CN102001937A - Preparation method of methyl acetate - Google Patents
Preparation method of methyl acetate Download PDFInfo
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- CN102001937A CN102001937A CN2010102400956A CN201010240095A CN102001937A CN 102001937 A CN102001937 A CN 102001937A CN 2010102400956 A CN2010102400956 A CN 2010102400956A CN 201010240095 A CN201010240095 A CN 201010240095A CN 102001937 A CN102001937 A CN 102001937A
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- methyl acetate
- rectifying tower
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- esterification
- rectifying
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Abstract
The invention relates to a preparation method of methyl acetate, in particular to a preparation method of the methyl acetate suitable for being used as raw materials of a device for synthetizing acetic anhydride by carbonyls, which belongs to the preparation of the methyl acetate. Methanol and acetic acid are used as raw materials, under the existence of catalysts and entrainers, an esterification rectifying operation system compounded by a rectifying tower (5) and a double-cavity overflowing phase divider (13) is adopted, wherein the rectifying tower (5) is provided with a preheater (2), an esterification kettle (3) and a chimney type tower disc (6), and a technical method of material inlet at the bottom of the preheater (2), catalyst dripping at the top of the esterification kettle (3), methyl acetate product extraction at the top of the rectifying tower (5), extraction and phase division at the side line and discharge of water generated by esterification reaction is designed. The invention provides the preparation method of the methyl acetate suitable for being used as raw materials of the device for synthetizing acetic anhydride by carbonyls, which has the advantages of high raw material conversion rate, good separation efficiency, low equipment investment, long service life and low integrated energy consumption and solves the problems of high equipment material requirement and high energy consumption.
Description
Technical field
The present invention is a kind of preparation method of methyl acetate, belongs to the preparation of acetic ester.Be particularly related to a kind of preparation method who is applicable to the raw acetic acid methyl esters of oxo process diacetyl oxide device.
Background technology
Diacetyl oxide is used in a large number as the raw material of producing rhodia.In addition, as the important source material of synthetic drugs, spices and dyestuff chemistry product, consumption constantly increases.Methyl acetate is the main raw material that carbonylation is produced diacetyl oxide, produces in the process of acetic anhydride at oxo process, and the state of the art of the methyl acetate that forms a complete production network with it plays an important role for the throughput and the economic and technical norms of diacetyl oxide device.
But the methyl acetate in the prior art diacetyl oxide device is to be raw material with methyl alcohol and acetate, produce by esterification, because methyl acetate, first alcohol and water form binary or ternary azeotrope, give technology and device that methyl alcohol and acetate are the feedstock production methyl acetate and bring many troubles, traditional technology needs a reactor and a plurality of rectifying tower.The separation system complexity, feed stock conversion is low.Two tower process that improved, concentrated sulfuric acid catalyst add in the catalytic rectifying tower still, seriously corroded, equipment material requires high, work-ing life is short, reaction raw materials must repeatedly circulate, separate that power consumption is high, facility investment is big etc. problem, have to be solved.Be applicable to the preparation method of the raw acetic acid methyl esters of oxo process diacetyl oxide device, also simply do not report as yet.
Summary of the invention
The objective of the invention is to avoid above-mentioned weak point of the prior art, and a kind of feed stock conversion height is provided, separation efficiency is good, low equipment investment, long service life, a kind of preparation method who is applicable to the raw acetic acid methyl esters of oxo process diacetyl oxide device that comprehensive energy consumption is low.
