CN116713003A - Catalyst for preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate, and preparation method and application thereof - Google Patents

Catalyst for preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate, and preparation method and application thereof Download PDF

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CN116713003A
CN116713003A CN202310700237.XA CN202310700237A CN116713003A CN 116713003 A CN116713003 A CN 116713003A CN 202310700237 A CN202310700237 A CN 202310700237A CN 116713003 A CN116713003 A CN 116713003A
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catalyst
dimethyl oxalate
mixture
ethanol
methyl acetate
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陈兴坤
李峥
王雪鹏
丁云杰
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Zhejiang Normal University CJNU
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Zhejiang Normal University CJNU
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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
    • B01J23/84—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
    • B01J23/888—Tungsten
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a catalyst for preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate and a preparation method thereof, wherein the catalyst comprises an active component, an auxiliary component and a carrier, wherein the active component is a simple substance or oxide of Cu, the auxiliary component is a simple substance or oxide of W, a high active site is a Cu-W alloy interface and Cu and W metals independently, and the carrier is one or more than two of silicon dioxide, aluminum oxide, zirconium oxide, zinc oxide, magnesium oxide and cerium oxide. The copper-tungsten alloy catalyst provided by the invention has the advantages of stable structure, high mechanical strength, good heat conduction performance, high substrate conversion rate, high product selectivity and the like, and the preparation method has the advantages of simple steps, readily available raw materials, low cost, greenness, no pollution, good preparation repeatability and easiness in realizing large-scale production. The catalyst has extremely high stability and catalytic activity in the reaction of preparing methyl acetate or ethanol by catalyzing dimethyl oxalate hydrogenation, and has high yield of ethanol or methyl acetate and high utilization rate of active components.

Description

Catalyst for preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate, and preparation method and application thereof
Technical Field
The invention relates to the technical field of synthesis of methyl acetate or ethanol, in particular to a catalyst for regulating and controlling selective hydrogenation of dimethyl oxalate to prepare methyl acetate or ethanol, and a preparation method and application thereof.
Background
Methyl Acetate (MA), also known as methyl acetate, is a common organic solvent and chemical raw material in industry, and is widely applied to industries such as paint coating, textile, spice, medicine, food and the like. The high-purity methyl acetate can be used for synthesizing acetic acid, anhydride, methyl acrylate, vinyl acetate and the like. In recent years, with the continuous development of C1 chemical industry, the demand of methyl acetate is increasing, and because of its properties very similar to acetone, methyl acetate is also used as a substitute for acetone. Meanwhile, methyl acetate is taken as an important intermediate product in the coal processing industry and is an important raw material for producing acetic anhydride by carbonylation.
At present, common preparation methods of methyl acetate mainly comprise a methanol dehydrogenation synthesis method, a methanol carbonylation method, a methanol esterification method and a dimethyl ether carbonylation method, and the methods for directly esterifying methanol and acetic acid to generate methyl acetate are most common due to raw material sources, production process conditions and the like. The catalyst widely used in direct esterification of acetic acid and methanol at present is mainly concentrated sulfuric acid, and the strong acid catalyst has high catalytic performance, can initiate side reaction, reduces the selectivity of methyl acetate, can generate a large amount of waste acid and waste water, and makes the separation of reaction products more difficult. In recent years, with the concept of green chemistry, less energy is consumed in the production process, the emission of waste is reduced, and the attention is increasingly paid. The traditional preparation method is difficult to adapt to the development requirement of the new era. Therefore, in recent years, the reaction of preparing methyl acetate by hydrogenating dimethyl oxalate is paid attention to, but the reaction is a continuous and complex reaction, methyl oxalate is firstly subjected to incomplete hydrogenation to obtain methyl glycolate, further hydrogenation is carried out to obtain ethylene glycol or methyl acetate, and deep hydrogenation is carried out to obtain ethanol, and as methyl acetate is easily hydrogenated to obtain ethanol, the obtaining of an intermediate product methyl acetate needs to seek a novel catalyst with high catalytic activity and selectivity and search for reaction conditions, so that the reaction becomes a hot research field.
Ethanol (EtOH) is an important chemical raw material and clean energy, and is widely applied to industries such as solvents, disinfectants, foods, fuels and the like, and can also be used for manufacturing beverages, dyes, essence, ethanol gasoline and the like. The ethanol can be added into the gasoline according to a certain proportion because of the pollution-free characteristic of the ethanol as fuel, so that the octane number of the gasoline is improved, the ethanol gasoline is combusted more fully, the emission of CO, hydrocarbon and other polluted gases is reduced, the pollution to the atmosphere is reduced, the consumption of the gasoline is reduced, the dependence degree of China on petroleum resources is reduced, and the national conditions of more coal, less oil and lean gas in China are met, so that the demand of China for ethanol is increased. The efficient synthesis of ethanol has attracted considerable attention from researchers.
