CN107892643B - Method for producing ethanol from acetic acid - Google Patents

Method for producing ethanol from acetic acid Download PDF

Info

Publication number
CN107892643B
CN107892643B CN201711245380.5A CN201711245380A CN107892643B CN 107892643 B CN107892643 B CN 107892643B CN 201711245380 A CN201711245380 A CN 201711245380A CN 107892643 B CN107892643 B CN 107892643B
Authority
CN
China
Prior art keywords
ethanol
methanol
acetic acid
methyl acetate
reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201711245380.5A
Other languages
Chinese (zh)
Other versions
CN107892643A (en
Inventor
吴永忠
潘勇
张云龙
唐子垚
杨艳
鹿康
张泽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Polytechnic Institute
Original Assignee
Nanjing Polytechnic Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Polytechnic Institute filed Critical Nanjing Polytechnic Institute
Priority to CN201711245380.5A priority Critical patent/CN107892643B/en
Publication of CN107892643A publication Critical patent/CN107892643A/en
Application granted granted Critical
Publication of CN107892643B publication Critical patent/CN107892643B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • 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
    • Y02P20/10—Process efficiency

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a method for producing ethanol by acetic acid, which takes acetic acid and hydrogen as raw materials and methanol as a mediator to continuously produce ethanol, and the process comprises two stages, wherein the first stage comprises the following steps: acetic acid reacts with methanol and is rectified to prepare pure methyl acetate and a small amount of methanol; the second stage is as follows: methyl acetate is subjected to catalytic hydrogenation reaction and rectification to obtain methanol and ethanol, and the methanol and the ethanol are separated to obtain a product ethanol. The invention is based on the traditional kettle type reactor, adopts two reaction rectification systems to realize the function of the modern complex fixed bed catalytic rectification reaction technology, adopts small particles, a special methyl acetate hydrogenation catalyst and a high-efficiency heat transfer system to avoid the generation of 2-3% of water in a common reactor, and has the advantages of simple production process, less production investment, low energy consumption of the device, high quality of the product ethanol and the like compared with the prior common process and the acetic ester fixed bed catalytic hydrogenation process.

