CN111686742A - Copper-based catalyst and preparation method thereof - Google Patents
Copper-based catalyst and preparation method thereof Download PDFInfo
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- CN111686742A CN111686742A CN201910191671.3A CN201910191671A CN111686742A CN 111686742 A CN111686742 A CN 111686742A CN 201910191671 A CN201910191671 A CN 201910191671A CN 111686742 A CN111686742 A CN 111686742A
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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
- B01J23/76—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
- B01J23/83—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 rare earths or actinides
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- 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
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- 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
Abstract
The invention relates to a copper-based catalyst and a preparation method thereof, wherein the catalyst comprises a silicon dioxide carrier and copper oxide and lanthanum oxide loaded on the silicon dioxide carrier, and the catalyst is prepared by adopting a method comprising the following steps: (1) dissolving a copper source and a lanthanum source in deionized water to obtain a copper-containing lanthanum ion aqueous solution; (2) mixing the copper-lanthanum ion-containing aqueous solution obtained in the step (1) with an alkaline substance for reaction, and then filtering and washing to obtain copper hydroxide and lanthanum hydroxide precipitate; (3) dissolving a silicon source in deionized water, and adjusting the pH value with ammonia water to obtain silica sol; (4) heating the silica sol obtained in the step (3) to obtain a silica solid; (5) mixing the materials in the step (2) and the step (4), adding ammonia water, aging, and evaporating to obtain a solid material; (6) and (5) washing, drying and roasting the solid material obtained in the step (5). The catalyst provided by the invention can give consideration to both high conversion rate and selectivity, low reaction temperature and large liquid hourly space velocity in the process of preparing ethylene glycol from oxalate.
Description
Technical Field
The invention relates to a copper-based catalyst and a preparation method thereof.
Background
Ethylene glycol is an important basic organic raw material for petrochemical industry, is mainly used for manufacturing polyester fibers, antifreeze (starting antifreeze), nonionic surfactant, ethanolamine, explosive and the like, and can also be directly used as a solvent. In addition, it has wide applications in the tobacco industry, textile industry and cosmetics industry.
Most of the existing ethylene glycol production processes adopt petroleum routes, namely ethylene oxide is produced by a direct oxidation method and then ethylene glycol is prepared by liquid-phase catalytic or non-catalytic hydration. Chinese patent 02112038.2, us patent 5874653 and japanese patent 82106631 all disclose this route. The methods have the defects of long production process, more required equipment, high energy consumption and the like, so that the production cost of the ethylene glycol is high.
At the end of the last 70 s, the technical route of preparing ethylene glycol by gas-phase hydrogenation of oxalate was first proposed by lr Jehner et al in japanese patents 5323011, 5542971; U.S. Pat. No. 4551565 to Haruhiko Miyazaki et al, 1985, discloses CuMokBapOxThe catalyst can completely convert diethyl oxalate under the conditions of 0.1MPa, 177 ℃, 200 hydrogen-ester ratio and about 0.036 g/gcat.h liquid hourly space velocity, and the ethylene glycol selectivity is 97.7 percent. In 1984, U.S. Pat. Nos. 4585890 and 4440873 disclose that a copper-based catalyst prepared by a cuprammonium-silica gel method is used, and in the reaction for preparing glycol by reducing diethyl oxalate, 100% of diethyl oxalate is converted and the selectivity of glycol is 99.5% when the reaction temperature is 188 ℃, the reaction pressure is 0.05MPa, the liquid hourly space velocity is 0.024 g/g cat h and the hydrogen-ester ratio is 300; under the condition that other reaction conditions are not changed, when the reaction temperature is changed to 215 ℃ and the hydrogen-ester ratio is changed to 50, the conversion rate of diethyl oxalate is 98 percent, the selectivity of ethylene glycol is reduced to 87 percent, and the catalyst is seen to achieve proper selectivity of ethylene glycol, the applicable liquid hourly space velocity (0.024 g/g cat h) is too low, and the hydrogen-ester ratio is high.
