KR-20260065884-A - Alkene hydrogenation integration in vinyl acetate manufacturing system and method

KR20260065884AKR 20260065884 AKR20260065884 AKR 20260065884AKR-20260065884-A

Abstract

A method for producing vinyl acetate at a higher production rate can be achieved by increasing the flammability limit of the mixture in the vinyl acetate reactor. For example, methane and/or higher-order carbon alkanes (e.g., alkanes having two or more carbons, also referred to herein as C2+ alkanes) among the diluents in the vinyl acetate reactor can increase the flammability limit. For example, a method for producing vinyl acetate may include the following steps: reacting one or more alkenes with hydrogen via a hydrogenation reaction in the presence of a hydrogenation catalyst to produce one or more alkanes; and reacting acetic acid, ethylene, and oxygen via an acetoxylation reaction in the presence of an acetoxylation catalyst and an alkane diluent to produce vinyl acetate and water (wherein the alkane diluent comprises one or more alkanes produced from the hydrogenation reaction).

Inventors

살라도, 마누엘 씨.
슈미트, 우르스 엠.
알렉산더, 스티브 알.
뮐러, 션
서머빌, 스테이시
첸, 라이위안

Assignees

셀라니즈 인터내셔날 코포레이션

Dates

Publication Date: 20260511
Application Date: 20240905
Priority Date: 20230906

Claims (20)