The industrial ethanol producing process includes biological fermentation process, ethylene hydration process, synthesis gas process, etc. Among them, the biological fermentation method is the most commonly used method for preparing ethanol at present. The method mainly takes grain crops such as corn, sugarcane and the like as raw materials to obtain the ethanol through fermentation, but the price of the grain is higher, and the situation of competing with people for the grain possibly occurs, which is not beneficial to the global supply of the grain. Besides the fermentation method, the ethylene hydration method needs a large amount of petroleum resources for preparing the ethanol, and petroleum is expensive, so that the cost for producing the ethanol is high, and the economy is not good. In addition, the method has high requirements on equipment materials and high investment cost due to strong corrosiveness of the used concentrated sulfuric acid. There is no obvious competitive power in the economic environment of our country. The synthesis gas is directly synthesized into ethanol, and although the process steps are required to be fewer, the conversion rate of the synthesis gas and the selectivity of the ethanol are low, so that the method for preparing the ethanol needs to explore a better catalyst to realize large-scale production. The indirect synthesis gas method for preparing ethanol mainly comprises the following three methods: 1. the synthesis gas is firstly prepared into methanol, the methanol is carbonylated to obtain acetic acid, the acetic acid is further hydrogenated to obtain ethanol, a plurality of side reactions can occur in the method, a large amount of byproducts such as acetaldehyde or ethyl acetate are generated, the catalyst is generally a noble metal catalyst such as Pt, pd, rh and the like, the cost is greatly increased, and the method is not beneficial to industrialized mass production. 2. The methyl acetate is obtained by the re-esterification of acetic acid produced by synthesis gas, and ethanol is obtained by further hydrogenation of methyl acetate, so that researchers have made a lot of researches on catalysts for the reaction, and at present, copper-based catalysts are mainly used, but the reaction temperature is higher, and the copper-based catalysts tend to be large in agglomeration and have the phenomenon of sintering deactivation. 3. The technology of obtaining dimethyl oxalate by catalytic coupling of synthesis gas is basically mature, and the dimethyl oxalate is hydrogenated to prepare ethanol, and because the dimethyl oxalate contains two ester functional groups and is not easy to hydrogenate to obtain alcoholic hydroxyl groups, a catalyst with high conversion rate and high ethanol selectivity is also required to be developed.
Patent CN101830776B reports a method for synthesizing ethanol, first preparing dimethyl oxalate with a Pd-based catalyst, and then hydrogenating dimethyl oxalate with a Cu-based catalyst to produce ethanol. In a fixed bed reactor, the selectivity to ethanol is up to 85%. Patent CN106563480a discloses a molybdenum carbide catalyst for preparing methyl acetate and ethanol by hydrogenating dimethyl oxalate, and the selectivity of ethanol is 83% at the highest when the conversion rate of dimethyl oxalate is 100%. The selectivity to methyl acetate is very low. Furthermore, no results are reported in the patent regarding the stability of the catalyst.
Current research shows that Cu/SiO 2 The catalyst is a catalyst commonly used for the hydrogenation of dimethyl oxalate. But Cu/SiO 2 The catalyst has the defects of poor selectivity, poor stability and the like in a dimethyl oxalate hydrogenation system. In addition, because methyl acetate is easy to further hydrogenate to prepare ethanol, reports for researching high selectivity of dimethyl oxalate hydrogenation to obtain methyl acetate are not much. In the reaction of preparing ethanol by hydrogenating dimethyl oxalate, various metal modified copper-based catalysts are reported, but the overall selectivity of ethanol is relatively low and the reaction conditions are severe. How to design a catalyst which can be highly active, highly selective and highly active under milder conditionsThe catalytic system for preparing methyl acetate or ethanol by catalyzing dimethyl oxalate hydrogenation with stability is still an urgent problem to be solved at present.
Disclosure of Invention
The invention aims to solve the technical problem of providing a catalyst for preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate, a preparation method and application thereof, wherein the high conversion rate of the dimethyl oxalate and the selective generation of the methyl acetate or ethanol are ensured by adjusting the mass ratio of copper to tungsten and controlling the reaction condition after the catalyst is prepared by adopting a specific method so as to solve the defects in the prior art.
The invention discloses a catalyst for preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate, which comprises an active component, an auxiliary component and a carrier, wherein the active component is a simple substance or oxide of Cu, the auxiliary component is a simple substance or oxide of W, a high active site is a Cu-W alloy interface and independent Cu and W metals, and the carrier is one or more than two of silicon dioxide, aluminum oxide, zirconium oxide, zinc oxide, magnesium oxide and cerium oxide;
the catalyst is prepared by the following steps:
(I) Mixing soluble salt of copper, deionized water, ammonia water and a carrier to prepare a mixture, so that the pH of the mixture is 8-12;
(II) subjecting the mixture obtained in step (I) to ultrasonic treatment at room temperature for 3-5 hours, followed by vigorous stirring at 1000-2000 rpm at 25-45 ℃ for 3-5 hours;
(III) heating and evaporating the mixture treated in the step (II) at 70-90 ℃ until the pH of the mixture is 6-7, and then placing the mixture into a hydrothermal reaction kettle for treatment at 120-180 ℃ for 3-8 hours;
(IV) filtering the mixture treated in the step (III), and washing with deionized water to obtain a solid;
(V) drying the solid obtained in the step (IV) at 120-150 ℃ for 6-24h, and calcining at 300-600 ℃ for 2-10h to obtain a Cu/carrier precursor; atomizing the soluble salt solution of W into micron-sized W salt mist drops through an ultrasonic atomization generator, and adsorbing and loading the micron-sized W salt mist drops through electrostatic acting force between a Cu/carrier precursor and the micron-sized mist drops to obtain a load;
(VI) naturally drying the load obtained in the step (V) in the shade for 24-48 hours to obtain a load solid;
(VII) drying the loaded solid obtained in the step (VI) at 100-150 ℃ for 6-24h, and roasting at 300-650 ℃ for 2-12h to obtain the catalyst Cu-W/SiO 2 。
Further, when the catalyst is used for selectively preparing methyl acetate, the content of the first active component is 1-30% by mass of the Cu elementary substance; the second active component accounts for 5-20% of the mass of the W simple substance; the rest is carrier.