Description

Method for producing ethanol from acetic acid
Technical Field
The invention belongs to the technical field of organic chemical industry, and particularly relates to a method for producing ethanol by using acetic acid.
Background
The absolute ethanol is widely applied to chemical production raw materials, organic solvents, locomotive fuels and the like, wherein the absolute ethanol used as the locomotive fuels is also called fuel ethanol.
Ethanol gasoline, as a new clean fuel, can provide chemical energy equivalent to gasoline, has high combustion efficiency and low pollutant emission, is considered to be one of the best fuels for replacing and saving gasoline, and can be used as an alternative fuel to relieve the contradiction of shortage of petroleum resources.
The ethanol can be directly prepared by catalysis of a biological fermentation method, acetic acid and esterification hydrogenation thereof and a synthesis gas method. Among them, ethanol that is obtained from biomass as a raw material by a biological fermentation or the like and is used as a fuel is called fuel ethanol. Fuel ethanol is widely regarded as the best fuel to replace and save gasoline and has become the largest biomass energy source for production scale in the world.
The synthesis method mainly comprises direct hydrogenation of acetic acid, esterification hydrogenation, synthesis gas method, ethylene hydration method and the like. The synthesis gas method is still in an experimental stage at home, and the economy is unknown; the ethylene hydration method is difficult to develop on a large scale due to the shortage of the domestic ethylene demand; the acetic acid method not only has the advantages of short process flow, low production cost and the like, but also can digest a large amount of acetic acid in serious surplus, although the direct acetic acid hydrogenation route of acetic acid has the advantages of short process flow, low production cost and the like theoretically, the process only realizes industrial production in Nanjing by overseas Sealanis at present, and has the defects of high requirements on equipment materials, high water production, high refining energy consumption, unstable catalyst in the operation process and the like, and the technology is difficult to embody in a production device; acetate hydrogenation is the mainstream technology of domestic research and report and industrial device production at present. The acetic ester comprises methyl acetate and ethyl acetate, although the ethyl acetate hydrogenation product is mainly ethanol, the process for producing ethanol by catalytic hydrogenation of methyl acetate is more advantageous because a certain amount of ethanol is consumed, the price of the ethanol is obviously higher than that of the methanol and the byproduct of 300 ten thousand t/a of methyl acetate and the like in the production of polyvinyl alcohol.
At present, in the research and production aspects of the technology for producing ethanol by catalytic hydrogenation of acetic ester, the method mainly focuses on a fixed bed method or a fixed bed catalytic rectification method, and the catalyst mostly adopts Cu-SiO2、Cu-Al2O3And Cu-ZnO and the like, so that carbon deposition and the like are easy to occur in the reaction, and the conversion rate of the raw material acetate, the selectivity of the product ethanol and the service life of the catalyst are greatly reduced.
CN102976892A discloses a method for preparing mesoporous molecular sieve loaded copper catalyst, wherein the reaction temperature is 220 ℃, the pressure is 3MPa, the molar ratio of hydrogen to ester is 30, and the space velocity of methyl acetate is 2h-1The conversion rate of the acetate is 98.5 percent; sunweiwu manganese and zirconium modified Cu-SiO2The catalyst finds that zirconium oxide and manganese oxide can improve the stability of the catalyst, for manganese oxide, the conversion rate of methyl acetate and the selectivity of ethanol can reach 95.7% and 95.8% after 100 hours, for zirconium oxide, the reaction temperature is 210-340 ℃, the activity of the catalyst is firstly increased along with the increase of the temperature, after the temperature exceeds 250 ℃, the activity of the catalyst is not greatly changed, the reaction pressure is within the range of 0-3 MPa, the activity of the catalyst is increased along with the increase of the reaction pressure, and the liquid hourly space velocity is 1-3 hours-1In the range, the activity of the catalyst is reduced along with the increase of the liquid hourly space velocity, the hydrogen-ester ratio is in the range of 10-30, the activity of the catalyst is increased along with the increase of the hydrogen-ester ratio, and the activity is lower when the hydrogen-ester ratio is less than 15; CN2012210032010 discloses a catalyst: nickel and/or copper are used as active components, one or more of cobalt, zinc, iron, chromium and silicon are used as cocatalyst, alumina is used as carrier, in the fixed bed production process, the conversion rate of methyl acetate can reach 82%, and the selectivity of ethanol is 90%; CN1230458A discloses a method for preparing ethanol by gas phase hydrogenation of acetaldehyde, ethyl acetate, acetic acid or a mixture thereof, the catalyst is CuO, an auxiliary agent and Al2O3Is a supporter; the Cu-Zn-Al-Ba catalyst is prepared from Liuchun red and the like by a coprecipitation method at 220 ℃ and