CN112871171A - Preparation method for preparing multi-element low-carbon alcohol by dimethyl oxalate gas-phase hydrogenation - Google Patents

Preparation method for preparing multi-element low-carbon alcohol by dimethyl oxalate gas-phase hydrogenation Download PDF

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CN112871171A
CN112871171A CN202110012879.1A CN202110012879A CN112871171A CN 112871171 A CN112871171 A CN 112871171A CN 202110012879 A CN202110012879 A CN 202110012879A CN 112871171 A CN112871171 A CN 112871171A
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catalyst
solution
dimethyl oxalate
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preparing
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CN112871171B (en
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王群
山炜巍
施春辉
肖本端
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Shanghai Huayi Energy Chemical Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/885—Molybdenum and copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • 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
    • C07C29/136—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention provides a catalyst for preparing polyhydric low-carbon alcohol by dimethyl oxalate gas-phase hydrogenation, which comprises the following components in percentage by mass: 15-40 wt% of CuO; SiO 2255-84 wt%; 1.0-5.0 wt% of an oxide of a metal additive. The invention further provides a preparation method of the catalyst for preparing the polyhydric low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate. The invention also provides a preparation method for preparing the polyhydric lower alcohol by gas-phase hydrogenation of dimethyl oxalate. The inventionThe preparation method for preparing the polyhydric low-carbon alcohol by gas-phase hydrogenation of the dimethyl oxalate changes the gas-phase hydrogenation reaction route of the dimethyl oxalate, converts the traditional generated glycol into low-carbon alcohols such as ethanol and n-propanol, and enables the prepared catalyst to have high activity and high selectivity in the reaction process of preparing the ethanol and the n-propanol by gas-phase hydrogenation of the oxalate.

Description

Preparation method for preparing multi-element low-carbon alcohol by dimethyl oxalate gas-phase hydrogenation
Technical Field
The invention belongs to the technical field of chemical raw material preparation, relates to a preparation method for preparing polyhydric low-carbon alcohol by dimethyl oxalate gas-phase hydrogenation, and particularly relates to a preparation method for preparing polyhydric low-carbon alcohol by dimethyl oxalate gas-phase hydrogenation and a preparation method of a catalyst thereof.
Background
Ethanol is an important organic raw material, is widely used as an organic solvent, a disinfectant, a beverage, a food additive, a preservative and the like, is a clean energy source without sulfur and ash, is considered to be one of the best fuels for replacing gasoline, and can emit about 30MJ of heat when per kilogram of ethanol is completely combusted. After a certain amount of fuel ethanol is added into gasoline, the oxygen content of the mixed fuel is increased, the octane number is improved, and the emission of harmful gases in automobile exhaust can be reduced. With the development of ethanol in the fuel industry, the ethanol yield of China is on an increasing trend.
N-propanol is an important solvent, organic raw material and intermediate, and is mainly used for solvent and special solvent of chemical intermediate flexographic printing ink, in particular for printing polyolefin and polyamide films. It can also be used as carboxymethylated solvent of cellulose, gelling agent and plasticizer of cellulose acetate, etc. The n-propanol can also be used for producing n-propanol acetate, di-n-propylamine, propylated urea and the like.
The main production methods of ethanol can be classified into a fermentation method using biomass as a raw material and a chemical synthesis method using coal as a raw material. Wherein the biomass material comprises high-saccharide non-grain materials such as grains, cassava and the like and cellulose such as plant straws. The method for preparing the ethanol by using the coal as the raw material comprises the steps of firstly preparing synthesis gas from the coal, then preparing the ethanol from the synthesis gas, and further dividing the method into a one-step method and a multi-step method according to different process routes. The one-step method is a technology for directly converting synthesis gas into ethanol, and has the defects of low CO conversion rate and low selectivity of a target product ethanol although the process flow is short. The multi-step method is also called as indirect ethanol preparation technology of synthesis gas, and refers to a technical route for producing ethanol by using methanol, acetic acid, acetic ester and the like as raw materials and performing carbonylation hydrogenation or direct hydrogenation. With the continuous maturation of acetic acid technology and the continuous expansion of the capacity of devices thereof, the current situation of serious surplus of acetic acid capacity in China promotes the development of the technology for indirectly preparing ethanol from synthesis gas by using acetic acid or acetate as an intermediate. Meanwhile, the acetic ester is synthesized by adopting a heterogeneous catalyst, and the technology for producing the ethanol by hydrogenation is developed and matured gradually.
The main synthesis method of n-propanol is to obtain propionaldehyde by carbonyl synthesis of ethylene, and then prepare n-propanol by hydrogenation of propionaldehyde, which is a route adopted by most of the existing industrial devices. The distribution of products mainly comprising the perhydrogenated product n-propanol can also be obtained by changing the reaction conditions and selecting a proper catalyst through a dimethyl malonate hydrogenation reaction system.
With the rapid development of the domestic process for preparing ethylene glycol from coal, the technology for preparing ethylene glycol by preparing dimethyl oxalate from synthetic gas and then hydrogenating the dimethyl oxalate from coal is quite mature, and a large amount of ten-thousand-ton-grade devices for preparing ethylene glycol from coal emerge domestically, so that the surplus of the ethylene glycol market is caused. Because the cost of preparing the ethanol by the dimethyl oxalate through hydrogenation is lower, the research on preparing the ethanol and the propanol by the dimethyl oxalate not only can provide a new conversion route for domestic coal chemical industry, but also relieves the domestic demand on the ethanol to a certain extent, and has more objective economic benefits like the n-propanol which is prepared by using the dimethyl oxalate as the raw material through hydrogenation and coproduction. Through adjusting reaction conditions, realize that same set of device both can produce ethylene glycol, also can produce ethanol, normal propyl alcohol, the enterprise can be according to market, and nimble switching adjustment product structure, the market risk that greatly reduced ethylene glycol productivity was surplus and is brought has important realistic meaning.