Purpose of the present invention can reach by following measure:
The preparation method of methyl acetate of the present invention, be applicable to supporting method for preparing raw material as oxo process diacetyl oxide device, it is characterized in that with methyl alcohol and acetate be raw material, catalyzer, entrainer exist down, employing is provided with preheater 2, esterifying kettle 3 and the rectifying tower 5 that funnel-shaped tower tray 6 is housed, and the esterification rectifying operating system that is composited of two-chamber overflow phase splitter 13; Design preheater 2 bottom feeds, esterifying kettle 2 tops drip catalyzer, rectifying tower 5 top extraction product methyl acetates, side line extraction and phase-splitting, discharge the processing method of the water of esterification generation, and technological process comprises following operation steps:
1. continuously feeding, the preheating esterification
At first, in esterifying kettle 3, add the good bed material of forming by acetate, catalyzer, entrainer, the material benzenemethanol of adding is through material benzenemethanol feeding line 1, raw acetic acid is through raw acetic acid feeding line 19, and from the material of rectifying tower 5 tower stills, through rectifying tower still feed liquid circulation line 11 according to process requirements, enter the bottom of preheater 2 according to a certain percentage continuously, after the preheating, send into esterifying kettle 3 through its overhead line, catalyzer adds pipeline 4 through catalyzer and adds from the esterifying kettle top, carries out esterification in esterifying kettle, and its processing condition control is as follows:
Preheating temperature ℃ 100～105
Esterifying kettle temperature ℃ 90～120;
2. rectifying, rectifying tower top extraction methyl acetate
Enter through the downside of outlet line 20 from esterifying kettle 3 top effluent airs from rectifying tower 5, the rectifying tower top temperature control is at 56～57 ℃, overhead fraction is after condenser 7 condensations, enter return tank 8, wherein a part realizes refluxing through reflux pipeline A9 as the top of tower phegma of rectifying tower 5, and another part is through 10 extraction of product extraction pipeline, send into the methyl acetate pan tank, standby;
3. the side line extraction separates, and discharges the water that esterification generates
Side line extraction cut temperature is controlled between 75～90 ℃, from the effluent in the dark weir of the funnel-shaped tower tray 6 at rectifying tower 5 middle parts, after condenser B 12 further condensations, enter phase-splitting chamber 16 phase-splittings of two-chamber overflow phase splitter 13, upper organic phase is crossed dividing plate 14, overflow to back cavity 15, the position below the funnel-shaped tower tray 6 at rectifying tower 5 middle parts is arrived in reflux pipeline B 17 total refluxs enters rectifying tower; Participate in rectifying separation;
Phase-splitting chamber 16 lower aqueous layer are gone to recovery system through water vent line 18, reclaim wherein useful composition;
4. the whole recycles of rectifying tower bottoms
The still liquid of rectifying still 5 through the bottom of rectifying tower still feed liquid circulation line 11 inflow preheaters 2, continues to participate in esterification.
Purpose of the present invention can also reach by following measure, is the disclosed optimized technical scheme of contriver below:
The preparation method of methyl acetate of the present invention, the theoretical plate number of its described rectifying tower 5 are 30～50.
The preparation method of methyl acetate of the present invention, described catalyst for esterification reaction is sulfuric acid or tosic acid.
The preparation method of methyl acetate of the present invention, described catalyst for esterification reaction is a tosic acid, its consumption is 0.1～10% of a reaction mixture total amount.
The preparation method of methyl acetate of the present invention, described catalyst for esterification reaction is a tosic acid, its consumption is 2～6% of a reaction mixture total amount.
The preparation method of methyl acetate of the present invention, described material benzenemethanol and second
The ratio of adding of acid is to wait mole.
The preparation method of methyl acetate of the present invention, the trim the top of column of described rectifying tower 5 is than moisture content shared weight ratio≤3% in total reaction material amount that keeps in the esterifying kettle 2.
The preparation method of methyl acetate of the present invention, described entrainer is any one that chooses from toluene, diisobutyl ether, n-butyl acetate, isobutyl acetate, methyl iso-butyl ketone (MIBK).
The preparation method of methyl acetate of the present invention, described entrainer is a n-butyl acetate.
The preparation method of methyl acetate of the present invention, described esterifying kettle 2 is glassed steel reaction vessels, and the 316L stainless steel is adopted in the bottom of the funnel-shaped tower tray 6 of rectifying tower, and the 304L stainless steel is adopted on the top of the funnel-shaped tower tray 6 of rectifying tower.
The preparation method of methyl acetate disclosed by the invention has following positively effect compared to existing technology:
1. a kind of feed stock conversion height is provided, and separation efficiency is good, low equipment investment, long service life, a kind of preparation method who is applicable to the raw acetic acid methyl esters of oxo process diacetyl oxide device that comprehensive energy consumption is low.