H2Pressure 3.0 MPa, n (H)2) The/n (methyl acetate) is 30.0, and the space velocity is 1.5h-1Under the condition, the conversion rate of methyl acetate on the Cu-Zn-Al-B catalyst is close to 96.0 percent, and the selectivity of ethanol is about 97.0 percent; CN201480076275 discloses that zinc oxide is used as a carrier, a copper catalyst is loaded, the reaction temperature is 200 ℃, the pressure is 5MPa, the volume ratio of hydrogen ester is 10.51, and the space velocity of raw materials is 4500h-1In the process, the conversion rate of the acetate is 97.3 percent, and the molar content of the ethanol is 50.74 percent; CN201310593601 discloses to adoptThe copper-based catalyst adopts silicon dioxide and alumina molecular sieve or graphite as carriers, and adopts a fixed bed reactor to carry out methyl acetate hydrogenation reaction and rectification to produce ethanol; CN201611076632 discloses a copper-based catalyst, which employs silica and alumina molecular sieves or graphite as carriers, and a fixed bed reactor to perform hydrogenation reaction and rectification of methyl acetate to produce ethanol, wherein the reaction temperature is 210-250 ℃, the pressure is 7.5-9.0 MPa, the acetate conversion rate is 89.25%, and the rectification fraction purity is 99.3%.
Currently, regarding the production of ethanol by using acetic acid as a raw material, a direct acetic acid hydrogenation process is mainly used, which is most typical by the company selanis, and the plant is built in Nanjing, but the operation results show that: too different from its desired result; the method is characterized in that acetic acid esterification and catalytic hydrogenation are used for producing ethanol, a kettle type reactor is generally used as a main body in the aspect of acetic acid esterification, then acetic ester is obtained through rectification and separation, a general tubular fixed bed or a reaction rectification fixed bed reactor is adopted in the production of ethanol through acetic ester hydrogenation, and as the reaction has large heat release amount, the catalyst is mostly Cu-SiO2、Cu-Al2O3And Cu-ZnO and the like, so that the reaction is easy to deposit carbon and the like, thereby greatly reducing the conversion rate of the raw material acetate, the selectivity of the product ethanol and the service life of the catalyst, generating water and improving the energy consumption and difficulty of the subsequent separation; in the synthesis of methyl acetate, the tubular fixed bed reactor or the fixed bed reactor catalytic distillation technology is mainly used for research and production, so that the method has the defects of high reaction temperature, large temperature difference of the reactor, high requirement on materials of a device, high control requirement on the device and the like, and the defects of serious pollution of equipment and pipelines, large amount of byproducts, poor product quality and the like due to the adoption of concentrated sulfuric acid and the like as a catalyst in an esterification reactor. The catalytic reaction rectification method adopts a kettle type reactor, a rectification tower and a reactor which are integrated, and adopts a catalyst which is small particles and adopts granular activated carbon added with special auxiliary agents as a carrier in the hydrogenation reaction process, so that the method has the advantages of simple process flow, lower equipment investment, convenient operation, lower energy consumption, high purity of target product ethanol and the like, and has obvious social benefit and economic benefit.
Disclosure of Invention
The purpose of the invention is as follows: in response to the deficiencies of the prior art, the present invention provides a process for producing ethanol from acetic acid.
The technical scheme is as follows: the invention relates to a method for producing ethanol by acetic acid, which takes acetic acid and hydrogen as raw materials and methanol as a mediator to continuously produce ethanol, and the process comprises two stages, wherein the first stage comprises the following steps: acetic acid reacts with methanol and is rectified to prepare pure methyl acetate and a small amount of methanol; the second stage is as follows: methyl acetate is subjected to catalytic hydrogenation reaction and rectification to obtain methanol and ethanol, and the methanol and the ethanol are separated to obtain a product ethanol.
Specifically, the first stage is that acetic acid and methanol react in a first reactor to generate methyl acetate and methanol, after simple rectification and deep rectification, unreacted methanol and acetic acid return to the first reactor to continue to react, and methyl acetate enters a second reactor.
Specifically, the methyl acetate is subjected to catalytic hydrogenation in the second reactor to obtain methanol and ethanol in the second stage, the ethanol is continuously removed from the reactor as a product after simple rectification and deep rectification, unreacted methyl acetate and hydrogen are returned to the second reactor for recycling, and the methanol is returned to the first reactor as a raw material for the first reaction.
Further, in the first stage, under the condition of non-concentrated sulfuric acid, the reaction temperature is 60-150 ℃, the molar ratio of alcohol to acid is 1.05-1.20, the reaction residence time is 0.5-2.0 h, the acetic acid conversion rate can reach 99.5%, and the selectivity of methyl acetate can reach 99%.
