CN112299990A - Method and reaction system for preparing methyl allyl alcohol acetate through isobutene oxoacetylation - Google Patents
Method and reaction system for preparing methyl allyl alcohol acetate through isobutene oxoacetylation Download PDFInfo
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- CN112299990A CN112299990A CN202011255711.5A CN202011255711A CN112299990A CN 112299990 A CN112299990 A CN 112299990A CN 202011255711 A CN202011255711 A CN 202011255711A CN 112299990 A CN112299990 A CN 112299990A
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Abstract
The invention discloses a method and a reaction system for producing methyl allyl alcohol acetate by carrying out oxo-acetylation on isobutene. The method comprises the steps of extracting esters in an ester-poor phase by using an extracting agent, and independently sending an extraction liquid or sending the extraction liquid and an ester-rich phase to a rectification system to separate products; the raffinate only contains acetic acid and water, part of the raffinate is mixed with acetic acid material flow in the feeding system after adjusting the concentration of the acetic acid, and the mixture continues to participate in the reaction, and the other part of the raffinate is sent to an acetic acid recovery system to recover the acetic acid. In the method, 2-methylene-1, 3-propylene glycol diethyl ester which is one of reaction products in the system is preferably selected as the extractant, so that an outsourcing extractant is not needed, substances except the raw materials and the products can be prevented from being added into the system, and the purity of the product is ensured. The method and the reaction system method have the characteristics of high atom economy, easily controlled reaction conditions and low energy consumption.
Description
Technical Field
The invention belongs to the field of preparation of methyl allyl alcohol acetate, and particularly relates to a method and a reaction system for producing methyl allyl alcohol acetate through isobutene oxoacetylation.
Background
Patent document CN109942370A (entitled "Green high-efficiency Process for synthesizing methallyl alcohol") discloses a method for preparing 2-methallyl alcohol acetate by using isobutene, oxygen and acetic acid to perform an oxyacetylation reaction in a rectifying section of a reactive rectifying tower, wherein the reaction temperature is 100 ℃ and the pressure is 0.3-0.6MPa, and the catalyst is Pd/Au @ SiO2. This patent document has the following disadvantages:
(1) the raw material proportion is not easy to control: in the rectifying section of the rectifying tower, the flow rate of each material is related to the boiling point of the material, and the proportion of each material in each layer of the rectifying section is not easy to control.
(2) The reaction conditions are not easy to control: when the boiling point of the 2-methallyl alcohol acetate is 85 ℃, the boiling point of the acetic acid is 117.9 ℃ and the boiling point of the acetic acid is higher than that of the 2-methallyl alcohol acetate, a large amount of acetic acid is necessarily contained in a heavy component and the concentration of the acetic acid in a rectifying section is reduced if the 2-methallyl alcohol acetate is separated as the heavy component.
Disclosure of Invention
The invention provides a method for producing methyl allyl alcohol acetate (2-methyl allyl alcohol acetate) by isobutene oxyacetylation, which comprises the following steps:
1) the acetic acid, the isobutene and the oxygen are contacted with a catalyst to react, and the nitrogen is used as a carrier gas of a gas material to obtain a reaction product;
2) separating the reaction product obtained in the step 1) under high pressure to obtain a gas part I and a liquid part;
3) separating the liquid part obtained in the step 2) at low pressure and optionally carrying out phase separation to obtain a gas part II, an ester-rich liquid and an ester-poor liquid;
4) extracting the low-ester liquid obtained in the step 3) to obtain an extraction liquid and an extraction raffinate; rectifying and separating the extract liquor to obtain an extracting agent, methyl allyl alcohol acetate and 2-methylene-1, 3-propylene glycol diethyl ester;
5) rectifying and separating the ester-rich liquid obtained in the step 3) to obtain isobutene, methyl allyl alcohol acetate, acetic acid solution and 2-methylene-1, 3-propylene glycol diethyl ester.
According to the embodiment of the inventionThe catalyst in the step 1) can be Pd/Au @ SiO supported on silica and taking potassium acetate as an auxiliary agent2Catalyst and Pd/Cu @ SiO with Pd and Cu loaded on silicon dioxide and potassium acetate as auxiliary agent2At least one of a catalyst.
According to an embodiment of the invention, in step 1), the temperature of the reaction is 130-. Preferably, the pressure of the reaction is from 0.6 to 2.2MPa, such as from 0.8 to 2.0MPa, exemplary 0.7MPa, 0.9MPa, 1.0MPa, 1.2MPa, 1.4MPa, 1.5MPa, 1.7MPa, 2.0 MPa.
According to an embodiment of the invention, the gas fraction I and/or the gas fraction II is returned to step 1) for further use.
According to an embodiment of the invention, in step 2), the operating pressure of the high pressure separation is in the range of 1.0 to 2.0MPa, such as 1.2 to 1.8MPa, exemplary 1.0MPa, 1.2MPa, 1.4MPa, 1.6MPa, 1.8MPa, 2.0 MPa. Further, the high pressure separation is performed at an operating temperature of-10 to 30 deg.C, such as-5 to 25 deg.C, illustratively-10 deg.C, -5 deg.C, 0 deg.C, 10 deg.C, 20 deg.C, 30 deg.C.
According to an embodiment of the invention, in step 3), the operating pressure of the low-pressure separation is in the range of 0.1 to 1.0MPa, such as 0.2 to 0.8MPa, exemplary 0.1MPa, 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa, 1.0 MPa. Further, the low pressure separation is performed at an operating temperature of-10 to 30 deg.C, such as-5 to 25 deg.C, illustratively-10 deg.C, -5 deg.C, 0 deg.C, 10 deg.C, 20 deg.C, 30 deg.C.
According to the embodiment of the invention, the ester-rich liquid obtained in the step 3) and the extract liquid obtained in the step 4) can enter different rectification systems respectively, or enter the same rectification system after being converged. When the ester-rich liquid and the extract liquid are converged and enter the same rectification system, five streams of material flows of isobutene, methyl allyl alcohol acetate, acetic acid solution, 2-methylene-1, 3-propylene glycol diethyl ester and an extracting agent are obtained after separation; preferably, the isobutylene is returned to the isobutylene feed system and the acetic acid solution is returned to the acetic acid feed system; preferably, the extractant is returned to the extractant feed system of the extraction apparatus.
