CN104529765A - Reaction device and method for producing methyl propionate - Google Patents
Reaction device and method for producing methyl propionate Download PDFInfo
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- CN104529765A CN104529765A CN201410797826.5A CN201410797826A CN104529765A CN 104529765 A CN104529765 A CN 104529765A CN 201410797826 A CN201410797826 A CN 201410797826A CN 104529765 A CN104529765 A CN 104529765A
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- methyl propionate
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- carbonylation reactor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
Abstract
The invention relates to a reaction device and a reaction method for producing methyl propionate. The reaction device comprises a static-state mixer, a carbonylation reactor, a flash evaporator, a light component removal tower, a catalyst recycling reactor and a liquid-liquid separation tower. According to the device and the method, a product which contains tar and is discharged by the carbonylation reactor is subjected to flash evaporation and separation; byproducts with low molecular weight produced in the reaction process is separated by using the light component removal tower; precious metal ions, methanol, propionic acid and methyl propionate are extracted by using warm water; a part of heavy phases which come out of the flash evaporator is fully mixed with the water, so that a part of organic matters with low molecular weight in the heavy phase and the precious metal ions are dissolved into a water phase; the separation of the tar and the water phase is realized in the liquid-liquid separation tower, and a water-phase mixture is finally sent back to the carbonylation reactor, so that the accumulation of the tar in the reaction system is reduced, and the loss of methanol is reduced.
Description
Technical field
The invention belongs to chemical preparation method field, particularly relate to a kind of reaction unit and method of producing methyl propionate.
Background technology
Methyl propionate is a kind of water white organic liquid, is widely used as the solvent of high-grade food and makeup, also can as a kind of excellent additive, sanitas or spices, among Partial Food, feed.Methyl propionate usually adopts propionic acid and methanol esterification to react and obtains, and domestic propionic acid main source is the propionic acid of acetic acid synthesis from methanol carbonylation byproduct in process.Along with the increase of propionic acid demand, oxo process methyl propionate is also brought into schedule.In the process of carbonylation synthesis methyl propionate, general use precious metal ion compound makees catalyzer, as the compound of palladium.Along with the carrying out of reaction, intrasystem higher molecular weight compound can accumulate gradually with tar form.These tar can reduce reaction efficiency, and increase the difficulty of later separation step.At our research process
(CN103319337A) find in, having of water is beneficial to the stable of reactive system, so introduce water as extraction agent in reaction process system, reclaim precious metal ion, methyl alcohol, propionic acid and methyl propionate, the tar in reactive system is made to control at a more stable content, to ensure the stability of reactive system.
Summary of the invention
The technical problem to be solved in the present invention is avoid above-mentioned the deficiencies in the prior art part and provide a kind of reaction unit and method of producing methyl propionate, effectively can control tar accumulation in systems in which, realize your catalyst recycling, ensure that the continuous stability of reactive system and the high efficiency of reaction.
The present invention is achieved through the following technical solutions:
Produce a reaction unit for methyl propionate, comprise the static mixer, carbonylation reactor and the flasher that connect successively, described flasher top is connected with lightness-removing column, and described flasher base is connected with catalyst recovery reactor; Described lightness-removing column tail gas is out by entering exhaust treatment system after condenser, and the bottom of described lightness-removing column is connected with rectified purified system; Described catalyst recovery reactor is connected with Liquid liquid Separation tower, and be separated through described Liquid liquid Separation tower the upper materials obtained and enter tar incineration system, the heavy phase obtained returns carbonylation reactor.
Preferably, gas distributor is provided with bottom described carbonylation reactor.
Utilize above-mentioned reaction unit to produce a method for methyl propionate, comprise the following steps:
(1) ethene and CO are transported to static mixer, then deliver into the gas distributor bottom carbonylation reactor from static mixer, methyl alcohol is delivered into carbonylation reactor, in carbonylation reactor, carry out stirring reaction and obtain product, be i.e. methyl propionate and a small amount of propionic acid;
(2) product that step (1) obtained is sent into flasher and is separated, the light phase obtained, i.e. mainly methyl alcohol, methyl propionate and water; The heavy phase obtained, i.e. mainly tar, methyl propionate, methyl alcohol, water and precious metal ion;
(3) the light lightness-removing column of sending into mutually step (2) obtained is separated, and from the organic phase that lightness-removing column top cools down, i.e. mainly methyl alcohol and methyl propionate, sends carbonylation reactor back to; Enter exhaust gas recovery system from condenser tail gas out, bottom lightness-removing column, material out enters rectified purified system;
(4) heavy phase portion circulation step (2) obtained enters carbonylation reactor, and part sends into catalyst recovery reactor.In catalyst recovery reactor, add deionized water, high-temperature stirring mixes, and obtains mixture;
(5) step (4) obtained being separated in Liquid liquid Separation tower that mixture sends into, the upper materials obtained, i.e. mainly tar, enter tar-processing system; The heavy phase obtained, i.e. mainly water, methyl alcohol, methyl propionate, propionic acid and precious metal ion, turn back to carbonylation reactor.