2. the esterifying catalyst vitriol oil directly is added in the esterification enamel still, solved the etching problem of rectifying tower, rectifying tower only needs 316L and 304L stainless steel to get final product, compare with the C-276 or the extraordinary steel lining of liner C-276 of available technology adopting, equipment cost can be saved 2,000,000 yuans of investments.
3. rectifying Tata still material without cooling, directly recycles, and acetate formic acid per ton is saved 1t low-pressure steam, 50KWh.
4. Zhi Bei methyl acetate is fit to the use of oxo process diacetyl oxide device.
Description of drawings
Fig. 1 be of the present invention be the process flow diagram of feedstock production methyl acetate with methyl alcohol and acetate, among the figure:
1-material benzenemethanol feeding line
The 2-preheater
The 3-esterifying kettle
The 4-catalyzer adds pipeline
The 5-rectifying tower
The funnel-shaped tower tray of 6-
7-condenser A
The 8-return tank
9-reflux pipeline A
10-product extraction pipeline
11-rectifying tower still material liquid outlet pipeline
12-condenser B
13-two-chamber phase splitter
The 14-dividing plate
The 15-back cavity
16-phase-splitting chamber
17-reflux pipeline B
18-water vent line
19-raw acetic acid feeding line.
Embodiment
The present invention is described in further detail below in conjunction with embodiment:
Embodiment 1
According to preparation method of the present invention and step, preparation is applicable to the raw acetic acid methyl esters of oxo process diacetyl oxide device
1. continuously feeding, the preheating esterification
At first, add the good bed material of being made up of acetate, n-butyl acetate, sulfuric acid in esterifying kettle 3, the material benzenemethanol of adding is through material benzenemethanol feeding line 1, flow 0.76m
3/ hour, raw acetic acid is through raw acetic acid feeding line 19, flow 1m
3/ hour, and from the material of rectifying tower 5 tower stills, through rectifying tower still feed liquid circulation line 11 according to process requirements, enter the bottom of preheater 2 according to a certain percentage continuously, after the preheating, send into esterifying kettle 3 through its overhead line, catalyzer adds pipeline 4 through catalyzer and adds from the esterifying kettle top, carry out esterification in esterifying kettle, its processing condition control is as follows:
Preheating temperature ℃ 103
Esterifying kettle temperature ℃ 90;
2. rectifying, rectifying tower top extraction methyl acetate
Enter through the downside of outlet line 20 from esterifying kettle 3 top effluent airs from rectifying tower 5, the rectifying tower top temperature control is at 56 ℃, overhead fraction is after condenser 7 condensations, enter return tank 8, wherein a part is as the top of tower phegma of rectifying tower 5, realize refluxing through reflux pipeline A 9, another part is through 10 extraction of product extraction pipeline, 1.5m
3/ hour send into the methyl acetate pan tank, standby;
3. the side line extraction separates, and discharges the water that esterification generates
Side line extraction cut temperature is controlled between 78 ℃, from the effluent in the dark weir of the funnel-shaped tower tray 6 at rectifying tower 5 middle parts, after condenser B 12 further condensations, enter phase-splitting chamber 16 phase-splittings of two-chamber overflow phase splitter 13, upper organic phase is crossed dividing plate 14, overflow to back cavity 15, the position below the funnel-shaped tower tray 6 at rectifying tower 5 middle parts is arrived in reflux pipeline B 17 total refluxs enters rectifying tower; Participate in rectifying separation;
Phase-splitting chamber 16 lower aqueous layer are gone to recovery system through water vent line 18, reclaim wherein useful composition;
4. the whole recycles of rectifying tower bottoms
The still liquid of rectifying still (5) through the bottom of rectifying tower still feed liquid circulation line 11 inflow preheaters 2, continues to participate in esterification.
According to method and the step of embodiment 1, difference only is
1. catalyzer adopts tosic acid.
2. advance acetic acid 2m
3/ hour; Methyl alcohol 1.5m
3/ hour, the control preheating temperature is 100 ℃, heats up 90 ℃ of esterification temperatures with low-pressure steam.
3. rectifying tower middle part cut extraction temperature is 75 ℃,
4. the rectifying tower top temperature is 57 ℃, extraction methyl acetate 3.2m
3/ hour.
