm, is preferably carried out under the speed of agitator of 1-5rpm.
After hydrothermal synthesis, need to detach and dry hydrothermal synthesis product.It therefore, will be in step (3) in step (4)
Obtained hydrothermal product filtering, is washed, then CO2Supercritical drying.The hydrothermal product obtained in step (3) is first filtered,
Solid is isolated, is then washed with deionized, which can carry out one or many.Then, by the hydrothermal synthesis after washing
Solid CO2Supercritical drying.Supercritical fluid refers to the fluid more than critical-temperature (Tc) and critical pressure (Pc), example
Such as carbon dioxide, ammonia, ethylene, propane.When the temperature of carbon dioxide is more than 31 DEG C, pressure is more than 7.38MPa, that is, enter
Supercritical carbon dioxide state.CO2Supercritical drying refers to：CO2As supercritical fluid drying medium, in supercriticality
Under, CO2The property of gas and liquid is had both, no gas-liquid interface also just without the presence of surface tension, therefore can drive away hydro-thermal conjunction
Into the water in solid, achieve the purpose that it is dry, so as to avoid the contraction of solid material structure in the drying process.Pass through CO2It is super
Critical drying can so that catalyst has high-specific surface area and particle diameter distribution is uniform., it is preferred according to the present invention that by such as
Under type carries out CO2Supercritical drying：Hydrothermal synthesis solid after washing is placed in enclosed high pressure kettle, is passed through overcritical
CO2, it is then dry under the conditions of 40-60 DEG C and 10-20MPa, it is dry preferably under 40-45 DEG C and 10-12MPa, such as 40
DEG C and 10MPa under the conditions of it is dry.CO2The supercritical drying time is usually 10-48h, preferably 24-48h.
After drying, gained desciccate is roasted to get to catalyst of the present invention.Therefore, in step (5),
By in step (4) through CO2The product roasting of supercritical drying, obtains catalyst.Roasting usually carries out at 200-900 DEG C, excellent
It is selected at 350-550 DEG C and carries out.Roasting time is usually 2-24h, preferably 3-10h.Calcination atmosphere is usually air or indifferent gas
Atmosphere.Here inert atmosphere refers to the atmosphere that chemical reaction is not involved under roasting condition, such as nitrogen, argon gas.
Catalyst of the present invention is prepared and in drying by using the hydrothermal synthesis method that urea is assisted using CO2It is super to face
Boundary is dried, and the catalyst so prepared can not only obtain the high selection of ethyl alcohol when for prepared by dimethyl oxalate plus hydrogen ethyl alcohol
Property, but also the high conversion of dimethyl oxalate can be obtained, especially obtain the highly selective of ethyl alcohol.
Therefore, according to another aspect of the present invention, a kind of method for preparing catalyst by the present invention is provided to be made
Catalyst.All features of the catalyst with above to identical described in catalyst preparation.
The last one aspect according to the present invention, provides through catalyst made from the method for the present invention in dimethyl oxalate
Purposes in preparation of ethanol by hydrogenating.
The catalyst of the present invention needs to restore the catalyst before for prepared by dimethyl oxalate plus hydrogen ethyl alcohol,
So that the catalytic active component in catalyst is in simple substance form with the catalyst aid being optionally present.For this purpose, usually by catalyst
It is restored with the atmosphere of hydrogen.Reduction temperature is usually 200-400 DEG C, preferably 250-350 DEG C.It is usually 1.0- to restore pressure
The gauge pressure of 4.0MPa, preferably 2.0-3.0MPa.Recovery time is usually 3-12h, preferably 3-6h.Reducing atmosphere can use pure hydrogen
Gas can also use the gaseous mixture of hydrogen.After reduction, the catalytic active component in catalyst is helped with the catalysis being optionally present
Agent is in simple substance form, shows catalytic activity.