According to an embodiment of the present invention, in step 3), when the low-pressure separation cannot be performed to obtain the ester-rich liquid and the ester-poor liquid, the liquid phase obtained by the low-pressure separation may be subjected to phase separation to separate the ester-rich liquid and the ester-poor liquid. For example, it is passed into a phase separator for phase separation.
According to the embodiment of the invention, part of the raffinate obtained in the step 4) is returned to the step 1) to continue the reaction, and part of the raffinate goes to an acetic acid recovery system to recover acetic acid.
According to an embodiment of the invention, the extractant obtained in step 4) is returned to the extraction step as extractant feed.
According to an embodiment of the present invention, the extractant is selected from one, two or more of toluene, chloroform, dichloromethane, carbon tetrachloride and diethyl 2-methylene-1, 3-propanediol. Preferably, the 2-methylene-1, 3-propanediol diethyl ester used is the product prepared by the above-described method. Preferably, the extractant is 2-methylene-1, 3-propanediol diethyl ester.
According to an embodiment of the invention, the isobutene and acetic acid solution obtained in step 5) is returned to step 1) as reactant feed.
The invention also provides a reaction system for preparing methyl allyl alcohol acetate by the isobutylene oxyacetylation reaction, which comprises a reactor, a first separator, a second separator, an extraction device and a rectification system; the rectification system comprises a first rectification system and a second rectification system;
the reactant outlet of the reactor is connected with the inlet of the first separator; the first separator liquid outlet is connected with the second separator inlet; the second separator comprises two liquid outlets: the ester-rich phase outlet is connected with the first rectification system, and the ester-poor phase outlet is connected with the extraction device; an extract liquid outlet of the extraction device is connected with the second rectification system; the first rectification system and the second rectification system both comprise a methyl allyl alcohol acetate outlet and a 2-methylene-1, 3-propylene glycol diethyl ester outlet.
According to an embodiment of the invention, the reaction system comprises a feed system connected to the reaction mass inlet of the reactor.
According to an embodiment of the invention, the feed system comprises an acetic acid feed unit, an isobutene feed unit, a nitrogen feed unit and an oxygen feed unit.
According to an embodiment of the invention, the first rectification system further comprises an isobutene outlet and an acetic acid solution outlet. Preferably, the isobutene outlet is connected to an isobutene feed unit. Preferably, the acetic acid solution outlet is connected to an acetic acid feed unit.
According to an embodiment of the invention, the reaction system further comprises an extractant feeding unit, which is connected to the extraction device material inlet.
According to an embodiment of the invention, the extractant outlet of the second rectification system is connected to an extractant feed unit.
The invention also provides a reaction system for preparing methyl allyl alcohol acetate by the isobutylene oxyacetylation reaction, which comprises a reactor, a first separator, a second separator, an extraction device and a rectification system;
the reactant outlet of the reactor is connected with the inlet of the first separator; the first separator liquid outlet is connected with the second separator; the second separator comprises two liquid outlets: the rich-ester phase outlet and the poor-ester phase outlet are connected with the extraction device; the ester-rich phase outlet and the extraction liquid outlet of the extraction device are both connected with a rectification system, and the rectification system comprises a methyl allyl alcohol acetate outlet and a 2-methylene-1, 3-propylene glycol diethyl ester outlet.
According to an embodiment of the invention, the rectification system comprises an isobutene outlet, an acetic acid solution outlet and an extractant outlet. Preferably, the isobutene outlet is connected to an isobutene feed unit. Preferably, the acetic acid solution outlet is connected to an acetic acid feed unit. Preferably, the extractant outlet is connected to an extractant feed unit.
According to an embodiment of the invention, the reaction system further comprises an extractant feeding unit, which is connected to the extraction device material inlet.
According to an embodiment of the invention, the number of rectification columns in the rectification system is adjusted according to the selected extractant.
In one embodiment of the invention, when 2-methylene-1, 3-propanediol diethyl ester which is one of non-system reaction products is used as the extractant, the rectification system can comprise four rectification towers, wherein a material inlet of the first rectification tower is connected with an ester-rich phase outlet, a material inlet of the second rectification tower is connected with an ester-poor phase outlet, the tower bottoms of the first rectification tower and the second rectification tower are both connected with a material inlet of the third rectification tower, and the tower bottom of the third rectification tower is connected with a material inlet of the fourth rectification tower. Preferably, isobutene is withdrawn from the top of the first rectification column. Preferably, the extractant is withdrawn from the top of the second rectification column. Preferably, 2-methyl propenol acetate is withdrawn from the top of the third rectification column. Preferably, the tower bottom of the fourth rectifying tower produces 2-methylene-1, 3-propanediol diethyl ester.
In another embodiment of the invention, when the extractant is 2-methylene-1, 3-propanediol diethyl ester which is one of the reaction products of the system, the rectification system can comprise three rectification towers, wherein a material inlet of the first rectification tower is connected with an ester-rich phase outlet, and a material inlet of the second rectification tower is connected with a tower bottom outlet of the first rectification tower and an extraction liquid outlet of the extraction device; the outlet of the second rectifying tower is connected with the inlet of the third rectifying tower. Preferably, isobutene is withdrawn from the top of the first rectification column. Preferably, 2-methyl propenol acetate is withdrawn from the top of the second rectification column. Preferably, the tower bottom of the third rectifying tower produces 2-methylene-1, 3-propanediol diethyl ester.
The invention also provides a reaction system for preparing methyl allyl alcohol acetate by the isobutylene oxyacetylation reaction, which comprises a reactor, a first separator, a second separator, a phase separator, an extraction device and a rectification system; the rectification system comprises a first rectification system and a second rectification system;
the reactant outlet of the reactor is connected with the inlet of the first separator; the first separator liquid outlet is connected with the second separator inlet; the liquid phase outlet of the second separator is connected with the material inlet of the phase separator; the phase separator includes two liquid outlets: an ester-rich phase outlet and an ester-poor phase outlet; the rich-ester phase outlet is connected with the first rectification system, the poor-ester phase outlet is connected with the extraction device, and the first rectification system and the second rectification system respectively comprise a methyl propenyl acetate outlet and a 2-methylene-1, 3-propylene glycol diethyl ester outlet.