Claims (10)
1. the preparation method of a methyl acetate, be applicable to supporting method for preparing raw material as oxo process diacetyl oxide device, it is characterized in that with methyl alcohol and acetate be raw material, catalyzer, entrainer exist down, employing is provided with preheater (2), esterifying kettle (3) and the rectifying tower (5) of funnel-shaped tower tray (6) is housed, and the esterification rectifying operating system that is composited of two-chamber overflow phase splitter (13); Design preheater (2) bottom feed, esterifying kettle (2) top drip catalyzer, rectifying tower (5) top extraction product methyl acetate, side line extraction and phase-splitting, discharge the processing method of the water of esterification generation, and technological process comprises following operation steps:
1. continuously feeding, the preheating esterification
At first, it is good by acetate to add in esterifying kettle (3), catalyzer, the bed material that entrainer is formed, the material benzenemethanol of adding is through material benzenemethanol feeding line (1), raw acetic acid is through raw acetic acid feeding line (19), and from the material of rectifying tower (5) tower still, through rectifying tower still feed liquid circulation line (11) according to process requirements, enter the bottom of preheater (2) according to a certain percentage continuously, after the preheating, send into esterifying kettle (3) through its overhead line, catalyzer adds pipeline (4) through catalyzer and adds from the esterifying kettle top, carries out esterification in esterifying kettle, and its processing condition control is as follows:
Preheating temperature ℃ 100～105
Esterifying kettle temperature ℃ 90～120;
2. rectifying, rectifying tower top extraction methyl acetate
Enter through the downside of outlet line (20) from esterifying kettle (3) top effluent air from rectifying tower (5), the rectifying tower top temperature control is at 56～57 ℃, overhead fraction is after condenser (7) condensation, enter return tank (8), wherein a part realizes refluxing through reflux pipeline A (9) as the top of tower phegma of rectifying tower (5), and another part is through product extraction pipeline (10) extraction, send into the methyl acetate pan tank, standby;
3. the side line extraction separates, and discharges the water that esterification generates
Side line extraction cut temperature is controlled between 75～90 ℃, from the effluent in the dark weir of the funnel-shaped tower tray (6) in the middle part of the rectifying tower (5), after the further condensation of condenser B (12), enter phase-splitting chamber (16) phase-splitting of two-chamber overflow phase splitter (13), upper organic phase is crossed dividing plate (14), overflow to back cavity (15),, enter rectifying tower through the position of reflux pipeline B (17) total reflux below the funnel-shaped tower tray (6) at rectifying tower (5) middle part; Participate in rectifying separation;
Phase-splitting chamber (16) lower aqueous layer is gone to recovery system through water vent line (18), reclaims wherein useful composition;
4. the whole recycles of rectifying tower bottoms
The still liquid of rectifying still (5) through the bottom of rectifying tower still feed liquid circulation line (11) inflow preheater (2), continues to participate in esterification.
2. according to the preparation method of the methyl acetate of claim 1, the theoretical plate number that it is characterized in that described rectifying tower (5) is 30～50.
3. according to the preparation method of the methyl acetate of claim 1, it is characterized in that described catalyst for esterification reaction is sulfuric acid or tosic acid.
4. according to the preparation method of the methyl acetate of claim 1, it is characterized in that described catalyst for esterification reaction is a tosic acid, its consumption is 0.1～10% of a reaction mixture total amount.
5. according to the preparation method of the methyl acetate of claim 1, it is characterized in that described catalyst for esterification reaction is a tosic acid, its consumption is 2～6% of a reaction mixture total amount.
6. according to the preparation method of the methyl acetate of claim 1, the ratio of adding that it is characterized in that described material benzenemethanol and acetate such as is at a mole.
7. according to the preparation method of the methyl acetate of claim 1, the trim the top of column that it is characterized in that described rectifying tower (5) is than moisture content shared weight ratio≤3% in total reaction material amount that keeps in the esterifying kettle (2).
8. according to the preparation method of the methyl acetate of claim 1, it is characterized in that described entrainer is any one that chooses from toluene, diisobutyl ether, n-butyl acetate, isobutyl acetate, methyl iso-butyl ketone (MIBK).
9. according to the preparation method of the methyl acetate of claim 1, it is characterized in that described entrainer is a n-butyl acetate.