Patents relating to catalysts for synthesizing ethanol by hydrogenating oxalate have also been reported, such as CN101830776, CN 106565632480, CN105085167, CN111229247, etc., and these patents also solve the preparation technology of catalysts for preparing ethanol by hydrogenating oxalate. However, the above patent does not describe other substances produced during the reaction, such as lower alcohols like n-propanol.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a method for preparing polyhydric lower alcohols by gas-phase hydrogenation of dimethyl oxalate, in which the prepared catalyst can change the reaction route of gas-phase hydrogenation of dimethyl oxalate, and convert conventionally produced ethylene glycol into lower alcohols such as ethanol and n-propanol, and the prepared catalyst has high activity and high selectivity when applied to the reaction process of preparing ethanol and n-propanol by gas-phase hydrogenation of oxalate, and can effectively convert dimethyl oxalate to produce polyhydric lower alcohols such as ethanol and n-propanol with high selectivity.
In order to achieve the above objects and other related objects, a first aspect of the present invention provides a catalyst for preparing polyhydric lower alcohols by gas phase hydrogenation of dimethyl oxalate, comprising the following components by mass:
CuO 9～50wt％；
SiO2 45～90wt％；
0.5-6.0 wt% of an oxide of the metal additive.
Preferably, the catalyst for preparing the polyhydric low carbon alcohol by gas phase hydrogenation of dimethyl oxalate comprises the following components in percentage by mass:
CuO 15～40wt％；
SiO2 55～84wt％；
1.0-5.0 wt% of an oxide of a metal additive.
Preferably, the metal additive is selected from one or more of Li, Na, K, Cs, Ba, Mn, Mo, Ni, Al, Ag or Zn.
More preferably, the oxide of Li is Li2O; the oxide of Na is Na2O; the oxide of K is K2O; the oxide of Cs is Cs2O; the oxide of Ba is BaO; the oxide of Mn is MnO; the oxide of Mo is MoO3(ii) a The oxide of the Ni is NiO; the oxide of Al is Al2O3(ii) a The oxide of Ag is AgO; the oxide of Zn is ZnO.
The second aspect of the invention provides a preparation method of a catalyst for preparing polyhydric lower alcohols by gas-phase hydrogenation of dimethyl oxalate, which comprises the following steps:
1) providing a first solution comprising a silica sol, a precipitating agent, and water;
2) providing a second solution, wherein the second solution comprises a copper salt solution and a soluble salt of a metal auxiliary agent;
3) mixing the first solution and the second solution, stirring and reacting under heating condition, filtering and washing the obtained reaction product,
to provide a filter cake;
4) and (3) fully mixing the filter cake with an organic pore-expanding agent, standing the obtained gel-like solid, drying and roasting to provide the catalyst.
Preferably, in the step 1), the silica sol is selected from one of SW-25, SW-30, JA-25, JA-30, JN-25 or JN-30 silica sol. The SW-25, SW-30, JA-25, JA-30, JN-25 or JN-30 silica sol is a conventionally used silica sol and can be purchased from the market.
Preferably, in step 1), SiO in the silica sol2The concentration is 25-30%.
Preferably, in step 1), the precipitating agent is selected from NaOH and Na2CO3、NaHCO3Ammonia water (NH)3H2O) or urea.
In the first solution, the addition amount of the silica sol is used for ensuring SiO in the prepared catalyst2Corresponding content ranges are met.
In the first solution, the addition amount of the precipitant is added to ensure that copper is completely precipitated and slightly excessive after the subsequent first solution and the second solution are mixed.
Preferably, in step 1), after the silica sol is mixed with water, a precipitating agent is added and mixed in the first solution.
Preferably, in step 2), the copper salt solution is an aqueous copper nitrate solution.
More preferably, the copper nitrate aqueous solution is a copper nitrate aqueous solution containing 8.0 to 12.6 wt% of Cu.
Preferably, in the step 2), the metal additive is selected from one or more of Li, Na, K, Cs, Ba, Mn, Mo, Ni, Al, Ag or Zn.
Preferably, in step 2), the soluble salt of the metal promoter includes, but is not limited to, chloride, nitrate, and molybdate of the metal promoter.
In the second solution, the addition amounts of the copper salt solution and the soluble salt of the metal additive ensure that the CuO and the oxide of the metal additive in the prepared catalyst meet the corresponding content ranges.
Preferably, in the step 3), the heating is carried out in a water bath, and the temperature of the water bath is 70-90 ℃.
Preferably, in the step 3), the stirring reaction time is 18-35 hours.
Preferably, in the step 3), the stirring speed of the stirring reaction is 250-350 rpm, and preferably 300 rpm.
Preferably, in the step 3), the filtration is to filter the suspension obtained by the stirring reaction by using a filter press to obtain a filter cake.
Preferably, in the step 3), the washing is to wash the filtered filter cake with deionized water until the washing liquid is colorless.
Preferably, in step 4), the organic pore-expanding agent is polyethylene glycol.
More preferably, the polymerization degree n of the polyethylene glycol is 300-2000.
Preferably, in the step 4), the standing time is 1-3 hours.
Preferably, in the step 4), the drying temperature is 80-120 ℃, and the drying time is 10-24 hours.