According to an embodiment of the invention, the reaction system comprises a feed system connected to the reaction mass inlet of the reactor.
According to an embodiment of the invention, the feed system comprises an acetic acid feed unit, an isobutene feed unit, a nitrogen feed unit and an oxygen feed unit.
According to an embodiment of the invention, the first rectification system further comprises an isobutene outlet and an acetic acid solution outlet. Preferably, the isobutene outlet is connected to an isobutene feed unit. Preferably, the acetic acid solution outlet is connected to an acetic acid feed unit.
According to an embodiment of the invention, the reaction system further comprises an extractant feeding unit, which is connected to the extraction device material inlet.
According to an embodiment of the invention, the extractant outlet of the second rectification system is connected to an extractant feed unit.
According to an embodiment of the present invention, in the three reaction systems described above, the gas outlet of the first separator is connected to a feed system, preferably to a nitrogen feed unit.
According to an embodiment of the present invention, in the three reaction systems described above, the gas outlet of the second separator is connected to a feed system, preferably to an isobutene feed unit.
According to an embodiment of the present invention, the three reaction systems may further comprise an acetic acid recovery system for recovering acetic acid in the raffinate discharged from the extraction unit and/or acetic acid produced by the rectification system.
According to an embodiment of the present invention, in the above three reaction systems, the raffinate outlet of the extraction apparatus is connected to the feeding system and/or the acetic acid recovery system, preferably to the acetic acid feeding unit and/or the acetic acid recovery system.
According to an embodiment of the present invention, the first rectification system may include three rectification columns connected in series, the material inlet of the first rectification column is connected with the ester-rich phase outlet, the bottom of the first rectification column is connected with the material inlet of the second rectification column, and the bottom of the second rectification column is connected with the material inlet of the third rectification column. Preferably, isobutene is extracted from the top of the first rectifying tower. Preferably, 2-methyl allyl alcohol acetate is extracted from the top of the second rectifying tower. Preferably, the tower bottom of the third rectifying tower produces 2-methylene-1, 3-propanediol diethyl ester. Preferably, acetic acid is taken out from the top of the third rectifying tower.
According to an embodiment of the present invention, the second rectification system may include two rectification columns connected in series, the material inlet of the first rectification column is connected to the extract outlet, and the bottom of the first rectification column is connected to the material inlet of the second rectification column. Preferably, the extractant is extracted from the top of the first rectifying tower. Preferably, 2-methyl allyl alcohol acetate is extracted from the top of the second rectifying tower. Preferably, 2-methylene-1, 3-propanediol diethyl ester is extracted from the tower bottom of the second rectifying tower.
In the above three reaction systems, according to an embodiment of the present invention, a compressor may be provided on the connection line returning to each feeding unit as required.
According to an embodiment of the present invention, coolers may be further included in the three reaction systems. Preferably, the cooler is arranged between the reactor and the first separator for cooling the reaction mass withdrawn from the reactor.
Preferably, the method for preparing the methyl allyl alcohol acetate by the oxo acetylation of the isobutene can be implemented in any reaction system.
According to an embodiment of the present invention, in the above system, each of the first separator and the second separator is a gas-liquid separator.
The invention has the beneficial effects that:
the inventors have found that in the isobutylene oxyacetylation reaction, an acetic acid stream is added in the form of an aqueous solution of acetic acid at a certain concentration, and the isobutylene oxyacetylation reaction produces water. Two phases exist in the isobutylene oxyacetylated product, one is an ester-rich phase, is rich in esters, and only contains a small amount of acetic acid and isobutylene; the second is an ester-poor phase containing most of the unreacted acetic acid and a small amount of esters. The poor ester phase only contains a small amount of esters and unreacted acetic acid, and if the poor ester phase is directly sent to a rectification system for separating products, the energy consumption is high and the method is not economical. The invention firstly uses an extracting agent to extract the esters in the lean ester phase, and the extract liquid is independently or together with the rich ester phase sent to a rectification system to separate the product; the raffinate only contains acetic acid and water, part of the acetic acid is mixed with acetic acid material flow in the feeding system after adjusting the concentration of the acetic acid, the acetic acid material flow continuously participates in the reaction, and part of the acetic acid material flow is sent to an acetic acid recovery system to recover the acetic acid. In the method, 2-methylene-1, 3-propylene glycol diethyl ester which is one of reaction products in the system is preferably selected as the extractant, so that an outsourcing extractant is not needed, substances except the raw materials and the products can be prevented from being added into the system, and the purity of the product is ensured. The method and the reaction system method have the characteristics of high atom economy, easily controlled reaction conditions and low energy consumption.
Drawings
FIG. 1 is a schematic diagram of the reaction system for the oxoacetylation of isobutylene to produce methyl propenol acetate as provided in example 1.
FIG. 2 is a schematic view of the structure of a first rectification system in the reaction system of example 1.
FIG. 3 is a schematic view of the structure of a second rectification system in the reaction system of example 1.
FIG. 4 is a schematic diagram of the reaction system for the oxoacetylation of isobutylene to produce methyl propenol acetate provided in example 2 and example 3.
FIG. 5 is a schematic view showing the structure of a rectifying system in the reaction system of example 2.
FIG. 6 is a schematic view showing the structure of a rectifying system in the reaction system of example 3.
FIG. 7 is a schematic diagram of the reaction system for the oxoacetylation of isobutylene to produce methyl propenol acetate as provided in example 4.