Further, the first stage adopts a non-concentrated sulfuric acid catalyst, which can be one or more selected from p-toluenesulfonic acid, sodium bisulfate, ferric chloride, ionic liquid, solid acid and the like, and is preferably a solid acid catalyst.
Further, the reaction conditions of the second stage are as follows: the temperature is 50-200 ℃, the pressure is 0.1-2.0MPa, the molar ratio of hydrogen to ester is 5: 1-100: 1, the acetic acid conversion rate can reach 99.5%, and the selectivity of ethanol can reach 99.9%.
Further, the second stage adopts Cu-ZnO-MexO/activated carbon catalyst, Cu-ZnO-MexThe O/active carbon catalyst comprises the following components in percentage by mass: CuO 20% -50%, ZnO30% -50%, Me2The mass content of O is 0.05-0.5 percent, and the balance is active carbon. The Cu-ZnO-MexThe preparation method of the O/active carbon catalyst adopts an impregnation method or a precipitation method.
Furthermore, the process is a continuous process, and the production of the ethanol is realized by automatic liquid level feeding and automatic liquid level control systems of the two reactors. (1) The acetic acid and the methanol are reacted and rectified to prepare pure methyl acetate and a small amount of methanol, and the reaction is realized by adopting a stirred tank reactor and two devices of a rectifying tower which is arranged above the stirred tank reactor and connected with the stirred tank reactor: in the reaction process, methyl acetate and water generated by the reaction are continuously removed from the reactor through the rectifying tower, and unreacted acetic acid and methanol are continuously returned to the reactor for continuous reaction, so that the original reaction balance is broken, and the complete conversion of the acetic acid is realized; (2) methyl acetate is subjected to catalytic hydrogenation reaction and rectification to obtain methanol and ethanol, and the methanol and the ethanol are subjected to rectification separation: the methanol produced by rectification returns to the methyl acetate reaction rectifying still, the ethanol is rectified and separated to become a high-purity product, and the high-purity product is realized by adopting two devices, namely a stirred tank reactor and a rectifying tower which is arranged above the stirred tank reactor and is connected with the stirred tank reactor: in the reaction process, the ethanol generated by the reaction is continuously removed from the reactor through the rectifying tower, and the unreacted methyl acetate and hydrogen are continuously returned to the reactor for continuous reaction, so that the original reaction balance is broken, and the complete conversion of the methyl acetate is realized; both stages are continuous processes.
Has the advantages that: the method for producing the ethanol by using the acetic acid as the raw material and the methanol as the intermediate medium has the advantages that the method for producing the ethanol provided by the invention adopts the solid catalyst, so the process has simple process flow, adopts a stirred tank reactor and has low reaction pressure, low equipment investment, convenient operation and low energy consumption; compared with the existing fixed bed reactor catalytic hydrogenation process, the invention adopts the stirred tank reactor and the special catalyst, so that the temperature distribution in the reactor is more uniform, the product selectivity is higher, and particularly the generation amount of water is almost correct, therefore, the process has the advantages of lower energy consumption of rectification separation, high purity of the target product ethanol and the like.
The specific implementation mode is as follows:
the method provided by the present invention is further illustrated below with reference to examples.
The technology of the invention is widely applied to the process of finishing ethanol production by using acetic acid and hydrogen as raw materials and methanol as a mediator through two stirred tank reactors and a simple rectifying tower arranged above the two stirred tank reactors to realize esterification and hydrogenation processes, six application examples are selected for better illustrating the advantages of the invention in the aspects of reaction conditions, product purity, yield and the like, but the application range of the technology is not limited, the examples are designed for illustrating the invention and do not limit the specific application of the invention.
Example 1 uses an activated carbon supported 5% concentrated sulfuric acid catalyst, the catalyst size: 10-20 meshes, the addition amount is 5% (calculated by the mass of phthalic anhydride, the following is the same), and the reaction conditions are as follows: the reaction temperature is 100 ℃, the molar ratio of the alcohol to the acid is 1.20, the reaction residence time is 1.5h, the acetic acid conversion rate can reach 99.60 percent under the condition, and the selectivity of the methyl acetate can reach 99.04 percent; by using Cu-ZnO-K2The O/active carbon catalyst comprises the following components: CuO50%, ZnO30% -, K20.05 percent of O and the balance of activated carbon, the preparation method of the catalyst adopts a precipitation method, the activated carbon is pretreated by potassium hydroxide impregnation, and the catalyst particles are as follows: 10-100 meshes; the reaction conditions are as follows: the temperature is 200 ℃, the pressure is 0.1MPa, the molar ratio of hydrogen to ester is 100:1, the acetic acid conversion rate can reach 99.5 percent, and the selectivity of ethanol can reach 99.90 percent under the condition.
