CN1562937A - Modified method for producing acetic acid through carbonylation, and equipment - Google Patents

Modified method for producing acetic acid through carbonylation, and equipment Download PDF

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Publication number
CN1562937A
CN1562937A CN 200310108290 CN200310108290A CN1562937A CN 1562937 A CN1562937 A CN 1562937A CN 200310108290 CN200310108290 CN 200310108290 CN 200310108290 A CN200310108290 A CN 200310108290A CN 1562937 A CN1562937 A CN 1562937A
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reactor
methods
iodide
improving
acetic acid
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CN100430363C (en
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陈大胜
刘艳
曹智龙
吴文晶
姚长根
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WUJING CHEMICAL CO Ltd SHANGHAI
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Abstract

This invention relates to carbonylation prodn. of acetic acid with an additional forced cooling reactor between reactor and flash column, under pressure of 20-40 bar and temp. of 170 deg.C to 220 deg.C, and controlling feeding ratio of flash liquid to methanol=7-20. So, now the prodn. needes no removing heat by flash column. And rectifying still is not the neck of said prodn, and it can keep stable rhodium catalyst.

Description

A kind of carbonylation is produced improving one's methods and installing of acetic acid
One, technical field:
The present invention relates to a kind of production method and device thereof of acetic acid, particularly a kind ofly produce improving one's methods of acetic acid by methyl alcohol and carbon monoxide carbonylation, and the device that uses this method.
Two, background technology:
The seventies in 20th century, Pu Like has proposed among the US3769329 in United States Patent (USP) with carbon monoxide and methanol carbonylation process.With rhodium catalyst add methyl-iodide, ritalin, water and with acetic acid as the solvent composition reaction solution, carbon monoxide and methyl alcohol carbonylation in reaction solution generates acetic acid, method by the reaction solution flash distillation, from reaction solution, take out the thick acetic acid that has light component, by method with known rectifying in the chemical field, obtain pure product acetic acid, the finally industrialization in worldwide of this method.The eighties in 20th century, people such as Celanese Bu Leide L Smith improve the Pu Like method.In patent CN85101460, propose, in the catalyst system of Pu Like, add inorganic salt compounded of iodine, stablize rhodium concentration, reduce moisture content.In people's such as cloth Randt L Smith the CN85101460 patent, think that carbon monoxide and carbonylation of methanol produce acetic acid, after the inorganic salt compounded of iodine of interpolation reaches finite concentration, moisture content no longer requires to reach 14% of Pu Like proposition in the catalyst system, can unexpectedly be lower than below 4%, and can make catalyst system can keep stable, and do not reduce speed of reaction, can improve on the contrary.
The tank reactor that has all used the band stirring in these patents is as carbonylation reactor.Though people such as cloth Randt L. Smith have proposed the catalyzer of carbon monoxide and carbonylation of methanol production acetic acid is improved in the CN85101460 patent, have improved catalyst reaction speed.But, in patent CN85101460 and later patent of applying for, all only proposed the prescription that catalyzer is stable and speed of reaction improves, do not mentioned in the complete reaction system that constitutes by reactor, flasher etc. how implementing this improved method in these patents and the patent afterwards.
Not proposing this improved catalyst system in patent CN85101460 needs supporting belt to force the refrigerative reactor, needs to optimize the flasher operational condition.This patent is still continued to use the method for flash distillation product and is taken away heat, after moisture content had reduced to a certain degree in the catalyst system when method that this flash distillation product tape is walked heat had been ignored this patent and added a large amount of inorganic iodide, the bad effect that in the product flash distillation, produces because of: (1) inorganic iodide is a kind of nonvolatile substances, in circulation flash distillation temperature-fall period, this embodiment be that a kind of thermal barrier heats reaction solution; (2) because evaporation of water latent heat is ritalin, acetic acid, methyl-iodide about 5 times, that is to say that 1 part of evaporation of water of every minimizing will evaporate other organism of 5 parts more, the reduction of moisture content in the reaction solution, gas phase content reduces in the flasher, make liquid that reaction solution advances flasher when flash distillation produces the flash steam of a unit of every generation, caloric receptivity reduces.The result that this ill effect causes is: when the catalyst system water-content reduces, remove heat, maintenance stopping reaction condition that reactor reaction generates, the gaseous substance amount that flasher need flash off increases greatly than reaction system gaseous substance amount of flash distillation output when water-content is high, cause the bottleneck in rectifying zone to produce like this, and make that the stratified liquid in the decanting vessel is more difficult.In the patent of appearance afterwards, the improved method to carbonylation reaction system is not proposed yet.
Three, summary of the invention:
Technical problem to be solved by this invention is: be provided at by methyl alcohol and carbon monoxide carbonylation and produce in the process of acetic acid, make that rate of catalysis reaction is high and stable, a kind of of the bottleneck of removing rectification zone improve one's methods and install.
The present invention is achieved like this: a kind ofly produce improving one's methods of acetic acid by methyl alcohol and carbon monoxide carbonylation, it comprises:
A. in reaction process, adopt the reactor that has external water cooler, the pressure of controlling reactor is at 20～40bar, and temperature is at 170～220 ℃;
B. the ratio of controlling flasher load responsive fluid and methyl alcohol charging capacity is 7～20.
In the reaction solution that contains rhodium catalyst, methyl-iodide, ritalin, water, inorganic iodide and acetic acid, can add the ion or the complex ions of platinum group except that rhodium as promotor.
The weight percent of methyl-iodide, ritalin, water, inorganic iodide is respectively 7～20%, 0.5～5%, 3～14.5%, 2.5～20% in the described reaction solution, the content of rhodium is 300～2000ppm, promotor is the ruthenium in the preferred platinum group, and its content is 0～5000ppm.
Described inorganic iodide is a kind of in the iodide of hydrogen iodide and alkali and alkaline-earth metal or two or more miscellany.
The described reactor of external water cooler that has is for adopting the outer pump circulation refrigerative reactor of jacketed type cooling or reaction liquid.
A kind of device that adopts aforesaid method to produce acetic acid, comprise reactor, flasher, rectification zone, vent gas treatment district, it is characterized in that: between reactor, flasher, be provided with one and force water cooler, force water cooler to link to each other with reactor by a reaction solution recycle pump, flasher links to each other with reactor by flash liquid returning charge pump.
The present invention with reactor and flasher on heat balance, be divided into two independently, the system of non-interference, band forces the refrigerative reactor to make reactor thermal equilibrium independently to control, and makes the heat of moving of reaction fully no longer rely on flash distillation; Outside reactor body, force under the refrigerative condition, can keep high rate of catalysis reaction and Primary Catalysts rhodium and promotor satisfactory stability, make the throughput of reactor reach maximum as far as possible; The ratio of control flasher load responsive fluid and methyl alcohol charging capacity, the purpose that makes flash distillation only is to remove a kind of effect of product, and no longer is moving heat and removing two kinds of effects of product in the original technology, and makes the rectifying zone not produce bottleneck.Referring to table 1 and table 2, experiment 1 is for adopting catalyst formulation, reaction conditions and the device of former processing method, and experiment 2～5 is for adopting processing method of the present invention and device, and contrast as can be seen, the speed of catalyzed reaction obviously improves, and the acetate yield that is produced also significantly increases.
Four, description of drawings:
Accompanying drawing is produced the process flow sheet of acetic acid by methyl alcohol and carbon monoxide carbonylation
1, reactor 2, reaction solution recycle pump 3, pressure water cooler 4, flasher 5, flash liquid returning charge pump
6, the thick product 13 of rectification zone 7, vent gas treatment district 8, methyl alcohol 9, reaction solution 12, gas phase, the thick product 17 of liquid phase, carbon monoxide.
Five, embodiment:
With reference to the accompanying drawings, as follows by the technical process of methyl alcohol and carbon monoxide carbonylation production acetic acid:
Carbon monoxide 17 enters from the bottom, methyl alcohol 8 also adds from reactor 1 bottom, two strands of materials add continuously, reactor 1 temperature is controlled at 185 ℃～195 ℃, reactor 1 pressure-controlling is at 27～30bar, reaction product is brought flasher 4 into by reaction solution 9, flashing pressure is 1～3bar, the amount of reaction solution 9 is adjusted according to the charging capacity of methyl alcohol 8 and the ability of rectification zone 6, the ratio of the amount of the amount of reaction solution 9 and methyl alcohol 8 is controlled in certain scope, to the different catalysts prescription, ratio is different.Reaction solution 9 is separated into the thick product 12 of gas phase and the thick product 13 of liquid phase at flasher 4, the thick product 13 of liquid phase loops back reactor 1 as catalyzer by flash liquid returning charge pump 5, the thick product 12 of gas phase advances rectification zone 6 and purifies, be divided into three bursts of logistics after the purification, purity is that 99.8% acetic acid is as the product output, rectification zone 6 isolated gaseous components enter vent gas treatment district 7 and handle, the liquid of separating in the rectification zone 6 that contains acetic acid, water and other reaction mediums is by pump Returning reactor 1.The saturation steam of unreacted carbon monoxide and the reaction solution composition carried secretly reclaims by vent gas treatment district 7 and delivers to reactor 1 in the reactor 1, and with carbon monoxide emptying.The pressure of reactor 1 is controlled by the inlet amount of control methyl alcohol 8, carbon monoxide 17, the temperature of reactor 1 forces the cold of water cooler 3 to be controlled by regulating, and forces the cold of water cooler 3 to realize by the flow of conditioned reaction liquid recycle pump 2 and/or the water coolant of pressure water cooler 3.
During enforcement, in reactor 1, add catalyzer earlier, feed CO (carbon monoxide converter) gas then, with pressure-controlling 4～11bar, speed with 1 ℃ of per minute heats reactor 1 and catalyzer then, and the pressure＜27bar of heat-processed controlling reactor 1 is when the temperature of reactor 1 is raised to 170 ℃, the heating of stopped reaction device drops into methyl alcohol 8 experiments and formally begins.
Embodiment
Referring to table 1 and table 2, experiment 2～5 is four embodiment of the present invention.
Carbonylation before and after table 1 improves is produced the reaction solution prescription of acetic acid
The experiment sequence number Water (weight %) Methyl-iodide (weight %) Ritalin (weight %) Inorganic iodide (weight %) Rhodium (ppm) Ruthenium (ppm) Primary Catalysts reduction ppm/h
????1 ????14 ???12.5 ????0.5 ???3.5 ????300 ????0 ????≤0.1
????2 ????10 ????13 ????1.0 ????5 ????450 ????0 ????≤0.1
????3 ????8 ????9 ????1.5 ????9 ????600 ???500 ????≤0.1
????4 ????6 ????10 ????2.2 ????12 ????700 ???2000 ????≤0.1
????5 ????4 ????13 ????3.0 ???15.5 ???1000 ???5000 ????≤0.1
Carbonylation before and after table 2 improves is produced the reaction conditions and the effect thereof of acetic acid
The experiment sequence number Feed intake 8 ratio of flash evaporation feed 9 and methyl alcohol Interchanger (square unit) Reaction pressure (bar) Temperature of reaction (℃) Catalyst reaction speed * (STY) Device output (ton)
??1 ????18-20 ?????0 ????29 ????180 ????3.5 ?????A
??2 ????15-18 ????15 ????30 ????185 ????4.2 ???1.2A
??3 ????13-17 ????31 ????27 ????190 ????5.2 ???1.5A
??4 ????9-13 ????55 ????27 ????193 ???6.95 ???2.0A
??5 ????7-10 ????75 ????27 ????195 ????8.7 ???2.5A
* STY unit: mol/s.m 3

Claims (10)

1, a kind ofly produce improving one's methods of acetic acid by methyl alcohol and carbon monoxide carbonylation, it comprises:
A. in reaction process, adopt the reactor that has external water cooler, the pressure of controlling reactor is at 20～40bar, and temperature is at 170～220 ℃;
B. the ratio of controlling flasher load responsive fluid and methyl alcohol charging capacity is 7～20.
2, according to claim 1 improving one's methods is characterized in that: can add the ion or the complex ions of platinum group except that rhodium as promotor in the reaction solution that contains rhodium catalyst, methyl-iodide, ritalin, water, inorganic iodide and acetic acid.
3, according to claim 2 improving one's methods, it is characterized in that: the weight percent of methyl-iodide, ritalin, water, inorganic iodide is respectively 7～20%, 0.5～5%, 3～14.5%, 2.5～20% in the described reaction solution, the content of rhodium is 300～2000ppm, promotor is the ruthenium in the preferred platinum group, and its content is 0～5000ppm.
4, according to claim 3 improving one's methods, it is characterized in that: the weight percent of methyl-iodide, ritalin, water, inorganic iodide is respectively 10～15%, 0.5～3%, 4～8%, 10～15% in the described reaction solution, and the content of rhodium is 600～1500ppm.
5, improve one's methods according to one of claim 2～4 is described, it is characterized in that: described inorganic iodide is a kind of in the iodide of hydrogen iodide and alkali and alkaline-earth metal or two or more miscellany.
6, according to claim 1 improving one's methods is characterized in that: in the described reaction process, the pressure range of reactor is at 27～30bar, and temperature is at 180～195 ℃.
7, according to claim 1 improving one's methods is characterized in that: the ratio of described flasher load responsive fluid and methyl alcohol charging capacity is 8～15.
8, according to claim 1 improving one's methods is characterized in that: the described reactor of external water cooler that has is for adopting the outer pump circulation refrigerative reactor of jacketed type cooling or reaction liquid.
9, according to claim 1 or 8 described improving one's methods, it is characterized in that: described reactor at tank reactor that band stirs, not with the tower reactor of stirring, do not choose in the tank reactor with stirring a kind of.
10, a kind of device that adopts the described method of claim 1 to produce acetic acid, comprise reactor, flasher, rectification zone, vent gas treatment district, it is characterized in that: between reactor, flasher, be provided with one and force water cooler, force water cooler to link to each other with reactor by a reaction solution recycle pump, flasher links to each other with reactor by flash liquid returning charge pump.
CNB2003101082903A 2003-10-30 2003-10-30 Modified method for producing acetic acid through carbonylation, and equipment Ceased CN100430363C (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100450988C (en) * 2006-06-19 2009-01-14 上海吴泾化工有限公司 Low pressure device for synthesizing acetic acid by methanol carbonylation
CN102442897A (en) * 2010-10-13 2012-05-09 中国石油化工股份有限公司 Method for preparing acetic acid through hydroformylation reaction
US8785684B2 (en) 2010-06-14 2014-07-22 Celanese International Corporation Methanol carbonylation process with rhodium catalyst, an iodide salt and a metallic co-catalyst selected from transition metals, indium, strontium, barium, zinc, tin and heteropoly acids
US8835681B2 (en) 2010-06-14 2014-09-16 Celanese International Corporation Methanol carbonylation process with rhodium catalyst and a lanthanide metal co-catalyst
US9024061B2 (en) 2010-06-14 2015-05-05 Celanese International Corporation Methanol carbonylation process with rhodium catalyst and a metallic co-catalyst selected from transition metals, zinc, beryllium, indium, tin, strontium and barium
US20160102036A1 (en) * 2014-10-02 2016-04-14 Celanese International Corporation Process for producing acetic acid
CN114181034A (en) * 2020-09-15 2022-03-15 中国石油化工股份有限公司 Alkylation reaction system and method for aromatic hydrocarbon with more than eight carbon atoms
CN114644550A (en) * 2020-12-21 2022-06-21 大连理工江苏研究院有限公司 Reaction system and process for preparing acetic acid by methanol carbonylation
CN115197059A (en) * 2022-08-23 2022-10-18 上海优铖工逸技术有限公司 Method for preparing acetic acid by regulating and controlling methanol carbonylation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101665424B (en) * 2009-07-16 2012-04-25 北京泽华化学工程有限公司 Method for synthesizing acetic acid through low-pressure methanol carbonylation and device thereof

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US3769329A (en) * 1970-03-12 1973-10-30 Monsanto Co Production of carboxylic acids and esters
CN1014407B (en) * 1985-02-08 1991-10-23 赛拉尼斯公司 Improved methanol carbohylation process
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CN1043525C (en) * 1992-08-13 1999-06-02 化学工业部西南化工研究院 Reaction method for synthesizing acetic acid by methanol low-pressure liquid-phase carbonyl
US5783731A (en) * 1995-09-11 1998-07-21 Hoechst Celanese Corporation Removal of carbonyl impurities from a carbonylation process stream
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FR2826960B1 (en) * 2001-07-03 2005-10-21 Acetex Chimie METHOD FOR CONTROLLING CONTINUOUS PRODUCTION OF ACETIC ACID AND / OR METHYL ACETATE

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100450988C (en) * 2006-06-19 2009-01-14 上海吴泾化工有限公司 Low pressure device for synthesizing acetic acid by methanol carbonylation
US8785684B2 (en) 2010-06-14 2014-07-22 Celanese International Corporation Methanol carbonylation process with rhodium catalyst, an iodide salt and a metallic co-catalyst selected from transition metals, indium, strontium, barium, zinc, tin and heteropoly acids
US8835681B2 (en) 2010-06-14 2014-09-16 Celanese International Corporation Methanol carbonylation process with rhodium catalyst and a lanthanide metal co-catalyst
US9024061B2 (en) 2010-06-14 2015-05-05 Celanese International Corporation Methanol carbonylation process with rhodium catalyst and a metallic co-catalyst selected from transition metals, zinc, beryllium, indium, tin, strontium and barium
CN102442897A (en) * 2010-10-13 2012-05-09 中国石油化工股份有限公司 Method for preparing acetic acid through hydroformylation reaction
CN102442897B (en) * 2010-10-13 2014-05-28 中国石油化工股份有限公司 Method for preparing acetic acid through hydroformylation reaction
US20160102036A1 (en) * 2014-10-02 2016-04-14 Celanese International Corporation Process for producing acetic acid
US9505691B2 (en) * 2014-10-02 2016-11-29 Celanese International Corporation Process for producing acetic acid
CN114181034A (en) * 2020-09-15 2022-03-15 中国石油化工股份有限公司 Alkylation reaction system and method for aromatic hydrocarbon with more than eight carbon atoms
CN114644550A (en) * 2020-12-21 2022-06-21 大连理工江苏研究院有限公司 Reaction system and process for preparing acetic acid by methanol carbonylation
CN114644550B (en) * 2020-12-21 2024-03-12 大连理工江苏研究院有限公司 Reaction system and process for preparing acetic acid by methanol carbonylation
CN115197059A (en) * 2022-08-23 2022-10-18 上海优铖工逸技术有限公司 Method for preparing acetic acid by regulating and controlling methanol carbonylation
CN115197059B (en) * 2022-08-23 2024-04-05 上海优铖工逸技术有限公司 Method for preparing acetic acid by regulating and controlling methanol carbonylation

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