Reference numerals: 1-reactor, 2-first separator, 3-second separator, 4-extraction device, 5-first rectification system, 6-second rectification system, 7-rectification system, 8-phase separator, 9-compressor, 10-cooler, 11-acetic acid feeding unit, 12-isobutene feeding unit, 13-nitrogen feeding unit, 14-oxygen feeding unit, 19-extractant feeding unit, 20-acetic acid recovery system, rectification towers 5-1, 5-2-and 5-3 of the first rectification system 5, rectification towers 6-1 and 6-2 of the second rectification system 6, rectification towers 7-1, 7-2, 7-3, 7-4, 7-1', 7-2 7-3' are all rectification columns in the rectification system 7.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
The reaction system for preparing methyl allyl alcohol acetate by the isobutene oxyacetylation reaction shown in fig. 1 comprises a reactor 1, a first separator 2, a second separator 3, an extraction device 4, a first rectification system 5, a second rectification system 6, a feeding system, an extraction agent feeding unit 19 and an acetic acid recovery system 20;
the reactant outlet of the reactor 1 is connected with the inlet of the first separator 2; the first separator liquid outlet is connected with the inlet of the second separator 3; the second separator 3 comprises two liquid outlets: the rich-ester phase outlet is connected with the first rectification system 5, and the poor-ester phase outlet is connected with the extraction device 4; an extract liquid outlet of the extraction device 4 is connected with a second rectification system 6; the first rectification system 5 and the second rectification system 6 both comprise a methyl allyl alcohol acetate outlet and a 2-methylene-1, 3-propylene glycol diethyl ester outlet.
A feed system is connected to the reaction mass inlet of the reactor, the feed system comprising an acetic acid feed unit 11, an isobutylene feed unit 12, a nitrogen feed unit 13, and an oxygen feed unit 14.
The first rectification system 6 further comprises an isobutene outlet and an acetic acid solution outlet, the isobutene outlet is connected with the isobutene feeding unit 12, and the acetic acid solution outlet is connected with the acetic acid feeding unit 11.
The extractant feeding unit 19 is connected with a material inlet of the extraction device 4; the extractant outlet of the second rectification system is connected to an extractant feed unit 19. The raffinate outlet of the extraction apparatus 4 is connected to the acetic acid feed unit 11 and the acetic acid recovery system 20, respectively.
As shown in fig. 2, the first rectification system 5 includes three rectification columns connected in series: a first rectifying tower 5-1, a second rectifying tower 5-2 and a third rectifying tower 5-3. The material inlet of the first rectifying tower 5-1 is connected with the ester-rich phase outlet, the tower bottom of the first rectifying tower 5-1 is connected with the material inlet of the second rectifying tower 5-2, and the tower bottom of the second rectifying tower 5-2 is connected with the material inlet of the third rectifying tower 5-3. Isobutene is extracted from the top of the first rectifying tower, 2-methyl propenol acetate is extracted from the top of the second rectifying tower, 2-methylene-1, 3-propylene glycol diethyl ester is extracted from the bottom of the third rectifying tower, and acetic acid is extracted from the top of the third rectifying tower.
As shown in fig. 3, the second rectification system 6 includes two rectification columns connected in series: the device comprises a first rectifying tower 6-1 and a second rectifying tower 6-2, wherein a material inlet of the first rectifying tower 6-1 is connected with an extract liquid outlet, and the bottom of the first rectifying tower 6-1 is connected with a material inlet of the second rectifying tower 6-2. Extracting agent from the top of the first rectifying tower 6-1, 2-methyl propenol acetate from the top of the second rectifying tower 6-2, and 2-methylene-1, 3-propanediol diethyl ester from the bottom of the second rectifying tower 6-2.
Example 2
The reaction system shown in fig. 4 includes a reactor 1, a first separator 2, a second separator 3, an extraction device 4, a rectification system 7, an extractant feeding unit 19, a feeding system, and an acetic acid recovery system 20;
the reactant outlet of the reactor is connected with the inlet of the first separator; the first separator liquid outlet is connected with the second separator; the second separator comprises two liquid outlets: the rich-ester phase outlet and the poor-ester phase outlet are connected with the extraction device; the ester-rich phase outlet and the extraction liquid outlet of the extraction device are both connected with a rectification system, and the rectification system comprises a methyl allyl alcohol acetate outlet and a 2-methylene-1, 3-propylene glycol diethyl ester outlet.
The extractant feeding unit 19 is connected with the material inlet of the extraction device 4.
A feed system is connected to the reaction mass inlet of the reactor, the feed system comprising an acetic acid feed unit 11, an isobutylene feed unit 12, a nitrogen feed unit 13, and an oxygen feed unit 14.
The raffinate outlet of the extraction apparatus 4 is connected to the acetic acid feed unit 11 and the acetic acid recovery system 20, respectively. When 2-methylene-1, 3-propanediol diethyl ester, which is one of the non-systematic reaction products, is selected as the extractant, the structure of the rectification system 7 is shown in fig. 5, which comprises four rectification columns: the device comprises a first rectifying tower 7-1, a second rectifying tower 7-2, a third rectifying tower 7-3 and a fourth rectifying tower 7-4, wherein a material inlet of the first rectifying tower is connected with an ester-rich phase outlet, a material inlet of the second rectifying tower is connected with an extract liquid outlet, the tower bottoms of the first rectifying tower and the second rectifying tower are connected with a material inlet of the third rectifying tower, and the tower bottom of the third rectifying tower is connected with a material inlet of the fourth rectifying tower. Isobutene is extracted from the top of the first rectifying tower and enters an isobutene feeding unit. And extracting agent is extracted from the top of the second rectifying tower and returns to the extracting agent feeding unit. 2-methyl allyl alcohol acetate is extracted from the top of the third rectifying tower, 2-methylene-1, 3-propylene glycol diethyl ester is extracted from the tower bottom of the fourth rectifying tower, an acetic acid solution is extracted from the tower top of the fourth rectifying tower, and the acetic acid solution returns to the acetic acid feeding unit for connection.
Example 3
The difference between the system of example 3 and the system of example 2 is the rectification system.
The rectification system of example 3 is suitable for extracting agent 2-methylene-1, 3-propanediol diethyl ester, one of the reaction products of the system, is selected as the extracting agent.
As shown in fig. 6, the rectification system 7 includes three rectification columns: a first rectifying tower 7-1 ', a second rectifying tower 7-2 ' and a third rectifying tower 7-3 ', wherein a material inlet of the first rectifying tower is connected with an ester-rich phase outlet, and a material inlet of the second rectifying tower is connected with a tower kettle outlet of the first rectifying tower and an extraction liquid outlet of the extraction device; the outlet of the second rectifying tower is connected with the inlet of the third rectifying tower. Isobutene is extracted from the top of the first rectifying tower, 2-methyl propenol acetate is extracted from the top of the second rectifying tower, and 2-methylene-1, 3-propanediol diethyl ester is extracted from the tower bottom of the third rectifying tower.