Example 2 using activated carbon supported 5% p-toluene sulfonic acid catalyst, catalyst particles: 40-60 meshes; the reaction conditions are as follows: the reaction temperature is 120 ℃, the molar ratio of the alcohol to the acid is 1.10, the reaction residence time is 1.0h, the acetic acid conversion rate can reach 99.72 percent under the condition, and the selectivity of the methyl acetate can reach 99.15 percent; by using Cu-ZnO-Na2An O/activated carbon catalyst consisting of：CuO40.0％、ZnO30.8％，MexO2.0 percent and the balance of active carbon, the preparation method of the catalyst adopts a precipitation method, the active carbon is pretreated by potassium hydroxide impregnation, and the catalyst particles are as follows: 80-100 meshes; the reaction conditions are as follows: the temperature is 50 ℃, the pressure is 2.0MPa, the molar ratio of hydrogen to ester is 100:1, the acetic acid conversion rate can reach 99.59 percent, and the selectivity of ethanol can reach 99.98 percent under the condition.
Example 3 using an activated carbon supported 8.0% niobium oxide catalyst, catalyst particles: 30-50 meshes; the reaction conditions are as follows: the reaction temperature is 60 ℃, the molar ratio of the alcohol acid is 1.05, the reaction residence time is 2.0h, the acetic acid conversion rate can reach 99.51 percent under the condition, and the selectivity of the methyl acetate can reach 99.95 percent; a Cu-ZnO-CaO/active carbon catalyst is adopted, and the composition of the catalyst is as follows: CuO 20%, ZnO 50%, CaO5.0%, the rest is active carbon, the preparation method of the catalyst adopts an impregnation method or a precipitation method, and the catalyst particles are as follows: 80-100 meshes; the reaction conditions are as follows: the temperature is 140 ℃, the pressure is 1.0MPa, the molar ratio of hydrogen to ester is 5:1, the acetic acid conversion rate can reach 99.5 percent, and the selectivity of ethanol can reach 99.52 percent under the condition.
Example 4 using an activated carbon supported 5.0% teflon catalyst, catalyst particles: 30-60 meshes; the reaction conditions are as follows: the reaction temperature is 60 ℃, the molar ratio of the alcohol acid is 1.10, the reaction retention time is 2.0h, the acetic acid conversion rate can reach 99.85 percent under the condition, and the selectivity of the methyl acetate can reach 99.35 percent; a Cu-ZnO-BaO/active carbon catalyst is adopted, and the catalyst comprises the following components: CuO 35%, ZnO38.2%, BaO3.56%, the rest is active carbon, the catalyst preparation method adopts an impregnation method, the catalyst particles are: 80-100 meshes; the reaction conditions are as follows: the temperature is 180 ℃, the pressure is 1.50MPa, the molar ratio of hydrogen to ester is 20:1, the acetic acid conversion rate can reach 99.65 percent, and the selectivity of ethanol can reach 99.94 percent under the condition.
Example 5 with Alblyst-15 ion exchange resin catalyst, catalyst particles: 30-50 meshes; the reaction conditions are as follows: the reaction temperature is 140 ℃, the molar ratio of the alcohol to the acid is 1.20, the reaction residence time is 2.0h, the acetic acid conversion rate can reach 99.76 percent under the condition, and the selectivity of the methyl acetate can reach 99.84 percent; by using Cu-ZnO-Cs2The O/active carbon catalyst comprises the following components: CuO 45%, ZnO30%, Cs2O1.0％，The rest is active carbon, the preparation method of the catalyst adopts a precipitation method, and the catalyst particles are as follows: 10-30 meshes; the reaction conditions are as follows: the temperature is 150 ℃, the pressure is 1.5MPa, the molar ratio of hydrogen to ester is 50:1, the acetic acid conversion rate can reach 99.59 percent, and the selectivity of ethanol can reach 99.97 percent under the condition.
Example 6 using activated carbon loaded 10.0% ferric chloride catalyst, catalyst particles: 10-30 meshes; the reaction conditions are as follows: the reaction temperature is 140 ℃, the molar ratio of the alcohol to the acid is 1.20, the reaction residence time is 1.80h, the acetic acid conversion rate can reach 99.58 percent under the condition, and the selectivity of the methyl acetate can reach 99.29 percent; adopts a Cu-ZnO-SrO/active carbon catalyst, which comprises the following components: CuO 48%, ZnO 25%, SrO2.5%, the balance being activated carbon, the catalyst preparation method adopts a precipitation method, and the catalyst particles are as follows: 80-100 meshes; the reaction conditions are as follows: the temperature is 200 ℃, the pressure is 1.80MPa, the molar ratio of hydrogen to ester is 80:1, the acetic acid conversion rate can reach 99.65 percent, and the selectivity of ethanol can reach 99.95 percent under the condition.
While the present invention has been described with reference to preferred embodiments, it will be apparent to one skilled in the art that the present invention can be practiced by modifying or appropriately changing or combining the processes described herein without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.

