CN108236955B - Preparation method of catalyst for synthesizing ethanol by dimethyl oxalate hydrogenation, catalyst obtained by preparation method and application of catalyst - Google Patents
Preparation method of catalyst for synthesizing ethanol by dimethyl oxalate hydrogenation, catalyst obtained by preparation method and application of catalyst Download PDFInfo
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- CN108236955B CN108236955B CN201611217916.8A CN201611217916A CN108236955B CN 108236955 B CN108236955 B CN 108236955B CN 201611217916 A CN201611217916 A CN 201611217916A CN 108236955 B CN108236955 B CN 108236955B
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- 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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- C07C29/149—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 invention relates to a method for preparing a catalyst for preparing ethanol by hydrogenating dimethyl oxalate, which comprises a carrier and a catalytic active component and an optional catalytic auxiliary agent loaded on the carrier, wherein the catalyst comprises the following components in parts by weight: (A) 1-50 wt% of an element selected from the group consisting of Cu, Fe, Ni, Co, Ag and Au as a catalytically active component, based on the element, (B) 0-10 wt% of an element selected from the group consisting of elements of the third main group of the periodic Table of the elements, transition elements and lanthanoids as a promoter, based on the element, and (C) a carrier, the catalyst of the present invention being prepared by hydrothermal synthesis using urea and using CO2Supercritical drying, and when the catalyst prepared in the way is used for preparing ethanol by hydrogenating dimethyl oxalate, high ethanol selectivity can be obtained, and high conversion rate of dimethyl oxalate can be obtained. The invention also relates to the catalyst prepared by the method and the application of the catalyst in preparing ethanol by hydrogenating dimethyl oxalate.
Description
Technical Field
The invention relates to a preparation method of a catalyst for synthesizing ethanol by hydrogenating dimethyl oxalate, and also relates to the catalyst obtained by the method and application of the catalyst.
Background
Ethanol is commonly called alcohol and is an important chemical raw material. The polymer can be used as a raw material for synthesizing a series of micromolecular chemical products and polymers, is a potential liquid fuel resource, and is widely concerned by countries in the world. Currently, ethanol production is mainly via two pathways: (1) fermenting grains; (2) ethylene from petroleum cracking is hydrated. The ethylene hydration method not only depends heavily on increasingly exhausted petroleum resources, but also has high requirements on equipment materials, and is not suitable for large-scale production of ethanol. Although most of the ethanol currently on the market is produced by grain fermentation routes, the production of fuel-grade ethanol is expensive and energy-intensive. In the eighties of the last century, Kenji and William et al proposed a synthetic route for the preparation of ethanol from synthesis gas via oxalic acid diester. The route firstly prepares synthesis gas from non-petroleum resources, then synthesizes dimethyl oxalate through CO oxidative coupling, and the dimethyl oxalate is further catalyzed and hydrogenated to generate ethanol. The carbon-synthesis route not only has the advantages of environmental protection, mild reaction conditions and high atom economy, but also has important strategic significance for adjusting the world energy structure and improving the dependency on petroleum resources. Wherein, the development of the catalyst in the reaction of synthesizing ethanol by dimethyl oxalate through hydrogenation is the key point for realizing the industrialization of the route.
Studies have shown that the dimethyl oxalate hydrogenation reaction is a typical tandem reaction: firstly, dimethyl oxalate is hydrogenated to generate an intermediate product methyl glycolate, methyl glycolate is hydrogenated to generate ethylene glycol, and the ethylene glycol is deeply hydrogenated to generate ethanol. Based on the synthesis of oxalate by CO catalytic coupling, ARCO company in America firstly researches the gas-phase catalytic hydrogenation process of oxalate, wherein the catalyst adopts copper-zinc-chromium or copper-chromium as an active component and Al2O3Or SiO2The ethylene glycol yield is 11.7-18.9% under the conditions of the temperature of 200-230 ℃ and the pressure of 1.07-3.39MPa and the like. In 1986, the american ARCO company first applied US 4112242245 for the oxalate hydrogenation to ethylene glycol, in which a Cu — Cr catalyst was used to achieve a yield of 97.2% ethylene glycol at a pressure of 3.0 MPa.
Although the Cu-Cr catalyst is a high-efficiency catalyst, the research of the Cr-free catalyst gradually becomes the research trend of the dimethyl oxalate hydrogenation catalyst because Cr has great harm to human bodies and environment.
In the beginning of 80 s of the future of the Ministry of Japan, a great deal of research is carried out on the application of a chromium-free copper-based catalyst in the reaction of preparing ethylene glycol by hydrogenating dimethyl oxalate. WhereinCatalysts based on copper were reported in Sho 57-122946, Sho 57-123127, Sho 57-180432 and Sho 57-122941, and the carrier (Al) was examined2O3、SiO2、La2O3Etc.), auxiliaries (K, Si, Ag, Mo, Ba, etc.), and preparation methods, etc., on the catalytic activity and selectivity. U.S. UCC also claims U.S. 4628U8, U.S. 4649226, U.S. 4628U9 series copper-silicon series catalysts for vapor phase hydrogenation of dimethyl oxalate to ethylene glycol. The copper-silicon catalyst is prepared by adopting an impregnation method, is related to the relationship between the physical property parameters of a carrier and the activity of the catalyst, provides a carrier pretreatment method, and obtains 95 percent of glycol yield at about 220 ℃ and 3 MPa. In patent CN101455976 of China Compound denier university, a catalyst which is modified by adopting magnesium, manganese or aluminum as an auxiliary agent and is loaded on a mesoporous molecular sieve is reported, wherein the catalyst has the advantages of temperature of 210 ℃, pressure of 3MPa, hydrogen-ester ratio of 180 and space velocity of 0.1-1Under the condition, the conversion rate of dimethyl oxalate reaches 100%, and the selectivity of ethylene glycol reaches 96%.