Example 4
The reaction system shown in fig. 7 includes: the system comprises a reactor 1, a first separator 2, a second separator 3, a phase separator 8, an extraction device 4, a first rectification system 5, a second rectification system 6, a feeding system, an extractant feeding unit 19 and an acetic acid recovery system 20;
the reactant outlet of the reactor 1 is connected with the inlet of the first separator 2; the first separator liquid outlet is connected with the inlet of the second separator 3; the liquid phase outlet of the second separator 3 is connected with the material inlet of the phase separator 8; the phase separator 8 comprises two liquid outlets: an ester-rich phase outlet and an ester-poor phase outlet; the rich ester phase outlet is connected with the first rectification system 5, the poor ester phase outlet is connected with the extraction device 4, and the first rectification system 5 and the second rectification system 6 both comprise a methyl propenyl acetate outlet and a 2-methylene-1, 3-propylene glycol diethyl ester outlet.
A feed system is connected to the reaction mass inlet of the reactor, the feed system comprising an acetic acid feed unit 11, an isobutylene feed unit 12, a nitrogen feed unit 13, and an oxygen feed unit 14.
The first rectification system further comprises an isobutene outlet and an acetic acid solution outlet, the isobutene outlet is connected with the isobutene feeding unit, and the acetic acid solution outlet is respectively connected with the acetic acid feeding unit 11 and the acetic acid recovery system 20.
The extractant feeding unit 19 is connected with the material inlet of the extraction device 4, and the extractant outlet of the second rectification system 6 is connected with the extractant feeding unit 19. The raffinate outlet of the extraction apparatus 4 is connected to the acetic acid feed unit 11 and the acetic acid recovery system 20, respectively.
Example 5
The reaction system provided in example 1 was used. The reactor was filled with 15.0g Pd/Cu @ SiO2Catalyst, the molar ratio of oxygen to acetic acid in the feed is 1.0, the molar ratio of isobutene to acetic acid is 7.87, the acetic acid solution adopts 30.0% acetic acid water solution, the flow rate is 0.18ml/min, and the nitrogen flow rate is 380ml/min, the reaction temperature is 160 ℃, and the reaction pressure is 1.6 MPa.
Pd/Cu@SiO2The preparation method of the catalyst comprises the following steps: dissolving 1.65g of sodium tetrachloropalladate and 0.21g of copper chloride dihydrate in 60ml of deionized water, soaking the mixture on 40g of 20-40 mesh silica gel loaded with 6% sodium metasilicate, standing for 1h, drying at 150 ℃ for 12h, and roasting at 400 ℃ for 5 h; taking out, cooling, reducing with 120ml 20% hydrazine hydrate, washing, and drying; dipping 6 percent of potassium acetate to obtain Pd/Cu @ SiO2A catalyst.
Cooling the reaction product to-5 ℃ through a cooler, then feeding the reaction product into a first separator, wherein the temperature of the first separator is-5 ℃, the pressure of the first separator is 1.6MPa, the gas outlet of the first separator is nitrogen, returning the nitrogen to a nitrogen feeding system for continuous use, and feeding the liquid outlet into a second separator;
the material flow at the outlet of the first separator enters a second separator, the temperature of the second separator is 20 ℃, the pressure of the second separator is 0.1MPa, the gas outlet of the second separator is isobutene and returns to an isobutene feeding unit for continuous application, and a liquid outlet is an ester-rich phase and enters a first rectification system; the other liquid outlet is a poor ester phase and enters an extraction device;
the first rectification system 5 includes three rectification columns: the temperature of a condenser at the top of the first rectifying tower is-7.4 ℃, the temperature of a tower kettle is 91.6 ℃, the number of tower plates is 10, the number of feed plates is 3, the reflux ratio is 3, the material flow at the top of the rectifying tower is isobutene, the isobutene returns to an isobutene feed unit to be continuously used, and the material flow at the bottom of the rectifying tower enters a second rectifying tower; in the second rectifying tower, the temperature of a condenser at the top of the tower is 84.5 ℃, the temperature of a kettle of the tower is 136.8 ℃, the number of tower plates is 22, the number of feed plates is 12, the reflux ratio is 5, the material flow at the top of the rectifying tower is methyl propenyl acetate, and the material flow at the kettle of the tower enters a third rectifying tower; in the third rectifying tower, the temperature of a condenser at the top of the tower is 117.6 ℃, the temperature of a kettle of the tower is 224.4 ℃, the number of tower plates is 8, the number of feed plates is 8, the reflux ratio is 5, the material flow at the top of the rectifying tower is acetic acid, water is added to dilute the material flow until the concentration is 30.0%, the material flow returns to an acetic acid feed unit to be continuously used, and the material flow at the kettle of the rectifying tower is 2-methylene-1, 3-propylene glycol diethyl ester;
the volume ratio of the extractant to the lean ester phase in the extraction device is 1:5, the extractant adopts chloroform, the extraction temperature is 30 ℃, the pressure is 0.1MPa, the extract liquid is sent into a second rectification system, the raffinate is an aqueous solution containing a small amount of acetic acid, part of the extract liquid is added with acetic acid to 30.0 percent and then returns to an acetic acid feeding unit for continuous application, and part of the extract liquid is sent to an acetic acid recovery system 20 for recovering the acetic acid;
the second rectification system 6 comprises two rectification columns: in the first rectifying tower, the temperature of a condenser at the top of the tower is 60.7 ℃, the temperature of a tower kettle is 95.3 ℃, the number of tower plates is 30, the number of feed plates is 16, and the reflux ratio is 3. The material flow at the top of the rectifying tower is an extracting agent (chloroform), returns to an extraction device for continuous application, and enters a second rectifying tower from the tower bottom; in the second rectifying tower, the temperature of a condenser at the top of the tower is 84.6 ℃, the temperature of a kettle of the tower is 224.5 ℃, the number of tower plates is 9, the number of feed plates is 5, the reflux ratio is 2, the material flow at the top of the rectifying tower is methyl propenyl acetate, and the material flow at the kettle of the rectifying tower is 2-methylene-1, 3-propylene glycol diethyl ester.
Example 6
The reaction system provided in example 2 was used. The difference from example 5 is in the rectification system, in this example, both the ester-rich phase and the extract enter the rectification system 7.
