CN102766044A - Reaction and rectification system and method for recycling acetic acid from diluted acetic acid solution - Google Patents
Reaction and rectification system and method for recycling acetic acid from diluted acetic acid solution Download PDFInfo
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- CN102766044A CN102766044A CN2012102780507A CN201210278050A CN102766044A CN 102766044 A CN102766044 A CN 102766044A CN 2012102780507 A CN2012102780507 A CN 2012102780507A CN 201210278050 A CN201210278050 A CN 201210278050A CN 102766044 A CN102766044 A CN 102766044A
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Abstract
The invention relates to a reaction and rectification system and a method for recycling acetic acid from diluted acetic acid solution. According to the method, strong-acid ion exchange resin serving as a catalyst and a common rectifying column are organically combined to form a reaction-rectifying coupling process; and in a reaction and rectifying column, carbinol and acetic acid have an esterification to produce methyl acetate, thus reaching the purpose of recycling acetic acid. The method is characterized by the coupling of a reactor and the rectifying column and has the advantages of greatly reduced equipment manufacturing cost, low investment, low cost, advanced process, no waste emission in the whole process, little erosion to equipment caused by materials as compared with the original process that refining operations by anesterification device and a rectifying column are carried out separately; moreover, compared with other methods for recycling acetic acid, the method provided by the invention is a good method for recycling acetic acid, which has the advantages of remarkable energy-saving effect and wide application prospect.
Description
Technical field
The invention belongs to chemical field, relate to a kind of dilute acetic acid recovery and utilization technology, the method for acetic acid in especially a kind of reactive distillation system and the recovery dilute acetic acid solution.
Background technology
Acetic acid is a kind of crucial basic Organic Chemicals, and purposes is quite extensive, and demand is also very big.In recent years, industries such as furfural, acetic anhydride, cellulose acetate develop rapidly at home, these enterprises for local bring economic benefit in, supervene a large amount of dilute acetic acid waste water and severe contamination surrounding environment.Because of low-concentration acetic acid reclaims difficulty; And cost recovery is higher, and each manufacturer is to these lower concentration acid-bearing wastewaters or handle not thoroughly, or is left intact at all and just directly emits; Not only brought serious harm, also caused the waste on the resource simultaneously to surrounding environment.Therefore, consider from environment and resource aspect, to the lower concentration acid-bearing wastewater of these industries carry out strict processing and the acetic acid that reclaims wherein imperative.
Along with the development of modern industry progress; The recovery and utilization technology level is increasingly high; On the basis of unit operations such as traditional distillation, extraction, absorption, absorption; Many new and multiple unit operations occurred and united the process of use, reaction rectification method is one of important method of strengthening of chemical process.Reactive distillation is with chemical reaction and rectifying combines and a kind of unit operation of in an equipment, carrying out simultaneously, can be used for some traditional technology process such as reactions such as esterification, etherificate, hydrogenation and alkylating aromatic hydrocarbon.Utilize esterification process to reclaim that acetic acid is a good method in the dilute acetic acid solution, but conventional process flow is very complicated, needs reactor drum, rectifying tower, ester treating tower, a plurality of equipment such as dehydration tower.Reaction rectification method is to organically combine the reactive distillation coupling process that forms with common rectifying tower; Compare with traditional technology; Reaching under the situation of same conversion, reactive distillation has significantly reduced the usage quantity of catalyzer, and is energy-saving and cost-reducing to a certain extent; And have that transformation efficiency height, selectivity are good, less investment, low, the low power consumption and other advantages of process cost, therefore obtain extensive studies in recent years.
Through retrieval, find following two pieces of reactive distillation processes relevant with acetic acid:
1, a kind of methyl acetate hydrolysis catalysis reaction rectifying device and realization process method (CN101209955); It comprises reboiler, catalytic rectifying tower, condensing surface, fixed-bed reactor and pipeline, and catalytic rectifying tower is made up of for three sections epimere, stage casing and hypomere.Utilize catalytic rectifying tower to combine the technical process of fixed-bed reactor, catalytic rectifying tower is divided into ritalin-water mixing preheating section, catalytic reaction rectification section and ritalin stripping section.Ritalin, water and phegma are drawn outside the tower through tower epimere mixing preheating rear section, part continues to flow into tower catalytic reaction rectification section.Extension entering fixed-bed reactor get into this tower methyl esters stripping section top after being hydrolyzed and reacting; Through the refinery distillation of hypomere, ritalin concentration improves the back and gets into the catalytic reaction rectification section, and is humble by ritalin content in the material after the tower still extraction hydrolysis, improves the methyl acetate hydrolysis rate.
2, a kind of is the technology (CN101560151) of the reactive distillation continuous production ritalin of catalyzer with the ionic liquid, and it is with raw material preheating, and acetic acid is from the epimere input of reaction fractionating tower; Ionic liquid is imported from the hypomere of tower from the middle part input and the methyl alcohol of tower simultaneously, and the middle part of reaction fractionating tower is a conversion zone, from cat head extraction product ritalin; Extraction catalyst ion liquid material gets into the flash tank flash distillation at the bottom of the tower, and the liquid of extraction is catalyst ion liquid at the bottom of the flash tank, returns reaction fractionating tower; The gas phase that flash tank steams is the mixing steam of water and methyl alcohol; The input methanol distillation column, Methanol Recovery column overhead extraction material benzenemethanol after separating returns reaction fractionating tower and makes raw material; Recovered water at the bottom of the Methanol Recovery Tata, discharging.
Through the technical characterictic contrast, above-mentioned two pieces of publication documents and present patent application have more different.
Summary of the invention
The objective of the invention is to overcome the weak point of prior art; A kind of method that adopts the reactive distillation system and reclaim acetic acid in the dilute acetic acid solution is provided; Adopting this method to recycle dilute acetic acid, to have an equipment flowsheet simple, invests little, advantages such as energy consumption is low, non-environmental-pollution.
The objective of the invention is to realize through following technical scheme:
A kind of reactive distillation system; Comprise reaction fractionating tower, ester treating tower, methanol distillation column, the cat head of reaction fractionating tower connects the ester treating tower; Connect methanol distillation column at the bottom of the tower of reaction fractionating tower; Reaction fractionating tower is divided into three sections, and epimere is for connecting the rectifying section of ester treating tower, is used for separating of methyl alcohol and ritalin; The stage casing is a conversion zone, at the reaction fractionating tower middle part, is catalyzer with the strong-acid ion exchange resin, and methyl alcohol and dilute acetic acid carry out esterification and generate ritalin in reaction fractionating tower; Hypomere is a stripping section, and this stripping section connects methanol distillation column, is used for separation of methanol and water.
A kind of method that adopts acetic acid in the reactive distillation system recoveries dilute acetic acid solution, step is:
⑴ reaction fractionating tower is the normal pressure operate continuously; Dilute acetic acid solution is epimere entering reaction fractionating tower from reaction fractionating tower continuously; The methanol solution add-on in dilute acetic acid solution in acetic acid mol ratio 1:1.2-2 ratio continuously from reaction fractionating tower hypomere get into reaction fractionating tower, methyl alcohol and dilute acetic acid adopt catalyzer to carry out esterification generation ritalin in reaction fractionating tower;
⑵ with carrying out that guarantees esterification and the generation of avoiding reversed reaction, it is refining after condensation, to get into the ester treating tower, obtains 99.7% ritalin from the continuous extraction of reactive distillation cat head for the ritalin that contain less water;
⑶ production gets into methanol distillation column at the bottom of the reaction fractionating tower, and the extraction of Methanol Recovery cat head contains methyl alcohol more than 98% to be returned feed system and utilize again, contains acetic acid containing waste water at the bottom of the tower and returns charging and reclaim acetic acid again.
And said catalyzer is granular strong-acid ion exchange resin.
Advantage of the present invention and beneficial effect are:
1, reactive distillation system involved in the present invention is with reactor drum and rectifying tower coupling, makes with extra care the process of carrying out respectively with original esterifier with rectifying tower and compares, and reduces equipment manufacturing cost greatly, invests for a short time, and cost is low.
2, technical process of the present invention is advanced, no waste discharging in whole process, and material is little to equipment corrosion; Cost is low, compares with other dilute acetic acid absorption method, and energy-saving effect is remarkable; Facility investment can reduce greatly, has a extensive future, and is the good method that acetic acid reclaims.
3, to adopt strong-acid ion exchange resin be catalyzer in the present invention; Organically combine formation reactive distillation coupling process with common rectifying tower; Methyl alcohol and acetic acid generation esterification generate ritalin in reaction fractionating tower; Thereby reach the purpose that reclaims acetic acid, it is simple to have an equipment flowsheet, invests little, advantages such as energy consumption is low, non-environmental-pollution.
Description of drawings
Fig. 1 is that reactive distillation of the present invention system constitutes synoptic diagram.
Embodiment
Below in conjunction with embodiment, the present invention is further specified; Following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
In order clearly to narrate the present invention, reactive system of the present invention is described at first.
A kind of reactive distillation system referring to Fig. 1, comprises reaction fractionating tower 1 and condensing surface 3 and reboiler 2; Ester treating tower 4 and condensing surface 6 thereof and reboiler 5, methanol distillation column 7 and condensing surface 9 and reboiler 8; The cat head of reaction fractionating tower connects the ester treating tower, connects methanol distillation column at the bottom of the tower of reaction fractionating tower, and reaction fractionating tower is divided into three sections; Epimere is for connecting the rectifying section of ester treating tower, is used for separating of methyl alcohol and ritalin; The stage casing is a conversion zone, and this conversion zone is catalyzer at the reaction fractionating tower middle part with the strong-acid ion exchange resin, and methyl alcohol and dilute acetic acid carry out esterification and generate ritalin in reaction fractionating tower; Hypomere is the stripping section under the conversion zone, and this stripping section connects methanol distillation column, is used for separation of methanol and water.
Through two embodiment process for purification of the present invention is described below.
Embodiment 1:
A kind of method that adopts acetic acid in the reactive distillation system recoveries dilute acetic acid solution, step is:
⑴ reaction fractionating tower is the normal pressure operate continuously; Volumetric concentration be 7.9% dilute acetic acid solution continuously from reaction fractionating tower epimere get into reaction fractionating tower; The methanol solution add-on in dilute acetic acid solution in the ratio hypomere input reaction fractionating tower from reaction fractionating tower continuously of acetic acid mol ratio 1:2, methyl alcohol and dilute acetic acid adopt catalyzer to carry out esterification generation ritalin in conversion zone:
Reversible esterification:
CH
3COOH+CH
3OH catalyzer CH
3COOCH
3+ H
2O;
Said catalyzer is granular strong-acid ion exchange resin.
⑵ the ritalin that contain less water from the continuous extraction of reactive distillation cat head with carrying out that guarantees esterification and the generation of avoiding reversed reaction; Tower top temperature is 57.3 ℃; The concentration of ritalin is 97.7%; It is refining after condensation, to get into the ester treating tower, obtains 99.7% ritalin, reaches industrial analytical pure standard; The reactive distillation column bottom temperature is 97 ℃, and production gets into methanol distillation column at the bottom of the tower.
⑶ the extraction of Methanol Recovery cat head contains methyl alcohol more than 98% to be returned feed system and utilizes again, and waste water contains acetic acid 4.6% and returns feed system and reclaim acetic acid again at the bottom of the tower.
Embodiment 2:
A kind of method that adopts acetic acid in the reactive distillation system recoveries dilute acetic acid solution, step is:
⑴ reaction fractionating tower is the normal pressure operate continuously; Volumetric concentration be 4.1% dilute acetic acid solution continuously from reaction fractionating tower epimere get into reaction fractionating tower; The methanol solution add-on in dilute acetic acid solution in the ratio hypomere input reaction fractionating tower from reaction fractionating tower continuously of acetic acid mol ratio 1:1.5, methyl alcohol and dilute acetic acid adopt catalyzer to carry out esterification generation ritalin in conversion zone.
⑵ the ritalin that contain less water from the continuous extraction of reactive distillation cat head with carrying out that guarantees esterification and the generation of avoiding reversed reaction; Tower top temperature is 58 ℃; The concentration of ritalin is 92%; It is refining after condensation, to get into the ester treating tower, obtains 99% ritalin, reaches industrial analytical pure standard.The reactive distillation column bottom temperature is 97.7 ℃, and production gets into methanol distillation column at the bottom of the tower.
⑶ the extraction of Methanol Recovery cat head contains methyl alcohol more than 98% to be returned feed system and utilizes again, and waste water contains acetic acid 2.8% and returns feed system and reclaim acetic acid again at the bottom of the tower.
Present embodiment is not chatted part and is same as embodiment 1.
Principle of work of the present invention is:
Granular strong-acid ion exchange resin is dispersed in the filler of conversion zone as catalyzer; Dilute acetic acid generates ritalin at conversion zone and methyl alcohol generation esterification; It is refining that ritalin and few portion water get into the ester treating tower from the continuous extraction of cat head; Water and excessive methyl alcohol get into methanol distillation column at the bottom of by tower, and Methanol Recovery cat head extraction methyl alcohol can return feed system and utilize again, contains the acetic acid containing waste water retrieval system at the bottom of the tower and reclaims again.
Claims (3)
1. reactive distillation system; It is characterized in that: comprise reaction fractionating tower, ester treating tower, methanol distillation column, the cat head of reaction fractionating tower connects the ester treating tower; Connect methanol distillation column at the bottom of the tower of reaction fractionating tower; Reaction fractionating tower is divided into three sections, and epimere is for connecting the rectifying section of ester treating tower, is used for separating of methyl alcohol and ritalin; The stage casing is a conversion zone, at the reaction fractionating tower middle part, is catalyzer with the strong-acid ion exchange resin, and methyl alcohol and dilute acetic acid carry out esterification and generate ritalin in reaction fractionating tower; Hypomere is a stripping section, and this stripping section connects methanol distillation column, is used for separation of methanol and water.
2. method that adopts acetic acid in the reactive distillation system recoveries dilute acetic acid solution as claimed in claim 1, it is characterized in that: step is:
⑴ reaction fractionating tower is the normal pressure operate continuously; Dilute acetic acid solution is epimere entering reaction fractionating tower from reaction fractionating tower continuously; The methanol solution add-on in dilute acetic acid solution in acetic acid mol ratio 1:1.2-2 ratio continuously from reaction fractionating tower hypomere get into reaction fractionating tower, methyl alcohol and dilute acetic acid adopt catalyzer to carry out esterification generation ritalin in reaction fractionating tower;
⑵ with carrying out that guarantees esterification and the generation of avoiding reversed reaction, it is refining after condensation, to get into the ester treating tower, obtains 99.7% ritalin from the continuous extraction of reactive distillation cat head for the ritalin that contain less water;
⑶ production gets into methanol distillation column at the bottom of the reaction fractionating tower, and the extraction of Methanol Recovery cat head contains methyl alcohol more than 98% to be returned feed system and utilize again, contains acetic acid containing waste water at the bottom of the tower and returns charging and reclaim acetic acid again.
3. the method for acetic acid in the employing reactive distillation system recoveries dilute acetic acid solution according to claim 2, it is characterized in that: said catalyzer is granular strong-acid ion exchange resin.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924275A (en) * | 2012-11-27 | 2013-02-13 | 福州大学 | Refining method for alcoholysis waste liquid in PVA (polyvinyl alcohol) production and test device for same |
| CN105237399A (en) * | 2015-10-21 | 2016-01-13 | 南京长江江宇石化有限公司 | Reactive distillation process for heavy component residue liquid produced in process of producing acetic acid through carbonylation |
| CN107162946A (en) * | 2017-07-04 | 2017-09-15 | 福州大学 | The method that continuous reaction rectification synthesizes isooctyl thioglycolate |
| CN109467499A (en) * | 2018-08-03 | 2019-03-15 | 天津大学 | The anticorrosion process and device of methyl acetate hydrolysis and acetic acid refining during polyvinyl alcohol disposing mother liquor |
| CN114195815A (en) * | 2021-12-31 | 2022-03-18 | 烟台国邦化工机械科技有限公司 | Continuous esterification production process of trimethyl borate |
| CN115634636A (en) * | 2022-10-26 | 2023-01-24 | 西南化工研究设计院有限公司 | Automatic control system and method for synthesizing acetic acid by methanol low-pressure carbonyl |
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| CN1796358A (en) * | 2004-12-27 | 2006-07-05 | 上海焦化有限公司 | Method for preparing methyl acetate, and reaction rectification tower possessing spatial column plates of mass transfer |
| CN101306994A (en) * | 2008-06-18 | 2008-11-19 | 河北工业大学 | Technological process for producing high-purity methyl acetate and device |
| CN201250193Y (en) * | 2008-06-18 | 2009-06-03 | 河北工业大学 | Device for producing high purity methyl acetate |
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Patent Citations (3)
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| CN1796358A (en) * | 2004-12-27 | 2006-07-05 | 上海焦化有限公司 | Method for preparing methyl acetate, and reaction rectification tower possessing spatial column plates of mass transfer |
| CN101306994A (en) * | 2008-06-18 | 2008-11-19 | 河北工业大学 | Technological process for producing high-purity methyl acetate and device |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924275A (en) * | 2012-11-27 | 2013-02-13 | 福州大学 | Refining method for alcoholysis waste liquid in PVA (polyvinyl alcohol) production and test device for same |
| CN105237399A (en) * | 2015-10-21 | 2016-01-13 | 南京长江江宇石化有限公司 | Reactive distillation process for heavy component residue liquid produced in process of producing acetic acid through carbonylation |
| CN107162946A (en) * | 2017-07-04 | 2017-09-15 | 福州大学 | The method that continuous reaction rectification synthesizes isooctyl thioglycolate |
| CN109467499A (en) * | 2018-08-03 | 2019-03-15 | 天津大学 | The anticorrosion process and device of methyl acetate hydrolysis and acetic acid refining during polyvinyl alcohol disposing mother liquor |
| CN114195815A (en) * | 2021-12-31 | 2022-03-18 | 烟台国邦化工机械科技有限公司 | Continuous esterification production process of trimethyl borate |
| CN115634636A (en) * | 2022-10-26 | 2023-01-24 | 西南化工研究设计院有限公司 | Automatic control system and method for synthesizing acetic acid by methanol low-pressure carbonyl |
| CN115634636B (en) * | 2022-10-26 | 2024-03-15 | 西南化工研究设计院有限公司 | Automatic control system and method for synthesizing acetic acid by methanol low-pressure carbonyl |
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Application publication date: 20121107 |