As a method for manufacturing vinyl acetate, A step of producing one or more alkanes by reacting one or more alkenes with hydrogen through a hydrogenation reaction in the presence of a hydrogenation catalyst; and A step of reacting acetic acid, ethylene, and oxygen via an acetoxylation reaction in the presence of an acetoxylation catalyst and an alkane diluent to produce vinyl acetate and water (wherein the alkane diluent comprises one or more alkanes produced from the hydrogenation reaction). A method including
A method according to claim 1, wherein the alkane diluent further comprises methane.
In paragraph 2, the method wherein the methane is present in the alkane diluent in an amount of 0.1 mol% to 5 mol% based on the total molar of the alkane diluent.
A method according to claim 1, wherein the one or more alkenes comprise one or more of ethylene, propylene, and butylene.
A method according to claim 4, wherein the alkane diluent comprises ethane, propane, and optionally methane, at least a portion of the ethane and propane is produced from the hydrogenation reaction, the ethane is present in the alkane diluent in an amount of 0.1 mol% to 99.9 mol% based on the total mole of the alkane diluent, the propane is present in the alkane diluent in an amount of 0.1 mol% to 99.9 mol% based on the total mole of the alkane diluent, and the methane is present in the alkane diluent in an amount of 0 mol% to 5 mol% based on the total mole of the alkane diluent.
A method according to claim 4, wherein the alkane diluent comprises ethane, propane, and optionally methane, at least a portion of the ethane and propane is produced from the hydrogenation reaction, the ethane is present in the alkane diluent at 0.1 mol% to 50 mol% based on the total mole of the alkane diluent, the propane is present in the alkane diluent at 50 mol% to 99.9 mol% based on the total mole of the alkane diluent, and the methane is present in the alkane diluent at 0 mol% to 5 mol% based on the total mole of the alkane diluent.
A method according to claim 1, wherein the alkane diluent comprises tail gas from a natural gas concentration process.
In paragraph 1, A step of performing the hydrogenation reaction in a hydrogenation reactor; A step of introducing a hydrogen stream into the above hydrogenation reactor; and A step of treating the hydrogen stream before introducing it into the hydrogenation reactor to reduce the concentration of carbon monoxide in the hydrogen stream. A method that additionally includes
In claim 1, the acetoxylation reaction produces an unpurified vinyl acetate stream, the unpurified vinyl acetate stream further comprises unreacted ethylene, and the method A step of processing the above-mentioned unpurified vinyl acetate stream to recover at least a portion of the above-mentioned unreacted ethylene and at least a portion of the above-mentioned alkane diluent in the ethylene recovery stream; and Step of recirculating the ethylene recovery stream to the acetoxylation reaction A method that additionally includes
In claim 1, the hydrogenation reaction produces a product stream comprising one or more alkanes and optionally hydrogen, and the method A step of monitoring the hydrogen concentration in the product stream generated from the above hydrogenation reaction; and When the hydrogen concentration in the product stream from the hydrogenation reactor exceeds 1 mol% based on the total moles present in the product stream, the step of reducing the amount of one or more alkanes produced from the hydrogenation reaction in the alkane diluent and adding methane to the alkane diluent. A method that additionally includes
As a method for manufacturing vinyl acetate, A step of reacting a feed stream comprising acetic acid, ethylene, oxygen, and an alkane diluent in a vinyl acetate reactor to produce a crude vinyl acetate stream comprising vinyl acetate, water, and said alkane diluent; A step of cooling the above unpurified vinyl acetate stream in a heat exchanger; A step of separating the above-mentioned unpurified vinyl acetate stream into a first tail gas stream, a flash gas stream, and a vinyl acetate stream (wherein the first tail gas stream comprises ethylene and the alkane diluent, the flash gas stream comprises ethylene, carbon dioxide, and the alkane diluent, and the vinyl acetate stream comprises vinyl acetate); A step of adding a second tail gas stream from a natural gas concentration system to the first tail gas stream (wherein one or more alkanes become part of the alkane diluent); A step of removing at least a portion of carbon dioxide from the flash gas stream to produce one or more recirculation streams comprising ethylene and the alkane diluent; A step of mixing the vaporized acetic acid in a vaporizer with at least one of the first tail gas stream and the one or more recirculation streams to produce a vaporized stream; and A step of adding oxygen to the above vaporized stream to generate the above supply stream. A method including
As a method for manufacturing vinyl acetate, A step of reacting a feed stream comprising acetic acid, ethylene, oxygen, and an alkane diluent in a vinyl acetate reactor to produce a crude vinyl acetate stream comprising vinyl acetate, water, and said alkane diluent; A step of cooling the above unpurified vinyl acetate stream in a heat exchanger; A step of separating the above-mentioned unpurified vinyl acetate stream into a tail gas stream, a flash gas stream, and a vinyl acetate stream (wherein the tail gas stream comprises ethylene and the alkane diluent, the flash gas stream comprises ethylene, carbon dioxide, and the alkane diluent, and the vinyl acetate stream comprises vinyl acetate); A step of reacting one or more alkenes with hydrogen through a hydrogenation reaction in a hydrogenation reactor in the presence of a hydrogenation catalyst to produce a product stream containing one or more alkanes and optionally hydrogen; A step of adding at least a portion of the product stream to the tail gas stream (wherein one or more alkanes become part of the alkane diluent); A step of monitoring the hydrogen concentration in the product stream (wherein when the hydrogen concentration exceeds 1 mol% based on the total moles present in the product stream, (a) a step of reducing the amount of the product stream from the hydrogenation reactor added to the tail gas stream; and (b) adding a methane feed stream to the tail gas stream to become part of the alkane diluent One or both are performed); A step of removing at least a portion of the carbon dioxide from the flash gas stream to produce one or more recirculation streams comprising ethylene and the alkane diluent; A step of mixing the vaporized acetic acid with at least one of the tail gas stream and the one or more recirculation streams in a vaporizer to produce a vaporized stream; and A step of adding oxygen to the above vaporized stream to generate the above supply stream. A method including
In paragraph 12, the tail gas stream is a first tail gas stream, and the method A method further comprising the step of adding a second tail gas stream from a natural gas concentration system to the first tail gas stream (wherein one or more alkanes become part of the alkane diluent).
A method according to claim 12, wherein the alkane diluent of the supply stream comprises 0.1 mol% to 5 mol% of methane based on the total mole of the alkane diluent.
A method according to claim 12, wherein the alkane diluent of the supply stream comprises 0 mol% to 0.1 mol% of methane based on the total mole of the alkane diluent.
In claim 12, the method wherein the one or more alkenes comprises one or more of ethylene, propylene, and butylene.
In claim 16, the alkane diluent of the feed stream comprises ethane, propane, and optionally methane, and at least a portion of the ethane and the propane is produced from the hydrogenation reaction, the ethane is present in the alkane diluent of the feed stream in an amount of 0.1 mol% to 99.9 mol% based on the total mole of the alkane diluent, the propane is present in the alkane diluent of the feed stream in an amount of 0.1 mol% to 99.9 mol% based on the total mole of the alkane diluent, and the methane is present in the alkane diluent of the feed stream in an amount of 0 mol% to 5 mol% based on the total mole of the alkane diluent.
In claim 16, the alkane diluent of the feed stream comprises ethane, propane, and optionally methane, and at least a portion of the ethane and the propane is produced from the hydrogenation reaction, the ethane is present in the alkane diluent of the feed stream in an amount of 0.1 mol% to 50 mol% based on the total mole of the alkane diluent, the propane is present in the alkane diluent of the feed stream in an amount of 50 mol% to 99.9 mol% based on the total mole of the alkane diluent, and the methane is present in the alkane diluent of the feed stream in an amount of 0 mol% to 5 mol% based on the total mole of the alkane diluent.
As a method for manufacturing vinyl acetate, (i) a step of producing one or more alkanes through a hydrogenation reaction and/or (ii) a step of producing concentrated natural gas and tail gas by performing a natural gas concentration process; and (i) a step of producing vinyl acetate through an acetoxylation reaction of acetic acid, ethylene, and oxygen, carried out in the presence of one or more alkanes produced from the hydrogenation reaction and/or (ii) an alkane diluent containing the tail gas. A method including
A method according to claim 19, wherein the alkane diluent comprises ethane, propane, and optionally methane, at least a portion of the ethane and the propane is produced from the hydrogenation reaction and/or the tail gas, the ethane is present in the alkane diluent in an amount of 0.1 mol% to 99.9 mol% based on the total mole of the alkane diluent, the propane is present in the alkane diluent in an amount of 0.1 mol% to 99.9 mol% based on the total mole of the alkane diluent, and the methane is present in the alkane diluent in an amount of 0 mol% to 5 mol% based on the total mole of the alkane diluent.