When for prepared by dimethyl oxalate plus hydrogen ethyl alcohol, reaction may be carried out batchwise the catalyst of the present invention, also can be continuous
It carries out.Catalyst can be used with any conventionally form, preferably be used with fixed bed form.When the catalyst of the present invention is used for oxalic acid
During dimethyl ester preparation of ethanol by hydrogenating, the stream comprising dimethyl oxalate and hydrogen is made to pass through the catalyst of the present invention.The work of the reaction
Skill condition is typically：DMO/H2Molar ratio is 50-300, and pressure is 1-5MPa (gauge pressure), and reaction temperature is 150-350 DEG C, during liquid
Air speed is 0.1-6.4h-1；Process conditions are preferably：DMO/H2Molar ratio is 100-200, and reaction pressure is 2-4MPa (gauge pressure),
Reaction temperature is 200-300 DEG C and liquid hourly space velocity (LHSV) is 0.4-3.2h-1。
Relative to prior art, beneficial effects of the present invention are：
Prepared by dimethyl oxalate plus hydrogen ethyl alcohol is strong exothermal reaction, and copper-based single-metal reforming catalyst leads to it anti-because of its low melting point
Ying Zhongyi reunites, sintering, inactivates.In the present invention, hydro-thermal synthetic preparation method is assisted and with reference to CO using urea2Supercritical drying
It is dry, using Cu, Fe, Ni, Co, Ag and/or Au metal as main active component, the prepared by dimethyl oxalate plus hydrogen of polymolecularity can be obtained
Ethyl alcohol catalyst the problem of advantageously accounting for catalyst thermal stability is poor during the reaction, improves the thermostabilization of catalyst
Property, the highly selective of ethyl alcohol particularly can be not only obtained, but also the high conversion of dimethyl oxalate can be obtained, especially obtained
Obtain the highly selective of ethyl alcohol.
Embodiment
Below with reference to specific embodiment, the invention will be further described, but should not be construed as protecting the present invention
The limitation of range.
Embodiment 1
The preparation of catalyst
It weighs 1.37g nitrate trihydrate copper and is dissolved in wiring solution-forming I in 50ml deionized waters, weigh 0.28g boric acid and be dissolved in 50ml
Solution II is obtained in deionized water, solution I and II is mixed to get solution III.2.4g urea is added in into solution III, mixing is stirred
After mixing 30min, 2g carbon nanotube carriers are added in acquired solution, and continue to stir 60min.Then gained mixture is put into
In hydrothermal synthesis kettle, 100 DEG C of hydrothermal synthesis are for 24 hours under 2r/min rotating speeds.Obtained hydrothermal synthesis product is filtered, uses deionization
After water washing, it is placed in enclosed high pressure kettle, and be continually fed into supercritical CO2, the dry 20h under the conditions of 40 DEG C, 10MPa.Then
500 DEG C of roasting 3h under nitrogen atmosphere, obtain catalyst A, include 15%Cu and 2%B based on the element in tube furnace.
Catalyst reduction and hydrogenation
Gained catalyst A is fitted into a diameter of 9 millimeters of the tubular reactor erect for 0.25 gram totally, catalyst A is with solid
Fixed bed is set.Hydrogen is passed through from the upper inlet of tubular reactor, by catalyst at 300 DEG C of temperature and the gauge pressure of 2.5MPa
A continued reductions 3h.After catalyst A reduction, temperature is reduced to 280 DEG C, continues to be passed through hydrogen, while also from tubular reactor
Upper inlet is passed through dimethyl oxalate (DMO), H2The control of/DMO molar ratios is 200, gauge pressure of the pressure control for 2.5MPa, during liquid
Air speed control is 0.4h-1, continuous hydrogenation is carried out to dimethyl oxalate.Reaction result is shown in Table 1.
Embodiment 2
It weighs nine water ferric nitrates of 0.80g and is dissolved in wiring solution-forming I in 50ml deionized waters, weigh 0.17g silver nitrates and be dissolved in
Solution II is obtained in 50ml deionized waters, solution I and II is mixed to get solution III.6.3g urea is added in into solution III, is mixed
After closing stirring 30min, the 40wt% Ludox of 5g is added dropwise, and continues to stir 120min.Then gained mixture is put into hydro-thermal
In synthesis reactor, 120 DEG C of hydrothermal synthesis 10h under 2r/min rotating speeds.Obtained hydrothermal synthesis product is filtered, spends ion-cleaning
Afterwards, it is placed in enclosed high pressure kettle, and is continually fed into supercritical CO2, dried for 24 hours under the conditions of 40 DEG C, 10MPa.Then in tubular type
The lower 350 DEG C of roastings 3h of air atmosphere, obtains catalyst B, includes 5%Fe and 5%Ag based on the element in stove.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent B.Reaction result is shown in Table 1.
Embodiment 3
It weighs 0.58g silver nitrates and is dissolved in wiring solution-forming I in 50ml deionized waters, weigh 0.23g lanthanum nitrate hexahydrates and be dissolved in
Solution II is obtained in 50ml deionized waters, solution I and II is mixed to get solution III.1.6g urea is added in into solution III, is mixed
After closing stirring 30min, 2g graphenes carrier is added in acquired solution, and continues to stir 60min.Then gained mixture is put
Enter in hydrothermal synthesis kettle, 180 DEG C of hydrothermal synthesis are for 24 hours under 2r/min rotating speeds.By obtained hydrothermal synthesis product filter, spend from
After sub- water washing, it is placed in enclosed high pressure kettle, and be continually fed into supercritical CO2, the dry 48h under the conditions of 40 DEG C, 10MPa.So
Afterwards in tube furnace under nitrogen atmosphere 500 DEG C roasting 3h, obtain catalyst C, based on the element include 15%Ag and 3%La.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent C.Reaction result is shown in Table 1.
Embodiment 4
It weighs 1.16g cobalt nitrate hexahydrates and nine water aluminum nitrates of 1.64g is dissolved in wiring solution-forming in 100ml deionized waters, treat it
After being completely dissolved, 5.4g urea is added in, after stirring 60min, 2g absorbent charcoal carriers are added in acquired solution, and continue to stir
30min is mixed thoroughly.Then gained mixture is put into hydrothermal synthesis kettle, 160 DEG C of hydrothermal synthesis under 4r/min rotating speeds
10h.Obtained hydrothermal synthesis product is filtered, after being washed with deionized, is placed in enclosed high pressure kettle, and is continually fed into super face
Boundary CO2, the dry 30h under the conditions of 40 DEG C, 10MPa.Then in tube furnace under nitrogen atmosphere 400 DEG C roasting 3h, be catalyzed
Agent D includes 10%Co and 5%Al based on the element.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent D.Reaction result is shown in Table 1.
Embodiment 5
It weighs 0.86g nitrate trihydrate copper and is dissolved in wiring solution-forming I in 50ml deionized waters, it is molten to weigh 0.14g cerium nitrate hexahydrates
Solution II is obtained in 50ml deionized waters, solution I and II is mixed to get solution III.1.4g urea is added in into solution III,
After stirring 60min, 2g ZSM-5 carriers are added in acquired solution, and continue to stir 60min, are mixed thoroughly.Then will
Gained mixture is put into hydrothermal synthesis kettle, 100 DEG C of hydrothermal synthesis 10h under 1r/min rotating speeds.Obtained hydrothermal synthesis is produced
Object filters, and after deionized water, is placed in enclosed high pressure kettle, and be continually fed into supercritical CO2, done under the conditions of 40 DEG C, 10MPa
It is dry for 24 hours.Then 550 DEG C of roasting 3h under air atmosphere in tube furnace, obtain catalyst E, based on the element comprising 10%Cu and
2%Ce.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent E.Reaction result is shown in Table 1.
