CN110746296A - Method for preparing vinyl acetate by using microchannel reactor - Google Patents
Method for preparing vinyl acetate by using microchannel reactor Download PDFInfo
- Publication number
- CN110746296A CN110746296A CN201911097960.3A CN201911097960A CN110746296A CN 110746296 A CN110746296 A CN 110746296A CN 201911097960 A CN201911097960 A CN 201911097960A CN 110746296 A CN110746296 A CN 110746296A
- Authority
- CN
- China
- Prior art keywords
- microchannel reactor
- catalyst
- vinyl acetate
- introducing
- microchannel
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
Abstract
The invention discloses a method for preparing vinyl acetate by using a microchannel reactor, which comprises the following steps: adding a catalyst into acetic acid, uniformly mixing to obtain a suspension, introducing the suspension into a microchannel reactor, introducing ethylene and oxygen into the microchannel reactor, controlling the temperature of the microchannel reactor, reacting, collecting a product at an outlet of the microchannel reactor by a condensing device to obtain gas containing an unreacted raw material and liquid containing the catalyst, separating the catalyst from the liquid containing the catalyst, distilling to obtain vinyl acetate, and introducing the gas containing the unreacted raw material into the microchannel reactor as a circulating gas. The invention adopts a microchannel reactor which is operated continuously, the reaction time is shortened from traditional hours to dozens of seconds to several minutes, and the reaction efficiency is obviously improved. The invention can strengthen the mass transfer and heat transfer performance, keep the reaction temperature constant, avoid the temperature runaway phenomenon, reduce the generation of by-products and simultaneously improve the safety of the reaction process.
Description
Technical Field
The invention belongs to the technical field of organic synthesis application, and particularly relates to a method for preparing vinyl acetate by using a microchannel reactor.
Background
Vinyl Acetate (VAC), also known as vinyl acetate, is an important organic chemical feedstock. Vinyl acetate can be formed into products of polyvinyl alcohol (PVA), vinyl acetate-ethylene copolymer (EVA), polyvinyl acetate (PVAC), vinyl acetate-vinyl chloride copolymer (EVC), and the like by self-polymerization or copolymerization with other monomers. These products are very versatile and can be used in general in adhesives, sizing agents for paper or textiles, paints, inks, leather processing, emulsifiers, water-soluble films, soil conditioners, etc.
In general, vinyl acetate production routes include both ethylene and acetylene processes. Worldwide, ethylene process production is currently predominant. The ethylene-process vinyl acetate production process is characterized in that raw materials of ethylene, oxygen and acetic acid gas are fed into a reactor to contact with a catalyst, and react at the pressure of 0.5-1.4MPa (gauge pressure) and the temperature of 130-220 ℃ to generate VAC, water and a small amount of byproducts, and the high-temperature reaction gas enters a gas separation device after being subjected to multi-stage cooling and condensation so as to achieve the purpose of gas-liquid separation. Unreacted ethylene gas is returned to the compressor. The condensed acetic acid and VAC mixed liquid is sent to a rectification process to carry out VAC purification.
Microchannel reaction equipment has a range of properties not found in conventional reactors: the device has the advantages of miniaturized channel size, larger heat exchange specific surface area, excellent mass and heat transfer characteristics, continuous reaction, capability of skipping direct amplification through a step-by-step amplification test, flexible production and high safety performance.
To date, no report has been made on the production of vinyl acetate by the ethylene process using microchannel reactors.
Disclosure of Invention
A process for making vinyl acetate with a microchannel reactor comprising the steps of: adding a catalyst into acetic acid to enable the final mass content of the catalyst to be 1% -10%, uniformly mixing to obtain a suspension, introducing the suspension into a microchannel reactor at a flow rate of 8-18g/min, simultaneously introducing ethylene into the microchannel reactor at a flow rate of 10-25g/min and oxygen at a flow rate of 3-5g/min, controlling the temperature of the microchannel reactor to be 100-220 ℃, reacting for 80-300 s, collecting a product at an outlet of the microchannel reactor through a condensing device to obtain gas containing unreacted raw materials and liquid containing the catalyst, separating the catalyst from the liquid containing the catalyst, distilling to obtain vinyl acetate, and introducing the gas containing the unreacted raw materials into the microchannel reactor as a circulating gas.
The microchannel structure of the microchannel reactor is a straight-flow tubular structure, and a mixed T-shaped structure, a spherical baffle structure, a water-drop structure or a heart-shaped structure is enhanced.
The catalyst is preferably a supported bimetallic catalyst Pd-Pt/Al2O3The particle size is 1-10 μm.
The temperature of the microchannel reactor is preferably 110-160 ℃.
The reaction time is preferably 120s to 200 s.