At present, in the existing technical scheme of dimethyl oxalate hydrogenation, the main product is methyl glycolate or ethylene glycol. Although current research on catalysts for the hydrogenation of dimethyl oxalate to produce methyl glycolate and ethylene glycol has been advanced to some extent, there has been little research on catalysts required for further deep hydrogenation to produce ethanol. In the technical scheme of preparing ethanol by dimethyl oxalate hydrogenation, a copper-based catalyst is widely adopted due to high activity, low price, easy obtaining and simple preparation. Research institutes such as coal chemical institute and recovery university of China academy of sciences are also engaged in research on catalysts for preparing ethanol by hydrogenating dimethyl oxalate, and due to the fact that catalyst systems, reaction conditions, evaluation devices, analysis means and the like are different, reported catalyst levels are different greatly, and comparability is not very strong.
It is well known that the hydrogenation of dimethyl oxalate to ethanol is a strongly exothermic reaction. For exothermic catalytic reactions, the continuous reaction heat generated inevitably accelerates the deactivation of the catalyst and affects the stability of the catalyst as the reaction proceeds. The copper-based catalyst is easy to sinter in the reaction of preparing ethanol by hydrogenating dimethyl oxalate due to the low melting point of copper which is the main active component, so that the large-scale application of the route is limited.
Disclosure of Invention
In view of the above-mentioned circumstances of the prior art, the present inventors have conducted extensive and intensive studies on a catalyst for the preparation of ethanol by the hydrogenation of dimethyl oxalate, and have found a novel method for preparing a catalyst for the preparation of ethanol by the hydrogenation of dimethyl oxalate, by which a catalyst for the preparation of ethanol by the hydrogenation of dimethyl oxalate can be obtained which not only has a high selectivity for ethanol but also has a high conversion rate for dimethyl oxalate, particularly a high selectivity for ethanol. The inventors have found that in the preparation of a catalyst for the hydrogenation of dimethyl oxalate to ethanol, if prepared by a urea-assisted hydrothermal synthesis and dried using CO2Supercritical drying, and when the catalyst prepared in the way is used for preparing ethanol by hydrogenating dimethyl oxalate, the high selectivity of the ethanol can be obtained, and the high conversion rate of the dimethyl oxalate, especially the high selectivity of the ethanol can be obtained. The present invention has been achieved based on the foregoing findings.
Therefore, an object of the present invention is to provide a method for preparing a catalyst for hydrogenation of dimethyl oxalate to ethanol. The method uses a urea-assisted hydrothermal synthesis method to prepare the catalyst and uses CO when drying2Supercritical drying, and when the catalyst prepared in the way is used for preparing ethanol by hydrogenating dimethyl oxalate, the high selectivity of the ethanol can be obtained, and the high conversion rate of the dimethyl oxalate, especially the high selectivity of the ethanol can be obtained.
Another object of the present invention is to provide a catalyst for hydrogenation of dimethyl oxalate to ethanol, which is prepared by the method of the present invention. When the catalyst is used for preparing ethanol by hydrogenating dimethyl oxalate, not only can high selectivity of the ethanol be obtained, but also high conversion rate of the dimethyl oxalate can be obtained, and particularly high selectivity of the ethanol can be obtained.
A final object of the present invention is to provide the use of the catalyst prepared by the process of the present invention as a catalyst in the hydrogenation of dimethyl oxalate to ethanol. When the catalyst is used for preparing ethanol by hydrogenating dimethyl oxalate, not only can high selectivity of the ethanol be obtained, but also high conversion rate of the dimethyl oxalate can be obtained, and particularly high selectivity of the ethanol can be obtained.
The technical solution for achieving the above object of the present invention can be summarized as follows:
1. a method for preparing a catalyst for preparing ethanol by hydrogenating dimethyl oxalate, wherein the catalyst is a supported catalyst and comprises a carrier, a catalytic active component and an optional catalytic auxiliary agent, wherein the catalytic active component and the optional catalytic auxiliary agent are loaded on the carrier, and the catalyst comprises the following components in percentage by weight based on the total weight of the catalyst:
(A) one or more elements selected from Cu, Fe, Ni, Co, Ag and Au in an amount of 1-50 wt% in terms of the element as a catalytically active component,
(B) 0 to 10% by weight, calculated as the element, of one or more elements other than the catalytically active component, selected from the group consisting of the elements of the third main group of the periodic Table of the elements, the transition elements and the lanthanides, and
(C) a carrier, a carrier and a water-soluble polymer,
characterized in that the catalyst is prepared by a process comprising the steps of:
(1) providing an aqueous solution of a soluble metal salt of the catalytically active component and optionally a soluble salt of the catalyst promoter in deionized water;
(2) adding urea serving as a precipitator into the aqueous solution obtained in the step (1), uniformly stirring, and then adding a carrier to obtain a mixture, wherein the adding amount of the urea is such that the mass ratio of the urea to the water content of the aqueous solution provided in the step (1) is 1:100-10: 100;
(3) performing hydrothermal synthesis on the mixture obtained in the step (2) in a hydrothermal reaction kettle at 100-200 ℃;
(4) filtering and washing the hydrothermal product obtained in the step (3), and then CO2Supercritical drying; and
(5) subjecting the solution in the step (4) to CO2And (4) roasting the supercritical dried product to obtain the catalyst.
2. The process according to item 1, wherein the catalyst comprises, based on the total weight of the catalyst:
(A) 5 to 30% by weight, calculated as element, of a catalytically active component, and
(B) 1-5% by weight of a catalytic promoter calculated on the element; and
(C) 65-94% by weight of a carrier.
3. The process according to item 1 or 2, wherein the catalytically active component is one or more elements selected from Cu, Ag and Fe, especially Cu or a combination of Cu and Ag, and/or the co-catalyst is one or more elements selected from B, Al, La, Ce and Zn, especially one or more elements selected from B, La and Ce, and/or the support is one or more elements selected from carbon nanotubes, graphene, activated carbon, SiO2、Al2O3、ZrO2SBA-15, MCM-41, MCM-48, HMS, ZnO and ZSM-5, and is preferably carbon nanotube, graphene, SiO2、Al2O3、ZrO2And ZSM-5, with the proviso that: when the catalytic assistant is Al, the carrier is not Al2O3When the catalyst promoter is Zr, the support is not ZrO2。
4. The process according to any one of items 1 to 3, wherein the soluble metal salt of the catalytically active component is a nitrate, acetate, chloride, hydrate thereof or any mixture thereof and/or the soluble salt of the co-agent is a nitrate, acetate, chloride, hydrate thereof or any mixture thereof.