Claims (5)

1. A method for producing ethanol from acetic acid is characterized in that the acetic acid and hydrogen are used as raw materials, methanol is used as a mediator to continuously produce ethanol, and the process comprises two stages, wherein the first stage comprises the following steps: acetic acid reacts with methanol and is rectified to prepare pure methyl acetate and a small amount of methanol; the second stage is as follows: methyl acetate is subjected to catalytic hydrogenation reaction and rectification to obtain methanol and ethanol, and the methanol and the ethanol are separated to obtain a product ethanol;
the first stage is that acetic acid and methanol react in a first reactor to generate methyl acetate, after simple rectification and deep rectification, unreacted methanol and acetic acid return to the first reactor to continue reacting, and methyl acetate enters a second reactor;
in the first stage, a solid acid catalyst is adopted;
the second stage is that methyl acetate is subjected to catalytic hydrogenation in a second reactor to obtain methanol and ethanol, the ethanol is continuously removed from the reactor as a product after simple rectification and deep rectification, unreacted methyl acetate and hydrogen are returned to the second reactor for recycling, and the methanol is returned to the first reactor as a raw material of the first reaction;
in the second stage, Cu-ZnO-K is adopted2O/activated carbon catalyst, Cu-ZnO-K2The O/active carbon catalyst comprises the following components in percentage by mass: CuO50%, ZnO30%, K20.05 percent of O and the balance of activated carbon.
2. The method for producing ethanol according to claim 1, wherein the first stage is carried out under the condition of non-concentrated sulfuric acid, the reaction temperature is 60 ℃ to 150 ℃, the molar ratio of the alcohol to the acid is 1.05 to 1.20, the reaction residence time is 0.5 to 2.0 hours, the acetic acid conversion rate can reach 99.5 percent, and the selectivity of the methyl acetate can reach 99 percent under the conditions.
3. The process for producing ethanol according to claim 1, wherein the reaction conditions in the second stage are: the temperature is 50-200 ℃, the pressure is 0.1-2.0MPa, and the molar ratio of hydrogen to ester is 5: 1-100: 1.
4. The process for producing ethanol according to claim 1, characterized in that Cu-ZnO-K2The preparation method of the O/active carbon catalyst adopts an impregnation method or a precipitation method.
5. The process for producing ethanol according to claim 1, wherein the process is a continuous process, and the production of ethanol is achieved by automatic liquid level feeding and automatic liquid level control systems for the two reactors.
CN201711245380.5A 2017-12-01 2017-12-01 Method for producing ethanol from acetic acid Active CN107892643B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711245380.5A CN107892643B (en) 2017-12-01 2017-12-01 Method for producing ethanol from acetic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711245380.5A CN107892643B (en) 2017-12-01 2017-12-01 Method for producing ethanol from acetic acid