Preferably, in described step (1), the mol ratio of ethene and CO is 1:1, and working pressure 1.5MPa in described carbonylation reactor, service temperature 110 DEG C, stirring velocity is r=200, residence time 70min.
Preferably, in described step (2), the working pressure of flasher is 0.2MPa, and service temperature is 100 DEG C.
Preferably, working pressure 0.1MPa in described step (4) catalyst recovery reactor, service temperature 140 DEG C, stirring velocity is r=300, residence time 40min.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention establishes the operational path of the continuous seepage methyl propionate of complete set, economic environmental protection, is applicable to industrialization scale operation, effectively can controls tar accumulation in systems in which, realize your catalyst recycling, ensure that the continuous stability of reactive system and the high efficiency of reaction.
First the present invention carries out flash separation to the mixture that carbonylation reactor is discharged, the heavy phase extracting part of flash separation is divided and is entered catalyst recovery reactor and process, be about to add deionized water containing the heavy phase portion such as tar, catalyzer and carry out comparatively high temps process and fully mixing, make the noble metal catalyst of the coal-tar middle oil absorption of heavy phase, methyl alcohol, methyl propionate and propionic acid be dissolved in aqueous phase, then enter Liquid liquid Separation tower.Subnatant in Liquid liquid Separation tower returns to carbonylation reactor through pump, achieves catalyst recovery, has also reclaimed part methyl alcohol, propionic acid and methyl propionate, thus decreases the emission loss of material.In Liquid liquid Separation tower, upper liquid mainly tar, finally enters tar incineration system.In order to remove the low molecular weight by-products produced in reaction process further, as acetaldehyde, methane etc., the material of going out through flashing tower enters the by product that lightness-removing column removes impact reaction further, the methyl alcohol that condenser of light component removal column reclaims, methyl propionate mixture return carbonylation reactor, decrease the emission loss of material.This technological process adopts water as extraction agent, and the noble metal catalyst that can realize more than 98% reclaims and recycle.
Figure of description
Fig. 1 is the process flow diagram that the present invention produces methyl propionate.
Mark in figure: (1) static mixer, (2) carbonylation reactor, (3) flasher, (4) lightness-removing column, (5) condenser, (6) catalyst recovery reactor, (7) Liquid liquid Separation tower.
Embodiment
Below in conjunction with embodiment, foregoing invention content of the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make various replacement and change, all should comprise within the scope of the invention.
Embodiment 1:
As shown in Figure 1, a kind of reaction unit producing methyl propionate, comprises the static mixer, carbonylation reactor and the flasher that connect successively, and described flasher top is connected with lightness-removing column, and described flasher base is connected with catalyst recovery reactor; Described lightness-removing column tail gas is out by entering exhaust treatment system after condenser, and the bottom of described lightness-removing column is connected with rectified purified system; Described catalyst recovery reactor is connected with Liquid liquid Separation tower, and be separated through described Liquid liquid Separation tower the upper materials obtained and enter tar incineration system, the heavy phase obtained returns carbonylation reactor.Gas distributor (not shown) is provided with bottom described carbonylation reactor.
Process flow diagram is see Fig. 1, and industrial ethylene (the ethene storage tank from raw material district) and CO (the CO gas holder from raw material district) enter static mixer by 1:1 through pipeline, enter carbonylation reactor after mixing; Industrial methanol (from raw material district methanol tank) enters carbonylation reactor through pipeline; Working pressure 1.5MPa in carbonylation reactor, service temperature 110 DEG C, stirring velocity is r=200, residence time 70min, reaction product (P2) enters flasher through pipeline, the working pressure of flasher is 0.2MPa, service temperature is 100 DEG C, tower top obtains material (SQ3) mainly containing methyl propionate, methyl alcohol and a small amount of low molecular weight by-products, resolution gas, obtains material (SZ3) mainly containing tar, water, precious metal ion and propionic acid, methyl propionate, methyl alcohol at the bottom of tower.
Material (SQ3) enters dehydrogenation tower and is separated, the organic phase (TY1) cooled down from lightness-removing column top, i.e. mainly methyl alcohol and methyl propionate, sends carbonylation reactor back to; Exhaust gas recovery system is entered from lightness-removing column water cooler tail gas (WQ3) out.Bottom lightness-removing column, material (TY2) out enters rectified purified system.
2/3rds circulations that material (ZS3-1) is about material (ZS3) enter carbonylation reactor, material (ZS3-2) is about 1/3rd of material (ZS3) and sends into catalyst recovery reactor, add deionized water and approximate material (ZS3-2), reclaim working pressure 0.1MPa in reactor, service temperature 140 DEG C, stirring velocity is r=300, residence time 40min, is uniformly mixed into material (RH6).Be separated in the Liquid liquid Separation tower that material (RH6) is sent into, the upper materials (CQ7) obtained, i.e. mainly tar, enter tar-processing system; The heavy phase (CZ7) obtained, i.e. mainly water, methyl alcohol, methyl propionate, propionic acid and precious metal ion, turn back to carbonylation reactor.
