CN112871171B - Preparation method for preparing multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate - Google Patents

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

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CN112871171B
CN112871171B CN202110012879.1A CN202110012879A CN112871171B CN 112871171 B CN112871171 B CN 112871171B CN 202110012879 A CN202110012879 A CN 202110012879A CN 112871171 B CN112871171 B CN 112871171B
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dimethyl oxalate
catalyst
reaction
carbon alcohol
gas
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CN112871171A (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 multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate, which comprises the following components in percentage by mass: 15-40 wt% of CuO; siO (SiO) 2 55 to 84 weight percent; 1.0 to 5.0 weight percent of oxide of metal auxiliary agent. The invention further provides a preparation method of the catalyst for preparing the multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate. The invention also provides a preparation method for preparing the multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate. The preparation method for preparing the multi-element 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 ethylene glycol into low-carbon alcohols such as ethanol and n-propanol, and ensures that the prepared catalyst has high activity and high selectivity in the reaction process of preparing the ethanol and n-propanol by gas-phase hydrogenation of the dimethyl oxalate.

Description

Preparation method for preparing multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate
Technical Field
The invention belongs to the technical field of chemical raw material preparation, relates to a preparation method for preparing multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate, and in particular relates to a preparation method for preparing multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate and a preparation method for a catalyst of the multi-element low-carbon alcohol.
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 as one of the best fuels for replacing gasoline, and can release 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 fuel industry, the ethanol yield in China is in an increasing trend.
N-propanol is an important solvent, organic raw material and intermediate, and is mainly used as a special solvent for solvent and chemical intermediate flexographic printing inks, especially for printing of polyolefin and polyamide films. In addition, the cellulose can be used as a solvent for cellulose carboxymethylation, a gelling agent and a plasticizer of cellulose acetate, and the like. N-propanol acetate, di-n-propylamine, propanol urea, etc. may also be produced from n-propanol.
The main production methods of ethanol can be classified into fermentation methods using biomass as a raw material and chemical synthesis methods using coal as a raw material. Wherein the biomass raw material comprises high-sugar non-grain substances such as grains, cassava and the like and cellulose such as plant straws. The method for preparing ethanol by using coal as raw material comprises the steps of preparing synthesis gas from coal, then preparing ethanol from the synthesis gas, and dividing the synthesis gas 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 target product ethanol although the process flow is short. The technology for preparing alcohol from synthetic gas by multi-step method is a technological route for preparing alcohol by using methanol, acetic acid, acetate and so on as raw materials and through carbonylation hydrogenation or direct hydrogenation. With the continuous maturity of acetic acid technology and the continuous expansion of device productivity, the current situation of serious surplus acetic acid productivity in China has contributed to the development of technology for indirectly preparing ethanol from synthesis gas by taking acetic acid or acetate as an intermediate. Meanwhile, the technology for synthesizing acetate by adopting a heterogeneous catalyst and further producing ethanol by hydrogenation is gradually developed.
The main synthesis method of n-propanol is that propanal is obtained by synthesizing ethylene through carbonyl, and then the propanal is hydrogenated to obtain n-propanol, which is a route adopted by most industrial devices at present. The product distribution mainly comprising the n-propanol which is a hydrogenation product can 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 technology for preparing ethylene glycol by coal, the technology for preparing dimethyl oxalate from coal by synthesis gas and preparing ethylene glycol by hydrogenation is quite mature, a large number of devices of ten thousand tons for preparing ethylene glycol by coal are developed in China, and surplus of the ethylene glycol market is caused. Because the cost for preparing the ethanol by using the dimethyl oxalate for hydrogenation is lower, the research on preparing the ethanol and the propanol by using the dimethyl oxalate not only can provide a new conversion route for domestic coal chemical industry, but also relieves the domestic requirement for the ethanol to a certain extent, and the method has objective economic benefit in the same way as the co-production of the n-propanol by using the dimethyl oxalate as the raw material for hydrogenation. Through adjusting reaction conditions, the same device can be used for producing ethylene glycol, ethanol and n-propanol, enterprises can flexibly switch and adjust the product structure according to markets, market risks caused by surplus ethylene glycol productivity are greatly reduced, and the device has important practical significance.
Patents related to catalysts for synthesizing ethanol by hydrogenating oxalate have also been reported, such as CN101830776, CN106563480, CN105085167, CN111229247 and the like, and the preparation technology of catalysts for preparing ethanol by hydrogenating oxalate is also solved by the patents. However, the above patent does not describe other substances generated during the reaction, such as lower alcohols such as n-propanol.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for preparing a multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate, wherein the prepared catalyst can change the gas-phase hydrogenation reaction route of dimethyl oxalate, convert the conventionally generated ethylene glycol into low-carbon alcohols such as ethanol and n-propanol, and the like, and has high activity and high selectivity in the reaction process of preparing ethanol and n-propanol by gas-phase hydrogenation of oxalic ester, so that the prepared catalyst can effectively convert dimethyl oxalate to generate multi-element low-carbon alcohols mainly comprising ethanol and n-propanol with high selectivity.
To achieve the above and other related objects, the first aspect of the present invention provides a catalyst for preparing a multi-component lower alcohol by gas phase hydrogenation of dimethyl oxalate, comprising the following components in percentage by mass:
CuO 9～50wt％；
SiO 2 45～90wt％；
0.5 to 6.0 weight percent of oxide of metal auxiliary agent.
Preferably, the catalyst for preparing the multi-element low-carbon alcohol by gas-phase hydrogenation of the dimethyl oxalate comprises the following components in percentage by mass:
CuO 15～40wt％；
SiO 2 55～84wt％；
1.0 to 5.0 weight percent of oxide of metal auxiliary agent.
Preferably, the metal promoter is selected from one or more combinations of Li, na, K, cs, ba, mn, mo, ni, al, ag or Zn.
More preferably, the oxide of Li is Li 2 O; the oxide of Na is Na 2 O; the oxide of K is K 2 O; the oxide of the Cs is Cs 2 O; the oxide of Ba is BaO; the oxide of Mn is MnO; the oxide of Mo is MoO 3 The method comprises the steps of carrying out a first treatment on the surface of the The oxide of Ni is NiO; the oxide of Al is Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the 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 multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate, which comprises the following steps:
1) Providing a first solution comprising a silica sol, a precipitant and water;
2) Providing a second solution comprising a copper salt solution and a soluble salt of a metal promoter;
3) Mixing the first solution and the second solution, stirring for reaction under heating, filtering and washing the obtained reaction product,
to provide a filter cake;
4) The filter cake is thoroughly mixed with an organic pore-expanding agent, and the obtained gel-like solid is left to stand and dried and calcined to provide a catalyst.
Preferably, 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. 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), the siliconSiO in sol 2 The concentration is 25-30%.
Preferably, in step 1), the precipitant is selected from NaOH, na 2 CO 3 、NaHCO 3 Ammonia (NH) 3 H 2 O) or urea.
The silica sol is added in the first solution in an amount to ensure SiO in the prepared catalyst 2 The content accords with the corresponding content range.
The addition amount of the precipitant in the first solution ensures that the copper is completely precipitated and slightly excessive after the subsequent first solution and the second solution are mixed.
Preferably, in step 1), the silica sol is mixed with water, and then the precipitant is added to mix.
Preferably, in step 2), the copper salt solution is an aqueous copper nitrate solution.
More preferably, the aqueous copper nitrate solution is an aqueous copper nitrate solution containing Cu in a concentration of 8.0 to 12.6 wt%.
Preferably, in step 2), the metal auxiliary is selected from one or more combinations of Li, na, K, cs, ba, mn, mo, ni, al, ag or Zn.
Preferably, in step 2), the soluble salts of the metal promoters include, but are not limited to, chloride salts, nitrate salts, molybdate salts of the metal promoters.
And in the second solution, the addition amount of the copper salt solution and the soluble salt of the metal auxiliary agent is used for ensuring that the oxides of CuO and the metal auxiliary agent in the prepared catalyst accord with the corresponding content range.
Preferably, in step 3), the heating is performed in a water bath, the temperature of which is 70-90 ℃.
Preferably, in step 3), the stirring reaction is carried out for 18 to 35 hours.
Preferably, in step 3), the stirring speed of the stirring reaction is 250 to 350 rpm, preferably 300 rpm.
Preferably, in step 3), the filtering is to filter the suspension obtained by stirring reaction by a filter press to obtain a filter cake.
Preferably, in step 3), the washing is to wash the filtered filter cake with deionized water until the washing solution is colorless.
Preferably, in step 4), the organic pore-expanding agent is polyethylene glycol.
More preferably, the polyethylene glycol has a polymerization degree n of 300 to 2000.
Preferably, in step 4), the standing time is 1 to 3 hours.
Preferably, in step 4), the drying temperature is 80-120 ℃ and the drying time is 10-24 hours.
Preferably, in step 4), the roasting temperature is 400-700 ℃, and the roasting time is 4-10 hours.
Preferably, in step 4), the calcined catalyst is formed by tabletting.
The above-mentioned sheeting is formed into conventional catalyst sheeting forming process.
The third aspect of the invention provides the use of the catalyst or the preparation method of the catalyst in preparing multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate.
The fourth aspect of the invention provides a method for preparing multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate, comprising the following steps: and adding hydrogen into dimethyl oxalate under the action of the activated catalyst to react, so as to generate the multi-element low-carbon alcohol.
Preferably, the activation is reduction of the catalyst by hydrogen-nitrogen mixture with a hydrogen volume content of 50-100 v%.
More preferably, the reduction temperature is 200 to 350 ℃.
Preferably, the molar ratio of the hydrogen to the 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 low-carbon alcohol is mainly ethanol or n-propanol.
As described above, the preparation method for preparing the multi-element low-carbon alcohol by gas-phase hydrogenation of the dimethyl oxalate has the following beneficial effects:
(1) The preparation method for preparing the multi-element low-carbon alcohol by the gas-phase hydrogenation of the dimethyl oxalate changes the traditional way for preparing the glycol by the gas-phase hydrogenation reaction of the dimethyl oxalate, transfers more to the reaction of the multi-element low-carbon alcohol such as ethanol and the like, adopts the low copper content Cu/SiO reamed by the pore-enlarging agent 2 The catalyst can simultaneously convert dimethyl oxalate into multi-element low-carbon alcohol mainly comprising ethanol and n-propanol with high conversion rate and high selectivity.
(2) The method for preparing the multi-element low-carbon alcohol by gas-phase hydrogenation of the dimethyl oxalate provided by the invention has the advantages that the conversion rate of the dimethyl oxalate raw material is close to 100%, and the content of byproducts, particularly impurities affecting ethanol and n-propanol, 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 the 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 is prolonged, the catalyst has high reactivity, the generation of target products is facilitated, the generation of some impurities is inhibited, and the requirements of industrial production can be met.
Detailed Description
The invention is further illustrated below in connection with specific examples, which are to be understood as being illustrative of the invention and not limiting the scope of the invention.
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
It should be understood that the process equipment or devices not specifically identified in the examples below are all conventional in the art; all pressure values and ranges refer to relative pressures.
Furthermore, it is to be understood that the reference to one or more method steps in this disclosure does not exclude the presence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise indicated; it should also be understood that the combined connection between one or more devices/means mentioned in the present invention does not exclude that other devices/means may also be present before and after the combined device/means or that other devices/means may also be interposed between these two explicitly mentioned devices/means, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.
The reduction activation reaction of the catalyst and the hydrogenation reaction of the feed after the reduction in the following examples were carried out in a 10 ml micro-reaction evaluation apparatus. When the same catalyst of the invention is used for hydrogenation to prepare ethylene glycol or polyhydric low-carbon alcohol, in order to obtain higher selectivity, the proper reaction conditions of the two are different, and the following examples are all descriptions of the method for preparing polyhydric low-carbon alcohol, and the method belongs to the scope of the invention.
Comparative example 1
Preparing a catalyst 1 for synthesizing ethylene glycol by gas phase hydrogenation of dimethyl oxalate, wherein the catalyst 1 comprises the following components in percentage by mass: 40wt% of CuO and 40wt% of SiO 2 55wt％、NiO 5.0wt％。
The 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 fully mixing to obtain a first solution. 8.0kg of a copper nitrate aqueous solution containing 10.0wt% Cu was weighed, and 485g of solid nickel nitrate was further weighed and dissolved in the copper nitrate aqueous solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixture into a reaction kettle together. The reaction vessel was heated with a water bath, the reaction temperature was raised to 90℃and the stirring speed was adjusted to 300 rpm, and the reaction was carried out for 18 hours. Taking out the suspension after reaction, filtering by a filter press, and cleaning a filter cake after filtering by deionized water until the washing liquid is colorless. Placing the filter cake in a stainless steel barrel, adding 14g of polyethylene glycol (n=1000), fully stirring uniformly to enable the filter cake to be gel-like solid, standing for 2 hours, then placing the filter cake in 80 ℃ for drying for 24 hours, roasting at 400 ℃ for 10 hours, and then tabletting and forming to obtain the required catalyst 1.
The catalyst 1 was reduced with a hydrogen nitrogen mixture having a hydrogen volume content of 50% at a reduction temperature of 350 ℃ before use. The 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 ethylene glycol. The reaction temperature is controlled to be 190 ℃, the reaction pressure is 3.0MPa, the liquid hourly space velocity of the dimethyl oxalate is 1.0g/mLcat.h, and the molar ratio of hydrogen to the dimethyl oxalate is 90:1. the evaluation results are shown in Table 1.
Comparative example 2
Preparing a catalyst 2 for synthesizing ethylene glycol by gas phase hydrogenation of dimethyl oxalate, wherein the catalyst 2 comprises the following components in percentage by mass: 15wt% of CuO and SiO 2 84wt％、MoO 3 1.0wt％。
The catalyst 2 was prepared as follows: 8.4kg of JA-25 silica sol is weighed, 12.0kg of deionized water is added, the mixture is fully mixed, 0.80kg of urea is weighed and dissolved in the mixture, and then the mixture is fully mixed to obtain a first solution. 3.8kg of a copper nitrate aqueous solution containing 8.0wt% Cu was weighed, and 33.0g of solid ammonium molybdate was dissolved in the copper nitrate aqueous solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixture into a reaction kettle together. The reaction vessel was heated with a water bath, the reaction temperature was raised to 90℃and the stirring speed was adjusted to 300 rpm, and the reaction was carried out for 18 hours. Taking out the suspension after reaction, filtering by a filter press, and cleaning a filter cake after filtering by deionized water until the washing liquid is colorless. Placing the filter cake in a stainless steel barrel, adding 14g of polyethylene glycol (n=1000), fully stirring uniformly to enable the filter cake to be gel-like solid, standing for 2 hours, then placing the filter cake in 80 ℃ for drying for 24 hours, roasting at 400 ℃ for 10 hours, and then tabletting and forming to obtain the required catalyst 2.
The catalyst 2 was reduced with a hydrogen nitrogen mixture having a hydrogen volume content of 50% at a reduction temperature of 350 ℃ before use. The 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 ethylene glycol. The reaction temperature is controlled to be 190 ℃, the reaction pressure is 3.0MPa, the liquid hourly space velocity of the dimethyl oxalate is 1.0g/mLcat.h, and the molar ratio of hydrogen to the dimethyl oxalate is 90:1. the evaluation results are shown in Table 1.
Comparative example 3
Preparing a catalyst 3 for synthesizing ethylene glycol by gas phase hydrogenation of dimethyl oxalate, wherein the catalyst 3 comprises the following components in percentage by mass: cuO 28wt% and SiO 2 69wt％、ZnO 3.0wt％。
The 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 fully mixing to obtain a first solution. 4.5kg of a copper nitrate aqueous solution containing 12.6wt% Cu was weighed, and 275g of solid zinc nitrate was dissolved in the copper nitrate aqueous solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixture into a reaction kettle together. The reaction vessel was heated with a water bath, the reaction temperature was raised to 90℃and the stirring speed was adjusted to 300 rpm, and the reaction was carried out for 18 hours. Taking out the suspension after reaction, filtering by a filter press, and cleaning a filter cake after filtering by deionized water until the washing liquid is colorless. Placing the filter cake in a stainless steel barrel, adding 14g of polyethylene glycol (n=1000), fully stirring uniformly to enable the filter cake to be gel-like solid, standing for 2 hours, then placing the filter cake in 80 ℃ for drying for 24 hours, roasting at 400 ℃ for 10 hours, and then tabletting and forming to obtain the required catalyst 3.
The catalyst 3 was reduced with a hydrogen nitrogen mixture having a hydrogen volume content of 50% at a reduction temperature of 350 ℃ before use. And (3) placing the catalyst 3 on a 10 ml micro-reaction device, taking dimethyl oxalate as a reaction raw material, and adding hydrogen to react to synthesize the ethylene glycol. The reaction temperature is controlled to be 190 ℃, the reaction pressure is 3.0MPa, the liquid hourly space velocity of the dimethyl oxalate is 1.0g/mLcat.h, and the molar ratio of hydrogen to the dimethyl oxalate is 90:1. the evaluation results are shown in Table 1.
Example 1
Preparing a catalyst 1# for synthesizing a multi-element low-carbon alcohol by gas phase hydrogenation of dimethyl oxalate, wherein the catalyst 1# comprises the following components in percentage by mass: 40wt% of CuO and 40wt% of SiO 2 55wt％、NiO 5.0wt％。
The preparation process of the catalyst 1# is 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 fully mixing to obtain a first solution. 8.0kg of a copper nitrate aqueous solution containing 10.0wt% Cu was weighed, and 485g of solid nickel nitrate was further weighed and dissolved in the copper nitrate aqueous solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixture into a reaction kettle together. The reaction vessel was heated with a water bath, the reaction temperature was raised to 90℃and the stirring speed was adjusted to 300 rpm, and the reaction was carried out for 18 hours. Taking out the suspension after reaction, filtering by a filter press, and cleaning a filter cake after filtering by deionized water until the washing liquid is colorless. Placing the filter cake in a stainless steel barrel, adding 14g of polyethylene glycol (n=1000), fully and uniformly stirring to enable the filter cake to be gel-like solid, standing for 2 hours, then placing the filter cake in 80 ℃ for drying for 24 hours, roasting at 400 ℃ for 10 hours, and then tabletting and forming to obtain the required catalyst No. 1.
The catalyst 1# is reduced by hydrogen-nitrogen mixture with the hydrogen volume content of 50% before use, and the reduction temperature is 350 ℃. The catalyst No. 1 is placed on a 10 ml micro-reaction device, dimethyl oxalate is used as a reaction raw material, hydrogen is added for reaction, and the multi-element low-carbon alcohol is synthesized, wherein the multi-element low-carbon alcohol is mainly ethanol and n-propanol. The reaction temperature is controlled to be 350 ℃, the reaction pressure is 4.0MPa, the liquid hourly space velocity of the dimethyl oxalate is 0.4g/mLcat.h, and the molar ratio of hydrogen to the dimethyl oxalate is 150:1. the evaluation results are shown in Table 1.
Example 2
Preparing a catalyst No. 2 for synthesizing the multi-element low-carbon alcohol by gas phase hydrogenation of dimethyl oxalate, wherein the catalyst No. 2 comprises the following components in percentage by mass: 15wt% of CuO and SiO 2 84wt％、MoO 3 1.0wt％。
The preparation process of the catalyst 2# is as follows: 8.4kg of JA-25 silica sol is weighed, 12.0kg of deionized water is added, the mixture is fully mixed, 0.80kg of urea is weighed and dissolved in the mixture, and then the mixture is fully mixed to obtain a first solution. 3.8kg of a copper nitrate aqueous solution containing 8.0wt% Cu was weighed, and 33.0g of solid ammonium molybdate was dissolved in the copper nitrate aqueous solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixture into a reaction kettle together. The reaction vessel was heated with a water bath, the reaction temperature was raised to 80℃and the stirring speed was adjusted to 300 rpm, and the reaction was carried out for 26 hours. Taking out the suspension after reaction, filtering by a filter press, and cleaning a filter cake after filtering by deionized water until the washing liquid is colorless. Placing the filter cake in a stainless steel barrel, adding 168g of polyethylene glycol (n=2000), fully stirring uniformly to make the filter cake be gel-like solid, standing for 1 hour, then placing into 100 ℃ for drying for 15 hours, roasting at 600 ℃ for 6 hours, and then tabletting and forming to obtain the required catalyst No. 2.
The catalyst No. 2 is reduced by hydrogen-nitrogen mixture with the hydrogen volume content of 75% before use, and the reduction temperature is 275 ℃. The catalyst No. 2 is placed on a 10 ml micro-reaction device, dimethyl oxalate is used as a reaction raw material, hydrogen is added for reaction, and the multi-element low-carbon alcohol is synthesized, wherein the multi-element low-carbon alcohol is mainly ethanol and n-propanol. The reaction temperature is controlled to 250 ℃, the reaction pressure is 2.5MPa, the liquid hourly space velocity of the dimethyl oxalate is 1.2g/mLcat.h, and the molar ratio of hydrogen to the dimethyl oxalate is 230:1. the evaluation results are shown in Table 1.
Example 3
Preparing a catalyst 3# for synthesizing a multi-component low-carbon alcohol by gas phase hydrogenation of dimethyl oxalate, wherein the catalyst 3# comprises the following components in percentage by mass: cuO 28wt% and SiO 2 69wt％、ZnO 3.0wt％。
The preparation process of the catalyst 3# is 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 fully mixing to obtain a first solution. 4.5kg of a copper nitrate aqueous solution containing 12.6wt% Cu was weighed, and 275g of solid zinc nitrate was dissolved in the copper nitrate aqueous solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixture into a reaction kettle together. The reaction vessel was heated with a water bath, the reaction temperature was raised to 70℃and the stirring speed was adjusted to 300 rpm, and the reaction was carried out for 35 hours. Taking out the suspension after reaction, filtering by a filter press, and cleaning a filter cake after filtering by deionized water until the washing liquid is colorless. Placing the filter cake in a stainless steel barrel, adding 78g of polyethylene glycol (n=2000), fully stirring uniformly to make the filter cake be gel-like solid, standing for 3 hours, then placing the filter cake in a 120 ℃ for drying for 10 hours, roasting at 700 ℃ for 4 hours, and then tabletting and forming to obtain the required catalyst No. 3.
The catalyst 3# was reduced with 100v% hydrogen before use at a reduction temperature of 200 ℃. The catalyst 3# is placed on a 10 ml micro-reaction device, dimethyl oxalate is used as a reaction raw material, hydrogen is added for reaction, and the multi-element low-carbon alcohol is synthesized, wherein the multi-element low-carbon alcohol is mainly ethanol and n-propanol. Controlling the reaction temperature to 300 ℃, the reaction pressure to 1.0MPa, the liquid hourly space velocity of the dimethyl oxalate to 2.0g/mLcat.h, and the molar ratio of the hydrogen to the dimethyl oxalate to 300:1. the evaluation results are shown in Table 1.
Example 4
Preparing a catalyst 4# for synthesizing a multi-element low-carbon alcohol by gas phase hydrogenation of dimethyl oxalate, wherein the catalyst 4# comprises the following components in percentage by mass: 40wt% of CuO and 40wt% of SiO 2 55wt％、NiO 5.0wt％。
The preparation process of the catalyst 4# is 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, dissolving in the mixture, fully mixing to obtain a first solution, and adding the ammonia water diluted to a solution with the concentration of 5% when the ammonia water is used. 8.0kg of a copper nitrate aqueous solution containing 10.0wt% Cu was weighed, and 485g of solid nickel nitrate was further weighed and dissolved in the copper nitrate aqueous solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixture into a reaction kettle together. The reaction vessel was heated with a water bath, the reaction temperature was raised to 80℃and the stirring speed was adjusted to 300 rpm, and the reaction was carried out for 26 hours. Taking out the suspension after reaction, filtering by a filter press, and cleaning a filter cake after filtering by deionized water until the washing liquid is colorless. Placing the filter cake in a stainless steel barrel, adding 78g of polyethylene glycol (n=2000), fully stirring uniformly to make the filter cake be gel-like solid, standing for 3 hours, then placing into 100 ℃ for drying for 17 hours, roasting for 7 hours at 550 ℃, and then tabletting and forming to obtain the required catalyst No. 4.
The catalyst 4# was reduced with a hydrogen nitrogen mixture having a hydrogen volume content of 75v% at a reduction temperature of 275 c before use. The catalyst 4# is placed on a 10 ml micro-reaction device, dimethyl oxalate is used as a reaction raw material, hydrogen is added for reaction, and the multi-element low-carbon alcohol is synthesized, wherein the multi-element low-carbon alcohol is mainly ethanol and n-propanol. The reaction temperature is controlled to 250 ℃, the reaction pressure is 2.5MPa, the liquid hourly space velocity of the dimethyl oxalate is 1.2g/mLcat.h, and the molar ratio of hydrogen to the dimethyl oxalate is 230:1. the evaluation results are shown in Table 1.
Example 5
Preparing a catalyst No. 5 for synthesizing the multi-element low-carbon alcohol by gas phase hydrogenation of dimethyl oxalate, wherein the catalyst No. 4 comprises the following components in percentage by mass: 40wt% of CuO and 40wt% of SiO 2 55wt％、NiO 5.0wt％。
The preparation process of the catalyst No. 5 is 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, dissolving in the mixture, fully mixing to obtain a first solution, and adding the ammonia water diluted to a solution with the concentration of 5% when the ammonia water is used. 8.0kg of a copper nitrate aqueous solution containing 10.0wt% Cu was weighed, and 485g of solid nickel nitrate was further weighed and dissolved in the copper nitrate aqueous solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixture into a reaction kettle together. The reaction vessel was heated with a water bath, the reaction temperature was raised to 70℃and the stirring speed was adjusted to 300 rpm, and the reaction was carried out for 35 hours. Taking out the suspension after reaction, filtering by a filter press, and cleaning a filter cake after filtering by deionized water until the washing liquid is colorless. Placing the filter cake in a stainless steel barrel, adding 78g of polyethylene glycol (n=2000), fully stirring uniformly to make the filter cake be gel-like solid, standing for 3 hours, then placing the filter cake in 80 ℃ for drying for 24 hours, roasting at 400 ℃ for 10 hours, and then tabletting and forming to obtain the required catalyst No. 5.
The catalyst 5# was reduced with 100v% hydrogen before use at a reduction temperature of 200 ℃. The catalyst No. 5 is placed on a 10 ml micro-reaction device, dimethyl oxalate is used as a reaction raw material, hydrogen is added for reaction, and the multi-element low-carbon alcohol is synthesized, wherein the multi-element low-carbon alcohol is mainly ethanol and n-propanol. Controlling the reaction temperature to 300 ℃, the reaction pressure to 1.0MPa, the liquid hourly space velocity of the dimethyl oxalate to 2.0g/mLcat.h, and the molar ratio of the hydrogen to the dimethyl oxalate to 300:1. the evaluation results are shown in Table 1.
Example 6
Preparing a catalyst 6# for synthesizing a multi-element low-carbon alcohol by gas phase hydrogenation of dimethyl oxalate, wherein the catalyst 6# comprises the following components in percentage by mass: 15wt% of CuO and SiO 2 84wt％、MoO 3 1.0wt％。
The preparation process of the catalyst 6# is as follows: 8.4kg of JA-25 silica sol is weighed, 12.0kg of deionized water is added, the mixture is fully mixed, 0.80kg of ammonia water is weighed and dissolved in the mixture, the mixture is fully mixed to obtain a first solution, and when the ammonia water is used, the ammonia water is diluted into a solution with the concentration of 5 percent, and the solution is added. 3.8kg of a copper nitrate aqueous solution containing 8.0wt% Cu was weighed, and 33.0g of solid ammonium molybdate was dissolved in the copper nitrate aqueous solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixture into a reaction kettle together. The reaction vessel was heated with a water bath, the reaction temperature was raised to 90℃and the stirring speed was adjusted to 300 rpm, and the reaction was carried out for 18 hours. Taking out the suspension after reaction, filtering by a filter press, and cleaning a filter cake after filtering by deionized water until the washing liquid is colorless. Placing the filter cake in a stainless steel barrel, adding 14g of polyethylene glycol (n=1000), fully and uniformly stirring to enable the filter cake to be gel-like solid, standing for 2 hours, then placing the filter cake in 80 ℃ for drying for 24 hours, roasting at 400 ℃ for 10 hours, and then tabletting and forming to obtain the required catalyst No. 6.
The catalyst 6# is reduced by hydrogen-nitrogen mixture with the hydrogen volume content of 50% before use, and the reduction temperature is 350 ℃. The catalyst 6# is placed on a 10 ml micro-reaction device, dimethyl oxalate is used as a reaction raw material, hydrogen is added for reaction, and the multi-element low-carbon alcohol is synthesized, wherein the multi-element low-carbon alcohol is mainly ethanol and n-propanol. The reaction temperature is controlled to be 350 ℃, the reaction pressure is 4.0MPa, the liquid hourly space velocity of the dimethyl oxalate is 0.4g/mLcat.h, and the molar ratio of hydrogen to the dimethyl oxalate is 150:1. the evaluation results are shown in Table 1.
Example 7
Preparing a catalyst No. 7 for synthesizing the multi-element low-carbon alcohol by gas phase hydrogenation of dimethyl oxalate, wherein the catalyst No. 7 comprises the following components in percentage by mass: 15wt% of CuO and SiO 2 84wt％、MoO 3 1.0wt％。
The preparation process of the catalyst 7# is as follows: 8.4kg of JA-25 silica sol is weighed, 12.0kg of deionized water is added, the mixture is fully mixed, 0.80kg of ammonia water is weighed and dissolved in the mixture, the mixture is fully mixed to obtain a first solution, and when the ammonia water is used, the ammonia water is diluted into a solution with the concentration of 5 percent, and the solution is added. 3.8kg of a copper nitrate aqueous solution containing 8.0wt% Cu was weighed, and 33.0g of solid ammonium molybdate was dissolved in the copper nitrate aqueous solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixture into a reaction kettle together. The reaction vessel was heated with a water bath, the reaction temperature was raised to 70℃and the stirring speed was adjusted to 300 rpm, and the reaction was carried out for 35 hours. Taking out the suspension after reaction, filtering by a filter press, and cleaning a filter cake after filtering by deionized water until the washing liquid is colorless. Placing the filter cake in a stainless steel barrel, adding 78g of polyethylene glycol (n=2000), fully stirring uniformly to make the filter cake be gel-like solid, standing for 3 hours, then placing the filter cake in a 120 ℃ for drying for 10 hours, roasting at 700 ℃ for 4 hours, and then tabletting and forming to obtain the required catalyst No. 7.
The catalyst 7# was reduced with 100v% hydrogen before use at a reduction temperature of 200 ℃. The catalyst No. 7 is placed on a 10 ml micro-reaction device, dimethyl oxalate is used as a reaction raw material, hydrogen is added for reaction, and the multi-element low-carbon alcohol is synthesized, wherein the multi-element low-carbon alcohol is mainly ethanol and n-propanol. Controlling the reaction temperature to 300 ℃, the reaction pressure to 1.0MPa, the liquid hourly space velocity of the dimethyl oxalate to 2.0g/mLcat.h, and the molar ratio of the hydrogen to the dimethyl oxalate to 300:1. the evaluation results are shown in Table 1.
Example 8
Preparing a catalyst 8# for synthesizing a multi-element low-carbon alcohol by gas phase hydrogenation of dimethyl oxalate, wherein the catalyst 8# comprises the following components in percentage by mass: cuO 28wt% and SiO 2 69wt％、ZnO 3.0wt％。
The preparation process of the catalyst 8# is 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, dissolving in the mixture, fully mixing to obtain a first solution, and adding the ammonia water diluted to a solution with the concentration of 5% when the ammonia water is used. 4.5kg of a copper nitrate aqueous solution containing 12.6wt% Cu was weighed, and 275g of solid zinc nitrate was dissolved in the copper nitrate aqueous solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixture into a reaction kettle together. The reaction vessel was heated with a water bath, the reaction temperature was raised to 90℃and the stirring speed was adjusted to 300 rpm, and the reaction was carried out for 18 hours. Taking out the suspension after reaction, filtering by a filter press, and cleaning a filter cake after filtering by deionized water until the washing liquid is colorless. Placing the filter cake in a stainless steel barrel, adding 14g of polyethylene glycol (n=1000), fully and uniformly stirring to enable the filter cake to be gel-like solid, standing for 2 hours, then placing the filter cake in 80 ℃ for drying for 24 hours, roasting at 400 ℃ for 10 hours, and then tabletting and forming to obtain the required catalyst No. 8.
The catalyst 8# is reduced by hydrogen-nitrogen mixture with the hydrogen volume content of 50% before use, and the reduction temperature is 350 ℃. The catalyst 8# is placed on a 10 ml micro-reaction device, dimethyl oxalate is used as a reaction raw material, hydrogen is added for reaction, and the multi-element low-carbon alcohol is synthesized, wherein the multi-element low-carbon alcohol is mainly ethanol and n-propanol. The reaction temperature is controlled to be 350 ℃, the reaction pressure is 4.0MPa, the liquid hourly space velocity of the dimethyl oxalate is 0.4g/mLcat.h, and the molar ratio of hydrogen to the dimethyl oxalate is 150:1. the evaluation results are shown in Table 1.
Example 9
Preparing a catalyst 9# for synthesizing a multi-element low-carbon alcohol by gas phase hydrogenation of dimethyl oxalate, wherein the catalyst 9# comprises the following components in percentage by mass: cuO 28wt% and SiO 2 69wt％、ZnO 3.0wt％。
The preparation process of the catalyst 9# is 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, dissolving in the mixture, fully mixing to obtain a first solution, and adding the ammonia water diluted to a solution with the concentration of 5% when the ammonia water is used. 4.5kg of a copper nitrate aqueous solution containing 12.6wt% Cu was weighed, and 275g of solid zinc nitrate was dissolved in the copper nitrate aqueous solution to obtain a second solution. And then uniformly mixing the first solution and the second solution, and pouring the mixture into a reaction kettle together. The reaction vessel was heated with a water bath, the reaction temperature was raised to 80℃and the stirring speed was adjusted to 300 rpm, and the reaction was carried out for 26 hours. Taking out the suspension after reaction, filtering by a filter press, and cleaning a filter cake after filtering by deionized water until the washing liquid is colorless. Placing the filter cake in a stainless steel barrel, adding 78g of polyethylene glycol (n=2000), fully stirring uniformly to make the filter cake be gel-like solid, standing for 3 hours, then placing into 100 ℃ for drying for 17 hours, roasting for 7 hours at 550 ℃, and then tabletting and forming to obtain the required catalyst No. 9.
The catalyst 9# was reduced with a hydrogen nitrogen mixture having a hydrogen volume content of 75v% at a reduction temperature of 275 c before use. The catalyst 9# is placed on a 10 ml micro-reaction device, dimethyl oxalate is used as a reaction raw material, hydrogen is added for reaction, and the multi-element low-carbon alcohol is synthesized, wherein the multi-element low-carbon alcohol is mainly ethanol and n-propanol. The reaction temperature is controlled to 250 ℃, the reaction pressure is 2.5MPa, the liquid hourly space velocity of the dimethyl oxalate is 1.2g/mLcat.h, and the molar ratio of hydrogen to the dimethyl oxalate is 230:1. the evaluation results are shown in Table 1.
TABLE 1
C DMO /％ S ET /％ S NPA /％ S NBA /％ S NAA /％ S MG /％ S BDO /％ S EG /％
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 that: 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 the conversion rate, and S represents the selectivity.
As is clear from Table 1, in 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 a polyhydric lower alcohol mainly composed of ethanol and n-propanol, and the content of by-products, particularly impurities affecting ethanol and n-propanol, is low as compared with comparative examples 1 to 3.
In summary, the preparation method for preparing the multi-element 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 ethylene glycol into low-carbon alcohols such as ethanol and n-propanol, and ensures that the prepared catalyst has high activity and high selectivity in the reaction process of preparing the ethanol and the n-propanol by gas-phase hydrogenation of the dimethyl oxalate. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.

Claims (6)

1. A preparation method for preparing multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate comprises the following steps: adding hydrogen into dimethyl oxalate under the action of an activated catalyst to react, so as to generate multi-element low-carbon alcohol;
the multi-element low-carbon alcohol is mainly ethanol and n-propanol;
the activation is that the catalyst is reduced by hydrogen-nitrogen mixed gas with the hydrogen volume content of 50-100 v%; the reduction temperature is 200-350 ℃; the molar ratio of the hydrogen to the dimethyl oxalate is 230-300: 1, a step of; the reaction temperature is 300-350 ℃, and the reaction pressure is 1.0-4.0 MPa; the liquid hourly space velocity of the dimethyl oxalate in the reaction is 0.4-2.0 g/mLcat.h;
the catalyst comprises the following components in percentage by mass:
CuO 15～40wt％；
SiO 2 55～84wt％；
1.0 to 5.0 weight percent of oxide of metal auxiliary agent;
the metal auxiliary agent is selected from one or more of Li, na, K, cs, ba, mn, mo, ni, al, ag or Zn; the oxide of Li is Li 2 O; the oxide of Na is Na 2 O; the oxide of K is K 2 O; the oxide of the Cs is Cs 2 O; the oxide of Ba is BaO; the oxide of Mn is MnO; the oxide of Mo is MoO 3 The method comprises the steps of carrying out a first treatment on the surface of the The oxide of Ni is NiO; the oxide of Al is Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The oxide of Ag is AgO; the oxide of Zn is ZnO;
the preparation method of the catalyst comprises the following steps:
1) Providing a first solution comprising a silica sol, a precipitant and water;
2) Providing a second solution comprising a copper salt solution and a soluble salt of a metal promoter;
3) Mixing the first solution and the second solution, reacting under heating, filtering and washing the obtained reaction product to provide a filter cake;
4) Fully mixing the filter cake with an organic pore-expanding agent, standing the obtained gel-like solid, and drying and roasting to provide a catalyst;
5) 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.
2. The method for preparing multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate according to claim 1, wherein in step 1), siO in the silica sol is as follows 2 The concentration is 25-30%.
3. The method for preparing multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate according to claim 1, wherein in step 1), the precipitant is selected from NaOH and Na 2 CO 3 、NaHCO 3 One of ammonia or urea.
4. The method for preparing multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate according to claim 1, wherein in the step 2), the copper salt is copper nitrate aqueous solution.
5. The method for preparing multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate according to claim 1, wherein in the step 4), the organic pore-expanding agent is polyethylene glycol.
6. The method for preparing multi-element low-carbon alcohol by gas-phase hydrogenation of dimethyl oxalate according to claim 1, wherein in the step 4), any one or more of the following conditions are further included:
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.
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