Publications (2)

Publication Number Publication Date
CN107892643A CN107892643A (en) 2018-04-10
CN107892643B true CN107892643B (en) 2020-12-15

Family

ID=61807078

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711245380.5A Active CN107892643B (en) 2017-12-01 2017-12-01 Method for producing ethanol from acetic acid

Country Status (1)

Country Link
CN (1) CN107892643B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102557931A (en) * 2011-09-28 2012-07-11 唐山市冀东溶剂有限公司 Process for separate production or joint production of ethanol and acetic ether through acetic acid indirect hydrogenation
CN103159591A (en) * 2011-12-19 2013-06-19 西南化工研究设计院 Technique of synthesizing ethanol with acetic acid
CN106687432A (en) * 2014-06-19 2017-05-17 英国石油有限公司 Process for producing ethanol

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102557931A (en) * 2011-09-28 2012-07-11 唐山市冀东溶剂有限公司 Process for separate production or joint production of ethanol and acetic ether through acetic acid indirect hydrogenation
CN103159591A (en) * 2011-12-19 2013-06-19 西南化工研究设计院 Technique of synthesizing ethanol with acetic acid
CN106687432A (en) * 2014-06-19 2017-05-17 英国石油有限公司 Process for producing ethanol

Also Published As

Publication number Publication date
CN107892643A (en) 2018-04-10

Similar Documents

Publication Publication Date Title
CN101475442B (en) Method for preparing ethylene glycol from oxalic ester
CN103113187B (en) By the method for acetic acid ethanol co-production ethyl acetate
CN106349011B (en) A method of producing cyclohexanol
CN101475443B (en) Method for preparing ethylene glycol
EP4424662A1 (en) Maleic anhydride hydrogenation method and succinic acid production method comprising same
CN102211978B (en) Method for synthesizing glycol by hydrogenation of dimethyl oxalate
CN111302885B (en) Method for efficiently synthesizing ethylene and 1,3-butadiene by bioethanol one-pot method
CN114702434A (en) Continuous synthesis method of tetramethyl piperidinol
CN110407725B (en) Preparation method of 2-mercaptoethanol
TW202005950A (en) Integrated systems and processes for chemical production
CN107892643B (en) Method for producing ethanol from acetic acid
CN106563394B (en) Gas-liquid distributor, trickle bed reactor and gas-liquid reaction method
CN110862302B (en) Method for preparing 1, 4-butanediol by combining slurry bed hydrogenation and fixed bed hydrogenation
CN101993350A (en) Production method of glycol
CN106977406A (en) The method of continuous autoclave catalytic hydrogenation synthesizing amino naphthalene
CN206599529U (en) A kind of device of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol
CN102649743B (en) Method for synthesizing glycollic acid ester
CN108707064B (en) Production method for co-producing dimethyl ether by using blast furnace gas
CN108707061B (en) Process for preparing ethanol from methyl acetate by using methanol
CN101879447A (en) Catalyst for preparing glycol by hydrogenating oxalate, preparation method and application thereof
CN115197047B (en) Coupling reaction method for preparing ethanol from dimethyl ether
CN107778151B (en) Method for preparing methyl ethyl ketone by sec-butyl alcohol dehydrogenation
CN114163298B (en) Process for producing chloroethylene from methanol
CN114075096B (en) Cyclohexene synthesis process
CN112661618B (en) Copper catalysis preparation method of cyclopentanone

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant