CN1740131A - Low pressure methanol carboxylating process to synthesize acetic acid - Google Patents
Low pressure methanol carboxylating process to synthesize acetic acid Download PDFInfo
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- CN1740131A CN1740131A CN 200510021617 CN200510021617A CN1740131A CN 1740131 A CN1740131 A CN 1740131A CN 200510021617 CN200510021617 CN 200510021617 CN 200510021617 A CN200510021617 A CN 200510021617A CN 1740131 A CN1740131 A CN 1740131A
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Abstract
The low pressure methanol carboxylating process to synthesize acetic acid includes acetic acid synthesis inside reaction liquid in the presence of rhodium-iodine catalyst system, adding morphinone compound, morphinone salt derivative or other additive to stabilize the catalyst system, and separating the coarse product through flash evaporation-evaporation process. The present invention has specific component added to constitute high activity and high stability catalyst system and has greatly raised production capacity of the reactor.
Description
Technical field
The present invention relates to a kind of method of synthesizing acetic acid by methanol low-pressure carbonylation, this method is included in rhodium-iodine catalyst system and exists the following acetic acid that carries out in reaction solution synthetic.
Background technology
Since going into operation, become the main production method of world production acetic acid by the acetic acid synthesis process by low-pressure methanol carbonylation of U.S. Monsanto Company exploitation at present.The halogenide of this process using rhodium is that catalyzer, methyl iodide are promotor, has realized methyl alcohol and carbon monoxide carbonyl synthesis acetic acid under 2.8-3.0MPa and 175-185 ℃.Because active ingredient rhodium complex [Ph (CO) in the reaction system
2I
2]
-Unstable, make and from reaction solution, to take out method based on the thick product of acetic acid, selected for use the recycle stock that is multiple times than methyl alcohol to carry out flash distillation.All a lot of improvement occur on the basis of technology at Meng Shan over more than 30 year, and formed many new technologies, as: the Cativa technology of the AO technology of U.S. Celanese Corp., Britain BP company.The former adds lithium iodide in rhodium-catalysis of iodine system, to improve the stability of rhodium catalyst, reduce water-content simultaneously; The latter then changes rhodium-catalysis of iodine system into iridium-catalysis of iodine system, and uses multiple new auxiliary agent, and as rhenium, ruthenium, osmium etc., the iridium catalyst systems activity is higher than rhodium catalyst, has reduced water-content simultaneously.The thick product of these technology takes out the method that all still adopts flash distillation.
Chinese patent CN1043525C discloses a kind of method, and it utilizes increases a convertor behind reactor, and the method that transforms ritalin and methyl alcohol with the degree of depth makes active rhodium complex [Rh (CO)
2I
2]
-Be converted into a class can bear indirect heating and do not precipitate, Undec stable complex compound, take out thick product with the method that flash distillation adds evaporation then, improved the technology of only taking out thick product in the present production with flash distillation.This method can not improve throughput by a larger margin owing to rhodium complex concentration in the reaction solution is limited.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of method of synthesizing acetic acid by methanol low-pressure carbonylation, this method is by adding the catalyst system that distinctive component constitutes high reactivity, high stability, can increase substantially reactor throughput, and separate thick product with flash distillation-evaporation technology.
For solving the problems of the technologies described above, technical scheme of the present invention is: a kind of method of synthesizing acetic acid by methanol low-pressure carbonylation, this method is included in rhodium-iodine catalyst system and exists the following acetic acid that carries out in reaction solution synthetic, and in reaction solution, add the additive of rugged catalyst system, separate thick product with flash distillation-evaporation technology then, described additive comprises:
A kind of morpholine kind compound with following general formula:
Wherein R is hydrogen, alkyl or acyl group, or
A kind of alkylbenzyldimethylasaltsum saltsum analog derivative with following general formula:
R wherein
1Be hydrogen or alkyl, R
2Be halogen or acid group, or
The mixture that any compound and a kind of glyoxaline compound with following general formula are formed in above-mentioned two general formulas:
R wherein
1, R
2, R
3And R
4Respectively do for oneself hydrogen, methyl or ethyl, or
The mixture that above-mentioned any compound or mixture and a kind of inorganic ionic compound are formed, the content of described additive in reaction solution, according to reaction solution flash distillation-evaporate in the 50% back mother liquor no rhodium complex precipitate and allocate.
The R group of wherein said morpholine kind compound is hydrogen or acyl group, preferred morpholine, N-formyl morpholine N-or acetyl morphine.
The R group of wherein said morpholine kind compound is an alkyl, preferable methyl morpholine, ethyl morpholine or propyl group morpholine.
Wherein said alkylbenzyldimethylasaltsum saltsum analog derivative preferably salt, acetic acid morpholine or iodate morpholine.
The preferred N-Methylimidazole of wherein said glyoxaline compound.
The preferred lithium iodide of wherein said inorganic ionic compound, potassiumiodide or nickelous iodide.
The mol ratio of wherein said additive and rhodium is 100: 1-1: 1.
In the reaction solution of synthesizing acetic acid by methanol low-pressure carbonylation, owing to added high boiling point organic ion compound or high boiling point organic ion compound and inorganic ionic compound, make rhodium complex [Rh (CO) in the reaction system
2I
2]
-Or the iodine complex negative ion of other rhodium combines with organic electrolyte solution or make that by rhodium in the iodide of rhodium and the complexing of organic electrolyte positively charged ion rhodium complex is stable in the reaction system, in flash distillation-evaporation technology, make active rhodium complex become more stable rhodium complex with regard to the method that need not to adopt the degree of depth to transform, can reach the purpose of direct evaporation; This method also can further reduce recycle ratio, and (the circulating mother liquor amount: quantity of methyl alcohol), its recycle ratio can be reduced between the 10-16, and the concentration of going into methyl alcohol in the reactor content can be increased to 10% from 6%; Can reduce water-content in the prescription, water-content can reduce to 5% in the desired prescription of this reaction system, helps the raising of flash distillation rate, and the concentration of rhodium can increase substantially 1-4 doubly simultaneously, can obtain higher throughput thereby make with volume reactor.
Description of drawings
Fig. 1 is single still schema of flash distillation-evaporation technology in the synthesizing acetic acid by methanol low-pressure carbonylation method of the present invention;
Fig. 2 is the parallel connection series connection general flow chart of flash distillation-evaporation technology in the synthesizing acetic acid by methanol low-pressure carbonylation method of the present invention.
Fig. 3 is the plural serial stage schema of flash distillation-evaporation technology in the synthesizing acetic acid by methanol low-pressure carbonylation method of the present invention.
Embodiment
The present invention is further detailed explanation below in conjunction with embodiment.
Material is formed (weight percent) in the reaction solution of synthesizing acetic acid by methanol low-pressure carbonylation: methyl alcohol, acetic acid, ritalin, iodate rhodium, methyl iodide, hydrogen iodide, water, additive.Wherein water accounts for 5-12%, rhodium 300-2000ppm, and methyl iodide 10-15%, hydrogen iodide 1-2%, the temperature 175-195 of carbongl group synthesis reaction ℃, reaction pressure is 2.8-4.0MPa, vaporization temperature＜150 ℃.
Embodiment 1
Methyl alcohol 6%, rhodium 300ppm, methyl iodide 10%, hydrogen iodide 1%, water 5%, morpholine, the mol ratio of morpholine and rhodium are 1: 1, and all the other are acetic acid.
Embodiment 2
Methyl alcohol 10%, rhodium 400ppm, methyl iodide 14%, hydrogen iodide 1%, water 8%, N-formyl morpholine N-, the mol ratio of N-formyl morpholine N-and rhodium are 30: 1, and all the other are acetic acid.
Embodiment 3
Methyl alcohol 10%, rhodium 700ppm, methyl iodide 12%, hydrogen iodide 1%, water 7%, acetyl morphine, lithium iodide, the mol ratio of acetyl morphine and lithium iodide and rhodium are 70: 1, and all the other are acetic acid.
Embodiment 4
Methyl alcohol 10%, rhodium 800ppm, methyl iodide 12%, hydrogen iodide 1.2%, water 6%, methylmorpholine, nickelous iodide, the mol ratio of methylmorpholine and nickelous iodide and rhodium are 60: 1, and all the other are acetic acid.
Embodiment 5
Methyl alcohol 10%, rhodium 1000ppm, methyl iodide 12%, hydrogen iodide 1.5%, water 10%, ethyl morpholine, N-Methylimidazole, nickelous iodide, the mol ratio of ethyl morpholine, N-Methylimidazole and nickelous iodide and rhodium is 50: 1, all the other are acetic acid.
Embodiment 6
Methyl alcohol 10%, rhodium 1500ppm, methyl iodide 13%, hydrogen iodide 1.5%, water 8%, salt, potassiumiodide, the mol ratio of salt and potassiumiodide and rhodium are 60: 1, and all the other are acetic acid.
Embodiment 7
Methyl alcohol 10%, rhodium 2000ppm, methyl iodide 15%, hydrogen iodide 2%, water 8%, acetic acid morpholine, N-Methylimidazole, potassiumiodide, the mol ratio of acetic acid morpholine, N-Methylimidazole and potassiumiodide and rhodium is 80: 1, all the other are acetic acid.
Embodiment 8
Methyl alcohol 10%, rhodium 1800ppm, methyl iodide 14%, hydrogen iodide 2%, water 12%, iodate morpholine, lithium iodide, the mol ratio of iodate morpholine and lithium iodide and rhodium are 100: 1, and all the other are acetic acid.
Above-mentioned reaction solution mother liquor after flash distillation-evaporate 50% does not all have the rhodium deposited phenomenon.
Technical process: shown in Fig. 1 list still flow process, methyl alcohol J and carbon monoxide I sent into carry out carbonylation reaction in the reactor A, reaction heat is derived by reaction solution recycle pump G2 and outer circulation water cooler and drum H1.Reaction end gas gas-liquid separation in separator D after tail gas condenser H2 condensation, uncooled gas send the vent gas treatment operation, condensate return reactor A; The reaction liquid product enters flasher E and vaporizer F successively, and vaporizer F provides heat by evaporation heater H3.The thick product K of gas phase of flash distillation-evaporate enters the later separation operation, and Qi Hua reaction solution does not loop back reactor A by Recycling Mother Solution pump G1.
Shown in Fig. 2 series connection in parallel general flow, methyl alcohol J and carbon monoxide I sent into respectively carry out carbonylation reaction among reactor A and the B, the reaction heat that produces in two reactors is respectively by reaction solution recycle pump G2, G2 ' and outer circulation water cooler and drum H1, H1 ' derivation.Reaction product continues reaction in subsequent reactor C after, reaction end gas is through tail gas condenser H2 condensation, gas-liquid separation in separator D, and uncooled gas send the vent gas treatment operation, condensate return reactor A, B and subsequent reactor C; The reaction liquid product enters flasher E and vaporizer F successively, and vaporizer F provides heat by evaporation heater H3.The thick product K of the gas phase that flash vaporization goes out enters the later separation operation, and Qi Hua reaction solution does not loop back reactor A, B by Recycling Mother Solution pump G1.
Shown in Fig. 3 plural serial stage flow process, methyl alcohol J and carbon monoxide I to be sent into carry out carbonylation reaction in the reactor A, reaction heat is derived by reaction solution recycle pump G2 and outer circulation water cooler and drum H1.Reaction product continues reaction in subsequent reactor C after, reaction end gas is through tail gas condenser H2 condensation, gas-liquid separation in separator D, and uncooled gas send the vent gas treatment operation, condensate return reactor A and subsequent reactor C; The reaction liquid product enters flasher E and vaporizer F successively, the same Fig. 1 of all the other technical process.
Flash distillation-evaporation technology is all adopted in above-mentioned reaction, this method does not also require set up a convertor behind reactor described in Chinese patent CN1043525C, but can adopt staged reactor from the kinetics relation of reaction process, more can improve throughput than a full reactor that returns that mixes, therefore can adopt second stage reactor or two reactor parallel connections to add a subsequent reactor on process selecting, concrete process selecting will be selected according to the construction scale of newly founding the factory and extend factory; The system that flash evaporation-evaporator takes out thick product draws the flash distillation mother liquor to add a vaporizer in addition and finish, and also can be to set up an evaporator section below flasher, as disclosed device among the Chinese patent CN2604435.The derivation of reaction heat needs an outer circulation water cooler and drum to carry out pump circulation heat conduction.
Claims (9)
1. the method for a synthesizing acetic acid by methanol low-pressure carbonylation, this method is included in rhodium-iodine catalyst system and exists the following acetic acid that carries out in reaction solution synthetic, it is characterized in that, the additive that adds the rugged catalyst system in the reaction solution, separate thick product with flash distillation-evaporation technology then, described additive comprises:
A kind of morpholine kind compound with following general formula:
Wherein R is hydrogen, alkyl or acyl group, or
A kind of alkylbenzyldimethylasaltsum saltsum analog derivative with following general formula:
R wherein
1Be hydrogen or alkyl, R
2Be halogen or acid group, or
The mixture that any compound and a kind of glyoxaline compound with following general formula are formed in above-mentioned two general formulas:
R wherein
1, R
2, R
3And R
4Respectively do for oneself hydrogen, methyl or ethyl, or
The mixture that above-mentioned any compound or mixture and a kind of inorganic ionic compound are formed, the content of described additive in reaction solution, according to reaction solution flash distillation-evaporate in the 50% back mother liquor no rhodium complex precipitate and allocate.
2. the method for synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, the R group of wherein said morpholine kind compound is hydrogen or acyl group.
3. the method for synthesizing acetic acid by methanol low-pressure carbonylation according to claim 2 is characterized in that, wherein said morpholine kind compound is morpholine, N-formyl morpholine N-or acetyl morphine.
4. the method for synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, the R group of wherein said morpholine kind compound is an alkyl.
5. the method for synthesizing acetic acid by methanol low-pressure carbonylation according to claim 4 is characterized in that, wherein said morpholine kind compound is methylmorpholine, ethyl morpholine or propyl group morpholine.
6. the method for synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, wherein said alkylbenzyldimethylasaltsum saltsum analog derivative is salt, acetic acid morpholine or iodate morpholine.
7. the method for synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, wherein said glyoxaline compound is the N-Methylimidazole.
8. the method for synthesizing acetic acid by methanol low-pressure carbonylation according to claim 1 is characterized in that, wherein said inorganic ionic compound is lithium iodide, potassiumiodide or nickelous iodide.
9. according to the method for each described synthesizing acetic acid by methanol low-pressure carbonylation in the claim 1 to 8, it is characterized in that the mol ratio of wherein said additive and rhodium is 100: 1-1: 1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415371C (en) * | 2006-04-13 | 2008-09-03 | 西南化工研究设计院 | Catalyst system for synthesizing acetic anhydride by carbonyl under low pressure |
| CN103896748A (en) * | 2014-04-04 | 2014-07-02 | 西南化工研究设计院有限公司 | Application of rhodium catalyst and aldehyde production method using same |
| CN107892648A (en) * | 2017-11-28 | 2018-04-10 | 西南化工研究设计院有限公司 | A kind of method of methanol by one-step method methyl acetate |
| CN113402374A (en) * | 2021-07-12 | 2021-09-17 | 西南化工研究设计院有限公司 | Reaction system for preparing propionic acid by ethanol liquid-phase carbonyl synthesis |
| CN113480422A (en) * | 2021-06-29 | 2021-10-08 | 煜格（北京）科技有限公司 | Production method for acetic acid and propionic acid single production or joint production |
| CN115634637A (en) * | 2022-10-26 | 2023-01-24 | 西南化工研究设计院有限公司 | Control system for propionic acid content in methanol low-pressure carbonyl synthesis acetic acid product |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1014146B (en) * | 1984-02-16 | 1991-10-02 | Bp化学有限公司 | Carbonylation process improvement |
| CN1031260C (en) * | 1990-05-07 | 1996-03-13 | 英国石油化学品有限公司 | Process for preparing carboxylic acids |
| US6858753B2 (en) * | 2002-03-14 | 2005-02-22 | Council Of Scientific And Industrial Research | Process for the preparation of carboxylic acids from aliphatic alcohols |
| CN2604435Y (en) * | 2003-01-30 | 2004-02-25 | 西南化工研究设计院 | Flash evaporator for technology of methyl alcohol low pressure carbonyl synthesizing acetic acid |
-
2005
- 2005-09-06 CN CNB2005100216172A patent/CN100393689C/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415371C (en) * | 2006-04-13 | 2008-09-03 | 西南化工研究设计院 | Catalyst system for synthesizing acetic anhydride by carbonyl under low pressure |
| CN103896748A (en) * | 2014-04-04 | 2014-07-02 | 西南化工研究设计院有限公司 | Application of rhodium catalyst and aldehyde production method using same |
| CN103896748B (en) * | 2014-04-04 | 2015-11-04 | 西南化工研究设计院有限公司 | A kind of purposes of rhodium catalyst and adopt the method for this Catalyst Production aldehyde |
| CN107892648A (en) * | 2017-11-28 | 2018-04-10 | 西南化工研究设计院有限公司 | A kind of method of methanol by one-step method methyl acetate |
| CN107892648B (en) * | 2017-11-28 | 2019-06-04 | 西南化工研究设计院有限公司 | A kind of method of methanol by one-step method methyl acetate |
| CN113480422A (en) * | 2021-06-29 | 2021-10-08 | 煜格（北京）科技有限公司 | Production method for acetic acid and propionic acid single production or joint production |
| CN113402374A (en) * | 2021-07-12 | 2021-09-17 | 西南化工研究设计院有限公司 | Reaction system for preparing propionic acid by ethanol liquid-phase carbonyl synthesis |
| CN115634637A (en) * | 2022-10-26 | 2023-01-24 | 西南化工研究设计院有限公司 | Control system for propionic acid content in methanol low-pressure carbonyl synthesis acetic acid product |
| CN115634637B (en) * | 2022-10-26 | 2023-12-29 | 西南化工研究设计院有限公司 | Control system for propionic acid content in methanol low-pressure oxo-synthesis acetic acid product |
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Application publication date: 20060301 Assignee: Serra nice (Nanjing) Chemical Co., Ltd. Assignor: Southwest Chemical Research & Design Institute Co., Ltd. Contract record no.: 2013990000015 Denomination of invention: Low pressure methanol carboxylating process to synthesize acetic acid Granted publication date: 20080611 License type: Exclusive License Record date: 20130114 |
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