Further, when the catalyst is used for selectively preparing ethanol, the content of the first active component is 5-30% by mass of the Cu elementary substance; the second active component accounts for 0.05-3% of the mass of the W simple substance; the rest is carrier.
Further, the soluble salt of copper in the step (I) is one or more of copper nitrate, copper chloride, copper sulfate or copper acetate.
Further, the soluble salt of tungsten in the step (V) is one or more than two of ammonium tungstate, ammonium meta-tungstate, sodium tungstate, cobalt tungstate or ferrous tungstate.
The invention also discloses a preparation method of the catalyst for preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate,
the preparation method comprises the following steps:
(I) Mixing soluble salt of copper, deionized water, ammonia water and a carrier to prepare a mixture, so that the pH of the mixture is 8-12;
(II) sonicating the mixture from step (I) at room temperature for 3-5 hours, followed by vigorous stirring at 25-45℃for 3-5 hours at 1000-2000 rpm;
(III) heating and evaporating the mixture treated in the step (II) at 70-90 ℃ until the pH of the mixture is 6-7, and then placing the mixture into a hydrothermal reaction kettle for treatment at 120-180 ℃ for 3-8 hours;
(IV) filtering the mixture treated in the step (III), and washing with deionized water to obtain a solid;
(V) drying the solid obtained in the step (IV) at 120-150 ℃ for 6-24h, and calcining at 300-600 ℃ for 2-10h to obtain a Cu/carrier precursor; atomizing the soluble salt solution of W into micron-sized W salt mist drops through an ultrasonic atomization generator, and adsorbing and loading the micron-sized W salt mist drops through electrostatic acting force between a Cu/carrier precursor and the micron-sized mist drops to obtain a load;
(VI) naturally drying the load obtained in the step (V) in the shade for 24-48 hours to obtain a load solid;
(VII) drying the loaded solid obtained in the step (VI) at 100-150 ℃ for 6-24h, and roasting at 300-650 ℃ for 2-12h to obtain the catalyst Cu-W/SiO 2 。
Further, the soluble salt of copper in the step (I) is one or more than two of copper nitrate, copper chloride, copper sulfate or copper acetate; the soluble salt of tungsten in the step (V) is one or more than two of ammonium tungstate, ammonium meta-tungstate, sodium tungstate, cobalt tungstate or ferrous tungstate.
The invention also discloses application of the catalyst in preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate,
when methyl acetate is prepared, the catalyst is filled in a reaction tube, then the whole reaction tube is filled with quartz sand, the catalyst is activated in hydrogen or hydrogen inert gas mixture before use, after the activation is finished, the reaction condition is regulated to a specified reaction condition, and dimethyl oxalate or a mixture of dimethyl oxalate and a methanol solvent is pumped in, wherein the reaction condition is as follows: the temperature is 120-350 ℃, the pressure is 0.3-6.0MPa, and the liquid hourly space velocity of the dimethyl oxalate is 0.01-6.0h -1 The molar ratio of the hydrogen to the dimethyl oxalate is 5:1-800:1.
When preparing ethanol, firstly filling the catalyst into a reaction tube, then filling the whole reaction tube with quartz sand, activating the catalyst in hydrogen or hydrogen inert gas mixture before use, adjusting to a specified reaction condition after the activation is finished, and pumping dimethyl oxalate or a mixture of dimethyl oxalate and a methanol solvent into the reaction tube, wherein the reaction condition is as follows: the temperature is 250-350 ℃, the pressure is 3.0-6.0Mpa, and the liquid hourly space velocity of dimethyl oxalate is 0.01-2h -1 The molar ratio of the hydrogen to the dimethyl oxalate is 400:1-800:1; wherein the preferred reaction conditions for the preparation of methyl acetate are: at a temperature of 120-28 DEG CThe temperature is 0 ℃, the pressure is 0.3-2.0Mpa, and the liquid hourly space velocity of the dimethyl oxalate is 2-6h -1 The molar ratio of the hydrogen to the dimethyl oxalate is 5:1-300:1.
Further, the catalyst activation condition is that the pressure is 0.1-0.5MPa and the gas space velocity is 10-300h -1 The activation temperature is 160-300 ℃, the temperature rising rate is 0.1-20 ℃/min, and the activation time is 0.5-8h.
The beneficial effects of the invention are as follows:
the bimetallic nano alloy heterogeneous catalyst prepared by the invention firstly uses ammonia water to load active component copper on a carrier, and the copper is uniformly distributed on the surface of the carrier by intense stirring for a long time; and then, uniformly dispersing the tungsten serving as a second active component on the surface of the copper catalyst obtained in the previous step by utilizing strong electric force between the ultrasonic atomized micron-sized mist drops and the Cu/carrier precursor, and modifying the tungsten serving as the second component on the surface of the copper component to form a copper-tungsten alloy structure of the active component. Then forming the bimetal alloy catalyst with the nano structure in situ in the post-treatment processes of roasting, reduction and the like. The formed bimetal alloy interface structure has better catalytic performance. In addition, due to the typical alloy structure, strong electronic effect exists between bimetallic in the catalyst and strong interaction is generated between active components and a carrier, so that the stability of the catalyst can be obviously improved.
Compared with the traditional copper catalyst, (1) the invention can improve the activity of the catalyst and the selectivity of target products: the hydrogenation selectivity of dimethyl oxalate is controlled to generate methyl acetate or ethanol by regulating and controlling the proportion of copper and tungsten, when the content of the second active component W is not lower than 5%, the selectivity of methyl acetate can reach more than 70%, and when the content of the second active component W is not higher than 3%, the selectivity of ethanol can reach more than 90%. (2) The reaction for preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate can be realized under milder conditions. (3) Effectively improves the stability of the catalytic system and is stable for more than or equal to 1000 hours.
In a word, the copper-tungsten alloy catalyst provided by the invention has the advantages of stable structure, high mechanical strength, good heat conduction performance, high substrate conversion rate, high product selectivity and the like, and the preparation method is simple in steps, easy in raw material acquisition, low in cost, green, pollution-free, good in preparation repeatability and easy to realize large-scale production. The catalyst has extremely high stability and catalytic activity in the reaction of preparing methyl acetate or ethanol by catalyzing dimethyl oxalate hydrogenation, and has high yield of ethanol or methyl acetate and high utilization rate of active components.
Drawings
FIG. 1 is a diagram of the Cu-W catalyst of example 1 showing the analysis of the element by a spherical aberration electron microscope, the top left corner shows the original electron microscope, and the rest shows the analysis of the element by Cu, O and W;
FIG. 2 is a plot of the physical adsorption of the copper tungsten catalyst of example 1;
FIG. 3 is a TEM image of the copper-tungsten catalyst of example 1;
FIG. 4a is a graph of performance stability test of the copper tungsten catalyst of example 1;
fig. 4b is a graph of performance stability test for the copper tungsten catalyst of example 2.
Detailed Description
The invention is further explained below with reference to examples. The following examples are only illustrative of the present invention and are not intended to limit the scope of the invention.
Example 1
7.55g of copper nitrate trihydrate was dissolved in 100mL of deionized water at room temperature to prepare a copper nitrate solution. To the copper nitrate solution, a certain amount of ammonia water and 7g of silica were added so as to have a pH of 8 to 12, and the resulting mixture was sonicated at room temperature for 3 hours, followed by vigorous stirring at 1000 rpm for 4 hours at 35 ℃. The temperature was then increased to 80 ℃ until the pH was at the end of 7. Placing the obtained mixture into a hydrothermal reaction kettle, treating for 3 hours at 120 ℃, filtering, washing with deionized water to obtain a solid, drying the obtained solid at 150 ℃ for 12 hours, and calcining at 450 ℃ for 5 hours to obtain Cu/SiO 2 A precursor. 1.34g of ammonium metatungstate was dissolved in 50mL of deionized water to prepare an ammonium metatungstate solution, which was atomized by an ultrasonic atomizer, followed by Cu/SiO 2 The precursors are mixed, and the strong electrostatic acting force between the precursors is utilized to adsorb and load the ammonium metatungstate component. And then standing the mixture at room temperature, and drying in the shade for 48 hours to obtain a loaded solid. Drying the obtained loaded solid at 150deg.CDrying for 12h. Then roasting for 4 hours at 550 ℃ in a muffle furnace to obtain the catalyst 20Cu-10W/SiO 2 。
The catalyst prepared in this example was 20Cu-10W/SiO 2 As shown in fig. 1-3, fig. 1 shows that the catalyst Cu and W are uniformly distributed on a microscopic scale, and the perfect fit of the Cu element analysis chart and the W element analysis chart illustrates that Cu and W are closely combined into an alloy phase on a nano scale, which also proves that the catalyst is a copper-tungsten nano alloy catalyst. FIG. 2 shows that the catalyst has a large specific surface area (up to 394.8m 2 /g) and exhibit a pronounced mesoporous structure distribution. Fig. 3 shows that the active component nano particles on the surface of the catalyst are uniformly distributed, and the prepared copper-tungsten catalyst is proved to be a nano catalyst by TEM statistical particle size.
Filling 1.0g of the catalyst into a fixed bed reaction tube, filling the whole reaction tube with quartz sand, and reducing the catalyst with H as the reducing gas 2 H at 5% v/v 2 Ar gas mixture, gas space velocity of the gas mixture is 150h -1 The reduction pressure is 0.5MPa, the reduction temperature is 230 ℃, the heating rate is 2 ℃/min, and the reduction time is 2h. Switching gas to H after reduction 2 Raising the pressure to 1.5MPa, pumping a methanol solution of 20% by mass of dimethyl oxalate (DMO) by using a horizontal pump, wherein the liquid hourly space velocity of the DMO is 1.0h -1 ，H 2 The molar ratio of/DMO was 20:1 and the reaction temperature was 260 ℃. The conversion of dimethyl oxalate was 100%, and the selectivity of methyl acetate was 71.0%.
Example 2
7.55g of copper nitrate trihydrate was dissolved in 100mL of deionized water at room temperature to prepare a copper nitrate solution. To the copper nitrate solution were added an amount of ammonia water and 7.95g of silica so as to have a pH of 8 to 12, and the resulting mixture was sonicated at room temperature for 3 hours, followed by vigorous stirring at 1200 rpm for 3 hours at 35 ℃. The temperature was then increased to 90 ℃ until the pH was at the end of 7. Placing the obtained mixture into a hydrothermal reaction kettle, treating at 120deg.C for 3 hr, filtering, washing with deionized water to obtain solid, drying at 150deg.C for 24 hr, calcining at 450deg.C for 5 hr, dissolving 0.067g ammonium metatungstate in 50ml deionized water to obtain ammonium metatungstate solution, and atomizing with ultrasonic atomizerChemical conversion and subsequent contact with Cu/SiO 2 The precursors are mixed, and the ammonium metatungstate component is loaded by utilizing strong electrostatic acting force between the precursors. And then standing the mixture at room temperature, and drying in the shade for 48 hours to obtain a loaded solid. The resulting supported solid was dried at 150℃for 24h. Then roasting for 4 hours at 550 ℃ in a muffle furnace to obtain the catalyst 20Cu-0.5W/SiO 2 。
Filling 1.0g of the catalyst into a fixed bed reaction tube, filling the whole reaction tube with quartz sand, and reducing the catalyst with H as the reducing gas 2 H at 5% v/v 2 Ar gas mixture, gas space velocity of the gas mixture is 200h -1 The reduction pressure is 0.5MPa, the reduction temperature is 280 ℃, the heating rate is 5 ℃/min, and the reduction time is 8h. Switching gas to H after reduction 2 Raising the pressure to 5.0MPa, pumping a methanol solution of dimethyl oxalate (DMO) with the mass fraction of 20% by using a horizontal pump, wherein the liquid hourly space velocity of the DMO is 0.8h -1 ，H 2 The molar ratio of/DMO was 400:1 and the reaction temperature was 280 ℃. The conversion of dimethyl oxalate was 100%, and the selectivity to ethanol was 94.0%.
Example 3
7.55g of copper nitrate trihydrate was dissolved in 100mL of deionized water at room temperature to prepare a copper nitrate solution. To the copper nitrate solution were added a certain amount of ammonia water and 7.8g of zinc oxide so as to have a pH of 8 to 12, and the resulting mixture was sonicated at room temperature for 3 hours, followed by vigorous stirring at 1500 rpm for 5 hours at 45 ℃. The temperature was then increased to 80 ℃ until the pH was at the end of 7. The obtained mixture is placed into a hydrothermal reaction kettle to be treated for 3 hours at 150 ℃, filtered and washed by deionized water to obtain a solid, the obtained solid is dried for 12 hours at 150 ℃ and calcined for 5 hours at 450 ℃, 0.268g of ammonium metatungstate is dissolved in 50mL of deionized water to prepare an ammonium metatungstate solution, the ammonium metatungstate solution is atomized by an ultrasonic atomizer, the ammonium metatungstate solution is mixed with a Cu/ZnO precursor, and an ammonium metatungstate component is loaded by utilizing strong electrostatic force between the ammonium metatungstate solution and the Cu/ZnO precursor. And then standing the mixture at room temperature, and drying in the shade for 48 hours to obtain a loaded solid. The resulting supported solid was dried at 150℃for 24h. And then roasting for 6 hours at 550 ℃ in a muffle furnace to obtain the catalyst 20Cu-2W/ZnO.
1.0g of the catalyst is filled into a fixed bed reaction tube, and quartz sand is used for filling the whole reactionTube for reducing catalyst and reducing gas into H 2 H at 5% v/v 2 Ar gas mixture, gas space velocity of the gas mixture is 100h -1 The reduction pressure is 0.5MPa, the reduction temperature is 300 ℃, the heating rate is 10 ℃/min, and the reduction time is 6h. Switching gas to H after reduction 2 Boosting to 6.0MPa, pumping into methanol solution of dimethyl oxalate (DMO) with mass fraction of 20% by using a horizontal pump, and controlling the liquid hourly space velocity of DMO to 2.0h -1 ，H 2 The molar ratio of/DMO was 20:1 and the reaction temperature was 260 ℃. The conversion of dimethyl oxalate was 100%, and the selectivity of methyl acetate was 60.3%.
In this example, the DMO liquid hourly space velocity was 0.8h, except that the conditions were the same -1 ，H 2 The molar ratio of/DMO was 300:1 and the reaction temperature was 320 ℃. The conversion of dimethyl oxalate was 100%, and the selectivity to ethanol was 93.6%.
Example 4
7.55g of copper nitrate trihydrate was dissolved in 100mL of deionized water at room temperature to prepare a copper nitrate solution. To the copper nitrate solution, a certain amount of ammonia water and 7.5g of zirconia were added so that the pH was 8 to 12, and the resultant mixture was sonicated at room temperature for 3 hours, followed by vigorous stirring at 1800 rpm for 3.5 hours at 35 ℃. The temperature was then increased to 90 ℃ until the pH was over to 6.5. Placing the obtained mixture into a hydrothermal reaction kettle, treating for 3 hours at 140 ℃, filtering, washing with deionized water to obtain a solid, drying the obtained solid at 150 ℃ for 12 hours, calcining at 450 ℃ for 5 hours, dissolving 0.67g of ammonium metatungstate into 50mL of deionized water to prepare an ammonium metatungstate solution, atomizing the ammonium metatungstate solution by an ultrasonic atomizer, and then mixing the ammonium metatungstate solution with Cu/ZrO 2 The precursors are mixed, and the ammonium metatungstate component is loaded by utilizing strong electrostatic acting force between the precursors. And then standing the mixture at room temperature, and drying in the shade for 48 hours to obtain a loaded solid. The resulting supported solid was dried at 150℃for 8h. Then roasting for 4 hours at 550 ℃ in a muffle furnace to obtain the catalyst 20Cu-5W/ZrO 2 。
Filling 1.0g of the catalyst into a fixed bed reaction tube, filling the whole reaction tube with quartz sand, and reducing the catalyst with H as the reducing gas 2 H at 5% v/v 2 Ar gas mixture, gas space velocity of the gas mixture is 100h -1 The reduction pressure is 0.5MPa, the reduction temperature is 230 ℃, the heating rate is 2 ℃/min, and the reduction time is 2h. Switching gas to H after reduction 2 Raising the pressure to 4.0MPa, pumping a methanol solution of dimethyl oxalate (DMO) with the mass fraction of 20% by using a horizontal pump, wherein the liquid hourly space velocity of the DMO is 2.5h -1 ，H 2 The molar ratio of/DMO was 30:1, the reaction temperature was 230 ℃, the conversion of dimethyl oxalate was 100%, and the selectivity of methyl acetate was 70%.