The hydrogenation of oxalate to ethylene glycol produces a multi-carbon alcohol byproduct, which can seriously affect the product quality even if the content of the multi-carbon alcohol byproduct is low (accounting for 0.1 weight percent in the product). Furthermore, this is achievedThe separation of the side products from the reaction product is difficult and requires a large amount of energy for the separation. European patent 0060787 reports a catalyst, the mass fraction of the by-products in the product is about 1% under the condition of accurately controlling the reaction conditions, but the patent has the disadvantages that the catalyst needs to add a highly toxic Cr element and the reaction conditions are harsh, and the industrialization is difficult. In 1985 Koichi Hirai reported in U.S. Pat. No. 4614728 a Cu/NH without addition of Cr element3The catalyst has the advantages that under the experimental conditions of 220 ℃, 2MPa, liquid hourly space velocity of 0.92 g/mL.h and hydrogen-ester ratio of 90, the conversion rate of dimethyl oxalate is 99.9%, and the selectivity of ethylene glycol is 90.4%.
In 1986, the American ARCO company adopted a Cu-Cr catalyst, and diethyl oxalate was converted into ethylene glycol under the reaction conditions of a catalyst loading of 100mL, a liquid hourly space velocity of 0.92 g/mL-h, a liquid hourly space velocity of 3.0MPa and a hydrogen-ester ratio of 100, wherein 99.9% of diethyl oxalate is converted in the reaction, the ethylene glycol yield is 95%, and the catalyst is operated for 466h at the longest. 200mL of modular research work for preparing ethylene glycol by diethyl oxalate hydrogenation is completed in the early nineties of the department of Chinese academy of health. Wherein, using Ec-13 copper chromium catalyst, operating for 1134h under the reaction conditions of 0.6 MPa-3.0 MPa, 205-240 ℃, liquid hourly space velocity of 0.327g/g cat h and hydrogen-ester ratio of 100, the space-time yield is 142g/l h, the diethyl oxalate is converted by 99.9 percent, and the ethylene glycol yield is 95 percent. However, these catalysts have the disadvantages of high reaction temperature and high hydrogen-ester ratio required in the reaction.
Based on the current situation of the prior art, a copper-based catalyst and a preparation method thereof are needed, wherein the copper-based catalyst has high oxalate conversion rate and glycol selectivity in the reaction process of preparing ethylene glycol by converting oxalic acid diester, and can ensure that the catalyst has low reaction temperature and high liquid hourly space velocity in the reaction process.
Disclosure of Invention
The invention aims to overcome the defects that the catalyst of the copper-based catalyst in the prior art cannot simultaneously meet the requirements of high conversion rate and selectivity, low reaction temperature and high liquid hourly space velocity, and provides the copper-based catalyst capable of overcoming the defects and the preparation method thereof.
The invention provides a copper-based catalyst, which comprises a silicon dioxide carrier, a copper oxide active component and a molybdenum oxide auxiliary agent, wherein the copper oxide active component and the molybdenum oxide auxiliary agent are loaded on the silicon dioxide carrier, and the copper-based catalyst is characterized by being prepared by adopting the following method comprising the following steps:
(1) dissolving a copper source and a lanthanum source in deionized water to obtain a copper-containing lanthanum ion aqueous solution;
(2) mixing the copper-lanthanum ion-containing aqueous solution obtained in the step (1) with an alkaline substance for reaction, and then filtering and washing to obtain copper hydroxide and lanthanum hydroxide precipitate;
(3) dissolving a silicon source in deionized water, and adjusting the pH value with ammonia water to obtain silica sol;
(4) heating the silica sol obtained in the step (3) to obtain a silica solid;
(5) mixing the materials in the step (2) and the step (4), adding ammonia water, aging, and evaporating to obtain a solid material;
(6) and (5) washing, drying and roasting the solid material obtained in the step (5).
The invention also provides a preparation method of the copper-based catalyst, which comprises the following steps:
(1) dissolving a copper source and a lanthanum source in deionized water to obtain a copper-containing lanthanum ion aqueous solution;
(2) mixing the copper-lanthanum ion-containing aqueous solution obtained in the step (1) with an alkaline substance for reaction, and then filtering and washing to obtain copper hydroxide and lanthanum hydroxide precipitate;
(3) dissolving a silicon source in deionized water, and adjusting the pH value to obtain silica sol;
(4) heating the silica sol obtained in the step (3) to obtain a silica solid;
(5) mixing the materials in the step (2) and the step (4), adding ammonia water, aging, and evaporating to obtain a solid material;
(6) and (5) washing, drying and roasting the solid material obtained in the step (5).
Compared with the existing copper-based catalyst, the catalyst provided by the invention has the advantages that in the process of preparing the ethylene glycol by hydrogenating oxalate, the selectivity and the conversion rate of the catalyst are obviously improved, and in the reaction process, the catalyst has low reaction temperature and large liquid hourly space velocity.