The rectification system 7 comprises four rectification towers, wherein the ester-rich phase enters the first rectification tower, and the extract liquid enters the second rectification tower. The temperature of a condenser at the top of the first rectifying tower is-7.4 ℃, the temperature of a tower kettle is 91.6 ℃, the number of tower plates is 10, the number of feed plates is 3, the reflux ratio is 3, the material flow at the top of the rectifying tower is isobutene, the isobutene returns to an isobutene feed system to be continuously used, and the material flow at the bottom of the rectifying tower enters a third rectifying tower; the temperature of a condenser at the top of the second rectifying tower is 60.7 ℃, the temperature of a tower kettle is 95.3 ℃, the number of tower plates is 30, the number of feed plates is 16, the reflux ratio is 3, the material flow at the top of the second rectifying tower is an extracting agent (chloroform), the extracting agent (chloroform) returns to an extraction device to be continuously used, and the material flow at the bottom of the second rectifying tower and the material flow at the bottom of the first rectifying tower are converged and enter a third rectifying tower; in the third rectifying tower, the temperature of a condenser at the top of the tower is 84.5 ℃, the temperature of a kettle of the tower is 136.8 ℃, the number of tower plates is 22, the number of feed plates is 12, the reflux ratio is 5, the material flow at the top of the rectifying tower is methyl propenyl acetate, and the material flow at the kettle of the tower enters a fourth rectifying tower; and in the fourth rectifying tower, the temperature of a condenser at the top of the tower is 117.6 ℃, the temperature of a kettle of the tower is 224.4 ℃, the number of tower plates is 8, the number of feed plates is 8, the reflux ratio is 5, the material flow at the top of the rectifying tower is acetic acid, water is added to dilute the material flow until the concentration is 31.1%, the material flow returns to an acetic acid feed system to be continuously used, and the material flow at the bottom of the rectifying tower is 2-methylene-1, 3-propylene glycol diethyl ester.
Example 7
The reaction system provided in example 3 was used. The difference from the example 6 is that the extractant adopted by the extraction device is 2-methylene-1, 3-propanediol diethyl ester; the rectification system is differently set up.
The rectification system 7 comprises three rectification towers, wherein the ester-rich phase enters the first rectification tower; and the material flow at the outlet of the first rectifying tower kettle and the extraction liquid enter a second rectifying tower together. And the material flow at the outlet of the second rectifying tower enters a third rectifying tower. The temperature of a condenser at the top of the first rectifying tower is-7.4 ℃, the temperature of a tower kettle is 91.6 ℃, the number of tower plates is 10, the number of feed plates is 3, the reflux ratio is 3, the material flow at the top of the rectifying tower is isobutene, the isobutene returns to an isobutene feed system to be continuously used, and the material flow at the bottom of the rectifying tower enters a second rectifying tower; in the second rectifying tower, the temperature of a condenser at the top of the tower is 84.5 ℃, the temperature of a kettle of the tower is 136.8 ℃, the number of tower plates is 22, the number of feed plates is 12, the reflux ratio is 5, the material flow at the top of the rectifying tower is methyl propenyl acetate, and the material flow at the kettle of the tower enters a third rectifying tower; and in the third rectifying tower, the temperature of a condenser at the top of the tower is 117.6 ℃, the temperature of a kettle of the tower is 224.4 ℃, the number of tower plates is 8, the number of feed plates is 8, the reflux ratio is 5, the material flow at the top of the rectifying tower is acetic acid, water is added to dilute the material flow until the concentration is 31.1%, the material flow returns to an acetic acid feed system to be continuously used, and the material flow at the bottom of the rectifying tower is 2-methylene-1, 3-propylene glycol diethyl ester. And returning part of the 2-methylene-1, 3-propylene glycol diethyl ester to the extraction device to be continuously used as an extracting agent, and discharging part of the diethyl ester serving as a product out of the system.
Example 8
The reaction system provided in example 4 was used. The difference from example 5 is that the low pressure separator has only two outlets, one gas outlet and one liquid outlet. The gas outlet is nitrogen, the nitrogen returns to the nitrogen feeding system to be continuously used, the liquid outlet material flow enters the phase separator to separate an ester-rich phase and an ester-poor phase, the ester-rich phase enters the first rectifying system, and the ester-poor phase enters the extracting device.
Example 9
The difference from example 5 is that the isobutylene oxyacetylation catalyst used was Pa/Au @ SiO2A catalyst.
Pd/Au@SiO2The preparation method of the catalyst comprises the following steps: dissolving 1.65g of sodium tetrachloropalladate and 0.50g of sodium tetrachloroaureate dihydrate in 60ml of deionized water, soaking the mixture on 40g of 20-40 mesh silica gel loaded with 6% sodium metasilicate, standing for 1h, drying at 150 ℃ for 12h, and roasting at 400 ℃ for 5 h; taking out, cooling, reducing with 120ml 20% hydrazine hydrate, washing, and drying; dipping 6 percent of potassium acetate to obtain Pd/Au @ SiO2A catalyst.
Example 10
The difference from example 5 is that the molar ratio of isobutylene to acetic acid in the feed is 5.0.
The performance parameters of the reaction system and method of the embodiment are calculated according to the following formula:
the conversion per pass of acetic acid (molar amount of methacryl alcohol acetate in the product + molar amount of 2-methylene-1, 3-propanediol diethyl ester in the product x 2)/molar amount of acetic acid in the feed;
the acetic acid yield (molar amount of methacryl alcohol acetate in the product + molar amount of 2-methylene-1, 3-propanediol diethyl ester in the product x 2)/molar amount of acetic acid in the feed;
selectivity to methacryl alcohol acetate ═ the molar amount of methacryl alcohol acetate in the product/(the molar amount of methacryl alcohol acetate in the product + the molar amount of 2-methylene-1, 3-propanediol diethyl ester in the product);
the yield of acetic acid liquid (molar amount of methyl allyl alcohol acetate produced in unit time + molar amount of 2-methylene-1, 3-propanediol diethyl ester produced in unit time x 2)/molar amount of acetic acid feed in unit time.
The results of the performance parameters of the example reaction system and process are shown in table 1.