5. The process according to any one of items 1 to 4, wherein in step (2) the urea is added in an amount such that the mass ratio of urea to the amount of water comprised in the aqueous solution provided in step (1) is from 1:100 to 8:100, preferably from 1:100 to 6: 100.
6. The process according to any one of items 1 to 5, wherein in the step (3), the mixture obtained in the step (2) is subjected to hydrothermal synthesis at 100 ℃ and 180 ℃; and/or the hydrothermal synthesis time is 4-72 hours, preferably 10-48 hours; and/or the hydrothermal synthesis is carried out at a stirring speed of 1-10rpm, preferably 1-5 rpm.
7. The method according to any one of items 1 to 6, wherein in the step (4), CO2The supercritical drying is carried out as follows: placing the washed hydro-thermal synthesis solid in a closed high-pressure kettle, and continuously introducing supercritical CO2At 40-60 ℃ and 10-20MPa, preferably at 40-Drying at 45 deg.C under 10-12 MPa; and/or CO2Supercritical drying is carried out for 10-48h, preferably 24-48 h.
8. The method according to any one of items 1 to 7, wherein the calcination in the step (5) is carried out at 350-550 ℃.
9. A catalyst produced by the method according to any one of items 1 to 8.
10. Use of a catalyst prepared by the process according to any one of items 1 to 8 in the hydrogenation of dimethyl oxalate to ethanol.
11. The use according to item 10, wherein DMO/H is used in the hydrogenation of dimethyl oxalate to ethanol2The molar ratio is 50-300, the pressure is 1-5MPa (gauge pressure), the reaction temperature is 150-350 ℃, and the liquid hourly space velocity is 0.1-6.4h-1(ii) a Preferably DMO/H2The molar ratio is 100-200--1。
These and other objects, features and advantages of the present invention will become readily apparent to those skilled in the art upon consideration of the following specification in conjunction with the invention.
Detailed Description
According to one aspect of the present invention, there is provided a method for preparing a catalyst for hydrogenation of dimethyl oxalate to ethanol, the catalyst being a supported catalyst comprising a carrier and a catalytically active component and optionally a catalyst promoter supported on the carrier, the catalyst comprising, based on the total weight of the catalyst:
(A) one or more elements selected from Cu, Fe, Ni, Co, Ag and Au in an amount of 1-50 wt% in terms of the element as a catalytically active component,
(B) 0 to 10% by weight, calculated as the element, of one or more elements other than the catalytically active component, selected from the group consisting of the elements of the third main group of the periodic Table of the elements, the transition elements and the lanthanides, and
(C) a carrier, a carrier and a water-soluble polymer,
characterized in that the catalyst is prepared by a process comprising the steps of:
(1) providing an aqueous solution of a soluble metal salt of the catalytically active component and optionally a soluble salt of the catalyst promoter in deionized water;
(2) adding urea serving as a precipitator into the aqueous solution obtained in the step (1), uniformly stirring, and then adding a carrier to obtain a mixture, wherein the adding amount of the urea is such that the mass ratio of the urea to the water content of the aqueous solution provided in the step (1) is 1:100-10: 100;
(3) performing hydrothermal synthesis on the mixture obtained in the step (2) in a hydrothermal reaction kettle at 100-200 ℃;
(4) filtering and washing the hydrothermal product obtained in the step (3), and then CO2Supercritical drying; and
(5) subjecting the solution in the step (4) to CO2And (4) roasting the supercritical dried product to obtain the catalyst.
The catalyst is a supported catalyst and comprises a catalytic active component, an optional catalytic promoter and a carrier, wherein the catalytic active component and the optional catalytic promoter are supported on the carrier. As catalytically active component, it is generally one or more elements from the group consisting of Cu, Fe, Ni, Co, Ag and Au, preferably one or more elements from the group consisting of Cu, Ag and Fe, in particular Cu and/or Ag. The catalytically active component may be present in the catalyst as the sole substance, as a compound such as an oxide, or as a mixture of the two. The catalysts of the invention generally comprise, calculated as element, from 1 to 50% by weight of catalytically active component, preferably from 5 to 30% by weight of catalytically active component, based on the total weight of the catalyst.
The promoter is an optional component of the catalyst of the present invention, and may or may not be included, preferably included. The presence of the catalytic promoter can further improve the selectivity of ethanol and the conversion rate of dimethyl oxalate in the process of preparing ethanol by hydrogenating dimethyl oxalate, and particularly further improve the selectivity of ethanol. As a catalyst auxiliary, it is generally one or more elements selected from the elements of the third main group of the periodic Table of the elements, the transition elements and the lanthanides, which are different from the catalytically active component. The third main group element includes B, Al, Ga and In. When a third main group element is used as a co-catalyst, B and/or Al are preferred. Transition elements are a series of metal elements in the d-block of the periodic table, which includes elements from a total of ten groups 3 to 12, but not the internal transition elements in the f-block, i.e., not including lanthanides and actinides. As the transition elements, there may be mentioned 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 a transition metal is used as a co-catalyst, it is preferably one or more selected from Mo, Mn, Pd and Zn, and Zn and/or Mn is particularly preferred. As the lanthanoid elements, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu can be mentioned. When a lanthanide is used as a co-catalyst, it is preferably one or more selected from La, Ce, Pr and Tb, with La and/or Ce being particularly preferred. The promoter may be present in the catalyst as an elemental substance, may be present in the catalyst as a compound such as an oxide, or may be present in the catalyst as a mixture of both. The catalysts of the invention generally comprise from 0 to 10% by weight, calculated as element, of a promoter, preferably from 1 to 5% by weight, based on the total weight of the catalyst.
The catalyst is a supported catalyst, and a catalytic active component and an optional catalytic auxiliary agent are supported on a carrier. As the carrier, it may be any carrier suitable for a catalyst for synthesizing ethanol by hydrogenating dimethyl oxalate. The carrier is preferably one or more selected from carbon nanotube, graphene, activated carbon and SiO2、Al2O3、ZrO2SBA-15 (mesoporous molecular sieve), MCM-41 (mesoporous molecular sieve), MCM-48 (mesoporous molecular sieve), HMS (hollow mesoporous silica), ZnO and ZSM-5, and more preferably one or more carriers selected from carbon nanotube, graphene, SiO2、Al2O3、ZrO2And a support in ZSM-5, especially one or more selected from carbon nanotube, graphene, SiO2And a support in ZSM-5, with the proviso that: when the catalytic assistant is Al, the carrier is not Al2O3When the catalyst promoter is Zr, the support is not ZrO2. The catalyst of the invention generally comprises from 40 to 99% by weight of support, preferably from 65 to 94% by weight of support, based on the total weight of the catalyst.
The catalyst of the invention is assisted by the use of ureaPrepared by hydrothermal synthesis and using CO when drying2Supercritical drying, and when the catalyst prepared in the way is used for preparing ethanol by hydrogenating dimethyl oxalate, the high selectivity of the ethanol can be obtained, and the high conversion rate of the dimethyl oxalate, especially the high selectivity of the ethanol can be obtained. For this purpose, the catalysts of the invention are generally prepared by a process comprising the following steps:
(1) providing an aqueous solution of a soluble metal salt of the catalytically active component and optionally a soluble salt of the catalyst promoter in deionized water;
(2) adding urea serving as a precipitator into the aqueous solution obtained in the step (1), uniformly stirring, and then adding a carrier to obtain a mixture, wherein the adding amount of the urea is such that the mass ratio of the urea to the water content of the aqueous solution provided in the step (1) is 1:100-10: 100;
(3) performing hydrothermal synthesis on the mixture obtained in the step (2) in a hydrothermal reaction kettle at 100-200 ℃;
(4) filtering and washing the hydrothermal product obtained in the step (3), and then CO2Supercritical drying; and
(5) subjecting the solution in the step (4) to CO2And (4) roasting the supercritical dried product to obtain the catalyst.
In step (1), an aqueous solution of a soluble metal salt of the catalytically active component and optionally a soluble salt of the catalyst promoter in deionized water is provided. If the catalyst contains a catalyst promoter, an aqueous solution of a soluble metal salt of the catalytically active component in deionized water and an aqueous solution of a soluble salt of the catalyst promoter in deionized water may be separately prepared for this purpose and then combined. Alternatively, the soluble metal salt of the catalytically active component and optionally the soluble salt of the promoter may be added to deionized water to prepare an aqueous solution of the soluble metal salt of the catalytically active component and optionally the soluble salt of the promoter in deionized water. The respective amounts of the soluble metal salt of the catalytically active component and the soluble salt of the promoter correspond to the catalytically active component and the promoter in the catalyst to be prepared. The concentration of the aqueous solution of the soluble metal salt of the catalytically active component and optionally the soluble salt of the catalyst promoter in deionized water is not particularly limited and may be generally from 5 to 50% by weight, preferably from 15 to 30% by weight. The soluble metal salt of the catalytically active component may be a nitrate, acetate, chloride, hydrate thereof, acid or any mixture thereof, preferably a nitrate, acetate and hydrate thereof. The soluble salt of the catalyst promoter may be nitrate, acetate, chloride, their hydrates, acid or any mixture thereof, preferably nitrate, acetate and their hydrates.
In the step (2), adding urea serving as a precipitating agent into the aqueous solution obtained in the step (1), uniformly stirring, and then adding a carrier to obtain a mixture, wherein the adding amount of the urea is such that the mass ratio of the urea to the water contained in the aqueous solution provided in the step (1) is 1:100-10: 100. The purpose of adding urea to the aqueous solution obtained in step (1) is: the urea may be decomposed to ammonia and CO in a subsequent hydrothermal process2The ammonia can precipitate the reactant, and the gaseous carbon dioxide can play a role in pore formation in the reaction system. Although there are many choices of reagents for precipitating the soluble metal salt of the catalytically active component and the soluble salt of the catalytic promoter, such as ammonia, sodium hydroxide, sodium carbonate, sodium bicarbonate, etc., the preparation of the catalyst of the present invention by hydrothermal synthesis after adding urea can make the precipitation uniform, avoid introducing impurity ions such as sodium ions, and reduce the washing difficulty, and in addition, the pore-forming effect of carbon dioxide generated by the decomposition of urea makes the catalytic carrier have a higher specific surface area, which is beneficial to the uniform distribution of the catalytically active component and the catalytic promoter. The urea is added in an amount such that the mass ratio of urea to the amount of water comprised in the aqueous solution provided in step (1) is from 1:100 to 10:100, preferably from 1:100 to 8:100, more preferably from 1:100 to 6: 100. The urea may be added either as urea itself or as an aqueous solution of urea in deionized water. After the urea is added, it is generally necessary to stir the resulting mixture to homogeneity. The stirring is usually carried out for 30 to 120 min. After stirring uniformly, the carrier was added to the resulting mixture to obtain a mixture. Advantageously, the mixture is also stirred to homogeneity and subjected to a hydrothermal treatment.
In the step (3), the mixture obtained in the step (2) is hydrothermally synthesized in a hydrothermal reaction kettle at 200 ℃ and 100 ℃, preferably at 180 ℃. The hydrothermal synthesis time is generally from 4 to 72 hours, preferably from 10 to 48 hours. Advantageously, the hydrothermal synthesis is carried out at a stirring speed of 1 to 10rpm, preferably 1 to 5 rpm.
After the hydrothermal synthesis, the product of the hydrothermal synthesis needs to be separated and dried. Thus, in step (4), the hydrothermal product obtained in step (3) is filtered, washed, and then CO2And (5) supercritical drying. And (3) filtering the hydrothermal product obtained in the step (3) to separate out solids, and then washing with deionized water, wherein the washing can be carried out for one time or multiple times. Then, the washed hydrothermally synthesized solid is treated with CO2And (5) supercritical drying. The supercritical fluid is a fluid having a critical temperature (Tc) and a critical pressure (Pc) or higher, and is, for example, carbon dioxide, ammonia, ethylene, propane, or the like. When the temperature of the carbon dioxide exceeds 31 ℃ and the pressure exceeds 7.38MPa, the carbon dioxide enters a supercritical carbon dioxide state. CO 22Supercritical drying refers to: CO 22As a supercritical fluid drying medium, CO is used in a supercritical state2The composite material has the properties of gas and liquid, has no gas-liquid interface, and has no surface tension, so that water in the hydrothermal synthesis solid can be driven off, the aim of drying is fulfilled, and the shrinkage of the solid material structure in the drying process is avoided. By CO2Supercritical drying can make the catalyst have high specific surface area and uniform particle size distribution. According to the invention, the CO is preferably carried out in the following manner2Supercritical drying: placing the washed hydro-thermal synthesis solid in a closed high-pressure kettle, and introducing supercritical CO2And then dried at 40-60 deg.C and 10-20MPa, preferably at 40-45 deg.C and 10-12MPa, for example at 40 deg.C and 10 MPa. CO 22The supercritical drying time is generally from 10 to 48 hours, preferably from 24 to 48 hours.
After drying, roasting the obtained dried product to obtain the catalyst of the invention. Thus, in step (5), the carbon monoxide in step (4) is reacted with CO2And (4) roasting the supercritical dried product to obtain the catalyst. Calcination is usually at 2At 00-900 ℃, preferably at 350-550 ℃. The calcination time is generally from 2 to 24 hours, preferably from 3 to 10 hours. The firing atmosphere is typically air or an inert atmosphere. The inert gas atmosphere here means an atmosphere which does not participate in chemical reactions under the conditions of calcination, such as nitrogen gas, argon gas.
The catalyst of the invention is prepared by hydrothermal synthesis with the aid of urea and, when dry, with CO2Supercritical drying, and when the catalyst prepared in the way is used for preparing ethanol by hydrogenating dimethyl oxalate, the high selectivity of the ethanol can be obtained, and the high conversion rate of the dimethyl oxalate, especially the high selectivity of the ethanol can be obtained.
Thus, according to another aspect of the present invention, there is provided a catalyst prepared by the catalyst preparation method of the present invention. All features of the catalyst are the same as described above for the catalyst preparation.
According to a final aspect of the invention, there is provided the use of a catalyst prepared by the process of the invention in the hydrogenation of dimethyl oxalate to ethanol.
Before the catalyst is used for preparing ethanol by hydrogenating dimethyl oxalate, the catalyst needs to be reduced so that the catalytic active components and the optional catalytic auxiliary agent in the catalyst are in an elementary form. For this purpose, the catalyst is usually reduced with an atmosphere containing hydrogen. The reduction temperature is generally 200 ℃ to 400 ℃, preferably 250 ℃ to 350 ℃. The reduction pressure is usually 1.0 to 4.0MPa, preferably 2.0 to 3.0MPa, gauge. The reduction time is generally from 3 to 12h, preferably from 3 to 6 h. The reducing atmosphere may be pure hydrogen or a mixture containing hydrogen. After reduction, the catalytically active components and optionally the co-catalyst in the catalyst are in elemental form and exhibit catalytic activity.
When the catalyst is used for preparing ethanol by hydrogenating dimethyl oxalate, the reaction can be carried out intermittently or continuously. The catalyst may be used in any conventional form, preferably in the form of a fixed bed. When the catalyst of the invention is used for the hydrogenation of dimethyl oxalate to ethanol, a stream comprising dimethyl oxalate and hydrogen is passed over the catalyst of the invention. The process conditions for this reaction are typically:DMO/H2the molar ratio is 50-300, the pressure is 1-5MPa (gauge pressure), the reaction temperature is 150-350 ℃, and the liquid hourly space velocity is 0.1-6.4h-1(ii) a The process conditions are preferably: DMO/H2The molar ratio is 100-200--1。
Compared with the prior art, the invention has the beneficial effects that:
the preparation of ethanol by dimethyl oxalate hydrogenation is a strong exothermic reaction, and the copper-based single metal catalyst is easy to agglomerate, sinter and inactivate in the reaction due to the low melting point of the copper-based single metal catalyst. In the invention, the urea is adopted to assist the hydrothermal synthesis preparation method and is combined with CO2The catalyst for preparing ethanol by hydrogenating dimethyl oxalate can be obtained by supercritical drying, and Cu, Fe, Ni, Co, Ag and/or Au are used as main active components, so that the problem of poor thermal stability of the catalyst in the reaction process can be solved, the thermal stability of the catalyst is improved, and particularly, the high selectivity of ethanol can be obtained, the high conversion rate of dimethyl oxalate can be obtained, and particularly, the high selectivity of ethanol can be obtained.
Examples
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention.
Example 1
Preparation of the catalyst
Weighing 1.37g of copper nitrate trihydrate, dissolving the copper nitrate trihydrate in 50ml of deionized water to prepare a solution I, weighing 0.28g of boric acid, dissolving the boric acid in 50ml of deionized water to obtain a solution II, and mixing the solution I and the solution II to obtain a solution III. And adding 2.4g of urea into the solution III, mixing and stirring for 30min, adding 2g of the carbon nano tube carrier into the obtained solution, and continuously stirring for 60 min. Then the obtained mixture is put into a hydro-thermal synthesis kettle and hydro-thermal synthesized for 24 hours at the rotating speed of 2r/min and the temperature of 100 ℃. Filtering the obtained hydrothermal synthesis product, washing with deionized water, placing in a closed high-pressure kettle, and continuously introducing supercritical CO2And drying at 40 deg.C under 10MPa for 20 hr. Then calcined in a tube furnace at 500 ℃ for 3h under nitrogen atmosphere to give catalyst a, which contains 15% Cu and 2% B by element.
Catalyst reduction and hydrogenation reactions
A total of 0.25 g of the catalyst A obtained was charged into a vertical tubular reactor having a diameter of 9 mm, the catalyst A being arranged in a fixed bed. Introducing hydrogen from an inlet at the upper part of the tubular reactor, and continuously reducing the catalyst A for 3 hours at the temperature of 300 ℃ and the gauge pressure of 2.5 MPa. After the catalyst A is reduced, the temperature is reduced to 280 ℃, hydrogen is continuously introduced, and dimethyl oxalate (DMO) and H are introduced from an upper inlet of the tubular reactor2The mol ratio of DMO is controlled to be 200, the pressure is controlled to be 2.5MPa of gauge pressure, and the liquid hourly space velocity is controlled to be 0.4h-1Continuous hydrogenation reaction is carried out on dimethyl oxalate. The reaction results are shown in Table 1.
Example 2
Weighing 0.80g of ferric nitrate nonahydrate, dissolving in 50ml of deionized water to prepare a solution I, weighing 0.17g of silver nitrate, dissolving in 50ml of deionized water to obtain a solution II, and mixing the solution I and the solution II to obtain a solution III. 6.3g of urea is added into the solution III, mixed and stirred for 30min, 5g of 40 wt% silica sol is added dropwise, and stirring is continued for 120 min. Then the obtained mixture is put into a hydro-thermal synthesis kettle and hydro-thermal synthesized for 10 hours at the rotating speed of 2r/min and the temperature of 120 ℃. Filtering the obtained hydrothermal synthesis product, washing with deionized water, placing in a sealed high-pressure kettle, and continuously introducing supercritical CO2And drying at 40 deg.C under 10MPa for 24 hr. Then calcined in a tube furnace at 350 ℃ for 3h under air atmosphere to give catalyst B containing 5% Fe and 5% Ag, calculated as elements.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst a was replaced with catalyst B. The reaction results are shown in Table 1.
Example 3
Weighing 0.58g of silver nitrate and dissolving the silver nitrate in 50ml of deionized water to prepare a solution I, weighing 0.23g of lanthanum nitrate hexahydrate and dissolving the lanthanum nitrate hexahydrate in 50ml of deionized water to obtain a solution II, and mixing the solution I and the solution II to obtain a solution III. And adding 1.6g of urea into the solution III, mixing and stirring for 30min, adding 2g of graphene carrier into the obtained solution, and continuously stirring for 60 min. Then the obtained mixture is put into a hydro-thermal synthesis kettle and hydro-thermal synthesized for 24 hours at 180 ℃ at the rotating speed of 2 r/min. Will obtainFiltering the hydrothermal synthesis product, washing with deionized water, placing in a closed high-pressure kettle, and continuously introducing supercritical CO2Drying at 40 deg.C under 10MPa for 48 hr. Then calcined in a tube furnace at 500 ℃ for 3h under nitrogen atmosphere to give catalyst C, which contains 15% Ag and 3% La by element.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst a was replaced with catalyst C. The reaction results are shown in Table 1.
Example 4
Weighing 1.16g of cobalt nitrate hexahydrate and 1.64g of aluminum nitrate nonahydrate, dissolving in 100ml of deionized water to prepare a solution, adding 5.4g of urea after the cobalt nitrate hexahydrate and the aluminum nitrate nonahydrate are completely dissolved, stirring for 60min, adding 2g of activated carbon carrier into the obtained solution, and continuously stirring for 30min to completely and uniformly mix. Then the obtained mixture is put into a hydro-thermal synthesis kettle and hydro-thermal synthesized for 10 hours at the rotating speed of 4r/min and the temperature of 160 ℃. Filtering the obtained hydrothermal synthesis product, washing with deionized water, placing in a closed high-pressure kettle, and continuously introducing supercritical CO2And drying at 40 deg.C under 10MPa for 30 hr. Then calcined in a tube furnace at 400 ℃ for 3h under nitrogen atmosphere to give catalyst D, which contains 10% Co and 5% Al by element.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst a was replaced with catalyst D. The reaction results are shown in Table 1.
Example 5
0.86g of copper nitrate trihydrate is weighed and dissolved in 50ml of deionized water to prepare a solution I, 0.14g of cerous nitrate hexahydrate is weighed and dissolved in 50ml of deionized water to obtain a solution II, and the solution I and the solution II are mixed to obtain a solution III. And adding 1.4g of urea into the solution III, stirring for 60min, adding 2g of ZSM-5 carrier into the obtained solution, and continuously stirring for 60min to completely and uniformly mix. Then the obtained mixture is put into a hydro-thermal synthesis kettle and hydro-thermal synthesized for 10 hours at the rotating speed of 1r/min and the temperature of 100 ℃. Filtering the obtained hydrothermal synthesis product, placing the product in a closed high-pressure kettle after deionized water is used, and continuously introducing supercritical CO2And drying at 40 deg.C under 10MPa for 24 hr. Then roasting the mixture for 3 hours at 550 ℃ in a tube furnace in the air atmosphere to obtain a catalyst E which is calculated by elementsContaining 10% Cu and 2% Ce.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst a was replaced with catalyst E. The reaction results are shown in Table 1.
Example 6
3.51g of ferric nitrate nonahydrate is weighed and dissolved in 50ml of deionized water to prepare a solution I, 0.88g of boric acid is weighed and dissolved in 50ml of deionized water to obtain a solution II, and the solution I and the solution II are mixed to obtain a solution III. Adding 1g of urea into the solution III, stirring for 120min, and adding 2g of Al2O3The carrier was added to the resulting solution and stirred for 100min, thoroughly mixed. Then the obtained mixture is put into a 100ml hydrothermal synthesis kettle and hydrothermally synthesized for 10h at 195 ℃ at the rotating speed of 2 r/min. Filtering the obtained hydrothermal synthesis product, washing with deionized water, placing in a closed high-pressure kettle, and continuously introducing supercritical CO2Drying at 40 deg.C under 10MPa for 36 hr. Then calcined in a tube furnace at 400 ℃ for 3h under an air atmosphere to give catalyst F, which contains 30% Fe and 5% B by element.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst a was replaced with catalyst F. The reaction results are shown in Table 1.