Detailed Description
The invention provides a copper-based catalyst, which comprises a silicon dioxide carrier, a copper oxide active component and a lanthanum oxide auxiliary agent, wherein the copper oxide active component and the lanthanum oxide auxiliary agent are loaded on the carrier, and the catalyst is prepared by adopting the following method comprising the following steps:
(1) dissolving a copper source and a lanthanum source in deionized water to obtain a copper-containing lanthanum ion aqueous solution;
(2) mixing the copper-lanthanum ion-containing aqueous solution obtained in the step (1) with an alkaline substance for reaction, and then filtering and washing to obtain copper hydroxide and lanthanum hydroxide precipitate;
(3) dissolving a silicon source in deionized water, and adjusting the pH value with ammonia water to obtain silica sol;
(4) heating the silica sol obtained in the step (3) to obtain a silica solid;
(5) mixing the materials in the step (2) and the step (4), adding ammonia water, aging, and evaporating to obtain a solid material;
(6) and (5) washing, drying and roasting the solid material obtained in the step (5).
Dissolving a copper source and a lanthanum source in deionized water according to the present invention is well known to those skilled in the art, for example, dissolving a copper source and a lanthanum source in deionized water at a temperature (20-60 ℃) with stirring; the amount of deionized water used for preparing the aqueous solution containing copper and lanthanum ions is not particularly required in the invention, and is preferably 1000 wt%, and more preferably 500 wt%, based on the weight of the copper source.
In the present invention, the copper-lanthanum ion-containing aqueous solution is mixed with an alkaline substance, which is at least one of ammonia water, sodium hydroxide or potassium hydroxide, to react, which is a precipitation reaction typical in the art. The amount of the alkaline substance used in the invention is 150-500 wt%, preferably 180-300 wt%, based on the weight of the copper source.
In the present invention, although various silicon sources used in the field of catalysts can be used for preparing the silica sol of the present invention; the inventors of the present invention have found that when the silicon source is at least one of methyl silicate, ethyl silicate or methyl propyl silicate, the performance of the resulting catalyst is significantly better and the by-products in the resulting product are significantly reduced. Therefore, in the present invention, the silicon source is preferably at least one of methyl silicate, ethyl silicate or propyl silicate, and the silicon source is particularly preferably ethyl silicate.
In the present invention, it is well known to those skilled in the art that the silicon source is dissolved in deionized water, for example, the silicon source may be dissolved in deionized water at a temperature (20 to 60 ℃) under stirring. Specifically, the silicon source may be slowly added to the deionized water under stirring, so that the silicon source is sufficiently dispersed to form the silica sol. The amount of deionized water used for preparing the silica sol is not particularly limited in the present invention, and is preferably 100-1000 wt%, preferably 200-500 wt%, based on the weight of the silicon source.
The concentration of the aqueous ammonia used for the pH adjustment of the silicon source dissolved in deionized water in the present invention is not particularly limited, and for example, the concentration of the aqueous ammonia may be 10 to 30% by weight, preferably 15 to 25% by weight.
The silica sol of the present invention is heated to obtain a silica solid, wherein the heating temperature is not particularly required, and is 80 to 150 ℃, preferably 90 to 120 ℃.
In the invention, ammonia water is added by mixing copper hydroxide, molybdenum hydroxide and silicon dioxide, the concentration of the ammonia water is not particularly limited, for example, the concentration of the ammonia water can be 10-30wt%, preferably 15-25 wt%; the amount of aqueous ammonia used is such that the ratio of the amount of the substance of aqueous ammonia to the amount of the substance of copper element is 6 to 50, preferably 16 to 40, based on the amount of the substance of copper element.
According to the present invention, the amount of the mixture of copper hydroxide, lanthanum hydroxide and silica in step (5) can be appropriately selected depending on the intended composition of the catalyst. Preferably, the copper hydroxide, lanthanum hydroxide and silicon dioxide are added in such a ratio that the content of the active component in terms of copper element is 10 to 30wt%, the content of the auxiliary agent in terms of lanthanum element is 0.1 to 1wt% and the content of the carrier is 61 to 87wt%, based on the total weight of the catalyst.
In the present invention, the aging and evaporating conditions in step (5) are not particularly limited, and preferably include: the temperature is 50-130 ℃; the time is 0.5 to 50 hours; further preferably at a temperature of 60 to 120 ℃; the time is 1-48 hours.