The invention has the advantages that:
1. the invention adopts a microchannel reactor which is operated continuously, the reaction time is shortened from traditional hours to dozens of seconds to several minutes, and the reaction efficiency is obviously improved.
2. The adopted reaction equipment microchannel reactor can enhance the mass transfer and heat transfer performance, keep the reaction temperature constant, avoid the temperature runaway phenomenon, reduce the generation of by-products and simultaneously improve the safety of the reaction process.
Drawings
FIG. 1 is a flow diagram of a process for preparing vinyl acetate using a microchannel reactor according to the present invention.
FIG. 2 is a diagram of a typical structural unit of a microchannel reactor module used in the present invention; (A) a reinforced mixed T-shaped structure, (B) a spherical structure, (C) a spherical baffle structure and (D) a drop structure; (E) a heart-shaped structure.
Detailed Description
The present invention will be further illustrated by the following specific examples, but the present invention is not limited to the following examples.
Example 1
A process for making vinyl acetate with a microchannel reactor comprising the steps of: adding a catalyst into acetic acid to enable the final mass content of the catalyst to be 5%, uniformly mixing to obtain a suspension, introducing the suspension into a microchannel reactor at a flow rate of 13g/min, controlling the temperature of the microchannel reactor to be 150 ℃ and reacting for 150s, collecting a product at an outlet of the microchannel reactor through a condensing device to obtain a gas containing an unreacted raw material and a liquid containing the catalyst, separating the catalyst from the liquid containing the catalyst, distilling to obtain vinyl acetate, and introducing the gas containing the unreacted raw material into the microchannel reactor as a circulating gas, wherein the microchannel structure of the microchannel reactor is a heart-shaped structure, the ethylene is introduced into the microchannel reactor at a flow rate of 18g/min and the oxygen is introduced into the microchannel reactor at a flow rate of 4 g/min.
The catalyst is a supported bimetallic catalyst Pd-Pt/Al2O3The particle size is 1-10 μm.
The single-pass conversion rates of ethylene, oxygen, and acetic acid were 11.5%, 55.7%, and 58.7%, respectively. The total yield was 95.2% based on acetic acid.
Example 2
A process for making vinyl acetate with a microchannel reactor comprising the steps of: adding a catalyst into acetic acid to enable the final mass content of the catalyst to be 3%, uniformly mixing to obtain a suspension, introducing the suspension into a microchannel reactor at a flow rate of 8g/min, controlling the temperature of the microchannel reactor to be 110 ℃ for reaction for 200s, collecting a product at an outlet of the microchannel reactor through a condensing device to obtain a gas containing an unreacted raw material and a liquid containing the catalyst, separating the catalyst from the liquid containing the catalyst, distilling to obtain vinyl acetate, and introducing the gas containing the unreacted raw material into the microchannel reactor as a circulating gas, wherein the microchannel structure of the microchannel reactor is a drop-shaped structure, the ethylene is introduced into the microchannel reactor at a flow rate of 10g/min and the oxygen is introduced into the microchannel reactor at a flow rate of 3 g/min.
The catalyst is a supported bimetallic catalyst Pd-Pt/Al2O3The particle size is 1-10 μm.
The single-pass conversion rates of ethylene, oxygen, and acetic acid were 10.7%, 52.3%, and 57.1%, respectively. The total yield was 94.1% based on acetic acid.
Example 3
A process for making vinyl acetate with a microchannel reactor comprising the steps of: adding a catalyst into acetic acid to ensure that the final mass content of the catalyst is 7%, uniformly mixing to obtain a suspension, introducing the suspension into a microchannel reactor at a flow rate of 18g/min, wherein the microchannel structure of the microchannel reactor is a straight-flow tubular structure, simultaneously introducing ethylene into the microchannel reactor at a flow rate of 25g/min and oxygen at a flow rate of 5g/min, controlling the temperature of the microchannel reactor to be 160 ℃, reacting for 120s, collecting a product at an outlet of the microchannel reactor through a condensing device to obtain gas containing unreacted raw materials and liquid containing the catalyst, separating the catalyst from the liquid containing the catalyst, distilling to obtain vinyl acetate, and introducing the gas containing the unreacted raw materials into the microchannel reactor as a circulating gas.
The catalyst is a supported bimetallic catalyst Pd-Pt/Al2O3The particle size is 1-10 μm.
The single-pass conversion rates of ethylene, oxygen, and acetic acid were 12.5%, 55.1%, and 60.3%, respectively. The total yield was 96.3% based on acetic acid.