In this example, the DMO liquid hourly space velocity was 0.8h, except that the conditions were the same -1 ，H 2 The molar ratio of/DMO was 350:1 and the reaction temperature was 310 ℃. The conversion of dimethyl oxalate was 100% and the selectivity to ethanol was 71.2%.
Example 5
7.55g of copper nitrate trihydrate was dissolved in 100mL of deionized water at room temperature to prepare a copper nitrate solution. To the copper nitrate solution, a certain amount of ammonia water and 7.8g of cerium oxide were added so that the pH was 8 to 12, and the resultant mixture was sonicated at room temperature for 5 hours, followed by vigorous stirring at 1300 rpm for 5 hours at 35 ℃. The temperature was then increased to 80 ℃ until the pH was at the end of 7. Placing the obtained mixture into a hydrothermal reaction kettle, treating for 3 hours at 140 ℃, filtering, washing with deionized water to obtain a solid, drying the obtained solid at 130 ℃ for 12 hours, calcining at 450 ℃ for 5 hours, dissolving 0.268g of ammonium metatungstate into 50mL of deionized water to prepare an ammonium metatungstate solution, atomizing the ammonium metatungstate solution by an ultrasonic atomizer, and then mixing the ammonium metatungstate solution with Cu/CeO 2 The precursors are mixed, and the ammonium metatungstate component is loaded by utilizing strong electrostatic acting force between the precursors. And then standing the mixture at room temperature, and drying in the shade for 48 hours to obtain a loaded solid. The resulting supported solid was dried at 150℃for 12h. Then roasting for 4 hours at 550 ℃ in a muffle furnace to obtain the catalyst 20Cu-2W/CeO 2 。
Filling 1.0g of the catalyst into a fixed bed reaction tube, filling the whole reaction tube with quartz sand, and reducing the catalyst with H as the reducing gas 2 H at 5% v/v 2 Ar gas mixture, gas space velocity of the gas mixture is 50h -1 The reduction temperature of the reduction pressure of 0.5MPa is 230 ℃, the heating rate is 2 ℃/min, and the reduction time is 2h. Switching gas to H after reduction 2 Boosting to 3.0MPa, using flatPumping a methanol solution of dimethyl oxalate (DMO) with the mass fraction of 20% into a flow pump, wherein the liquid hourly space velocity of DMO is 2.5h -1 ，H 2 The molar ratio of/DMO was 50:1 and the reaction temperature was 250 ℃. The conversion rate of the dimethyl oxalate is 100%, the selectivity of the methyl acetate is 61.2%,
in this example, the DMO liquid hourly space velocity was 1.0h, except that the conditions were the same -1 ，H 2 The molar ratio of/DMO was 500:1 and the reaction temperature was 300 ℃. The conversion of dimethyl oxalate was 100%, and the selectivity to ethanol was 92.8%.
Example 6
7.55g of copper nitrate trihydrate was dissolved in 100mL of deionized water at room temperature to prepare a copper nitrate solution. To the copper nitrate solution, a certain amount of ammonia water and 7.95g of magnesium oxide were added so that the pH was 8 to 12, and the resultant mixture was sonicated at room temperature for 4 hours, followed by vigorous stirring at 1300 rpm for 4 hours at 35 ℃. The temperature was then increased to 80 ℃ until the pH was at the end of 7. The obtained mixture is placed into a hydrothermal reaction kettle for 5 hours at 140 ℃, filtered and washed by deionized water to obtain a solid, the obtained solid is dried at 150 ℃ for 12 hours and calcined at 450 ℃ for 5 hours, 0.067g of ammonium metatungstate is dissolved in 50mL of deionized water to prepare an ammonium metatungstate solution, the ammonium metatungstate solution is atomized by an ultrasonic atomizer, the ammonium metatungstate solution is then mixed with a Cu/MgO precursor, and an ammonium metatungstate component is loaded by utilizing strong electrostatic force between the ammonium metatungstate solution and the Cu/MgO precursor. And then standing the mixture at room temperature, and drying in the shade for 48 hours to obtain a loaded solid. The resulting supported solid was dried at 150℃for 12h. Then roasting for 4 hours at 550 ℃ in a muffle furnace to obtain the catalyst 20Cu-0.5W/MgO.
Filling 1.0g of the catalyst into a fixed bed reactor, filling the whole reaction tube with quartz sand, and reducing the catalyst with H as the reducing gas 2 H at 5% v/v 2 Ar gas mixture, gas space velocity of the gas mixture is 150h -1 The reduction pressure is 0.5MPa, the reduction temperature is 230 ℃, the heating rate is 2 ℃/min, and the reduction time is 2h. Switching gas to H after reduction 2 Raising the pressure to 4.0MPa, pumping a methanol solution of 20% by mass of dimethyl oxalate (DMO) by using a horizontal pump, wherein the liquid hourly space velocity of the DMO is 2.0h -1 ，H 2 The molar ratio of/DMO is 100:1, the reaction temperature is 220 ℃,the conversion rate of the dimethyl oxalate is 100%, the selectivity of the methyl acetate is 50.6%,
in this example, the DMO liquid hourly space velocity was 0.8h, except that the conditions were the same -1 ，H 2 The molar ratio of/DMO was 400:1 and the reaction temperature was 300 ℃. The conversion of dimethyl oxalate was 100%, and the selectivity to ethanol was 91.5%.
Example 7
7.55g of copper nitrate trihydrate was dissolved in 100mL of deionized water at room temperature to prepare a copper nitrate solution. To the copper nitrate solution, a certain amount of ammonia water and 7g of aluminum oxide were added so that the pH was 8 to 12, and stirred at room temperature for 12 hours. The temperature was then increased to 80 ℃ until the pH was at the end of 7. The obtained mixture was centrifugally filtered and washed to obtain a solid, the obtained solid was then dried at 150℃for 12 hours and calcined at 450℃for 5 hours, 1.34g of ammonium metatungstate was dissolved in 50mL of deionized water to prepare an ammonium metatungstate solution, which was atomized by an ultrasonic atomizer, followed by Cu/Al reaction 2 O 3 The precursors are mixed, and the ammonium metatungstate component is loaded by utilizing strong electrostatic acting force between the precursors. The mixture was then left to stand at room temperature and dry in the shade for 48h. The resulting solid was dried at 150℃for 12h. Then roasting for 4 hours at 550 ℃ in a muffle furnace to obtain the catalyst 20Cu-10W/Al 2 O 3 。
Filling 1.0g of the catalyst into a fixed bed reactor, filling the whole reaction tube with quartz sand, and reducing the catalyst with H as the reducing gas 2 H at 5% v/v 2 Ar gas mixture, gas space velocity of the gas mixture is 50h -1 The reduction pressure is 0.3MPa, the reduction temperature is 250 ℃, the heating rate is 5 ℃/min, and the reduction time is 4 hours. Switching gas to H after reduction 2 Raising the pressure to 2.0MPa, pumping a methanol solution of dimethyl oxalate (DMO) with the mass fraction of 20% by using a horizontal pump, wherein the liquid hourly space velocity of the DMO is 4.0h -1 ，H 2 The molar ratio of/DMO is 30:1, the reaction temperature is 200 ℃, the conversion rate of dimethyl oxalate is 100%, the selectivity of methyl acetate is 70.6%,
in this example, the DMO liquid hourly space velocity was 0.8h, except that the conditions were the same -1 ，H 2 The molar ratio of/DMO was 300:1 and the reaction temperature was 260 ℃. Oxalic acid dimethyl esterThe conversion of (2) was 100%, and the selectivity to ethanol was 67.8%.
Example 8
Stability tests were performed on the catalysts of examples 1 and 2, and experiments found that under the same reduction and reaction conditions of the respective examples, analysis of catalyst performance showed that the catalyst did not find significant deactivation of the catalyst after 1000 hours of reaction, as shown in fig. 4a and 4 b. This indicates that the two catalysts have excellent catalytic stability properties.
Comparative example 1
Preparation of 20Cu-10W/SiO by conventional Co-impregnation 2 The catalyst comprises the following specific steps: firstly, 7g of SiO is taken 2 21g of water was added and SiO was observed 2 Just completely absorbing water; 7.55g of copper nitrate trihydrate and 1.34g of ammonium metatungstate are dissolved in 21g of water, and 7g of SiO are added 2 Airing under natural condition, putting into a baking oven at 100 ℃ for drying for 8 hours, and then roasting in a muffle furnace at 550 ℃ for 4 hours to obtain 20Cu-10W/SiO 2 The catalyst was subjected to catalytic performance testing under the reduction and reaction conditions of example 1. The conversion of dimethyl oxalate was 100%, and the selectivity of methyl acetate was 50.8%.
Comparative example 2
Preparation of 20Cu-0.5W/SiO by conventional Co-impregnation 2 The catalyst comprises the following specific steps: first 7.95g SiO was taken 2 23.85g of water was added and SiO was observed 2 Just completely absorbing water; 7.55g of copper nitrate trihydrate and 0.067g of ammonium metatungstate are dissolved in 23.8g of water, and 7g of SiO are added 2 Airing under natural condition, drying in oven at 100deg.C for 8 hr, and roasting in muffle furnace at 550deg.C for 4 hr to obtain 20Cu-0.5W/SiO 2 The catalyst was subjected to catalytic performance testing under the reduction and reaction conditions of example 2. The conversion of dimethyl oxalate was 100%, and the selectivity to ethanol was 60.5%.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. A catalyst for preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate is characterized in that: the catalyst comprises an active component, an auxiliary component and a carrier, wherein the active component is a simple substance or oxide of Cu, the auxiliary component is a simple substance or oxide of W, a high active site is a Cu-W alloy interface and Cu and W metals independently, and the carrier is one or more than two of silicon dioxide, aluminum oxide, zirconium oxide, zinc oxide, magnesium oxide and cerium oxide;
the catalyst is prepared by the following steps:
(I) Mixing soluble salt of copper, deionized water, ammonia water and a carrier to prepare a mixture, so that the pH of the mixture is 8-12;
(II) sonicating the mixture from step (I) at room temperature for 3-5 hours, followed by vigorous stirring at 25-45℃for 3-5 hours at 1000-2000 rpm;
(III) heating and evaporating the mixture treated in the step (II) at 70-90 ℃ until the pH of the mixture is 6-7, and then placing the mixture into a hydrothermal reaction kettle for treatment at 120-180 ℃ for 3-8 hours;
(IV) filtering the mixture treated in the step (III), and washing with deionized water to obtain a solid;
(V) drying the solid obtained in the step (IV) at 120-150 ℃ for 6-24h, and calcining at 300-600 ℃ for 2-10h to obtain a Cu/carrier precursor; atomizing the soluble salt solution of W into micron-sized W salt mist drops through an ultrasonic atomization generator, and adsorbing and loading the micron-sized W salt mist drops through electrostatic acting force between a Cu/carrier precursor and the micron-sized mist drops to obtain a load;
(VI) naturally drying the load obtained in the step (V) in the shade for 24-48 hours to obtain a load solid;
(VII) drying the loaded solid obtained in the step (VI) at 100-150 ℃ for 6-24h, and roasting at 300-650 ℃ for 2-12h to obtain the catalyst Cu-W/SiO 2 。
2. The catalyst for preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate according to claim 1, wherein the catalyst is characterized by: when the catalyst is used for selectively preparing methyl acetate, the content of the first active component is 1-30% by mass of Cu elementary substance; the second active component accounts for 5-20% of the mass of the W simple substance; the rest is carrier.
3. The catalyst for preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate according to claim 1, wherein the catalyst is characterized by: when the catalyst is used for selectively preparing ethanol, the content of the first active component is 5-30% by mass of the Cu elementary substance; the second active component accounts for 0.05-3% of the mass of the W simple substance; the rest is carrier.
4. The catalyst for preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate according to claim 1, wherein the catalyst is characterized by: the soluble salt of copper in the step (I) is one or more than two of copper nitrate, copper chloride, copper sulfate or copper acetate.
5. The catalyst for preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate according to claim 1, wherein the catalyst is characterized by: the soluble salt of tungsten in the step (V) is one or more than two of ammonium tungstate, ammonium meta-tungstate, sodium tungstate, cobalt tungstate or ferrous tungstate.
6. A process for preparing the catalyst for preparing methyl acetate or alcohol by hydrogenating dimethyl oxalate according to any one of claims 1-5,
the preparation method comprises the following steps:
(I) Mixing soluble salt of copper, deionized water, ammonia water and a carrier to prepare a mixture, so that the pH of the mixture is 8-12;
(II) sonicating the mixture from step (I) at room temperature for 3-5 hours, followed by vigorous stirring at 25-45℃for 3-5 hours at 1000-2000 rpm;
(III) heating and evaporating the mixture treated in the step (II) at 70-90 ℃ until the pH of the mixture is 6-7, and then placing the mixture into a hydrothermal reaction kettle for treatment at 120-180 ℃ for 3-8 hours;
(IV) filtering the mixture treated in the step (III), and washing with deionized water to obtain a solid;
(V) drying the solid obtained in the step (IV) at 120-150 ℃ for 6-24h, and calcining at 300-600 ℃ for 2-10h to obtain a Cu/carrier precursor; atomizing the soluble salt solution of W into micron-sized W salt mist drops through an ultrasonic atomization generator, and adsorbing and loading the micron-sized W salt mist drops through electrostatic acting force between a Cu/carrier precursor and the micron-sized mist drops to obtain a load;
(VI) naturally drying the load obtained in the step (V) in the shade for 24-48 hours to obtain a load solid;
(VII) drying the loaded solid obtained in the step (VI) at 100-150 ℃ for 6-24h, and roasting at 300-650 ℃ for 2-12h to obtain the catalyst Cu-W/SiO 2 。
7. The method of manufacturing according to claim 6, wherein: the soluble salt of copper in the step (I) is one or more than two of copper nitrate, copper chloride, copper sulfate or copper acetate; the soluble salt of tungsten in the step (V) is one or more than two of ammonium tungstate, ammonium meta-tungstate, sodium tungstate, cobalt tungstate or ferrous tungstate.
8. Use of the catalyst according to any one of claims 1-5 for the hydrogenation of dimethyl oxalate to methyl acetate, characterized in that: firstly, filling the catalyst into a reaction tube, filling the whole reaction tube with quartz sand, activating the catalyst in hydrogen or hydrogen inert gas mixture before use, adjusting to a specified reaction condition after activation, and pumping dimethyl oxalate or a mixture of dimethyl oxalate and a methanol solvent, wherein the reaction condition is as follows: the temperature is 120-350 ℃, the pressure is 0.3-6.0MPa, and the liquid hourly space velocity of the dimethyl oxalate is 0.01-6.0h -1 The molar ratio of the hydrogen to the dimethyl oxalate is 5:1-800:1.
9. Use of the catalyst according to any one of claims 1-5 for the hydrogenation of dimethyl oxalate to ethanol, characterized in that: the catalyst is firstly filled in a reaction tube, the whole reaction tube is filled with quartz sand, the catalyst is filled in the reaction tubeBefore the catalyst is used, the catalyst is activated in hydrogen or hydrogen inert gas mixture, after the activation is finished, the reaction condition is regulated to a specified reaction condition, dimethyl oxalate or a mixture of dimethyl oxalate and a methanol solvent is pumped in, and the reaction condition is as follows: the temperature is 250-350 ℃, the pressure is 3.0-6.0Mpa, and the liquid hourly space velocity of dimethyl oxalate is 0.01-2h -1 The molar ratio of the hydrogen to the dimethyl oxalate is 300:1-800:1; wherein the preferred reaction conditions for the preparation of methyl acetate are: the temperature is 120-280 ℃, the pressure is 0.3-2.0Mpa, and the liquid hourly space velocity of dimethyl oxalate is 2-6h -1 The molar ratio of the hydrogen to the dimethyl oxalate is 5:1-300:1.
10. Use according to claim 8 or 9, characterized in that: the catalyst activation condition is that the pressure is 0.1-0.5MPa and the gas space velocity is 10-300h -1 The activation temperature is 160-300 ℃, the temperature rising rate is 0.1-20 ℃/min, and the activation time is 0.5-8h.
CN202310700237.XA 2023-06-14 2023-06-14 Catalyst for preparing methyl acetate or ethanol by hydrogenating dimethyl oxalate, and preparation method and application thereof Pending CN116713003A (en)

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