CN116162023A - Method for preparing ethyl acetate by alcohol dehydrogenation condensation - Google Patents

Method for preparing ethyl acetate by alcohol dehydrogenation condensation Download PDF

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Publication number
CN116162023A
CN116162023A CN202111401014.0A CN202111401014A CN116162023A CN 116162023 A CN116162023 A CN 116162023A CN 202111401014 A CN202111401014 A CN 202111401014A CN 116162023 A CN116162023 A CN 116162023A
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oxide
ethanol
reaction
ethyl acetate
catalyst
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王峰
王业红
张健
张志鑫
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—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
    • 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

Abstract

The invention relates to a method for preparing ethyl acetate by alcohol dehydrogenation and condensation. The method adopts ethanol or ethanol aqueous solution as a reactant, and prepares the ethyl acetate through anaerobic dehydrogenation condensation reaction under the catalysis of a copper-based acid-base bifunctional catalyst. The reaction conditions are as follows: the reaction is carried out in a fixed bed reactor under normal pressure, the reaction temperature is 220-350 ℃, and the ethanol feeding mass airspeed is 0.5-3.5 h ‑1 . The method is characterized in that: the heterogeneous copper-based acid-base dual-function catalyst is nontoxic, the preparation is simple, the high selectivity of ethanol is catalyzed to generate ethyl acetate, meanwhile, hydrogen is co-produced, the highest selectivity of ethyl acetate can reach 95%, the highest conversion rate of ethanol can reach 75%, and the catalyst has better stabilityAnd (5) qualitative property.