Example 4
A process for making vinyl acetate with a microchannel reactor comprising the steps of: adding a catalyst into acetic acid to enable the final mass content of the catalyst to be 1%, uniformly mixing to obtain a suspension, introducing the suspension into a microchannel reactor at a flow rate of 10g/min, wherein the microchannel structure of the microchannel reactor is an enhanced mixed T-shaped structure, simultaneously introducing ethylene into the microchannel reactor at a flow rate of 20g/min and oxygen at a flow rate of 3g/min, controlling the temperature of the microchannel reactor to be 100 ℃, reacting for 300s, collecting a product at an outlet of the microchannel reactor through a condensing device to obtain gas containing unreacted raw materials and liquid containing the catalyst, separating the catalyst from the liquid containing the catalyst, distilling to obtain vinyl acetate, and introducing the gas containing the unreacted raw materials into the microchannel reactor as a circulating gas.
The catalyst is a supported bimetallic catalyst Pd-Pt/Al2O3The particle size is 1-10 μm.
The single-pass conversion rates of ethylene, oxygen, and acetic acid were 13.4%, 56.1%, and 61.2%, respectively. The total yield was 93.9% based on acetic acid.
Example 5
A process for making vinyl acetate with a microchannel reactor comprising the steps of: adding a catalyst into acetic acid to enable the final mass content of the catalyst to be 10%, uniformly mixing to obtain a suspension, introducing the suspension into a microchannel reactor at a flow rate of 14g/min, controlling the temperature of the microchannel reactor to be 220 ℃ and reacting for 80s, collecting a product at an outlet of the microchannel reactor through a condensing device to obtain a gas containing an unreacted raw material and a liquid containing the catalyst, separating the catalyst from the liquid containing the catalyst, distilling to obtain vinyl acetate, and introducing the gas containing the unreacted raw material into the microchannel reactor as a circulating gas, wherein the microchannel structure of the microchannel reactor is a spherical structure, the ethylene is introduced into the microchannel reactor at a flow rate of 15g/min and the oxygen is introduced into the microchannel reactor at a flow rate of 4 g/min.
The catalyst is a supported bimetallic catalyst Pd-Pt/Al2O3The particle size is 1-10 μm.
The single-pass conversion rates of ethylene, oxygen, and acetic acid were 9.6%, 52.0%, and 55.9%, respectively. The total yield was 91.1% based on acetic acid.
Vinyl acetate was produced in the same manner as in this example except that the spherical belt baffle structure was used instead of the spherical structure of this example.
The above embodiments are only specific embodiments of the present invention, and are not intended to limit the scope of the present invention, and other equivalent variations and modifications made by the above methods are within the scope of the present invention.
Claims (5)
1. A process for the production of vinyl acetate using a microchannel reactor, comprising the steps of: adding a catalyst into acetic acid to enable the final mass content of the catalyst to be 1% -10%, uniformly mixing to obtain a suspension, introducing the suspension into a microchannel reactor at a flow rate of 8-18g/min, simultaneously introducing ethylene into the microchannel reactor at a flow rate of 10-25g/min and oxygen at a flow rate of 3-5g/min, controlling the temperature of the microchannel reactor to be 100-220 ℃, reacting for 80-300 s, collecting a product at an outlet of the microchannel reactor through a condensing device to obtain gas containing unreacted raw materials and liquid containing the catalyst, separating the catalyst from the liquid containing the catalyst, distilling to obtain vinyl acetate, and introducing the gas containing the unreacted raw materials into the microchannel reactor as a circulating gas.
2. The method according to claim 1, wherein the microchannel structure of the microchannel reactor is a tubular structure of a straight-flow type, a reinforced hybrid type T-shaped structure, a spherical baffled structure, a drop-shaped structure, or a heart-shaped structure.
3. The method according to claim 1, characterized in that the catalyst is a supported bimetallic catalyst Pd-Pt/Al2O3The particle size is 1-10 μm.