TABLE 1
| Examples | Acetic acid conversion per pass (%) | Acetic acid yield (%) | Selectivity to methacryl alcohol acetate (%) |
| Example 5 | 70.3 | 99.2 | 83.5 |
| Example 6 | 70.2 | 99.3 | 83.7 |
| Example 7 | 70.5 | 99.8 | 84.1 |
| Example 8 | 70.5 | 99.8 | 82.9 |
| Example 9 | 74.2 | 99.7 | 82.5 |
| Example 10 | 67.4 | 99.8 | 80.4 |
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A process for the production of methallyl alcohol acetate (2-methallyl alcohol acetate) by the oxoacetylation of isobutylene, said process comprising the steps of:
1) the acetic acid, the isobutene and the oxygen are contacted with a catalyst to react, and the nitrogen is used as a carrier gas of a gas material to obtain a reaction product;
2) separating the reaction product of the step 1) under high pressure to obtain a gas part I and a liquid part;
3) separating the liquid part obtained in the step 2) at low pressure and optionally carrying out phase separation to obtain a gas part II, an ester-rich liquid and an ester-poor liquid;
4) extracting the low-ester liquid obtained in the step 3) to obtain an extraction liquid and a raffinate; rectifying and separating the extract liquor to obtain an extracting agent, methyl allyl alcohol acetate and 2-methylene-1, 3-propylene glycol diethyl ester;
5) rectifying and separating the ester-rich liquid obtained in the step 3) to obtain isobutene, methyl allyl alcohol acetate, acetic acid solution and 2-methylene-1, 3-propylene glycol diethyl ester.
2. The method as claimed in claim 1, wherein the catalyst in step 1) is Pd/Au @ SiO supported on silica and containing Pd and Au as an auxiliary agent and potassium acetate as an auxiliary agent2Catalyst and Pd/Cu @ SiO with Pd and Cu loaded on silicon dioxide and potassium acetate as auxiliary agent2At least one of a catalyst.
Preferably, in step 1), the temperature of the reaction is 130-230 ℃; preferably, the pressure of the reaction is 0.6-2.2 MPa.
3. The method according to claim 1 or 2, wherein in step 2), the gas fraction I and/or gas fraction II is returned to step 1) for further use.
Preferably, in step 2), the operating pressure of the high-pressure separation is 1.0-2.0 MPa; preferably, the operation temperature of the high-pressure separation is-10 to 30 ℃.
4. The process according to any one of claims 1 to 3, characterized in that, in step 3), the operating pressure of the low-pressure separation is between 0.1 and 1.0 MPa; preferably, the operating temperature of the low-pressure separation is in the range of-10 to 30 ℃.
Preferably, the ester-rich liquid obtained in the step 3) and the extract liquid obtained in the step 4) enter different rectification systems respectively, or enter the same rectification system after being converged. When the ester-rich liquid and the extract liquid are converged and enter the same rectification system, five streams of material flows of isobutene, methyl allyl alcohol acetate, acetic acid solution, 2-methylene-1, 3-propylene glycol diethyl ester and an extracting agent are obtained after separation; preferably, the isobutylene is returned to the isobutylene feed system and the acetic acid solution is returned to the acetic acid feed system; preferably, the extractant is returned for reuse.
Preferably, in step 3), when the low-pressure separation cannot be performed to obtain the ester-rich liquid and the ester-poor liquid, the liquid phase obtained by the low-pressure separation is subjected to phase separation to separate the ester-rich liquid and the ester-poor liquid.
Preferably, the raffinate obtained in the step 4) is partially returned to the step 1) for continuous reaction, and is partially sent to an acetic acid recovery system for recovering acetic acid.
Preferably, the extractant obtained in step 4) is returned to the extraction step as extractant feed.
Preferably, the extractant is selected from one, two or more of toluene, chloroform, dichloromethane, carbon tetrachloride and diethyl 2-methylene-1, 3-propanediol. Preferably, the extractant 2-methylene-1, 3-propanediol diethyl ester used is the reaction product prepared by the above method.
Preferably, the isobutene and acetic acid solution obtained in step 5) is returned to step 1) as reactant feed.
5. A reaction system for preparing methyl allyl alcohol acetate by isobutylene oxyacetylation reaction is characterized by comprising a reactor, a first separator, a second separator, an extraction device and a rectification system; the rectification system comprises a first rectification system and a second rectification system;
the reactant outlet of the reactor is connected with the inlet of the first separator; the first separator liquid outlet is connected with the second separator inlet; the second separator comprises two liquid outlets: the ester-rich phase outlet is connected with the first rectification system, and the ester-poor phase outlet is connected with the extraction device; an extract liquid outlet of the extraction device is connected with the second rectification system; the first rectification system and the second rectification system both comprise a methyl allyl alcohol acetate outlet and a 2-methylene-1, 3-propylene glycol diethyl ester outlet.
Preferably, the reaction system comprises a feed system connected to the reaction mass inlet of the reactor.
Preferably, the feed system comprises an acetic acid feed unit, an isobutylene feed unit, a nitrogen feed unit, and an oxygen feed unit.
Preferably, the first rectification system further comprises an isobutene outlet and an acetic acid solution outlet. Preferably, the isobutene outlet is connected to an isobutene feed unit. Preferably, the acetic acid solution outlet is connected to an acetic acid feed unit.
Preferably, the reaction system further comprises an extractant feeding unit, and the extractant feeding unit is connected with the material inlet of the extraction device.
Preferably, the extractant outlet of the second rectification system is connected to an extractant feed unit.
6. A reaction system for preparing methyl allyl alcohol acetate by isobutylene oxyacetylation reaction is characterized by comprising a reactor, a first separator, a second separator, an extraction device and a rectification system;
the reactant outlet of the reactor is connected with the inlet of the first separator; the first separator liquid outlet is connected with the second separator; the second separator comprises two liquid outlets: the rich-ester phase outlet and the poor-ester phase outlet are connected with the extraction device; the ester-rich phase outlet and the extraction liquid outlet of the extraction device are both connected with a rectification system, and the rectification system comprises a methyl allyl alcohol acetate outlet and a 2-methylene-1, 3-propylene glycol diethyl ester outlet.