Embodiment 6
It weighs nine water ferric nitrates of 3.51g and is dissolved in wiring solution-forming I in 50ml deionized waters, weigh 0.88g boric acid and be dissolved in 50ml
Solution II is obtained in deionized water, solution I and II is mixed to get solution III.1g urea, stirring are added in into solution III
After 120min, by 2g Al2O3Carrier is added in acquired solution, and continues to stir 100min, is mixed thoroughly.Then by gained
Mixture is put into the hydrothermal synthesis kettle of 100ml, 195 DEG C of hydrothermal synthesis 10h under 2r/min rotating speeds.The hydrothermal synthesis that will be obtained
Product filters, and after being washed with deionized, is placed in enclosed high pressure kettle, and be continually fed into supercritical CO2, in 40 DEG C, 10MPa items
Dry 36h under part.Then in tube furnace under air atmosphere 400 DEG C roasting 3h, obtain catalyst F, include based on the element
30%Fe and 5%B.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent F.Reaction result is shown in Table 1.
Embodiment 7
It weighs 0.36g chloraurides and is dissolved in 50ml deionized waters and obtain solution I, weigh 0.45g nitrate trihydrate copper and be dissolved in
Solution I and II is mixed to get solution III by wiring solution-forming II in 50ml deionized waters.9.7g urea is added in into solution III, is stirred
After mixing 120min, by 2g ZrO2Carrier is added in acquired solution, and continues to stir 60min, is mixed thoroughly.Then by institute
It obtains mixture to be put into hydrothermal synthesis kettle, 160 DEG C of hydrothermal synthesis 48h under 3r/min rotating speeds.The hydrothermal synthesis product that will be obtained
Filtering, after being washed with deionized, is placed in enclosed high pressure kettle, and be continually fed into supercritical CO2, under the conditions of 40 DEG C, 10MPa
Dry 36h.Then in tube furnace under air atmosphere 650 DEG C roasting 10h, obtain catalyst G, based on the element include 10%Au
And 5%Cu.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent G.Reaction result is shown in Table 1.
Embodiment 8
It weighs 0.11g Nickelous nitrate hexahydrates and is dissolved in wiring solution-forming I in 50ml deionized waters, weigh six nitric hydrates of 1.02g
Zinc, which is dissolved in 50ml deionized waters, obtains solution II, and solution I and II is mixed to get solution III.3.6g urine is added in into solution III
After 50min is mixed, 2g SBA-15 carriers are added in acquired solution for element, and continue to stir 60min.Then gained is mixed
It closes object to be put into hydrothermal synthesis kettle, 140 DEG C of hydrothermal synthesis 50h under 2r/min rotating speeds.Obtained hydrothermal synthesis product is filtered,
After spending ion-cleaning, it is placed in enclosed high pressure kettle, and be continually fed into supercritical CO2, it is dry under the conditions of 40 DEG C, 10MPa
18h.Then 600 DEG C of roasting 6h under air atmosphere in tube furnace, obtain catalyst H, based on the element comprising 1%Ni and
9.8%Zn.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent H.Reaction result is shown in Table 1.
Embodiment 9
It weighs 7.3g nitrate trihydrate copper and is dissolved in wiring solution-forming I in 100ml deionized waters.8.4g urea is added in into solution I,
After 60min is mixed, 2g carbon nanotube carriers are added in acquired solution, and continue to stir 30min.Then gained is mixed
Object is put into hydrothermal synthesis kettle, 120 DEG C of hydrothermal synthesis 18h under 2r/min rotating speeds.Obtained hydrothermal synthesis product is filtered, is used
After deionized water washing, it is placed in enclosed high pressure kettle, and be continually fed into supercritical CO2, it is dry under the conditions of 40 DEG C, 10MPa
24h.Then in tube furnace under nitrogen atmosphere 500 DEG C roasting 3h, obtain catalyst I, based on the element include 49%Cu.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent I.Reaction result is shown in Table 1.
Comparative example 1
The method for preparing catalyst in embodiment 1 is repeated, unlike：Control feeding quantity causes gained catalyst with element
Meter includes 15%Cu and 15%B, and based on the total weight of gained catalyst, gained catalyst is labeled as catalyst C-A.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent C-A.Reaction result is shown in Table 1.
Comparative example 2
The method for preparing catalyst in embodiment 2 is repeated, unlike：The additive amount of urea be 20g, gained catalyst mark
It is denoted as catalyst C-B.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent C-B.Reaction result is shown in Table 1.
Comparative example 3
The method for preparing catalyst in embodiment 3 is repeated, unlike：Hydrothermal synthesis product is filtering and is using deionized water
After washing, using common drying means, i.e. dried in 120 DEG C of air dry ovens for 24 hours, gained catalyst is labeled as catalyst C-
C。
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent C-C.Reaction result is shown in Table 1.
Comparative example 4
The method for preparing catalyst in embodiment 4 is repeated, unlike：Precipitating reagent urea is changed to the ammonium hydroxide of 28 weight %
Common 11.7g, gained catalyst are labeled as catalyst C-D.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent C-D.Reaction result is shown in Table 1.
Comparative example 5
The method for preparing catalyst in embodiment 5 is repeated, unlike：Hydrothermal synthesis temperature is 60 DEG C, gained catalyst
Labeled as catalyst C-E.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent C-E.Reaction result is shown in Table 1.
Comparative example 6
The method for preparing catalyst in embodiment 6 is repeated, unlike：Hydrothermal synthesis temperature is 205 DEG C, gained catalyst
Labeled as catalyst C-F-1.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent C-F-1.Reaction result is shown in Table 1.
Comparative example 7
The method for preparing catalyst in embodiment 6 is repeated, unlike：Hydrothermal synthesis temperature is 94 DEG C, gained catalyst
Labeled as catalyst C-F-2.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent C-F-2.Reaction result is shown in Table 1.
Comparative example 8
The method for preparing catalyst in embodiment 7 is repeated, unlike：The additive amount of urea be 10.9g, gained catalyst
Labeled as catalyst C-G-1.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent C-G-1.Reaction result is shown in Table 1.
Comparative example 9
The method for preparing catalyst in embodiment 7 is repeated, unlike：The additive amount of urea be 0.8g, gained catalyst
Labeled as catalyst C-G-2.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent C-G-2.Reaction result is shown in Table 1.
Comparative example 10
The catalyst preparation in embodiment 9 is repeated, unlike：Using preparation catalyst, detailed step is as follows：
7.3g nitrate trihydrate copper is taken to be dissolved in wiring solution-forming I in 100ml deionized waters.8.4g urea is added in into solution I, is mixed
Solution II is obtained after 60min, under Ultrasound-assisted, solution II is added dropwise in 2g carbon nanotube carriers, and continue to stir
30min.It is then placed in vacuum tank, vacuum 30min.Obtained solid product is placed in enclosed high pressure kettle, and is persistently led to
Enter supercritical CO2, dried for 24 hours under the conditions of 40 DEG C, 10MPa.Then in tube furnace under nitrogen atmosphere 500 DEG C roasting 3h.Institute
It obtains catalyst and is labeled as catalyst C-I.
The catalyst reduction in embodiment 1 and hydrogenation process are repeated, unlike：Catalyst A is replaced with into catalysis
Agent C-I.Reaction result is shown in Table 1.
Claims (11)
1. a kind of method for preparing prepared by dimethyl oxalate plus hydrogen ethyl alcohol catalyst, which is loaded catalyst, comprising
Carrier and the catalytic active component being carried on carrier and optional catalyst aid, the total weight based on the catalyst, the catalysis
Agent includes：
(A) catalysis is used as one or more elements in Cu, Fe, Ni, Co, Ag and Au of 1-50 weight % based on the element
Active component,
(B) periodic table of elements third is selected from for the one or more of catalytic active component that are different from of 0-10 weight % based on the element
Element in major element, transition elements and lanthanide series as catalyst aid and
(C) carrier,
It is characterized in that the catalyst is prepared by a method comprising the following steps：
(1) provide catalytic active component soluble metallic salt and optional catalyst aid soluble-salt in deionized water
Aqueous solution；
(2) urea is added into the aqueous solution that step (1) obtains as precipitating reagent, carrier is added after stirring evenly, obtains one
The additive amount of mixture, wherein urea should so that the mass ratio that urea includes water with the aqueous solution provided in step (1) is
1:100-10:100；
(3) by the mixture obtained in step (2) in hydrothermal reaction kettle in 100-200 DEG C of hydrothermal synthesis；
(4) hydrothermal product obtained in step (3) is filtered, washing, then CO2Supercritical drying；And
(5) by step (4) through CO2The product roasting of supercritical drying, obtains catalyst.
2. the method according to claim 1, wherein the total weight based on the catalyst, which includes：
(A) based on the element for 5-30 weight % catalytic active component and
(B) it is based on the element the catalyst aid of 1-5 weight %；And
(C) carrier of 65-94 weight %.
3. according to the method for claims 1 or 2, wherein catalytic active component is one or more members in Cu, Ag and Fe
The combination of element, especially Cu or Cu and Ag and/or catalyst aid are one or more members in B, Al, La, Ce and Zn
Element, one or more elements and/or carrier especially in B, La and Ce are selected from carbon nanotube, graphene, activity
Charcoal, SiO2、Al2O3、ZrO2, one or more in SBA-15, MCM-41, MCM-48, HMS, ZnO and ZSM-5, preferably carbon
Nanotube, graphene, SiO2、Al2O3、ZrO2With it is one or more in ZSM-5, on condition that：When catalyst aid is Al, carry
Body is not Al2O3, and when catalyst aid is Zr, carrier is not ZrO2.
4. the soluble metallic salt of method as claimed in one of claims 1-3, wherein catalytic active component is nitrate, vinegar
Hydrochlorate, chlorate, their hydrate or the soluble-salt of its any mixture and/or catalyst aid are nitrate, acetic acid
Salt, chlorate, their hydrate or its any mixture.
5. in method as claimed in one of claims 1-4, wherein step (2), the additive amount of urea should cause urea and step
Suddenly the mass ratio that the aqueous solution provided in (1) includes water is 1:100-8:100, preferably 1:100-6:100.
6. in method as claimed in one of claims 1-5, wherein step (3), by the mixture obtained in step (2) in
Hydrothermal synthesis is carried out at 100-180 DEG C；And/or the hydrothermal synthesis time is 4-72 hours, preferably 10-48h；And/or the hydro-thermal is closed
It is carried out under into the speed of agitator in 1-10rpm, preferably 1-5rpm.
7. in method as claimed in one of claims 1-6, wherein step (4), CO2Supercritical drying in the following way into
Row：Hydrothermal synthesis solid after washing is placed in enclosed high pressure kettle, and be continually fed into supercritical CO2, in 40-60 DEG C and 10-
20MPa is dry preferably under the conditions of 40-45 DEG C and 10-12MPa；And/or CO2Supercritical drying carries out 10-48h, preferably 24-
48h。
8. the roasting in method as claimed in one of claims 1-7, wherein step (5) carries out at 350-550 DEG C.
9. pass through catalyst made from method as claimed in one of claims 1-8.
10. by catalyst made from method as claimed in one of claims 1-8 in prepared by dimethyl oxalate plus hydrogen ethyl alcohol
Purposes.
11. in purposes according to claim 10, the wherein reaction of prepared by dimethyl oxalate plus hydrogen ethyl alcohol, DMO/H2Molar ratio is 50-
300, pressure is 1-5MPa (gauge pressure), and reaction temperature is 150-350 DEG C and liquid hourly space velocity (LHSV) is 0.1-6.4h-1；It is preferred that DMO/H2It rubs
You are than being 100-200, and reaction pressure is 2-4MPa (gauge pressure), and reaction temperature is 200-300 DEG C and liquid hourly space velocity (LHSV) is 0.4-
3.2h-1。
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| PCT/CN2017/116971 WO2018121326A1 (en) | 2016-12-26 | 2017-12-18 | Preparation method of catalyst for hydrogenation of dimethyl oxalate to synthesize ethanol, and catalyst obtained therefrom and use thereof |
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| CN (1) | CN108236955B (en) |
| WO (1) | WO2018121326A1 (en) |
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| CN108236955B (en) | 2021-05-18 |
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