Description

Alkene hydrogenation integration in vinyl acetate manufacturing system and method Cross-reference regarding related applications This application claims priority to U.S. Provisional Application No. 63/580,797 filed September 6, 2023 (Title of invention: "INCORPORATION OF ALKENE HYDROGENATION IN VINYL ACETATE PRODUCTION SYSTEMS AND METHODS"), the full text of which is incorporated herein by reference. Statement regarding rights to inventions made under U.S. federal government-supported research and development Not applicable Reference to "sequence lists," tables, or appendices to computer program lists submitted on compact disc Not applicable Vinyl acetate is typically produced through a gas-phase reaction of ethylene, oxygen, and acetic acid, where the ethylene is acetoxylated. As the oxygen concentration within the reactor increases, the rate of acetoxylation increases. However, the amount of oxygen that can be introduced into the reactor is limited by the flammability limit of the reaction mixture. The flammability limit is generally defined as the lowest concentration of oxygen in the mixture that causes a pressure rise when the mixture comes into contact with an ignition source. If the oxygen concentration exceeds this flammability limit, a fire or explosion may occur. It is desirable to change the reactor and/or gas-phase components to increase the flammability limit and, consequently, the production capacity of the reactor. Non-limiting examples of a method for producing vinyl acetate may include: a step of reacting one or more alkenes with hydrogen via a hydrogenation reaction in the presence of a hydrogenation catalyst to produce one or more alkanes; and a step of reacting acetic acid, ethylene, and oxygen via an acetoxylation reaction in the presence of an acetoxylation catalyst and an alkane diluent to produce vinyl acetate and water (wherein the alkane diluent comprises one or more alkanes produced from the hydrogenation reaction). Other non-limiting examples of a method for producing vinyl acetate may include: reacting a feed stream comprising acetic acid, ethylene, oxygen, and an alkane diluent in a vinyl acetate reactor to produce a raw vinyl acetate stream comprising vinyl acetate, water, and an alkane diluent; cooling the raw vinyl acetate stream in a heat exchanger; separating the raw vinyl acetate stream into a first tail gas stream, a flash gas stream, and a vinyl acetate stream (wherein the first tail gas stream comprises ethylene and an alkane diluent, the flash gas stream comprises ethylene, carbon dioxide, and an alkane diluent, and the vinyl acetate stream comprises vinyl acetate); adding a second tail gas stream from a natural gas concentration system to the first tail gas stream (wherein one or more alkanes become part of the alkane diluent); removing at least a portion of carbon dioxide from the flash gas stream to produce one or more recirculation streams comprising ethylene and an alkane diluent; A step of mixing vaporized acetic acid in a vaporizer with at least one of a first tail gas stream and one or more recirculation streams to produce a vaporized stream; and a step of adding oxygen to the vaporized stream to produce a feed stream. Another non-limiting example of a method for producing vinyl acetate may include: reacting a feed stream comprising acetic acid, ethylene, oxygen, and an alkane diluent in a vinyl acetate reactor to produce a raw vinyl acetate stream comprising vinyl acetate, water, and an alkane diluent; cooling the raw vinyl acetate stream in a heat exchanger; separating the raw vinyl acetate stream into a tail gas stream, a flash gas stream, and a vinyl acetate stream (wherein the tail gas stream comprises ethylene and an alkane diluent, the flash gas stream comprises ethylene, carbon dioxide, and an alkane diluent, and the vinyl acetate stream comprises vinyl acetate); reacting one or more alkenes with hydrogen via a hydrogenation reaction in a hydrogenation reactor in the presence of a hydrogenation catalyst to produce a product stream comprising one or more alkanes and optionally hydrogen; adding at least a portion of the product stream to the tail gas stream (wherein one or more alkanes become part of the alkane diluent); A step of monitoring the hydrogen concentration in an alkane feed stream (wherein when the hydrogen concentration exceeds 1 mol% based on the total moles present in the product stream, one or both of (a) reducing the amount of product stream from the hydrogenation reactor added to the tail gas stream; and (b) adding a methane feed stream to the tail gas stream to become part of the alkane diluent); a step of removing at least a portion of carbon dioxide from a flash gas stream to produce one or more recirculation streams containing ethylene and an alkane diluent; a step of mixing vaporized acetic acid in a vaporizer with at least one of the tail gas stream and one or more recirculation streams to produce a vaporized stream; and a step of