CN1069262A - A new process for the production of acetic acid reaction system by methanol low-pressure liquid-phase carbonylation - Google Patents
A new process for the production of acetic acid reaction system by methanol low-pressure liquid-phase carbonylation Download PDFInfo
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- CN1069262A CN1069262A CN 92108244 CN92108244A CN1069262A CN 1069262 A CN1069262 A CN 1069262A CN 92108244 CN92108244 CN 92108244 CN 92108244 A CN92108244 A CN 92108244A CN 1069262 A CN1069262 A CN 1069262A
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Abstract
The invention provides a novel reaction system suitable for low-pressure liquid-phase carbonylation of methanol to synthesize acetic acid, which is characterized in that reaction liquid flowing out of a reactor flows through 1-2 converters, and active rhodium complex Rh in the reaction liquid2I2 -Then converted into a stable rhodium complex which can bear external heating without precipitation and decomposition, and then the crude product is taken out by an evaporation method. Improves the prior flash evaporator for production to take out crude products.
The process is suitable for reaction liquid with acetic acid as solvent, and can reduce the circulation amount of catalyst and cocatalyst, reduce loss, reduce the rigor of process control, and reduce corrosion of apparatus by reaction at low temperature.
Description
The synthetic system of low-pressure methanol liquid phase carbonyl acetic acid has now become a main production of world production acetic acid since going into operation on November 18th, 1970.This technology is that the halogenide with rhodium is catalyzer, and methyl iodide is a promotor, realizes down that 3.0～2.8Mpa and 175 ℃～185 ℃ methyl alcohol and carbon monoxide are acetic acid synthesized.Usually the reaction zone of this technology with tell thick product flash zone from reaction solution and be referred to as reactive system.Its flow process signal is as figure one.
One of core technology of this technology, be to enter by throttling valve H from the reaction solution of the effusive about 3.0Mpa of reactor A and 175 ℃～185 ℃ among the vaporizer B of no any hot face, pressure reduces to below the 0.2Mpa, utilize the sensible heat of reaction solution to be converted into gasification latent heat, a part of light constituent and product acetic acid are evaporated to gas phase, take out and catalyst separating from the flasher top, become thick product.Stay the liquid of flasher bottom, wherein contain the catalyst rhodium co-ordination complex by recycling in the pump G Returning reactor.
Adopting the vaporizer that does not have heating is that flasher has been avoided decomposition and the precipitation of rhodium co-ordination complex in the presence of no CO in the reaction solution.Therefore this reactive system flash evaporation technology is a main patent (UP:3845121) of this technology.
Owing to adopted flash process, thick product acetic acid proportion is increased, promotor proportion reduces, to reduce the internal circulating load of methyl iodide.Has only the sensible heat that increases reaction solution.Therefore select the corrosion resistant material, improving temperature of reaction is the striving direction of initial stage of development.
Owing to adopted flash process, make the distillation zone stable simultaneously, must keep the temperature of reaction solution and form stable.Because at present Processes for Producing Acetic Acid is the wet acetic acid circulation technology, and multiply material Returning reactor is arranged, so the adjusting of process system and control require very harsh.
The present invention proposes a novel reaction system that is applicable to the acetic acid synthesized technology of low-pressure methanol liquid phase carbonyl, reactive system is by a reactor, 1～2 convertor and a vaporizer and a mother liquid evaporation recycle unit that supplies to heat outside having are formed its schematic flow sheet such as figure two.As shown in the figure: carbon monoxide, methyl alcohol and the various recycle stocks that returned by distillation zone, uptake zone are through pipeline 1 inflow reactor A, and the mother liquor that has catalyzer that is returned by vaporizer B is through piping 8 inflow reactor A.After reacting in reactor, reaction heat takes out by pump F and water cooler E.Reactor operating pressure is at 3.2～2.8Mpa, and temperature can be selected 175 ℃～200 ℃, also applicable to 130 ℃～175 ℃.Temperature selection principle is to want the solidity to corrosion of integrated equipment, cost and activity of such catalysts to decide.
Reaction solution flow to convertor C through pipeline 2 and flow to conversion tube D through pipeline 3 again, and the intact carbon monoxide of unreacted is then sent into convertor C and convertor D through piping 9.Transform the back gas phase and send into condensation uptake zone recovery organic component wherein by pipeline 20.Reaction solution after transforming is sent into vaporizer through pipeline 4 and reducing valve H.With the evaporation of liquid material, the working pressure of vaporizer E allows controlled temperature between 120 ℃～150 ℃ about 0.2Mpa to vaporizer by heating tube j heat supply.The gas phase that evaporates is sent into the distillation zone as thick product.The mother liquor that contains catalyzer is discharged in the vaporizer bottom, sends reaction tubes back to through pipeline 6, pump G and pipeline 8.Also can deliver in the convertor and circulate through pipeline 6, valve i, pipeline 7.
Reactive system of the present invention is compared with the reactive system of the acetic acid synthesized production equipment of existing low-pressure methanol liquid phase carbonyl, it is characterized in that:
1. 1～2 convertor of behind carbonyl synthesis reactor, connecting, will be from the reaction solution that reactor flows out active rhodium complex Rh(CO)
2I
-
2Be converted in the time of to bear heating evaporation and do not decompose, non-setting stable rhodium complex.Such as: Rh(CO) I
-
4, Rh(CO) I
=
5Deng.
2. adopt and have the vaporizer of hot face by outside heat supply.
Vaporizer can also utilize outer thermal conditioning except the flash distillation function, evaporate more acetic acid.The reaction solution of low-pressure methanol oxo process is to be solvent with acetic acid, and acetic acid content so a part of solvent acetic acid is steamed as product acetic acid, can increase substantially acetic acid content in the thick product up to 70～80% in the reaction solution.To producing the acetic acid of same quantity, light component in the thick product, particularly the methyl iodide amount can be reduced to 1/2～1/3 of flash distillation flow process.Naturally reduced the internal circulating load of distillation zone load and vaporizer mother liquor significantly.
3. to be implemented in rhodium complex form transformation in the convertor, utilize following chemical reaction:
Realize above-mentioned reaction, must increase HI concentration in the solution, can realize by following chemical equilibrium.
As long as by carbongl group synthesis reaction, ritalin and methanol conversion is comparatively complete, and then concentration of hydrogen iodide can rise rapidly naturally.The rhodium complex form just begins to transform.So convertor is again a reactor that material depth is transformed.
In order to promote the carrying out of carbongl group synthesis reaction, can add some and contain the denseer vaporizer mother liquor of HI in convertor, the concentration of methyl alcohol and ritalin can be reduced rapidly after the adding, thereby transformation time can be shortened.
In order to promote reaction process to finish faster, can in convertor, add solid-supported rhodium catalyst, the carrier of solid-supported rhodium catalyst is with the Al of gac or year carbon
2O
3With molecular sieve and high molecular functional carrier for well.
The reaction solution of discharging from convertor enters before the vaporizer again, and it is transformed quality should monitor and control to some extent.
When material evaporates in vaporizer, evaporation heating medium temperature not should greater than trivalent rhodium co-ordination complex such as: Rh(CO)
-
4, Rh(CO)
=
5Decomposition temperature Deng carbonyl removes should be limited in below 150 ℃.
Superiority of the present invention: reactive system provided by the invention has increased convertor, and it is complicated that flow process becomes, but have following superiority.
First, the present invention is owing to can take out solvent acetic acid substitute products acetic acid in vaporizer, thereby take out the material quantity that enters convertor and vaporizer from reactor and compare with flash method, can reduce to 1/2～1/3, so convertor and evaporator plant volume are all smaller.And take rectification zone out of and need reclaim, the methyl iodide of recirculation Returning reactor and wet acetic acid quantity descend significantly.The vaporizer circulating mother liquor also reduces significantly simultaneously, helps to reduce rhodium consumption and iodine consumption.
The second, the present invention is owing to adopt the evaporation flow process, and unlike the flash distillation flow process, product acetic acid takes out the sensible heat of full dependent reaction liquid.So needn't necessarily select high temperature of reaction operation.Can reduce the corrosion of reactor.
The 3rd, the present invention adopts the evaporation flow process, can guarantee that the distillation zone raw material is stable with outer heat regulation steam output.Thereby the control of full production system is just harsh unlike the flash distillation flow process.Particularly the Returning reactor inventory reduces significantly, and to compare proportion less with reactor content material quantity, helps the reactor stable operation.
Example one:
Use flow process of the present invention, on annual output 2T scale mold trial device, test continuously.The vaporizer mother liquor of the rhodium-containing that material benzenemethanol, promotor, water, acetic acid and circulation are returned injects the batching still continuously, and 98%CO also enters the batching still continuously, under 110 ℃, 3.0Mpa condition, mixes, and enters the reactor parallel-series then and enters convertor.Go into about reaction tubes flow 1350g/hr.Going into reactor content forms: (w%)
CH
3I:10%, methyl alcohol: 10%, acetic acid: 70%, water: 8.0%, total iodine: 2.0%, rhodium: 500ppm.
Reactor and convertor are operated down about 3.0Mpa all at 175 ℃.From the gas phase of reactor and convertor discharge, except that the intact CO of unreacted, CO is arranged still
2, H
2, and CH
3Organic component such as I, the material after the conversion are 1.12 times of reactor inlet material, its composition: (w%)
CH
3I:5.95%, methyl alcohol: 0.07%, ritalin: 0.40%, H
2O:6.90%, total iodine: 3.12%, acetic acid: 83.56%, rhodium: 445ppm.
Transform back liquid material and send into vaporizer through reducing valve, evaporation conditions: 120 ℃ of normal pressures, gas phase is cooled to thick product, and evaporation section is not a mother liquor, and mother liquor loops back the batching still with pump.Rate of evaporation is 60%, and thick group of products becomes: (w%)
CH
3I:9.81%, methyl alcohol: 0.12%, ritalin: 0.65%, H
2O:6.54%, total iodine: 0.15%, acetic acid: 82.73%.
Mother liquor consists of: (w%)
H
2O:7.43%, HAC:84.66%, total iodine: 7.91%, rhodium: 1130ppm.
Cycle operation amounts to 730 hours, and reaction process is stable.Carry out rhodium balance check at last, record rhodium loss 91.3mg/tHAC.Produce acetic acid 184.7kg altogether.
Example two:
With above-mentioned experiment flow and experimental technique, in reaction solution, add nickelous iodide, ferric iodide, potassium bichromate, ammonium molybdate, make Ni in the reaction solution
+1400ppm, Mo
+++340ppm, Cr
+++2010ppm, Fe
++1820ppm.The reaction solution prescription is with example one, and stable circulation turned round 100 hours, no rhodium deposited phenomenon.
Example three:
With above-mentioned experiment flow and experimental technique, in reaction solution (reaction solution after being example-730 hour running), add potassiumiodide, aluminum iodide, sodium iodide.Make in the reaction solution K
+: 8100ppm, Na
+: 4800ppm, Al
+++: 5600ppm, Ni
++: 48ppm, Cr
+++: 70ppm, Fe
++: 200ppm.Reaction solution is filled a prescription with example one, stable circulation 520 hours, no rhodium deposited phenomenon.Because under industrial full-scale condition, have many metal ions in the reaction solution.Example one and example two are to add the ion experiment, confirm that there is the precipitation that can not cause rhodium in they in this flow process.
Example four:
With the reaction solution of example one by the reactor discharge, its composition: (w%) HAC:79.0%, CH
3I:8.61%, methyl alcohol: 0.04%, ritalin: 2.28%, H
2O:7.79%, total iodine: 2.28%, rhodium: 455ppm.Get 100 parts, add 20 parts of aqueous acetic acids containing HI8% again,, excluding refluxed evaporator under the air, more than half an hour, observe the throw out that rhodium is arranged and generate these two kinds of mixing.
Claims (5)
1, novel reaction system that is applicable to the synthetic system of low-pressure methanol liquid phase carbonyl acetic acid technology.This reactive system is by reactor, convertor and have the vaporizer of outer well heater and vaporizer Recycling Mother Solution equipment and corresponding pipeline, valve are formed.It is characterized in that raw material enters vaporizer by reactor again through convertor, outside replenishing, take out thick product under the heat.
2, press claim 1 described reactive system, it is characterized in that must be with the Rh(CO that contains in the reaction solution in convertor)
2I
-
2Complex compound is converted into and can bears outer heating evaporation and do not decompose sedimentary other rhodium carbonylcomplex.
The mode that transforms: 1. adopt evaporation back mother liquor partly to loop back convertor and promote to transform.
2. loading catalyst promotes to transform in the employing convertor.
3. adopt Recycling Mother Solution and the loading catalyst method that develops simultaneously.
4. not adding any matter utilization reaction self transforms.
3, press claim 1 described reactive system, it is characterized in that evaporative process will be realized by the vaporizer of outside heat supply by hot face is arranged, evaporative medium temperature≤150 ℃.
4, press claim 1 described reactive system, it is characterized in that temperature of reaction can operate under 130 ℃～175 ℃ condition, to reduce the reactor material corrosion rate.
5, press described in the claim 2, the catalyzer that is seated in the convertor is the loaded catalyst that contains rhodium complex, and its carrier can be a gac, or carries the molecular sieve and the Al of carbon
2O
3, or high molecular functional type carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108244 CN1043525C (en) | 1992-08-13 | 1992-08-13 | Methanol low-pressure liquid-phase oxo synthesis of acetic acid reaction method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108244 CN1043525C (en) | 1992-08-13 | 1992-08-13 | Methanol low-pressure liquid-phase oxo synthesis of acetic acid reaction method |
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| Publication Number | Publication Date |
|---|---|
| CN1069262A true CN1069262A (en) | 1993-02-24 |
| CN1043525C CN1043525C (en) | 1999-06-02 |
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|---|---|---|---|
| CN 92108244 Expired - Lifetime CN1043525C (en) | 1992-08-13 | 1992-08-13 | Methanol low-pressure liquid-phase oxo synthesis of acetic acid reaction method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5932764A (en) * | 1996-12-05 | 1999-08-03 | Bp Chemicals Limited | Iridium-catalyzed carbonylation process for the production of a carboxylic acid |
| CN100363321C (en) * | 2005-12-29 | 2008-01-23 | 西南化工研究设计院 | Distillation method in methanol low-pressure carbonylation process of acetic acid |
| CN100430363C (en) * | 2003-10-30 | 2008-11-05 | 上海吴泾化工有限公司 | Modified method for producing acetic acid through carbonylation, and equipment |
| US7820855B2 (en) | 2008-04-29 | 2010-10-26 | Celanese International Corporation | Method and apparatus for carbonylating methanol with acetic acid enriched flash stream |
| US7884237B2 (en) | 2008-11-07 | 2011-02-08 | Celanese International Corp. | Methanol carbonylation with improved aldehyde removal |
| CN102441434A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Rhodium catalyst system |
| RU2493142C1 (en) * | 2009-07-07 | 2013-09-20 | Селаниз Интернэшнл Корпорейшн | Producing acetic acid by carbonylation with high reactivity and flash evaporation |
| US9446363B2 (en) | 2008-04-29 | 2016-09-20 | Celanese International Corporation | Methanol carbonylation system with multiple absorber feed options |
| CN109092359A (en) * | 2018-09-25 | 2018-12-28 | 煜格（北京）科技有限公司 | Catalyst system and its application of a kind of methanol carbonyl synthesized acetic acid and methyl acetate |
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| US10807935B2 (en) | 2018-11-02 | 2020-10-20 | Celanese International Corporation | Process for continuous acetic acid production |
| US20230127564A1 (en) | 2020-04-01 | 2023-04-27 | Celanese International Corporation | Processes for removing and/or reducing permanganate reducing compounds and alkyl iodides |
| US12577189B2 (en) | 2020-06-03 | 2026-03-17 | Celanese International Corporation | Removal of acetals from process streams |
| EP4161888A1 (en) | 2020-06-03 | 2023-04-12 | Celanese International Corporation | Process for acetic acid production by removing permanganate reducing compounds |
| KR20230019134A (en) | 2020-06-03 | 2023-02-07 | 셀라니즈 인터내셔날 코포레이션 | Production and purification of acetic acid |
-
1992
- 1992-08-13 CN CN 92108244 patent/CN1043525C/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5932764A (en) * | 1996-12-05 | 1999-08-03 | Bp Chemicals Limited | Iridium-catalyzed carbonylation process for the production of a carboxylic acid |
| CN100430363C (en) * | 2003-10-30 | 2008-11-05 | 上海吴泾化工有限公司 | Modified method for producing acetic acid through carbonylation, and equipment |
| CN100363321C (en) * | 2005-12-29 | 2008-01-23 | 西南化工研究设计院 | Distillation method in methanol low-pressure carbonylation process of acetic acid |
| US7820855B2 (en) | 2008-04-29 | 2010-10-26 | Celanese International Corporation | Method and apparatus for carbonylating methanol with acetic acid enriched flash stream |
| JP2011518880A (en) * | 2008-04-29 | 2011-06-30 | セラニーズ・インターナショナル・コーポレーション | Method and apparatus for carbonylation of methanol giving a flash stream rich in acetic acid |
| US8329944B2 (en) | 2008-04-29 | 2012-12-11 | Celanese International Corporation | Method and apparatus for carbonylating methanol with acetic acid enriched flash stream |
| US9446363B2 (en) | 2008-04-29 | 2016-09-20 | Celanese International Corporation | Methanol carbonylation system with multiple absorber feed options |
| US7884237B2 (en) | 2008-11-07 | 2011-02-08 | Celanese International Corp. | Methanol carbonylation with improved aldehyde removal |
| RU2493142C1 (en) * | 2009-07-07 | 2013-09-20 | Селаниз Интернэшнл Корпорейшн | Producing acetic acid by carbonylation with high reactivity and flash evaporation |
| CN102441434A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Rhodium catalyst system |
| CN109092359A (en) * | 2018-09-25 | 2018-12-28 | 煜格（北京）科技有限公司 | Catalyst system and its application of a kind of methanol carbonyl synthesized acetic acid and methyl acetate |
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| Publication number | Publication date |
|---|---|
| CN1043525C (en) | 1999-06-02 |
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Owner name: XINAN CHEMICAL RESEARCH + DESIGN INST. Free format text: FORMER OWNER: SOUTHWEST INST. OF CHEM. TECHNOLOGY, MINISTRY OF CHEM. INDUSTRY Effective date: 20120517 |
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Effective date of registration: 20120517 Address after: No. 5 high tech Zone Gaopeng road in Chengdu city of Sichuan Province in 610041 Patentee after: Xinan Chemical Research & Design Inst. Address before: 646300, Luzhou, Sichuan province Ann Fu town Patentee before: Southwest Inst. of Chem. Technology, Ministry of Chem. Industry |
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