Description

Method for preparing ethyl acetate by alcohol dehydrogenation condensation
Technical Field
The invention relates to a preparation method of ethyl acetate, in particular to a preparation method of ethyl acetate by taking ethanol as a reactant through a direct dehydrogenation condensation process.
Background
Ethyl acetate is one of the most widely used fatty acid esters, has excellent solubility, is an important green industrial solvent which is quick-dried, and is widely used in the production process of chemical products such as acetate fiber, ethyl fiber, chlorinated rubber, vinyl resin, synthetic rubber, paint and the like; as industrial solvents for products such as paints, adhesives, ethylcellulose, artificial leather, linoleum colorants, and artificial fibers; as a binder for the production of printing inks and artificial pearls; as extractant for the production of medicine, organic acid and other products; the perfume raw material is a main raw material of fruit flavors such as pineapple, banana and strawberry, and perfumes such as whiskey and cream.
The production method of ethyl acetate is mainly based on the traditional esterification method. Although domestic large-scale methanol oxo-acetic acid enterprises or enterprises with bioethanol devices provide rich and cheap acetic acid and ethanol raw materials, the esterification process still has a plurality of defects of low utilization rate of acetic acid, unfriendly environment and the like. Although the production process is relatively mature, the technical threshold is low, and the process and the production technology tend to be stable, the prior art cannot meet the demands more and more from the market demands and the interests of manufacturers. Therefore, the development of the ethyl acetate production process with high efficiency, energy conservation and small environmental load has practical significance. The route for preparing the ethyl acetate by the alcohol dehydrogenation condensation one-step method has high economy and is environment-friendly, and is an ideal route for preparing the ethyl acetate. The method for preparing ethyl acetate by alcohol dehydrogenation condensation takes alcohol as a raw material, and synthesizes the ethyl acetate by one-step dehydrogenation through gas-solid phase reaction, and has the advantages of simple flow, green process and easy separation of products and catalysts. In 2001, davy uses a toxic copper-chromium catalyst to perform a reaction for preparing ethyl acetate by alcohol dehydrogenation condensation, the selectivity of ethyl acetate is about 94%, but the conversion rate of alcohol is only about 27%. The selectivity of ethyl acetate is 90-95% by copper zinc aluminum zirconium catalyst adopted by Japan asphyxin petrochemical company, but the ethanol conversion rate is 45%.
Although the catalyst realizes the preparation of ethyl acetate by alcohol dehydrogenation condensation, the adopted catalyst has low conversion rate of toxic or alcohol. Therefore, the development of a solid catalyst system which is nontoxic, easy to obtain, high in reaction activity and good in selectivity has important significance.
Disclosure of Invention
The method has the significance of overcoming the defects existing in the current process of preparing the ethyl acetate by directly dehydrogenating and condensing the ethanol. The preparation method has the advantages of simple reaction process, non-toxic catalyst, high selectivity to ethyl acetate, good stability and long service life.
The ethyl acetate according to the present invention is prepared by the following scheme.
Ethanol is used as a raw material, the reaction is carried out in a fixed bed reactor, a multiphase copper-based acid-base bifunctional catalyst is filled in a reaction tube, and then the reaction tube is placed in the fixed bed reactor, wherein the reaction temperature is 220-350 ℃. The copper-based acid-base bifunctional catalyst consists of active Cu and acid-base metal oxide; the copper-based acid-base bifunctional catalyst comprises one, two or more than two of zirconium oxide, yttrium oxide, ytterbium oxide, indium oxide, tungsten oxide, scandium oxide, tantalum oxide, niobium oxide, gallium oxide, tin oxide and aluminum oxide; the alkaline oxide is one, two or more of zinc oxide, cerium oxide, lanthanum oxide, praseodymium oxide, magnesium oxide and strontium oxide. The copper-based acid-base bifunctional catalyst has an active metal Cu content of 5-35 wt% (based on weight). The copper-based acid-base bifunctional catalyst, wherein the content of the active metal Cu is preferably 10-25 percent (by weight). The acid metal content is as follows: 45wt% to 90wt% (based on weight). The thickness of the catalyst bed layer filled in the reaction tube is 5 cm-30 cm, the reaction is normal pressure, and the feeding mass airspeed of the ethanol is 0.5-3.5 h -1 . The preferred reaction conditions are: the thickness of the catalyst bed layer filled in the reaction tube is 10 cm-25 cm, and the space velocity of the ethanol feeding mass is 0.5-3.5 h -1 . The ethanol can be absolute ethanol or ethanol water solution, and the water content is 1.0-10% (by weight). The reaction temperature for preparing ethyl acetate by alcohol dehydrogenation condensation is 220-260 ℃.
The multiphase copper-based acid-base bifunctional catalyst for catalyzing alcohol to dehydrogenate and condense to prepare ethyl acetate has the following characteristics: (1) the introduction of active Cu promotes the dehydrogenation of ethanol; (2) The proper Lewis site on the surface of the oxide carrier is derived from coordination unsaturated metal ions on the surface, and the site acts with active Cu species to generate electron transfer, so that the active Cu species are dispersed, the sintering of Cu ions in the reaction process is avoided, the stability is improved, the dehydrogenation activity of Cu is partially inhibited, the excessive dehydrogenation of ethanol is avoided, and the dehydrogenation selectivity is improved; (3) The balance of acid and alkali in the heterogeneous copper-based acid-base bifunctional catalyst is important, and the excessive acidity causes ethanol dehydration side reaction; excessive dehydrogenation is initiated by the over-strong alkalinity, so that ethanol is decomposed; the balance of acid-base sites can promote the condensation of acetaldehyde obtained by ethanol dehydrogenation and ethanol into hemiacetal, and then the dehydrogenation is carried out to obtain ethyl acetate. Wherein the combination and the content of metal oxides in the heterogeneous copper-based acid-base bifunctional catalyst are critical factors.
The method has the advantages that: (1) The heterogeneous copper-based acid-base bifunctional catalyst is used for catalyzing alcohol to prepare ethyl acetate by dehydrogenation and condensation, the catalyst is simple to prepare and can catalyze the reaction with high efficiency, and the catalyst can be activated and regenerated through simple roasting and reduction operation. (2) The process for preparing ethyl acetate by catalyzing alcohol dehydrogenation condensation by the catalytic system has certain superiority, the selectivity of target products is up to 95%, the conversion rate is up to 75%, and hydrogen is coproduced.
Detailed Description
For further detailed description of the present invention, several specific embodiments are given below, but the present invention is not limited to these embodiments.
Carrying out reaction in a fixed bed reactor, filling a catalyst in a reaction tube, and then placing the reaction tube in the fixed bed reactor;
example 1
10wt％Cu-80wt％ZrO 2 -10wt％CeO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: copper nitrate trihydrate 7.6g, cerium nitrate hexahydrate 5.0g and zirconyl nitrate 30.0g were weighed and dissolved together in 200 ml of water, and aqueous NaOH (3 mol/L) solution adjusted ph=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-80wt% ZrO 2 -10wt％CeO 2 A catalyst. Screening 14-25 mesh catalyst, filling into reaction tube, and filling 15cm bed layer with 5% raw materialThe ethanol aqueous solution (weight concentration, same applies below) had a mass space velocity of 1.5h -1 . The reaction was carried out at 230℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 2
10wt％Cu-80wt％In 2 O 3 -10wt％CeO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: 7.6g of copper nitrate trihydrate, 5.0g of cerium nitrate hexahydrate and 34.6g of indium nitrate hydrate were weighed and dissolved in 200 ml of water, and an aqueous solution of NaOH (3 mol/L) was used to adjust the pH=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-80wt% in 2 O 3 -10wt％CeO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 15cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 230℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 3
10wt％Cu-80wt％In 2 O 3 -10wt％PrO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: 3.0g of copper nitrate trihydrate, 5.0g of praseodymium nitrate hydrate and 34.6g of indium nitrate hydrate are weighed and dissolved in 200 ml of water, and an aqueous solution of NaOH (3 mol/L) adjusts the pH value to be 10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-80wt% in 2 O 3 -10wt％PrO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 15cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 230℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 4
10wt％Cu-10wt％La 2 O 3 -80wt％ZrO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: 3.0g of copper nitrate trihydrate and nitric acid are weighedZirconyl 30.0g, lanthanum nitrate hydrate 5.4g and zirconyl nitrate 15.0g were dissolved in 200 ml of water, and aqueous NaOH (3 mol/L) solution adjusted ph=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt percent of Cu-10wt percent of La 2 O 3 -80wt％ZrO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 15cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 230℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 5
10wt％Cu-10wt％ZnO-80wt％ZrO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: copper nitrate trihydrate 3.0g, zinc nitrate hexahydrate 7.3 and zirconyl nitrate 15.0g were weighed and dissolved together in 200 ml of water, and aqueous NaOH (3 mol/L) solution adjusted ph=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-10wt% Sn-80wt% ZrO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 15cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 230℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 6
10wt％Cu-10wt％SrO-80wt％Y 2 O 3 Adopts a coprecipitation method for preparation. The specific operation is as follows: copper nitrate trihydrate 3.0g, yttrium nitrate hexahydrate 54g and strontium nitrate 4.1g were weighed and dissolved together in 200 ml of water, and aqueous NaOH (3 mol/L) solution was used to adjust ph=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt percent Cu-10wt percent SrO-80wt percent Y 2 O 3 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 15cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . Reacting at 230 DEG CThe conversion of ethanol and the selectivity of ethyl acetate were analyzed by sample chromatography after 2 hours and are shown in the following Table 1.
Example 7
5wt％Cu-84wt％In 2 O 3 -11wt％CeO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: copper nitrate trihydrate 3.8g, cerium nitrate hexahydrate 5.5g and indium nitrate hydrate 36.3g were weighed and dissolved together in 200 ml of water, and aqueous NaOH (3 mol/L) solution adjusted ph=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 5wt% Cu-84wt% in 2 O 3 -11wt％CeO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 15cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 230℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 8
20wt％Cu-71wt％In 2 O 3 -9wt％CeO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: 15.2g of copper nitrate trihydrate, 4.5g of cerium nitrate hexahydrate and 30.7g of indium nitrate hydrate were weighed and dissolved in 200 ml of water, and an aqueous solution of NaOH (3 mol/L) was used to adjust the pH=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 20wt% Cu-71wt% in 2 O 3 -9wt％CeO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 15cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 230℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 9
10wt％Cu-80wt％In 2 O 3 -10wt％CeO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: weighing 7.6g of copper nitrate trihydrate, 5.0g of cerium nitrate hexahydrate and 34.6g of indium nitrate hydrate, dissolving in 200 ml of water, and adjusting the pH value by using a NaOH (3 mol/L) aqueous solution=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-80wt% in 2 O 3 -10wt％CeO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 15cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 240℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 10
10wt％Cu-80wt％In 2 O 3 -10wt％CeO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: 7.6g of copper nitrate trihydrate, 5.0g of cerium nitrate hexahydrate and 34.6g of indium nitrate hydrate were weighed and dissolved in 200 ml of water, and an aqueous solution of NaOH (3 mol/L) was used to adjust the pH=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-80wt% in 2 O 3 -10wt％CeO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 15cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 220℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 11
10wt％Cu-80wt％In 2 O 3 -10wt％CeO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: 7.6g of copper nitrate trihydrate, 5.0g of cerium nitrate hexahydrate and 34.6g of indium nitrate hydrate were weighed and dissolved in 200 ml of water, and an aqueous solution of NaOH (3 mol/L) was used to adjust the pH=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-80wt% in 2 O 3 -10wt％CeO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 10cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . Reacting at 220 deg.C, sampling and chromatographic analysis after 2h reaction, and thenThe conversion of alcohol and the selectivity to ethyl acetate are shown in Table 1.
Example 12
10wt％Cu-80wt％In 2 O 3 -10wt％CeO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: 7.6g of copper nitrate trihydrate, 5.0g of cerium nitrate hexahydrate and 34.6g of indium nitrate hydrate were weighed and dissolved in 200 ml of water, and an aqueous solution of NaOH (3 mol/L) was used to adjust the pH=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-80wt% in 2 O 3 -10wt％CeO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 20cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 220℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 13
10wt％Cu-45wt％In 2 O 3 -45wt％CeO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: 7.6g of copper nitrate trihydrate, 22.5g of cerium nitrate hexahydrate and 19.5g of indium nitrate hydrate were weighed and dissolved in 200 ml of water, and an aqueous solution of NaOH (3 mol/L) was used to adjust the pH=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-45wt% in 2 O 3 -45wt％CeO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 10cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 220℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 14
10wt％Cu-70wt％In 2 O 3 -20wt％CeO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: 7.6g of copper nitrate trihydrate, 10.0g of cerium nitrate hexahydrate and 30.3g of indium nitrate hydrate were weighed and dissolved in 200 ml of water, and an aqueous solution of NaOH (3 mol/L) was used to adjust ph=10. Old in 80 ℃ oil bathStirring for 2h, filtering and washing to neutrality. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-70wt% in 2 O 3 -20wt％CeO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 10cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 220℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 15
10wt％Cu-80wt％In 2 O 3 -10wt％CeO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: 7.6g of copper nitrate trihydrate, 5.0g of cerium nitrate hexahydrate and 34.6g of indium nitrate hydrate were weighed and dissolved in 200 ml of water, and an aqueous solution of NaOH (3 mol/L) was used to adjust the pH=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-80wt% in 2 O 3 -10wt％CeO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 10cm bed, wherein the raw material is 10% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 220℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 16
10wt％Cu-80wt％In 2 O 3 -10wt％CeO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: 7.6g of copper nitrate trihydrate, 5.0g of cerium nitrate hexahydrate and 34.6g of indium nitrate hydrate were weighed and dissolved in 200 ml of water, and an aqueous solution of NaOH (3 mol/L) was used to adjust the pH=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-80wt% in 2 O 3 -10wt％CeO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 10cm bed layer, wherein the raw material is absolute ethyl alcohol, and the mass space velocity is 1.5h -1 . Reacting at 220 deg.C, sampling and chromatographic analysis after 2h reaction, ethanol conversion rate and ethyl acetate selectionThe selectivity is shown in the attached table 1.
Example 17
Collecting the catalyst used in example 2, roasting in a muffle furnace at 500 ℃ for 4h, reducing with hydrogen at 300 ℃ for 1h, filling into a reaction tube, filling a 15cm bed, and taking 5% ethanol water solution as raw material with a mass space velocity of 1.5h -1 . The reaction was carried out at 230℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 18
Collecting the catalyst used in example 17, roasting in a muffle furnace at 500 ℃ for 4h, reducing with hydrogen at 300 ℃ for 1h, filling into a reaction tube, filling a 15cm bed, and taking 5% ethanol water solution as raw material with a mass space velocity of 1.5h -1 . The reaction was carried out at 230℃and after 8 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 19
Collecting the catalyst used in example 18, roasting in a muffle furnace at 500 deg.C for 4h, reducing with hydrogen at 300 deg.C for 1h, filling into a reaction tube, filling into a 15cm bed, and taking 5% ethanol water solution as raw material with mass space velocity of 1.5h -1 . The reaction was carried out at 230℃and after 10 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Example 20
Collecting the catalyst used in example 19, roasting in a muffle furnace at 500 deg.C for 4 hr, reducing with hydrogen at 300 deg.C for 1 hr, filling into a reaction tube, filling into a 15cm bed, and taking 5% ethanol water solution as raw material with mass space velocity of 1.5 hr -1 . The reaction was carried out at 230℃and, after 18 hours of reaction, the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Comparative example 1
10wt％Cu-90wt％In 2 O 3 Adopts a coprecipitation method for preparation. The specific operation is as follows: copper nitrate trihydrate 7.6g and indium nitrate hydrate 38.9g were weighed out and dissolved in 200 ml of water, and aqueous NaOH (3 mol/L) solution adjusted ph=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-90wt% in 2 O 3 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 15cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 230℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Comparative example 2
10wt％Cu-90wt％CeO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: copper nitrate trihydrate 7.6g and cerium nitrate hexahydrate 45.0g were weighed out and dissolved in 200 ml of water, and aqueous NaOH (3 mol/L) solution adjusted ph=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-90wt% CeO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 15cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 230℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Comparative example 3
10wt％Cu-10wt％In 2 O 3 -80wt％CeO 2 Adopts a coprecipitation method for preparation. The specific operation is as follows: 7.6g of copper nitrate trihydrate, 40.0g of cerium nitrate hexahydrate and 4.3g of indium nitrate hydrate were weighed and dissolved in 200 ml of water, and an aqueous solution of NaOH (3 mol/L) was used to adjust the pH=10. Aging and stirring for 2h in an oil bath at 80 ℃, filtering and washing to be neutral. Drying overnight at 80deg.C, 500 deg.C N 2 Roasting for 3h (nitrogen flow rate is 30 ml/min) to obtain 10wt% Cu-10wt% in 2 O 3 -80wt％CeO 2 A catalyst. Screening and filling 14-25 mesh catalyst into a reaction tube, filling a 15cm bed, wherein the raw material is 5% ethanol water solution, and the mass space velocity is 1.5h -1 . The reaction was carried out at 230℃and after 2 hours the reaction was analyzed by sample chromatography, and the conversion of ethanol and the selectivity of ethyl acetate were shown in Table 1.
Table 1. Reaction results of alcohol dehydrocondensation to ethyl acetate catalyzed by copper-based acid-base bifunctional catalyst
Figure BDA0003371522520000081
Figure BDA0003371522520000091
The results show that: the composition and the content of each component of the multiphase copper-based acid-base bifunctional catalyst are key factors influencing the reaction effect. Suitable levels of Cu sites and acid-base sites are critical to achieving high selectivity catalysis, and the absence of acidic sites or basic sites or improper ratios will cause a mismatch in reaction rates, resulting in a significant decrease in ethyl acetate selectivity of the target product. In addition, the reaction temperature, space velocity and other conditions also affect the reaction effect.

Claims (9)

1. A method for preparing ethyl acetate by alcohol dehydrogenation and condensation is characterized in that:
the process for preparing ethyl acetate by dehydrogenating and condensing ethanol comprises the following steps: ethanol is taken as a raw material, and the reaction is carried out in a fixed bed reactor, wherein the reaction temperature is 220-350 ℃;
the heterogeneous copper-based acid-base bifunctional catalyst consists of active Cu and acid-base metal oxide.
2. A method according to claim 1, characterized in that:
the copper-based acid-base bifunctional catalyst consists of active Cu and acid-base metal oxide;
the copper-based acid-base bifunctional catalyst comprises one, two or more than two of zirconium oxide, yttrium oxide, ytterbium oxide, indium oxide, tungsten oxide, scandium oxide, tantalum oxide, niobium oxide, gallium oxide, tin oxide and aluminum oxide;
the alkaline oxide is one, two or more of zinc oxide, cerium oxide, lanthanum oxide, praseodymium oxide, magnesium oxide and strontium oxide.
3. A method according to claim 1 or 2, characterized in that:
the copper-based acid-base bifunctional catalyst comprises 5-35 wt% of active metal Cu;
the mass ratio of the acidic oxide to the basic oxide is 1:1 to 10:1.
4. a method according to claim 1 or 2, characterized in that:
the copper-based acid-base bifunctional catalyst, wherein the content of active metal Cu is preferably 10-25 percent (by weight), and the mass ratio of acid oxide to alkaline oxide is preferably 4:1 to 8:1.
5. a method according to claim 1, characterized in that:
the thickness of the catalyst bed layer is 5 cm-30 cm, the reaction is normal pressure, and the feeding mass airspeed of the ethanol is 0.5-3.5 h -1 。
6. A method according to claim 1 or 5, characterized in that:
the preferred reaction conditions are: the thickness of the catalyst bed layer filled in the reaction tube is 10 cm-25 cm, and the space velocity of the ethanol feeding mass is 1.0-2.0 h -1 。
7. A method according to claim 1 or 5 or 6, characterized in that:
the ethanol can be absolute ethanol or ethanol water solution, and the water content is 1.0-10% (by weight).
8. A method according to claim 1, characterized in that:
the reaction temperature for preparing ethyl acetate by alcohol dehydrogenation condensation is 220-260 ℃.
9. A method according to any one of claims 1-4, characterized in that: the heterogeneous copper-based acid-base bifunctional catalyst is prepared by a coprecipitation method by dissolving Cu, an acidic oxide and a soluble salt corresponding to an alkaline oxide in a solution.
CN202111401014.0A 2021-11-24 2021-11-24 Method for preparing ethyl acetate by alcohol dehydrogenation condensation Pending CN116162023A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117326946A (en) * 2023-12-01 2024-01-02 泰兴金江化学工业有限公司 Method for preparing ethyl acetate from ethanol

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117326946A (en) * 2023-12-01 2024-01-02 泰兴金江化学工业有限公司 Method for preparing ethyl acetate from ethanol
CN117326946B (en) * 2023-12-01 2024-03-22 泰兴金江化学工业有限公司 Method for preparing ethyl acetate from ethanol

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