Example 7
Weighing 0.36g of gold chloride, dissolving the gold chloride in 50ml of deionized water to obtain a solution I, weighing 0.45g of copper nitrate trihydrate, dissolving the copper nitrate trihydrate in 50ml of deionized water to prepare a solution II, and mixing the solution I and the solution II to obtain a solution III. 9.7g of urea was added to the solution III, and after stirring for 120min, 2g of ZrO was added2The carrier was added to the resulting solution and stirred for a further 60min to mix thoroughly. Then the obtained mixture is put into a hydro-thermal synthesis kettle and hydro-thermal synthesized for 48 hours at the rotating speed of 3r/min and the temperature of 160 ℃. Filtering the obtained hydrothermal synthesis product, washing with deionized water, placing in a closed high-pressure kettle, and continuously introducing supercritical CO2Drying at 40 deg.C under 10MPa for 36 hr. Then calcined in a tube furnace at 650 ℃ for 10h under an air atmosphere to give catalyst G, which contains 10% Au and 5% Cu by element.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst a was replaced with catalyst G. The reaction results are shown in Table 1.
Example 8
0.11g of nickel nitrate hexahydrate is weighed and dissolved in 50ml of deionized water to prepare a solution I, 1.02g of zinc nitrate hexahydrate is weighed and dissolved in 50ml of deionized water to obtain a solution II, and the solution I and the solution II are mixed to obtain a solution III. Adding 3.6g of urea into the solution III, mixing and stirring for 50min, adding 2g of SBA-15 carrier into the obtained solution, and continuously stirring for 60 min. Then the obtained mixture is put into a hydro-thermal synthesis kettle and hydro-thermal synthesized for 50 hours at 140 ℃ at the rotating speed of 2 r/min. Filtering the obtained hydrothermal synthesis product, washing with deionized water, placing in a sealed high-pressure kettle, and continuously introducing supercritical CO2Drying at 40 deg.C under 10MPa for 18 hr. Then calcined in a tube furnace at 600 ℃ for 6H under air atmosphere to give catalyst H, which contains 1% Ni and 9.8% Zn by element.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst a was replaced with catalyst H. The reaction results are shown in Table 1.
Example 9
7.3g of copper nitrate trihydrate was weighed and dissolved in 100ml of deionized water to prepare a solution I. And adding 8.4g of urea into the solution I, mixing and stirring for 60min, adding 2g of the carbon nano tube carrier into the obtained solution, and continuously stirring for 30 min. Then the obtained mixture is put into a hydro-thermal synthesis kettle and hydro-thermal synthesized for 18 hours at the rotating speed of 2r/min and the temperature of 120 ℃. Filtering the obtained hydrothermal synthesis product, washing with deionized water, placing in a closed high-pressure kettle, and continuously introducing supercritical CO2And drying at 40 deg.C under 10MPa for 24 hr. Then calcined in a tube furnace at 500 ℃ for 3h under nitrogen atmosphere to give catalyst I containing 49% Cu by element.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst a was replaced with catalyst I. The reaction results are shown in Table 1.
Comparative example 1
The catalyst preparation process in example 1 was repeated except that: the amount of charge was controlled such that the resulting catalyst comprised 15% Cu and 15% B on an elemental basis, based on the total weight of the resulting catalyst, which was designated catalyst C-a.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst a was replaced with catalyst C-a. The reaction results are shown in Table 1.
Comparative example 2
The catalyst preparation process in example 2 was repeated except that: the amount of urea added was 20g and the catalyst obtained was labeled catalyst C-B.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst A was replaced with catalyst C-B. The reaction results are shown in Table 1.
Comparative example 3
The catalyst preparation process in example 3 was repeated except that: after filtering and washing the hydrothermal synthesis product with deionized water, drying the hydrothermal synthesis product for 24 hours in a common drying method, namely a 120 ℃ air blast drying oven, and marking the obtained catalyst as a catalyst C-C.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst A was replaced with catalyst C-C. The reaction results are shown in Table 1.
Comparative example 4
The catalyst preparation in example 4 was repeated except that: the precipitant urea was changed to 28 wt% aqueous ammonia for a total of 11.7g, and the resulting catalyst was labeled as catalysts C-D.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst A was replaced with catalysts C-D. The reaction results are shown in Table 1.
Comparative example 5
The catalyst preparation in example 5 was repeated except that: the hydrothermal synthesis temperature was 60 ℃ and the obtained catalyst was labeled as catalyst C-E.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst A was replaced with catalysts C-E. The reaction results are shown in Table 1.
Comparative example 6
The catalyst preparation in example 6 was repeated except that: the hydrothermal synthesis temperature was 205 ℃ and the catalyst obtained was labeled as catalyst C-F-1.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst A was replaced with catalyst C-F-1. The reaction results are shown in Table 1.
Comparative example 7
The catalyst preparation in example 6 was repeated except that: the hydrothermal synthesis temperature is 94 ℃, and the obtained catalyst is marked as catalyst C-F-2.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst A was replaced with catalyst C-F-2. The reaction results are shown in Table 1.
Comparative example 8
The catalyst preparation in example 7 was repeated except that: the amount of urea added was 10.9G and the catalyst obtained was designated catalyst C-G-1.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst A was replaced with catalyst C-G-1. The reaction results are shown in Table 1.
Comparative example 9
The catalyst preparation in example 7 was repeated except that: the amount of urea added was 0.8G and the catalyst obtained was designated catalyst C-G-2.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst a was replaced with catalyst C-G-2. The reaction results are shown in Table 1.
Comparative example 10
The catalyst preparation in example 9 was repeated except that: the catalyst is prepared by adopting an impregnation method, and the detailed steps are as follows: 7.3g of copper nitrate trihydrate was dissolved in 100ml of deionized water to prepare a solution I. Adding 8.4g of urea into the solution I, mixing and stirring for 60min to obtain a solution II, dropwise adding the solution II into 2g of the carbon nano tube carrier under the assistance of ultrasonic waves, and continuously stirring for 30 min. Then put into a vacuum container and vacuumized for 30 min. Placing the obtained solid product in a closed high-pressure kettle, and continuously introducing supercritical CO2And drying at 40 deg.C under 10MPa for 24 hr. Then the mixture is roasted for 3 hours in a tube furnace at the temperature of 500 ℃ in a nitrogen atmosphere. The resulting catalyst was labeled catalyst C-I.
The catalyst reduction and hydrogenation reaction sequence in example 1 was repeated except that: catalyst A was replaced with catalyst C-I. The reaction results are shown in Table 1.
Claims (19)
1. A method for preparing a catalyst for preparing ethanol by hydrogenating dimethyl oxalate, wherein the catalyst is a supported catalyst and comprises a carrier, a catalytic active component and an optional catalytic auxiliary agent, wherein the catalytic active component and the optional catalytic auxiliary agent are loaded on the carrier, and the catalyst comprises the following components in percentage by weight based on the total weight of the catalyst:
(A) one or more elements selected from Cu, Fe, Ni, Co, Ag and Au in an amount of 1-50 wt% in terms of the element as a catalytically active component,
(B) 0 to 10% by weight, calculated as the element, of one or more elements other than the catalytically active component, selected from the group consisting of the elements of the third main group of the periodic Table of the elements, the transition elements and the lanthanides, and
(C) a carrier, a carrier and a water-soluble polymer,
characterized in that the catalyst is prepared by a process comprising the steps of:
(1) providing an aqueous solution of a soluble metal salt of the catalytically active component and optionally a soluble salt of the catalyst promoter in deionized water;
(2) adding urea serving as a precipitator into the aqueous solution obtained in the step (1), uniformly stirring, and then adding a carrier to obtain a mixture, wherein the adding amount of the urea is such that the mass ratio of the urea to the water content of the aqueous solution provided in the step (1) is 1:100-10: 100;
(3) performing hydrothermal synthesis on the mixture obtained in the step (2) in a hydrothermal reaction kettle at 100-200 ℃;
(4) filtering and washing the hydrothermal product obtained in the step (3), and then CO2Supercritical drying; and
(5) subjecting the solution in the step (4) to CO2And (4) roasting the supercritical dried product to obtain the catalyst.
2. The process according to claim 1, wherein the catalyst comprises, based on the total weight of the catalyst:
(A) 5 to 30% by weight, calculated as element, of a catalytically active component, and
(B) 1-5% by weight of a catalytic promoter calculated on the element; and
(C) 65-94% by weight of a carrier.
3. The process according to claim 1, wherein the catalytically active component is one or more elements selected from the group consisting of Cu, Ag and Fe, and/or the co-catalyst is one or more elements selected from the group consisting of B, Al, La, Ce and Zn, and/or the support is selected from the group consisting of carbon nanotubes, graphene, activated carbon, SiO2、Al2O3、ZrO2One or more of SBA-15, MCM-41, MCM-48, HMS, ZnO and ZSM-5, with the provisos that: when the catalytic assistant is Al, the carrier is not Al2O3When the catalyst promoter is Zr, the support is not ZrO2。
4. The method according to claim 2, wherein the catalytically active component is one or more elements selected from the group consisting of Cu, Ag and Fe, and/or the promoter is one or more elements selected from the group consisting of B, Al, La, Ce and Zn, and/or the support is selected from the group consisting of carbon nanotubes, graphene, activated carbon, SiO2、Al2O3、ZrO2One or more of SBA-15, MCM-41, MCM-48, HMS, ZnO and ZSM-5, with the provisos that: when the catalytic assistant is Al, the carrier is not Al2O3When the catalyst promoter is Zr, the support is not ZrO2。
5. The method according to claim 3, wherein the catalytically active component is Cu or a combination of Cu and Ag, and/or the co-catalyst is one or more elements selected from B, La and Ce, and/or the support is selected from carbon nanotubes, graphene, SiO2、Al2O3、ZrO2And ZSM-5, with the proviso that: when the catalytic assistant is Al, the carrier is not Al2O3When the catalyst promoter is Zr, the support is not ZrO2。
6. The process according to any of claims 1 to 5, wherein the soluble metal salt of the catalytically active component is a nitrate, an acetate, a chloride, a hydrate thereof or any mixture thereof and/or the soluble salt of the co-catalyst is a nitrate, an acetate, a chloride, a hydrate thereof or any mixture thereof.
7. Process according to any one of claims 1 to 5, wherein in step (2) the urea is added in an amount such that the mass ratio of urea to the amount of water comprised in the aqueous solution provided in step (1) is between 1:100 and 8: 100.
8. Process according to claim 7, wherein in step (2) the urea is added in an amount such that the mass ratio of urea to the amount of water comprised in the aqueous solution provided in step (1) is between 1:100 and 6: 100.
9. The process according to any one of claims 1 to 5, wherein in the step (3), the mixture obtained in the step (2) is subjected to hydrothermal synthesis at 100 ℃ and 180 ℃; and/or the hydrothermal synthesis time is 4-72 hours; and/or the hydrothermal synthesis is carried out at a stirring speed of 1-10 rpm.
10. The process according to claim 9, wherein the hydrothermal synthesis time is from 10 to 48 h.
11. The process according to claim 9, wherein the hydrothermal synthesis is carried out at a stirring speed of 1-5 rpm.
12. The process according to any one of claims 1 to 5, wherein in step (4), CO2The supercritical drying is carried out as follows: placing the washed hydro-thermal synthesis solid in a closed high-pressure kettle, and continuously introducing supercritical CO2Drying at 40-60 deg.C under 10-20 MPa; and/or CO2Supercritical drying for 10-48 h.
13. The process according to claim 12, wherein the drying is carried out at 40-45 ℃ and 10-12 MPa.
14. The process according to claim 12, wherein the CO is2Supercritical drying for 24-48 h.
15. The process as claimed in any one of claims 1 to 5, wherein the calcination in step (5) is carried out at 350-550 ℃.
16. A catalyst made by the process according to any one of claims 1-15.
17. Use of a catalyst prepared by the process according to any one of claims 1 to 15 in the hydrogenation of dimethyl oxalate to ethanol.
18. The use according to claim 17, wherein DMO and H are reacted in the hydrogenation of dimethyl oxalate to ethanol2The molar ratio is 50-300, the pressure is 1-5MPa gauge pressure, the reaction temperature is 150-350 ℃, and the liquid hourly space velocity is 0.1-6.4h-1。
19. The use according to claim 18, wherein DMO and H are reacted in the hydrogenation of dimethyl oxalate to ethanol2The molar ratio is 100-200--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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