4. The process of claim 1 wherein the microchannel reactor temperature is from 110 to 160 ℃.
5. The method of claim 1, wherein the reaction time is 120s to 200 s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911097960.3A CN110746296A (en) | 2019-11-12 | 2019-11-12 | Method for preparing vinyl acetate by using microchannel reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911097960.3A CN110746296A (en) | 2019-11-12 | 2019-11-12 | Method for preparing vinyl acetate by using microchannel reactor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110746296A true CN110746296A (en) | 2020-02-04 |
Family
ID=69282942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911097960.3A Pending CN110746296A (en) | 2019-11-12 | 2019-11-12 | Method for preparing vinyl acetate by using microchannel reactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110746296A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111349010A (en) * | 2020-04-18 | 2020-06-30 | 云南正邦科技有限公司 | Method for continuously synthesizing carboxylic acid enol ester |
| CN111420655A (en) * | 2020-04-18 | 2020-07-17 | 云南正邦科技有限公司 | Method for chemically plating metal catalyst on tube pass inner wall of continuous flow reaction module |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040220434A1 (en) * | 2003-05-02 | 2004-11-04 | Brophy John H. | Process for converting a hydrocarbon to an oxygenate or a nitrile |
| US20060167306A1 (en) * | 2002-10-07 | 2006-07-27 | Ditzel Evert J | Process for the production of alkenyl carboxylates |
| CN101084182A (en) * | 2004-11-03 | 2007-12-05 | 维罗西股份有限公司 | Process and apparatus for improved methods for making vinyl acetate monomer (vam) |
| CN102574092A (en) * | 2009-06-30 | 2012-07-11 | 蒂森克虏伯伍德有限公司 | Catalyst-coated support, method for the production thereof, a reactor equipped therewith, and use thereof |
-
2019
- 2019-11-12 CN CN201911097960.3A patent/CN110746296A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060167306A1 (en) * | 2002-10-07 | 2006-07-27 | Ditzel Evert J | Process for the production of alkenyl carboxylates |
| US20040220434A1 (en) * | 2003-05-02 | 2004-11-04 | Brophy John H. | Process for converting a hydrocarbon to an oxygenate or a nitrile |
| CN101084182A (en) * | 2004-11-03 | 2007-12-05 | 维罗西股份有限公司 | Process and apparatus for improved methods for making vinyl acetate monomer (vam) |
| CN102574092A (en) * | 2009-06-30 | 2012-07-11 | 蒂森克虏伯伍德有限公司 | Catalyst-coated support, method for the production thereof, a reactor equipped therewith, and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| WWW.BIO-EQUIP.COM/SHOWARTICLE.ASP?ID=453106126: "氢化反应如何处理微通道反应器中的固体？", 《中国生物器材网》 * |
| 李寒羿等: "微通道反应器浅析", 《宁波化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111349010A (en) * | 2020-04-18 | 2020-06-30 | 云南正邦科技有限公司 | Method for continuously synthesizing carboxylic acid enol ester |
| CN111420655A (en) * | 2020-04-18 | 2020-07-17 | 云南正邦科技有限公司 | Method for chemically plating metal catalyst on tube pass inner wall of continuous flow reaction module |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107827711B (en) | System and process for coproducing methyl butynol and dimethyl hexynediol | |
| CN101255109B (en) | Technique for producing propenoic acid by dehydrating biomass lactic acid | |
| CN110746296A (en) | Method for preparing vinyl acetate by using microchannel reactor | |
| CN106810528A (en) | A kind of method that microchannel plate should prepare chlorocarbonic acid vinyl acetate | |
| CN101659597A (en) | Method for preparing Guerbet alcohol | |
| CN108892607B (en) | Preparation method of hydroxycitronellal | |
| CN111269080B (en) | Perfluoro 1, 3-butadiene microreactor preparation system and preparation method thereof | |
| CN114163413B (en) | Method for preparing high-purity chloroethylene carbonate by continuous double-stage liquid phase reaction | |
| CN110511157A (en) | A method of trifluoroacetamide is prepared using microchannel reaction technology | |
| CN105879892A (en) | Solid base catalyst for synthesizing dimethyl carbonate through transesterification method and preparation method and application | |
| CN111269079B (en) | Preparation system and preparation method of perfluoro 1, 3-butadiene | |
| CN107814689B (en) | Method for preparing perfluoromethyl vinyl ether by fluidized bed | |
| CN102464633B (en) | Synthetic method for (methyl) glycidyl acrylate | |
| CN115650825A (en) | Method for synthesizing dihydric alcohol monovinyl ether | |
| CN104529730B (en) | A kind of method being prepared propione by 2-amylene | |
| CN110028396A (en) | A kind of method of the continuous synthesis of trans -2- hexenoic aldehyde of micro passage reaction | |
| CN100439313C (en) | Multistage fluidized bed reactor for preparing propenoic acid from propene oxidation and preparing method | |
| CN110903180B (en) | Preparation method and device of isophorone | |
| CN105585468B (en) | A method of cyclopentanone is prepared by raw material of cyclopentene | |
| CN112479858A (en) | Methanol carbonylation enhanced reaction system and process with aldehyde recovery function | |
| CN110038609B (en) | Dehydration catalyst and application thereof in preparation of organic carboxylic anhydride | |
| CN113717224B (en) | MPP microchannel reaction preparation process and MPP | |
| CN109438175A (en) | A kind of method that cyclohexyl hydroperoxide decomposition prepares cyclohexanol and cyclohexanone | |
| CN219168389U (en) | Continuous chlorination system of ethylene carbonate | |
| CN104447255A (en) | Method for preparing 2-pentanone from 2-amylene |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200204 |
|
| WD01 | Invention patent application deemed withdrawn after publication |