In the present invention, the washing, drying and baking can be carried out by various washing, drying and baking methods in the prior art, for example, the drying temperature is generally 60 to 150 ℃ and the drying time can be 2 to 24 hours. The drying temperature is preferably 60-120 deg.C, and the drying time is preferably 4-16 hr.
The roasting temperature can be 300-800 ℃, the roasting time can be 2-12 hours, the roasting temperature is preferably 350-700 ℃, and the roasting time is preferably 3-10 hours. It is further preferable that the calcination temperature is 400-.
The conditions for the deionized water washing in the present invention are not particularly limited as long as the solution is washed to a neutral solution.
In the invention, the content of the active component calculated by copper element is 10-30wt%, the content of the auxiliary agent calculated by lanthanum element is 0.1-1wt%, and the content of the carrier is 61-87wt% based on the total weight of the catalyst; more preferably, the content of the copper element is 15-25 wt%, the content of the auxiliary agent calculated by the lanthanum element is 0.2-0.5wt%, and the content of the carrier is 66-81wt% based on the total weight of the catalyst. In the present invention, the total weight of the catalyst refers to the total weight of the active component oxide, the auxiliary oxide and the carrier.
The invention also provides a preparation method of the copper-based catalyst, which comprises the following steps:
(1) dissolving a copper source and a lanthanum source in deionized water to obtain a copper-containing lanthanum ion aqueous solution;
(2) mixing the copper-lanthanum ion-containing aqueous solution obtained in the step (1) with an alkaline substance for reaction, and then filtering and washing to obtain copper hydroxide and lanthanum hydroxide precipitate;
(3) dissolving a silicon source in deionized water, and adjusting the pH value with ammonia water to obtain silica sol;
(4) heating the silica sol obtained in the step (3) to obtain a silica solid;
(5) mixing the materials in the step (2) and the step (4), adding ammonia water, aging, and evaporating to obtain a solid material;
(6) and (5) washing, drying and roasting the solid material obtained in the step (5).
In a preferred embodiment, the process for the preparation of the copper-based catalyst of the invention may comprise the steps of:
(1) dissolving a copper source and a lanthanum source in deionized water at normal temperature (about 25 ℃) under stirring, wherein the stirring speed is 50-600 rpm, and the stirring time is 5-120 min, so as to obtain a copper-lanthanum ion-containing aqueous solution;
(2) mixing and reacting the copper-containing lanthanum ion aqueous solution with an alkaline substance at normal temperature (about 25 ℃) under stirring, wherein the weight ratio of the alkaline substance to copper element in the solution is 1.5-5; the stirring speed is 300-600 rpm; stirring for 5-120 min; filtering and washing to obtain copper hydroxide and lanthanum hydroxide solids;
(3) dissolving a silicon source in deionized water at the temperature of 50-70 ℃ under stirring, adjusting the pH value to 7-9 by ammonia water, and stirring at the speed of 50-600 rpm for 15-240 min to obtain silica sol;
(4) drying the silica sol obtained in the step (3) for 3-24 hours at the temperature of 50-160 ℃ to obtain a silica solid;
(5) stirring the solid obtained in the step (2) and the step (4) at the temperature of 50-130 ℃ and the stirring speed of 350-500 rpm, mixing with ammonia water, aging, and evaporating for 2-48 hours to form a solid material;
(6) and (4) washing the solid material obtained in the step (4) by using deionized water, drying for 2-24 hours, roasting for 2-12 hours at the temperature of 300-800 ℃, and forming to obtain the catalyst.
Examples
The present invention will be described in more detail with reference to the following examples. These examples are intended to describe only the preferred embodiments of the present invention and are not intended to limit the scope of the present invention in any way.
The invention determines the copper content by elemental analysis. Elemental analysis (X-ray fluorescence analysis) was performed on an Axios-Advanced fluorescence analyser from PANALYTICALLV, the Netherlands.
Preparation of example 1
(1) Dissolving 44g of copper nitrate and 0.36g of lanthanum nitrate in deionized water at normal temperature (25 ℃), and stirring for 120min at a stirring speed of 50rpm to obtain a copper-lanthanum ion-containing aqueous solution;
(2) mixing the copper-containing lanthanum ion aqueous solution obtained in the step (1) with 17g of potassium hydroxide at normal temperature (25 ℃) under stirring, and stirring for 120min at the stirring speed of 300 rpm; filtering and washing to obtain copper hydroxide and lanthanum hydroxide solids;
(3) dissolving 256g of methyl silicate in deionized water at the temperature of 50 ℃ under stirring, adjusting the pH value to 7 by ammonia water, stirring at the speed of 50rpm for 240min to obtain silica sol;
(4) drying the silica sol obtained in the step (3) at the temperature of 50 ℃ for 24 hours to obtain a silica solid;
(5) mixing the solid obtained in the steps (2) and (4) with ammonia water at the temperature of 50 ℃ under stirring, aging, evaporating to dryness, stirring at the speed of 350rpm for 48 hours to obtain a solid material;
(6) washing the solid material obtained in the step (5) by deionized water, drying for 24 hours at 100 ℃, molding, and roasting for 12 hours at 300 ℃ to obtain the catalyst Cu/SiO2(A)115g；
The weight content of the copper element in the catalyst and the weight content of the lanthanum element in the catalyst are respectively 10 wt% and 0.1 wt%.
Preparation of example 2
(1) Dissolving 44g of copper nitrate and 1.2g of lanthanum nitrate in deionized water at normal temperature (25 ℃), and stirring for 5min at the stirring speed of 600rpm to obtain a copper-lanthanum ion-containing aqueous solution;
(2) mixing the copper-containing lanthanum ion aqueous solution obtained in the step (1) with 56g of potassium hydroxide at normal temperature (25 ℃) under stirring, and stirring for 5min at the stirring speed of 300 rpm; filtering and washing to obtain copper hydroxide and lanthanum hydroxide solids;
(3) dissolving 100g of propyl silicate in deionized water at the temperature of 50 ℃ under stirring, adjusting the pH value to 9 by ammonia water, stirring at the speed of 600rpm for 15min to obtain silica sol;
(4) drying the silica sol obtained in the step (3) at the temperature of 160 ℃ for 3 hours to obtain a silica solid;
(5) mixing the solid obtained in the steps (2) and (4) with ammonia water at the temperature of 130 ℃ under stirring, aging, evaporating to dryness, stirring at the speed of 500rpm for 2 hours to obtain a solid material;
(6) washing the solid material obtained in the step (5) by deionized water, drying for 2 hours at 150 ℃, molding, and roasting for 2 hours at 800 ℃ to obtain the catalyst Cu/SiO2(B)38.5g；
The weight content of the copper element in the catalyst and the weight content of the lanthanum element in the catalyst are respectively 30wt% and 1 wt%.
Preparation of example 3
(1) Dissolving 44g of copper nitrate and 0.9g of lanthanum nitrate in deionized water at normal temperature (25 ℃), and stirring for 60min at the stirring speed of 300rpm to obtain a copper-lanthanum ion-containing aqueous solution;
(2) mixing the copper-containing lanthanum ion aqueous solution obtained in the step (1) with 34g of potassium hydroxide at normal temperature (25 ℃) under stirring, and stirring for 60min at the stirring speed of 450 rpm; filtering and washing to obtain copper hydroxide and lanthanum hydroxide solids;
(3) dissolving 150g of ethyl silicate in deionized water at the temperature of 60 ℃ under stirring, adjusting the pH value to 8 by ammonia water, stirring at the speed of 450rpm for 120min to obtain silica sol;
(4) drying the silica sol obtained in the step (3) at the temperature of 100 ℃ for 12 hours to obtain a silica solid;
(5) mixing the solid obtained in the steps (2) and (4) with ammonia water at the temperature of 100 ℃ under stirring, aging, evaporating to dryness, stirring at the speed of 400rpm for 12 hours to obtain a solid material;
(6) washing the solid material obtained in the step (5) by deionized water, drying at 120 ℃ for 2 hours, molding, and roasting at 500 ℃ for 8 hours to obtain the catalystAgent Cu/SiO2(C)57.8g；
The weight content of the copper element in the catalyst and the weight content of the lanthanum element in the catalyst are respectively 20 wt% and 0.5 wt%.
Preparation of example 4
(1) Dissolving 45.5g of copper sulfate and 0.6g of lanthanum sulfate in deionized water at normal temperature (25 ℃), and stirring for 60min at the stirring speed of 300rpm to obtain a copper-lanthanum ion-containing aqueous solution;
(2) mixing the copper-containing lanthanum ion aqueous solution obtained in the step (1) with 34g of potassium hydroxide at normal temperature (25 ℃) under stirring, and stirring for 60min at the stirring speed of 450 rpm; filtering and washing to obtain copper hydroxide and lanthanum hydroxide solids;
(3) dissolving 150g of ethyl silicate in deionized water at the temperature of 60 ℃ under stirring, adjusting the pH value to 8 by ammonia water, stirring at the speed of 450rpm for 120min to obtain silica sol;
(4) drying the silica sol obtained in the step (3) at the temperature of 100 ℃ for 12 hours to obtain a silica solid;
(5) mixing the solid obtained in the steps (2) and (4) with ammonia water at the temperature of 100 ℃ under stirring, aging, evaporating to dryness, stirring at the speed of 400rpm for 12 hours to obtain a solid material;
(6) washing the solid material obtained in the step (5) by deionized water, drying at 120 ℃ for 2 hours, molding, and roasting at 500 ℃ for 8 hours to obtain the catalyst Cu/SiO2(D)57.8g；
The weight content of the copper element in the catalyst and the weight content of the lanthanum element in the catalyst are respectively 20 wt% and 0.5 wt%.
Preparation of example 5
(1) Dissolving 31g of copper chloride and 0.5g of lanthanum chloride in deionized water at normal temperature (25 ℃), and stirring for 60min at the stirring speed of 300rpm to obtain a copper-lanthanum ion-containing aqueous solution;
(2) mixing the copper-containing lanthanum ion aqueous solution obtained in the step (1) with 34g of potassium hydroxide at normal temperature (25 ℃) under stirring, and stirring for 60min at the stirring speed of 450 rpm; filtering and washing to obtain copper hydroxide and lanthanum hydroxide solids;
(3) dissolving 150g of ethyl silicate in deionized water at the temperature of 60 ℃ under stirring, adjusting the pH value to 8 by ammonia water, stirring at the speed of 450rpm for 120min to obtain silica sol;
(4) drying the silica sol obtained in the step (3) at the temperature of 100 ℃ for 12 hours to obtain a silica solid;
(5) mixing the solid obtained in the steps (2) and (4) with ammonia water at the temperature of 100 ℃ under stirring, aging, evaporating to dryness, stirring at the speed of 400rpm for 12 hours to obtain a solid material;
(6) washing the solid material obtained in the step (5) by deionized water, drying at 120 ℃ for 2 hours, molding, and roasting at 500 ℃ for 8 hours to obtain the catalyst Cu/SiO2(E)57.8g；
The weight content of the copper element in the catalyst and the weight content of the lanthanum element in the catalyst are respectively 20 wt% and 0.5 wt%.
Preparation of example 6
(1) Dissolving 36g of copper acetate and 0.9g of lanthanum nitrate in deionized water at normal temperature (25 ℃), and stirring for 60min at the stirring speed of 300rpm to obtain a copper-lanthanum ion-containing aqueous solution;
(2) mixing the copper-containing lanthanum ion aqueous solution obtained in the step (1) with 34g of potassium hydroxide at normal temperature (25 ℃) under stirring, and stirring for 60min at the stirring speed of 450 rpm; filtering and washing to obtain copper hydroxide and lanthanum hydroxide solids;
(3) dissolving 150g of ethyl silicate in deionized water at the temperature of 60 ℃ under stirring, adjusting the pH value to 8 by ammonia water, stirring at the speed of 450rpm for 120min to obtain silica sol;
(4) drying the silica sol obtained in the step (3) at the temperature of 100 ℃ for 12 hours to obtain a silica solid;
(5) mixing the solid obtained in the steps (2) and (4) with ammonia water at the temperature of 100 ℃ under stirring, aging, evaporating to dryness, stirring at the speed of 400rpm for 12 hours to obtain a solid material;
(6) washing the solid material obtained in the step (5) by deionized water, and carrying out treatment at 120 DEG CDrying for 2 hours, molding, and roasting at 500 ℃ for 8 hours to obtain the catalyst Cu/SiO2(F)57.8g；
The weight content of the copper element in the catalyst and the weight content of the lanthanum element in the catalyst are respectively 20 wt% and 0.5 wt%.
Testing of catalyst Performance
The catalytic crushing and screening of the catalyst obtained in preparation examples 1-6 are 20-60 meshes, and the catalyst is activated by pure hydrogen at 280 ℃ for 12 hours and then adjusted to the reaction process conditions for reaction.
The catalysts prepared in preparation examples 1 to 6 were placed in a miniature fixed bed continuous flow reactor having an inner diameter of 8mm, a thermowell was installed inside the reactor, the loading of the catalyst was 5g, and the feed gas passed through the catalyst bed from top to bottom.
The reaction conditions for preparing ethylene glycol by hydrogenating oxalate are as follows: the reaction temperature is 165 ℃, the reaction pressure is 2.5MPa, the catalyst load (the feeding speed of the oxalic ester serving as a reaction raw material) is 4.2 kg/h.kg of the catalyst, the hydrogen/oxalic ester ratio is 55 (molar ratio), and the reaction time is 24 hours. The reaction results are shown in table 1.
TABLE 1 results of catalyst Performance testing
| Sources of catalyst | Conversion of dimethyl oxalate/%) | Ethylene glycol selectivity/%) | Conversion of diethyl oxalate/%) | Ethylene glycol selectivity/%) |
| Preparation of example 1 | 100 | 98.1 | 100 | 97.8 |
| Preparation of example 2 | 100 | 98.1 | 100 | 98.0 |
| Preparation of example 3 | 100 | 99.2 | 100 | 99.0 |
| Preparation of example 4 | 100 | 98.5 | 100 | 98.2 |
| Preparation of example 5 | 100 | 98.4 | 100 | 98.2 |
| Preparation of example 6 | 100 | 99.1 | 100 | 99.1 |
Claims (10)
1. A copper-based catalyst, which contains a silicon dioxide carrier, a copper oxide active component and a lanthanum oxide auxiliary agent, wherein the copper oxide active component and the lanthanum oxide auxiliary agent are loaded on the silicon dioxide carrier, and the copper-based catalyst is characterized by being prepared by adopting the following method comprising the following steps:
(1) dissolving a copper source and a lanthanum source in deionized water to obtain a copper-containing molybdenum ion aqueous solution;
(2) mixing the copper-lanthanum ion-containing aqueous solution obtained in the step (1) with an alkaline substance for reaction, and then filtering and washing to obtain copper hydroxide and molybdenum hydroxide precipitate;
(3) dissolving a silicon source in deionized water, and adjusting the pH value with ammonia water to obtain silica sol;
(4) heating the silica sol obtained in the step (3) to obtain a silica solid;
(5) mixing the materials in the step (2) and the step (4), adding ammonia water, aging, and evaporating to obtain a solid material;
(6) and (5) washing, drying and roasting the solid material obtained in the step (5).
2. The catalyst according to claim 1, wherein the content of the active component is 10-30wt% in terms of copper element, the content of the promoter is 0.1-1wt% in terms of lanthanum element, and the content of the carrier is 61-87wt%, based on the total weight of the catalyst.
3. The catalyst of claim 1, wherein the copper source is selected from at least one of copper nitrate, copper sulfate, copper chloride, or copper acetate; copper nitrate is preferred; the lanthanum source is selected from at least one of lanthanum nitrate, lanthanum sulfate or lanthanum chloride; lanthanum nitrate is preferred; the silicon source is at least one of methyl silicate, ethyl silicate or propyl silicate; preferably ethyl silicate; the alkaline substance is selected from at least one of ammonia water, sodium hydroxide or potassium hydroxide; preferably potassium hydroxide; the drying conditions include: the drying temperature is 80-150 ℃; the drying time is 3-20 hours.
4. The catalyst of any one of claims 1-3, wherein the pH is adjusted to 5-7 in step (3).
5. The catalyst of any one of claims 1-4, wherein the conditions of calcination include: the roasting temperature is 300-800 ℃; the roasting time is 3-20 hours.
6. A method for preparing a copper-based catalyst, the method comprising the steps of:
(1) dissolving a copper source and a lanthanum source in deionized water to obtain a copper-containing lanthanum ion aqueous solution;
(2) mixing the copper-lanthanum ion-containing aqueous solution obtained in the step (1) with an alkaline substance for reaction, and then filtering and washing to obtain copper hydroxide and lanthanum hydroxide precipitate;
(3) dissolving a silicon source in deionized water, and adjusting the pH value with ammonia water to obtain silica sol;
(4) heating the silica sol obtained in the step (3) to obtain a silica solid;
(5) mixing the materials in the step (2) and the step (4), adding ammonia water, aging, and evaporating to obtain a solid material;
(6) and (5) washing, drying and roasting the solid material obtained in the step (5).
7. The process as claimed in claim 6, wherein the content of the active component is 10-30wt% in terms of copper element, the content of the auxiliary agent is 0.1-1wt% in terms of lanthanum element, and the content of the carrier is 61-87wt%, based on the total weight of the catalyst.
8. The method of claim 6, wherein the copper source is selected from at least one of copper nitrate, copper sulfate, copper chloride, or copper acetate; copper nitrate is preferred; the lanthanum source is selected from at least one of lanthanum nitrate, lanthanum sulfate or lanthanum chloride; lanthanum nitrate is preferred; the silicon source is at least one of methyl silicate, ethyl silicate or propyl silicate; preferably ethyl silicate; the alkaline substance is selected from at least one of ammonia water, sodium hydroxide or potassium hydroxide; preferably potassium hydroxide; the drying conditions include: the drying temperature is 80-150 ℃; the drying time is 3-20 hours.
9. The process according to any one of claims 6 to 8, wherein the pH is adjusted to 5 to 7 in step (3).
10. The method of any one of claims 6-9, wherein the conditions of the firing comprise: the roasting temperature is 300-800 ℃; the roasting time is 3-20 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116139874A (en) * | 2023-04-20 | 2023-05-23 | 潍坊学院 | Catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590407A (en) * | 2009-07-13 | 2009-12-02 | 西南化工研究设计院 | A kind of Catalysts and its preparation method and application of dicarboxylic acids ester through hydrogenation produce diatomic alcohol |
| CN101733108A (en) * | 2008-11-27 | 2010-06-16 | 上海焦化有限公司 | Catalyst for hydrogenation, preparation method thereof and use thereof |
| CN101844079A (en) * | 2009-03-24 | 2010-09-29 | 上海焦化有限公司 | Catalyst for preparing glycol through oxalate hydrogenation and preparation and application thereof |
| CN102764656A (en) * | 2012-08-06 | 2012-11-07 | 久泰能源科技有限公司 | High-efficiency hydrogenation catalyst and method for preparing same |
| US20130123550A1 (en) * | 2010-06-24 | 2013-05-16 | Tianjin University | Copper hydrogenation catalyst, especially for converting oxalate to ethylene glycol, method of preparing the catalyst and applications thereof |
| WO2018121326A1 (en) * | 2016-12-26 | 2018-07-05 | 高化学技术株式会社 | Preparation method of catalyst for hydrogenation of dimethyl oxalate to synthesize ethanol, and catalyst obtained therefrom and use thereof |
| CN109317155A (en) * | 2018-11-30 | 2019-02-12 | 华东理工大学 | The rare-earth type Cu-series catalyst of ethyl acetate preparation of ethanol by hydrogenating and correlation method application |
-
2019
- 2019-03-14 CN CN201910191671.3A patent/CN111686742A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733108A (en) * | 2008-11-27 | 2010-06-16 | 上海焦化有限公司 | Catalyst for hydrogenation, preparation method thereof and use thereof |
| CN101844079A (en) * | 2009-03-24 | 2010-09-29 | 上海焦化有限公司 | Catalyst for preparing glycol through oxalate hydrogenation and preparation and application thereof |
| CN101590407A (en) * | 2009-07-13 | 2009-12-02 | 西南化工研究设计院 | A kind of Catalysts and its preparation method and application of dicarboxylic acids ester through hydrogenation produce diatomic alcohol |
| US20130123550A1 (en) * | 2010-06-24 | 2013-05-16 | Tianjin University | Copper hydrogenation catalyst, especially for converting oxalate to ethylene glycol, method of preparing the catalyst and applications thereof |
| CN102764656A (en) * | 2012-08-06 | 2012-11-07 | 久泰能源科技有限公司 | High-efficiency hydrogenation catalyst and method for preparing same |
| WO2018121326A1 (en) * | 2016-12-26 | 2018-07-05 | 高化学技术株式会社 | Preparation method of catalyst for hydrogenation of dimethyl oxalate to synthesize ethanol, and catalyst obtained therefrom and use thereof |
| CN109317155A (en) * | 2018-11-30 | 2019-02-12 | 华东理工大学 | The rare-earth type Cu-series catalyst of ethyl acetate preparation of ethanol by hydrogenating and correlation method application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116139874A (en) * | 2023-04-20 | 2023-05-23 | 潍坊学院 | Catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide and preparation method thereof |
| CN116139874B (en) * | 2023-04-20 | 2023-06-16 | 潍坊学院 | Catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide and preparation method thereof |
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