Preferably, the rectification system comprises an isobutene outlet, an acetic acid solution outlet and an extractant outlet. Preferably, the isobutene outlet is connected to an isobutene feed unit. Preferably, the acetic acid solution outlet is connected to an acetic acid feed unit. Preferably, the extractant outlet is connected to an extractant feed unit.
Preferably, the reaction system further comprises an extractant feeding unit, and the extractant feeding unit is connected with the material inlet of the extraction device.
Preferably, the number of rectification columns in the rectification system is adjusted according to the selected extractant.
Preferably, when the extractant is not 2-methylene-1, 3-propanediol diethyl ester, the rectification system can comprise four rectification towers, wherein the material inlet of the first rectification tower is connected with the ester-rich phase outlet, the material inlet of the second rectification tower is connected with the ester-poor phase outlet, the tower bottoms of the first rectification tower and the second rectification tower are both connected with the material inlet of the third rectification tower, and the tower bottom of the third rectification tower is connected with the material inlet of the fourth rectification tower. Preferably, isobutene is withdrawn from the top of the first rectification column. Preferably, the extractant is withdrawn from the top of the second rectification column. Preferably, 2-methyl propenol acetate is withdrawn from the top of the third rectification column. Preferably, the tower bottom of the fourth rectifying tower produces 2-methylene-1, 3-propanediol diethyl ester.
Preferably, when the extractant is 2-methylene-1, 3-propanediol diethyl ester which is one of reaction products in the system, the rectification system can comprise three rectification towers, wherein a material inlet of the first rectification tower is connected with an ester-rich phase outlet, and a material inlet of the second rectification tower is connected with a tower kettle outlet of the first rectification tower and an extraction liquid outlet of the extraction device; the outlet of the second rectifying tower is connected with the inlet of the third rectifying tower. Preferably, isobutene is withdrawn from the top of the first rectification column. Preferably, 2-methyl propenol acetate is withdrawn from the top of the second rectification column. Preferably, the tower bottom of the third rectifying tower produces 2-methylene-1, 3-propanediol diethyl ester.
7. A reaction system for preparing methyl allyl alcohol acetate by isobutylene oxyacetylation reaction is characterized by comprising a reactor, a first separator, a second separator, a phase separator, an extraction device and a rectification system; the rectification system comprises a first rectification system and a second rectification system;
the reactant outlet of the reactor is connected with the inlet of the first separator; the first separator liquid outlet is connected with the second separator inlet; the liquid phase outlet of the second separator is connected with the material inlet of the phase separator; the phase separator includes two liquid outlets: an ester-rich phase outlet and an ester-poor phase outlet; the rich-ester phase outlet is connected with the first rectification system, the poor-ester phase outlet is connected with the extraction device, and the first rectification system and the second rectification system respectively comprise a methyl propenyl acetate outlet and a 2-methylene-1, 3-propylene glycol diethyl ester outlet.
Preferably, the reaction system comprises a feed system connected to the reaction mass inlet of the reactor.
Preferably, the feed system comprises an acetic acid feed unit, an isobutylene feed unit, a nitrogen feed unit, and an oxygen feed unit.
Preferably, the first rectification system further comprises an isobutene outlet and an acetic acid solution outlet. Preferably, the isobutene outlet is connected to an isobutene feed unit. Preferably, the acetic acid solution outlet is connected to an acetic acid feed unit.
Preferably, the reaction system further comprises an extractant feeding unit, and the extractant feeding unit is connected with the material inlet of the extraction device.
Preferably, the extractant outlet of the second rectification system is connected to an extractant feed unit.
8. A system according to any of claims 5 to 7, wherein the gas outlet of the first separator is connected to a feed system, preferably to a nitrogen feed unit.
Preferably, the gas outlet of the second separator is connected to a feed system, preferably to an isobutene feed unit.
Preferably, the reaction system further comprises an acetic acid recovery system for recovering acetic acid from the raffinate exiting the extraction unit and/or acetic acid from the rectification system.
Preferably, the raffinate outlet of the extraction unit is connected to a feed system and/or an acetic acid recovery system, preferably to an acetic acid feed unit and/or an acetic acid recovery system.
Preferably, the first separator and the second separator are both gas-liquid separators.
9. The system according to claim 5 or 7, wherein the first rectification system comprises three rectification columns connected in series, the material inlet of the first rectification column is connected with the ester-rich phase outlet, the bottom of the first rectification column is connected with the material inlet of the second rectification column, and the bottom of the second rectification column is connected with the material inlet of the third rectification column. Preferably, isobutene is extracted from the top of the first rectifying tower. Preferably, 2-methyl allyl alcohol acetate is extracted from the top of the second rectifying tower. Preferably, the tower bottom of the third rectifying tower produces 2-methylene-1, 3-propanediol diethyl ester. Preferably, acetic acid is taken out from the top of the third rectifying tower.
Preferably, the second rectification system comprises two rectification towers connected in series, a material inlet of the first rectification tower is connected with an extract liquid outlet, and the tower bottom of the first rectification tower is connected with a material inlet of the second rectification tower. Preferably, the extractant is extracted from the top of the first rectifying tower. Preferably, 2-methyl allyl alcohol acetate is extracted from the top of the second rectifying tower. Preferably, 2-methylene-1, 3-propanediol diethyl ester is extracted from the tower bottom of the second rectifying tower.
10. The method for preparing methyl allyl alcohol acetate by the oxo acetylation of isobutylene as described in any one of claims 1 to 4 is carried out in the reaction system as described in any one of claims 5 to 9.
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| CN103119007A (en) * | 2010-09-21 | 2013-05-22 | 昭和电工株式会社 | Process for production of allyl acetate |
| CN103351279A (en) * | 2013-07-01 | 2013-10-16 | 太仓市恒益医药化工原料厂 | Method for continuous preparation of allyl alcohol from propylene |
| WO2020022365A1 (en) * | 2018-07-27 | 2020-01-30 | 株式会社クラレ | Method for producing 1-acyloxy-2-methyl-2-propene |
| CN109942370A (en) * | 2019-04-03 | 2019-06-28 | 山东理工大学 | The technique of green high-efficient synthesizing methyl allyl alcohol |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114160156A (en) * | 2021-11-16 | 2022-03-11 | 北京水木滨华科技有限公司 | Olefin oxygen acetylation catalyst, preparation method and application thereof |
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