Preferably, in the step 4), the roasting temperature is 400-700 ℃, and the roasting time is 4-10 hours.
Preferably, in the step 4), the calcined catalyst is subjected to sheet forming and molding.
The sheet forming is a conventional sheet forming process of the catalyst.
The third aspect of the invention provides the use of the catalyst or the preparation method of the catalyst in the preparation of polyhydric lower alcohols by gas phase hydrogenation of dimethyl oxalate.
The fourth aspect of the invention provides a preparation method for preparing polyhydric lower alcohols by dimethyl oxalate gas phase hydrogenation, which comprises the following steps: adding hydrogen into dimethyl oxalate under the action of the activated catalyst to react to generate the polyhydric low-carbon alcohol.
Preferably, the activation is that the catalyst is reduced by a hydrogen-nitrogen mixture with the hydrogen volume content of 50-100 v%.
More preferably, the reduction temperature is 200-350 ℃.
Preferably, the molar ratio of the added hydrogen to the added dimethyl oxalate is 150-300: 1.
preferably, the reaction temperature is 250-350 ℃, and the reaction pressure is 1.0-4.0 MPa.
Preferably, the liquid hourly space velocity of the dimethyl oxalate in the reaction is 0.4-2.0 g/mlcat.
The polyhydric lower alcohol is mainly ethanol and n-propanol.
As mentioned above, the preparation method for preparing the polyhydric lower alcohol by gas-phase hydrogenation of dimethyl oxalate provided by the invention has the following beneficial effects:
(1) the invention provides a method for preparing multi-element low-carbon alcohol by dimethyl oxalate gas-phase hydrogenation, which changes the traditional route for preparing glycol by dimethyl oxalate gas-phase hydrogenation reaction, more transfers the reaction to the reaction of multi-element low-carbon alcohol such as ethanol and the like, and adopts Cu/SiO with low copper content and hole expansion by a hole expanding agent2The catalyst can simultaneously convert dimethyl oxalate into polyhydric lower alcohols mainly comprising ethanol and n-propanol with high conversion rate and high selectivity.
(2) According to the preparation method for preparing the polyhydric low-carbon alcohol by gas-phase hydrogenation of the dimethyl oxalate, provided by the invention, the conversion rate of the dimethyl oxalate raw material is close to 100%, and the content of impurities, which particularly affect ethanol and n-propanol, of the by-product is low.
(3) According to the preparation method for preparing the multi-element low-carbon alcohol by gas-phase hydrogenation of the dimethyl oxalate, provided by the invention, the pore structure of the catalyst is effectively improved by selecting the proper pore-expanding agent and the environment-friendly auxiliary agent, so that a proper catalyst structure is obtained, the mechanical strength of the catalyst is not negatively influenced, the wear resistance of the catalyst is improved, the service life of the catalyst can be prolonged, the catalyst has high reaction activity, the generation of a target product is facilitated, the generation of impurities is inhibited, and the requirements of industrial production can be met.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It should be understood that the processing equipment or devices not specifically mentioned in the following examples are conventional in the art; all pressure values and ranges refer to relative pressures.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
The reduction activation reaction of the catalyst and the hydrogenation reaction of the reduced feed in the following examples were carried out in a 10-ml microreaction evaluating apparatus. When the same catalyst of the present invention is used for hydrogenation to prepare ethylene glycol or polyhydric lower alcohols, in order to obtain higher selectivity, the suitable reaction conditions of the two are different, and the following examples are all descriptions of the method for preparing polyhydric lower alcohols, and fall within the scope of the present invention.
Comparative example 1
The catalyst 1 for preparing the ethylene glycol by gas-phase hydrogenation of dimethyl oxalate comprises the following components in percentage by mass: 40 wt% of CuO and SiO2 55wt％、NiO 5.0wt％。
Catalyst 1 was prepared as follows: firstly weighing 5.5kg of JA-25 silica sol, adding 9.6kg of deionized water, fully mixing, weighing 1.9kg of urea, dissolving in the mixture, and then fully mixing to obtain a first solution. 8.0kg of an aqueous copper nitrate solution containing 10.0 wt% of Cu was weighed, and 485g of solid nickel nitrate was weighed and dissolved in the aqueous copper nitrate solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixed solution into a reaction kettle. The reaction kettle is heated by water bath, the reaction temperature is increased to 90 ℃, the stirring speed is adjusted to 300 r/min, and the reaction lasts 18 hours. And taking out the suspension after the reaction, filtering by using a filter press, and washing the filtered filter cake by using deionized water until the washing liquid is colorless. Putting the filter cake into a stainless steel barrel, adding 14g of polyethylene glycol (n is 1000), fully and uniformly stirring to make the filter cake be a gelatinous solid, standing for 2 hours, then drying for 24 hours at 80 ℃, roasting for 10 hours at 400 ℃, and then tabletting and forming to obtain the required catalyst 1.
Catalyst 1 was reduced before use with a mixture of hydrogen and nitrogen containing 50% by volume of hydrogen at a reduction temperature of 350 ℃. Catalyst 1 is placed on a 10 ml micro-reactor, dimethyl oxalate is used as a reaction raw material, and hydrogen is added for reaction to synthesize the ethylene glycol. Controlling the reaction temperature to be 190 ℃, the reaction pressure to be 3.0MPa, the liquid hourly space velocity of dimethyl oxalate to be 1.0g/mlcat.h, and the molar ratio of hydrogen to dimethyl oxalate to be 90: 1. the evaluation results are shown in Table 1.
Comparative example 2
Preparing a catalyst 2 for synthesizing the ethylene glycol by gas-phase hydrogenation of dimethyl oxalate, wherein the catalyst 2 comprises the following components in percentage by massThe following components: 15 wt% of CuO and SiO2 84wt％、MoO3 1.0wt％。
Catalyst 2 was prepared as follows: firstly weighing 8.4kg of JA-25 silica sol, adding 12.0kg of deionized water, fully mixing, weighing 0.80kg of urea, dissolving in the mixture, and then fully mixing to obtain a first solution. 3.8kg of an aqueous copper nitrate solution containing 8.0 wt% of Cu was weighed, and 33.0g of solid ammonium molybdate was further weighed and dissolved in the aqueous copper nitrate solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixed solution into a reaction kettle. The reaction kettle is heated by water bath, the reaction temperature is increased to 90 ℃, the stirring speed is adjusted to 300 r/min, and the reaction lasts 18 hours. And taking out the suspension after the reaction, filtering by using a filter press, and washing the filtered filter cake by using deionized water until the washing liquid is colorless. Putting the filter cake into a stainless steel barrel, adding 14g of polyethylene glycol (n is 1000), fully and uniformly stirring to make the filter cake be a gelatinous solid, standing for 2 hours, then drying for 24 hours at 80 ℃, roasting for 10 hours at 400 ℃, and then tabletting and forming to obtain the required catalyst 2.
Catalyst 2 was reduced before use with a mixture of hydrogen and nitrogen containing 50% by volume of hydrogen at a reduction temperature of 350 ℃. Catalyst 2 is placed on a 10 ml micro-reactor, dimethyl oxalate is used as a reaction raw material, and hydrogen is added for reaction to synthesize the ethylene glycol. Controlling the reaction temperature to be 190 ℃, the reaction pressure to be 3.0MPa, the liquid hourly space velocity of dimethyl oxalate to be 1.0g/mlcat.h, and the molar ratio of hydrogen to dimethyl oxalate to be 90: 1. the evaluation results are shown in Table 1.
Comparative example 3
Preparing a catalyst 3 for synthesizing the ethylene glycol by gas-phase hydrogenation of dimethyl oxalate, wherein the catalyst 3 comprises the following components in percentage by mass: 28 wt% of CuO and SiO2 69wt％、ZnO 3.0wt％。
Catalyst 3 was prepared as follows: firstly weighing 6.9kg of JA-25 silica sol, adding 12.0kg of deionized water, fully mixing, weighing 1.5kg of urea, dissolving in the mixture, and then fully mixing to obtain a first solution. 4.5kg of an aqueous copper nitrate solution containing 12.6 wt% of Cu was weighed, and 275g of solid zinc nitrate was further weighed and dissolved in the aqueous copper nitrate solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixed solution into a reaction kettle. The reaction kettle is heated by water bath, the reaction temperature is increased to 90 ℃, the stirring speed is adjusted to 300 r/min, and the reaction lasts 18 hours. And taking out the suspension after the reaction, filtering by using a filter press, and washing the filtered filter cake by using deionized water until the washing liquid is colorless. Putting the filter cake into a stainless steel barrel, adding 14g of polyethylene glycol (n is 1000), fully and uniformly stirring to make the filter cake be a gelatinous solid, standing for 2 hours, then drying for 24 hours at 80 ℃, roasting for 10 hours at 400 ℃, and then tabletting and forming to obtain the required catalyst 3.
Catalyst 3 was reduced before use with a mixture of hydrogen and nitrogen with a hydrogen content of 50% by volume, at a reduction temperature of 350 ℃. Catalyst 3 is placed on a 10 ml micro-reactor, dimethyl oxalate is used as a reaction raw material, and hydrogen is added for reaction to synthesize the ethylene glycol. Controlling the reaction temperature to be 190 ℃, the reaction pressure to be 3.0MPa, the liquid hourly space velocity of dimethyl oxalate to be 1.0g/mlcat.h, and the molar ratio of hydrogen to dimethyl oxalate to be 90: 1. the evaluation results are shown in Table 1.
Example 1
Preparing a catalyst 1# for synthesizing the polyhydric low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate, wherein the catalyst 1# comprises the following components in percentage by mass: 40 wt% of CuO and SiO2 55wt％、NiO 5.0wt％。
Catalyst # 1 was prepared as follows: firstly weighing 5.5kg of JA-25 silica sol, adding 9.6kg of deionized water, fully mixing, weighing 1.9kg of urea, dissolving in the mixture, and then fully mixing to obtain a first solution. 8.0kg of an aqueous copper nitrate solution containing 10.0 wt% of Cu was weighed, and 485g of solid nickel nitrate was weighed and dissolved in the aqueous copper nitrate solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixed solution into a reaction kettle. The reaction kettle is heated by water bath, the reaction temperature is increased to 90 ℃, the stirring speed is adjusted to 300 r/min, and the reaction lasts 18 hours. And taking out the suspension after the reaction, filtering by using a filter press, and washing the filtered filter cake by using deionized water until the washing liquid is colorless. Putting the filter cake into a stainless steel barrel, adding 14g of polyethylene glycol (n is 1000), fully and uniformly stirring to make the filter cake be a gelatinous solid, standing for 2 hours, then drying for 24 hours at 80 ℃, roasting for 10 hours at 400 ℃, and then tabletting and forming to obtain the required catalyst 1 #.
Before use, the catalyst 1# was reduced with a hydrogen-nitrogen mixture having a hydrogen content of 50 v% at a reduction temperature of 350 ℃. Catalyst No. 1 is placed on a 10 ml micro-reactor, dimethyl oxalate is taken as a reaction raw material, hydrogen is added for reaction, and polyhydric lower alcohol is synthesized, wherein the polyhydric lower alcohol mainly comprises ethanol and n-propanol. Controlling the reaction temperature to be 350 ℃, the reaction pressure to be 4.0MPa, the liquid hourly space velocity of the dimethyl oxalate to be 0.4g/mlcat.h, and the molar ratio of the hydrogen to the dimethyl oxalate to be 150: 1. the evaluation results are shown in Table 1.
Example 2
Preparing a catalyst 2# for synthesizing polyhydric low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate, wherein the catalyst 2# comprises the following components in percentage by mass: 15 wt% of CuO and SiO2 84wt％、MoO3 1.0wt％。
Catalyst 2# was prepared as follows: firstly weighing 8.4kg of JA-25 silica sol, adding 12.0kg of deionized water, fully mixing, weighing 0.80kg of urea, dissolving in the mixture, and then fully mixing to obtain a first solution. 3.8kg of an aqueous copper nitrate solution containing 8.0 wt% of Cu was weighed, and 33.0g of solid ammonium molybdate was further weighed and dissolved in the aqueous copper nitrate solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixed solution into a reaction kettle. The reaction kettle is heated by a water bath, the reaction temperature is increased to 80 ℃, the stirring speed is adjusted to 300 r/min, and the reaction lasts 26 hours. And taking out the suspension after the reaction, filtering by using a filter press, and washing the filtered filter cake by using deionized water until the washing liquid is colorless. Putting the filter cake into a stainless steel barrel, adding 168g of polyethylene glycol (n is 2000), fully and uniformly stirring to make the filter cake be a gelatinous solid, standing for 1 hour, then drying for 15 hours at 100 ℃, roasting for 6 hours at 600 ℃, and then tabletting and forming to obtain the required catalyst No. 2.
Catalyst 2# was reduced with a hydrogen-nitrogen mixture having a hydrogen content of 75% by volume before use at a reduction temperature of 275 ℃. Catalyst 2# is placed on a 10 ml micro-reactor, dimethyl oxalate is taken as a reaction raw material, hydrogen is added for reaction, and polyhydric lower alcohol is synthesized, wherein the polyhydric lower alcohol mainly comprises ethanol and n-propanol. Controlling the reaction temperature to be 250 ℃, the reaction pressure to be 2.5MPa, the liquid hourly space velocity of dimethyl oxalate to be 1.2g/mlcat.h, and the molar ratio of hydrogen to dimethyl oxalate to be 230: 1. the evaluation results are shown in Table 1.
Example 3
Preparing a catalyst 3# for synthesizing the polyhydric low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate, wherein the catalyst 3# comprises the following components in percentage by mass: 28 wt% of CuO and SiO2 69wt％、ZnO 3.0wt％。
Catalyst # 3 was prepared as follows: firstly weighing 6.9kg of JA-25 silica sol, adding 12.0kg of deionized water, fully mixing, weighing 1.5kg of urea, dissolving in the mixture, and then fully mixing to obtain a first solution. 4.5kg of an aqueous copper nitrate solution containing 12.6 wt% of Cu was weighed, and 275g of solid zinc nitrate was further weighed and dissolved in the aqueous copper nitrate solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixed solution into a reaction kettle. The reaction kettle is heated by water bath, the reaction temperature is increased to 70 ℃, the stirring speed is adjusted to 300 r/min, and the reaction lasts for 35 hours. And taking out the suspension after the reaction, filtering by using a filter press, and washing the filtered filter cake by using deionized water until the washing liquid is colorless. Putting the filter cake into a stainless steel barrel, adding 78g of polyethylene glycol (n is 2000), fully and uniformly stirring to make the filter cake be a gelatinous solid, standing for 3 hours, then drying for 10 hours at 120 ℃, roasting for 4 hours at 700 ℃, and then tabletting and forming to obtain the required catalyst No. 3.
Catalyst # 3 was reduced with 100 v% hydrogen by volume before use at a reduction temperature of 200 ℃. Catalyst No. 3 is placed on a 10 ml micro-reactor, dimethyl oxalate is taken as a reaction raw material, hydrogen is added for reaction, and polyhydric lower alcohol is synthesized, wherein the polyhydric lower alcohol mainly comprises ethanol and n-propanol. Controlling the reaction temperature to be 300 ℃, the reaction pressure to be 1.0MPa, the liquid hourly space velocity of the dimethyl oxalate to be 2.0g/mlcat.h, and the molar ratio of the hydrogen to the dimethyl oxalate to be 300: 1. the evaluation results are shown in Table 1.
Example 4
Preparing a catalyst 4# for synthesizing polyhydric low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate, wherein the catalyst 4# is calculated according to the mass percentage,comprises the following components: 40 wt% of CuO and SiO2 55wt％、NiO 5.0wt％。
Catalyst # 4 was prepared as follows: firstly weighing 5.5kg of JA-25 silica sol, adding 9.6kg of deionized water, fully mixing, weighing 1.9kg of ammonia water to be dissolved in the mixture, then fully mixing to obtain a first solution, and diluting the ammonia water into a solution with the concentration of 5% when the ammonia water is used, and adding the solution. 8.0kg of an aqueous copper nitrate solution containing 10.0 wt% of Cu was weighed, and 485g of solid nickel nitrate was weighed and dissolved in the aqueous copper nitrate solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixed solution into a reaction kettle. The reaction kettle is heated by a water bath, the reaction temperature is increased to 80 ℃, the stirring speed is adjusted to 300 r/min, and the reaction lasts 26 hours. And taking out the suspension after the reaction, filtering by using a filter press, and washing the filtered filter cake by using deionized water until the washing liquid is colorless. Putting the filter cake into a stainless steel barrel, adding 78g of polyethylene glycol (n is 2000), fully and uniformly stirring to make the filter cake be a gelatinous solid, standing for 3 hours, then drying for 17 hours at 100 ℃, roasting for 7 hours at 550 ℃, and then tabletting and forming to obtain the required catalyst No. 4.
Catalyst No. 4 was reduced with a hydrogen-nitrogen mixture having a hydrogen content of 75% by volume before use at a reduction temperature of 275 ℃. Catalyst No. 4 is placed on a 10 ml micro-reactor, dimethyl oxalate is taken as a reaction raw material, hydrogen is added for reaction, and polyhydric lower alcohol is synthesized, wherein the polyhydric lower alcohol mainly comprises ethanol and n-propanol. Controlling the reaction temperature to be 250 ℃, the reaction pressure to be 2.5MPa, the liquid hourly space velocity of dimethyl oxalate to be 1.2g/mlcat.h, and the molar ratio of hydrogen to dimethyl oxalate to be 230: 1. the evaluation results are shown in Table 1.
Example 5
Preparing a catalyst No. 5 for synthesizing polyhydric low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate, wherein the catalyst No. 4 comprises the following components in percentage by mass: 40 wt% of CuO and SiO2 55wt％、NiO 5.0wt％。
Catalyst # 5 was prepared as follows: firstly weighing 5.5kg of JA-25 silica sol, adding 9.6kg of deionized water, fully mixing, weighing 1.9kg of ammonia water to be dissolved in the mixture, then fully mixing to obtain a first solution, and diluting the ammonia water into a solution with the concentration of 5% when the ammonia water is used, and adding the solution. 8.0kg of an aqueous copper nitrate solution containing 10.0 wt% of Cu was weighed, and 485g of solid nickel nitrate was weighed and dissolved in the aqueous copper nitrate solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixed solution into a reaction kettle. The reaction kettle is heated by water bath, the reaction temperature is increased to 70 ℃, the stirring speed is adjusted to 300 r/min, and the reaction lasts for 35 hours. And taking out the suspension after the reaction, filtering by using a filter press, and washing the filtered filter cake by using deionized water until the washing liquid is colorless. Putting the filter cake into a stainless steel barrel, adding 78g of polyethylene glycol (n is 2000), fully and uniformly stirring to make the filter cake be a gelatinous solid, standing for 3 hours, then drying for 24 hours at 80 ℃, roasting for 10 hours at 400 ℃, and then tabletting and forming to obtain the required catalyst No. 5.
Catalyst # 5 was reduced with 100 v% hydrogen by volume before use at a reduction temperature of 200 ℃. Catalyst No. 5 is placed on a 10 ml micro-reactor, dimethyl oxalate is taken as a reaction raw material, hydrogen is added for reaction, and polyhydric lower alcohol is synthesized, wherein the polyhydric lower alcohol mainly comprises ethanol and n-propanol. Controlling the reaction temperature to be 300 ℃, the reaction pressure to be 1.0MPa, the liquid hourly space velocity of the dimethyl oxalate to be 2.0g/mlcat.h, and the molar ratio of the hydrogen to the dimethyl oxalate to be 300: 1. the evaluation results are shown in Table 1.
Example 6
Preparing a catalyst 6# for synthesizing the polyhydric low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate, wherein the catalyst 6# comprises the following components in percentage by mass: 15 wt% of CuO and SiO2 84wt％、MoO3 1.0wt％。
Catalyst # 6 was prepared as follows: firstly weighing 8.4kg of JA-25 silica sol, adding 12.0kg of deionized water, fully mixing, weighing 0.80kg of ammonia water to be dissolved in the mixture, then fully mixing to obtain a first solution, and diluting the ammonia water into a solution with the concentration of 5% when the ammonia water is used, and adding the solution. 3.8kg of an aqueous copper nitrate solution containing 8.0 wt% of Cu was weighed, and 33.0g of solid ammonium molybdate was further weighed and dissolved in the aqueous copper nitrate solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixed solution into a reaction kettle. The reaction kettle is heated by water bath, the reaction temperature is increased to 90 ℃, the stirring speed is adjusted to 300 r/min, and the reaction lasts 18 hours. And taking out the suspension after the reaction, filtering by using a filter press, and washing the filtered filter cake by using deionized water until the washing liquid is colorless. Putting the filter cake into a stainless steel barrel, adding 14g of polyethylene glycol (n is 1000), fully and uniformly stirring to make the filter cake be a gelatinous solid, standing for 2 hours, then drying for 24 hours at 80 ℃, roasting for 10 hours at 400 ℃, and then tabletting and forming to obtain the required catalyst No. 6.
Catalyst No. 6 was reduced with a hydrogen-nitrogen mixture having a hydrogen content of 50% by volume before use at a reduction temperature of 350 ℃. Catalyst No. 6 is placed on a 10 ml micro-reactor, dimethyl oxalate is taken as a reaction raw material, hydrogen is added for reaction, and polyhydric lower alcohol is synthesized, wherein the polyhydric lower alcohol mainly comprises ethanol and n-propanol. Controlling the reaction temperature to be 350 ℃, the reaction pressure to be 4.0MPa, the liquid hourly space velocity of the dimethyl oxalate to be 0.4g/mlcat.h, and the molar ratio of the hydrogen to the dimethyl oxalate to be 150: 1. the evaluation results are shown in Table 1.
Example 7
Preparing a catalyst 7# for synthesizing polyhydric low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate, wherein the catalyst 7# comprises the following components in percentage by mass: 15 wt% of CuO and SiO2 84wt％、MoO3 1.0wt％。
Catalyst # 7 was prepared as follows: firstly weighing 8.4kg of JA-25 silica sol, adding 12.0kg of deionized water, fully mixing, weighing 0.80kg of ammonia water to be dissolved in the mixture, then fully mixing to obtain a first solution, and diluting the ammonia water into a solution with the concentration of 5% when the ammonia water is used, and adding the solution. 3.8kg of an aqueous copper nitrate solution containing 8.0 wt% of Cu was weighed, and 33.0g of solid ammonium molybdate was further weighed and dissolved in the aqueous copper nitrate solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixed solution into a reaction kettle. The reaction kettle is heated by water bath, the reaction temperature is increased to 70 ℃, the stirring speed is adjusted to 300 r/min, and the reaction lasts for 35 hours. And taking out the suspension after the reaction, filtering by using a filter press, and washing the filtered filter cake by using deionized water until the washing liquid is colorless. Putting the filter cake into a stainless steel barrel, adding 78g of polyethylene glycol (n is 2000), fully and uniformly stirring to make the filter cake be a gelatinous solid, standing for 3 hours, then drying for 10 hours at 120 ℃, roasting for 4 hours at 700 ℃, and then tabletting and forming to obtain the required catalyst No. 7.
Catalyst 7# was reduced with 100 v% hydrogen by volume before use at a reduction temperature of 200 ℃. Catalyst No. 7 is placed on a 10 ml micro-reactor, dimethyl oxalate is taken as a reaction raw material, hydrogen is added for reaction, and polyhydric lower alcohol is synthesized, wherein the polyhydric lower alcohol mainly comprises ethanol and n-propanol. Controlling the reaction temperature to be 300 ℃, the reaction pressure to be 1.0MPa, the liquid hourly space velocity of the dimethyl oxalate to be 2.0g/mlcat.h, and the molar ratio of the hydrogen to the dimethyl oxalate to be 300: 1. the evaluation results are shown in Table 1.
Example 8
Preparing a catalyst 8# for synthesizing the polyhydric low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate, wherein the catalyst 8# comprises the following components in percentage by mass: 28 wt% of CuO and SiO2 69wt％、ZnO 3.0wt％。
Catalyst # 8 was prepared as follows: firstly weighing 6.9kg of JA-25 silica sol, adding 12.0kg of deionized water, fully mixing, weighing 1.5kg of ammonia water to be dissolved in the mixture, then fully mixing to obtain a first solution, and diluting the ammonia water into a solution with the concentration of 5% when the ammonia water is used, and adding the solution. 4.5kg of an aqueous copper nitrate solution containing 12.6 wt% of Cu was weighed, and 275g of solid zinc nitrate was further weighed and dissolved in the aqueous copper nitrate solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixed solution into a reaction kettle. The reaction kettle is heated by water bath, the reaction temperature is increased to 90 ℃, the stirring speed is adjusted to 300 r/min, and the reaction lasts 18 hours. And taking out the suspension after the reaction, filtering by using a filter press, and washing the filtered filter cake by using deionized water until the washing liquid is colorless. Putting the filter cake into a stainless steel barrel, adding 14g of polyethylene glycol (n is 1000), fully and uniformly stirring to make the filter cake be a gelatinous solid, standing for 2 hours, then drying for 24 hours at 80 ℃, roasting for 10 hours at 400 ℃, and then tabletting and forming to obtain the required catalyst 8 #.
Catalyst No. 8 was reduced with a hydrogen-nitrogen mixture having a hydrogen content of 50% by volume before use at a reduction temperature of 350 ℃. Catalyst No. 8 is placed on a 10 ml micro-reactor, dimethyl oxalate is taken as a reaction raw material, hydrogen is added for reaction, and polyhydric lower alcohol is synthesized, wherein the polyhydric lower alcohol mainly comprises ethanol and n-propanol. Controlling the reaction temperature to be 350 ℃, the reaction pressure to be 4.0MPa, the liquid hourly space velocity of the dimethyl oxalate to be 0.4g/mlcat.h, and the molar ratio of the hydrogen to the dimethyl oxalate to be 150: 1. the evaluation results are shown in Table 1.
Example 9
Preparing a catalyst 9# for synthesizing polyhydric low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate, wherein the catalyst 9# comprises the following components in percentage by mass: 28 wt% of CuO and SiO2 69wt％、ZnO 3.0wt％。
Catalyst # 9 was prepared as follows: firstly weighing 6.9kg of JA-25 silica sol, adding 12.0kg of deionized water, fully mixing, weighing 1.5kg of ammonia water to be dissolved in the mixture, then fully mixing to obtain a first solution, and diluting the ammonia water into a solution with the concentration of 5% when the ammonia water is used, and adding the solution. 4.5kg of an aqueous copper nitrate solution containing 12.6 wt% of Cu was weighed, and 275g of solid zinc nitrate was further weighed and dissolved in the aqueous copper nitrate solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixed solution into a reaction kettle. The reaction kettle is heated by a water bath, the reaction temperature is increased to 80 ℃, the stirring speed is adjusted to 300 r/min, and the reaction lasts 26 hours. And taking out the suspension after the reaction, filtering by using a filter press, and washing the filtered filter cake by using deionized water until the washing liquid is colorless. Putting the filter cake into a stainless steel barrel, adding 78g of polyethylene glycol (n is 2000), fully and uniformly stirring to make the filter cake be a gelatinous solid, standing for 3 hours, then drying for 17 hours at 100 ℃, roasting for 7 hours at 550 ℃, and then tabletting and forming to obtain the required catalyst 9 #.
Catalyst No. 9 was reduced with a hydrogen-nitrogen mixture having a hydrogen content of 75% by volume before use at a reduction temperature of 275 ℃. Catalyst No. 9 is placed on a 10 ml micro-reactor, dimethyl oxalate is taken as a reaction raw material, hydrogen is added for reaction, and polyhydric lower alcohol is synthesized, wherein the polyhydric lower alcohol mainly comprises ethanol and n-propanol. Controlling the reaction temperature to be 250 ℃, the reaction pressure to be 2.5MPa, the liquid hourly space velocity of dimethyl oxalate to be 1.2g/mlcat.h, and the molar ratio of hydrogen to dimethyl oxalate to be 230: 1. the evaluation results are shown in Table 1.
TABLE 1
CDMO/％ SET/％ SNPA/％ SNBA/％ SNAA/％ SMG/％ SBDO/％ SEG/％
Comparative example 1 100 2.8 0.1 0.1 0 0.1 2.5 94.4
Comparative example 2 99.5 2.3 0.1 0 0 0.2 2.1 95.3
Comparative example 3 100 2.6 0.1 0 0 0.1 2.3 94.9
Example 1 100 71.7 20.1 5.9 2.3 0 0 0
Example 2 99.5 77.9 13.7 2.6 1.3 0.6 1.5 2.4
Example 3 100 78.3 14.6 4.6 2.0 0.1 0.1 0.3
Example 4 100 78.5 14.5 3.8 1.5 0.1 0.5 1.1
Example 5 100 79.1 15.0 4.0 1.9 0 0 0
Example 6 100 73.0 19.2 5.7 2.1 0 0 0
Example 7 100 79.7 14.6 3.7 1.8 0.1 0.1 0
Example 8 100 72.4 19.8 5.6 2.2 0 0 0
Example 9 100 77.0 14.2 4.1 1.7 0.4 1.1 1.5
Note: DMO is dimethyl oxalate, ET is ethanol, NPA is n-propanol, NBA is n-butanol, NAA is n-pentanol, MG is methyl glycolate, BDO is 1, 2-butanediol, EG is ethylene glycol, C represents conversion rate, and S represents selectivity.
As is clear from Table 1, in each of examples 1 to 9 and comparative examples 1 to 3, the conversion of dimethyl oxalate was very good, and the conversion of dimethyl oxalate was close to 100%. However, examples 1 to 9 have high selectivity for conversion into polyhydric lower alcohols based on ethanol and n-propanol, and low levels of impurities affecting ethanol and n-propanol, in particular, as by-products, as compared with comparative examples 1 to 3.
In conclusion, the preparation method for preparing the polyhydric low-carbon alcohol by gas-phase hydrogenation of the dimethyl oxalate changes the gas-phase hydrogenation reaction route of the dimethyl oxalate, converts the traditional generated glycol into low-carbon alcohols such as ethanol and n-propanol, and enables the prepared catalyst to have high activity and high selectivity in the reaction process of preparing the ethanol and the n-propanol by gas-phase hydrogenation of the oxalate. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (10)

1. The catalyst comprises the following components in percentage by mass:
CuO 9～50wt％；
SiO2 45～90wt％；
0.5-6.0 wt% of an oxide of the metal additive.
2. The catalyst of claim 1, wherein the metal promoter is selected from one or more of Li, Na, K, Cs, Ba, Mn, Mo, Ni, Al, Ag, or Zn.
3. A process for the preparation of a catalyst according to any one of claims 1-2, comprising the steps of:
1) providing a first solution comprising a silica sol, a precipitating agent, and water;
2) providing a second solution, wherein the second solution comprises a copper salt solution and a soluble salt of a metal auxiliary agent;
3) mixing the first solution and the second solution, reacting under a heating condition, and filtering and washing an obtained reaction product to provide a filter cake;
4) and (3) fully mixing the filter cake with an organic pore-expanding agent, standing the obtained gel-like solid, drying and roasting to provide the catalyst.
4. The method for preparing a catalyst according to claim 3, wherein in step 1), the silica sol is selected from one of SW-25, SW-30, JA-25, JA-30, JN-25 or JN-30 silica sol; SiO in the silica sol2The concentration is 25-30%.
5. The method for preparing a catalyst according to claim 3, wherein in step 1), the precipitating agent is selected from NaOH and Na2CO3、NaHCO3Ammonia water or urea.
6. The method of claim 3, wherein in step 2), the copper salt is an aqueous solution of copper nitrate.
7. The method of claim 3, wherein in step 4), the organic pore-expanding agent is polyethylene glycol.
8. The method for preparing the catalyst according to claim 3, wherein the step 4) further comprises any one or more of the following conditions:
A) the standing time is 1-3 hours;
B) the drying temperature is 80-120 ℃, and the drying time is 10-24 hours;
C) the roasting temperature is 400-700 ℃, and the roasting time is 4-10 hours.
9. Use of a catalyst according to any one of claims 1 to 2, or a process for the preparation of a catalyst according to any one of claims 3 to 8, in the vapour phase hydrogenation of dimethyl oxalate to polyhydric lower alcohols.
10. A method for preparing polyhydric low-carbon alcohol by dimethyl oxalate gas phase hydrogenation comprises the following steps: adding hydrogen into dimethyl oxalate under the action of an activated catalyst as claimed in any one of claims 1-2 to react to generate polyhydric lower alcohol.
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