The each material composition of table 1
Claims (6)
1. produce a reaction unit for methyl propionate, it is characterized in that: comprise the static mixer, carbonylation reactor and the flasher that connect successively, described flasher top is connected with lightness-removing column, and described flasher base is connected with catalyst recovery reactor; Described lightness-removing column tail gas is out by entering exhaust treatment system after condenser, and the bottom of described lightness-removing column is connected with rectified purified system; Described catalyst recovery reactor is connected with Liquid liquid Separation tower, and be separated through described Liquid liquid Separation tower the upper materials obtained and enter tar incineration system, the heavy phase obtained returns carbonylation reactor.
2. the reaction unit of production methyl propionate according to claim 1, is characterized in that: be provided with gas distributor bottom described carbonylation reactor.
3. utilize reaction unit as claimed in claim 2 to produce a method for methyl propionate, its feature comprises the following steps:
(1) ethene and CO are transported to static mixer, then deliver into the gas distributor bottom carbonylation reactor from static mixer, methyl alcohol is delivered into carbonylation reactor, in carbonylation reactor, carry out stirring reaction and obtain product, be i.e. methyl propionate and a small amount of propionic acid;
(2) product that step (1) obtained is sent into flasher and is separated, the light phase obtained, i.e. mainly methyl alcohol, methyl propionate and water; The heavy phase obtained, i.e. mainly tar, methyl propionate, methyl alcohol, water and precious metal ion;
(3) the light lightness-removing column of sending into mutually step (2) obtained is separated, and from the organic phase that lightness-removing column top cools down, i.e. mainly methyl alcohol and methyl propionate, sends carbonylation reactor back to; Enter exhaust gas recovery system from condenser tail gas out, bottom lightness-removing column, material out enters rectified purified system;
(4) heavy phase portion circulation step (2) obtained enters carbonylation reactor, and part sends into catalyst recovery reactor, in catalyst recovery reactor, add deionized water, and high-temperature stirring mixes, and obtains mixture;
(5) step (4) obtained being separated in Liquid liquid Separation tower that mixture sends into, the upper materials obtained, i.e. mainly tar, enter tar-processing system; The heavy phase obtained, i.e. mainly water, methyl alcohol, methyl propionate, propionic acid and precious metal ion, turn back to carbonylation reactor.
4. the method for production methyl propionate according to claim 3, it is characterized in that: in described step (1), the mol ratio of ethene and CO is 1:1, working pressure 1.5MPa in described carbonylation reactor, service temperature 110 DEG C, stirring velocity is r=200, residence time 70min.
5. the method for production methyl propionate according to claim 3, is characterized in that: in described step (2), the working pressure of flasher is 0.2MPa, and service temperature is 100 DEG C.
6. the method for production methyl propionate according to claim 3, is characterized in that: working pressure 0.1MPa in described step (4) catalyst recovery reactor, service temperature 140 DEG C, and stirring velocity is r=300, residence time 40min.
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| CN201410797826.5A CN104529765B (en) | 2014-12-18 | 2014-12-18 | A kind of reaction unit and method of producing methyl propionate |
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| CN201410797826.5A CN104529765B (en) | 2014-12-18 | 2014-12-18 | A kind of reaction unit and method of producing methyl propionate |
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| CN104529765A true CN104529765A (en) | 2015-04-22 |
| CN104529765B CN104529765B (en) | 2016-04-13 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409541A (en) * | 2020-10-28 | 2022-04-29 | 上海浦景化工技术股份有限公司 | System for preparing propionate through ethylene carbonylation |
| CN115282913A (en) * | 2022-08-12 | 2022-11-04 | 中国海洋石油集团有限公司 | Reaction system and method for preparing methyl propionate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999036385A1 (en) * | 1998-01-17 | 1999-07-22 | Ineos Acrylics Uk Limited | Production of alkyl esters |
| CN103319337A (en) * | 2013-06-28 | 2013-09-25 | 西南化工研究设计院有限公司 | Method for synthesizing methyl propionate by ethylene |
| CN203451407U (en) * | 2013-07-30 | 2014-02-26 | 常州市松盛香料有限公司 | Device for producing methyl propionate |
-
2014
- 2014-12-18 CN CN201410797826.5A patent/CN104529765B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999036385A1 (en) * | 1998-01-17 | 1999-07-22 | Ineos Acrylics Uk Limited | Production of alkyl esters |
| CN103319337A (en) * | 2013-06-28 | 2013-09-25 | 西南化工研究设计院有限公司 | Method for synthesizing methyl propionate by ethylene |
| CN203451407U (en) * | 2013-07-30 | 2014-02-26 | 常州市松盛香料有限公司 | Device for producing methyl propionate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409541A (en) * | 2020-10-28 | 2022-04-29 | 上海浦景化工技术股份有限公司 | System for preparing propionate through ethylene carbonylation |
| CN115282913A (en) * | 2022-08-12 | 2022-11-04 | 中国海洋石油集团有限公司 | Reaction system and method for preparing methyl propionate |
| CN115282913B (en) * | 2022-08-12 | 2024-01-09 | 中国海洋石油集团有限公司 | Reaction system and method for preparing methyl propionate |
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| CN104529765B (en) | 2016-04-13 |
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