10. according to the preparation method of the methyl acetate of claim 1, it is characterized in that described esterifying kettle (2) is a glassed steel reaction vessels, the 316L stainless steel is adopted in the bottom of the funnel-shaped tower tray of rectifying tower (6), and the 304L stainless steel is adopted on the top of the funnel-shaped tower tray of rectifying tower (6).
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| CN2010102400956A CN102001937A (en) | 2010-07-29 | 2010-07-29 | Preparation method of methyl acetate |
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|---|---|---|---|
| CN2010102400956A CN102001937A (en) | 2010-07-29 | 2010-07-29 | Preparation method of methyl acetate |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113222A (en) * | 2013-01-31 | 2013-05-22 | 江门谦信化工发展有限公司 | Novel technique for producing methyl acetate |
| CN105152855A (en) * | 2015-09-28 | 2015-12-16 | 中建安装工程有限公司 | Method and device for performing azeotropic distillation separation on methyl acetate and methyl alcohol mixture |
| CN106045851A (en) * | 2016-06-02 | 2016-10-26 | 南京师范大学 | Preparation method of methyl salicylate |
| CN107540547A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | The separation method of allyl acetate |
| CN107827779A (en) * | 2017-10-30 | 2018-03-23 | 烟台国邦化工机械科技有限公司 | Batch reactive distillation production cyanoacetate compound, malonate compound device and its production technology |
| CN107840808A (en) * | 2017-10-30 | 2018-03-27 | 烟台国邦化工机械科技有限公司 | Continuous reaction rectification production cyanoacetate compound, malonate compound device and its production technology |
| CN110357779A (en) * | 2018-04-10 | 2019-10-22 | 山东华鲁恒升化工股份有限公司 | Prepare acetic acid esters technique and its equipment |
| CN110449097A (en) * | 2019-08-16 | 2019-11-15 | 泰兴金江化学工业有限公司 | A kind of Intubaction device for butyl acetate reaction kettle |
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| EP0060717A1 (en) * | 1981-03-17 | 1982-09-22 | BP Chemicals Limited | Process for the production of methyl acetate by esterifying methanol with acetic acid |
| CN1069966A (en) * | 1991-08-24 | 1993-03-17 | 英国石油化学品有限公司 | The production method of methyl acetate |
| CN101735045A (en) * | 2009-12-18 | 2010-06-16 | 中山大学 | Method for producing ethyl acetate by using entrainer |
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2010
- 2010-07-29 CN CN2010102400956A patent/CN102001937A/en active Pending
Patent Citations (3)
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|---|---|---|---|---|
| EP0060717A1 (en) * | 1981-03-17 | 1982-09-22 | BP Chemicals Limited | Process for the production of methyl acetate by esterifying methanol with acetic acid |
| CN1069966A (en) * | 1991-08-24 | 1993-03-17 | 英国石油化学品有限公司 | The production method of methyl acetate |
| CN101735045A (en) * | 2009-12-18 | 2010-06-16 | 中山大学 | Method for producing ethyl acetate by using entrainer |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113222A (en) * | 2013-01-31 | 2013-05-22 | 江门谦信化工发展有限公司 | Novel technique for producing methyl acetate |
| CN105152855A (en) * | 2015-09-28 | 2015-12-16 | 中建安装工程有限公司 | Method and device for performing azeotropic distillation separation on methyl acetate and methyl alcohol mixture |
| CN105152855B (en) * | 2015-09-28 | 2017-06-16 | 中建安装工程有限公司 | A kind of method and device of azeotropic distillation separating methyl acetate ester and carbinol mixture |
| CN106045851A (en) * | 2016-06-02 | 2016-10-26 | 南京师范大学 | Preparation method of methyl salicylate |
| CN107540547A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | The separation method of allyl acetate |
| CN107827779A (en) * | 2017-10-30 | 2018-03-23 | 烟台国邦化工机械科技有限公司 | Batch reactive distillation production cyanoacetate compound, malonate compound device and its production technology |
| CN107840808A (en) * | 2017-10-30 | 2018-03-27 | 烟台国邦化工机械科技有限公司 | Continuous reaction rectification production cyanoacetate compound, malonate compound device and its production technology |
| CN107827779B (en) * | 2017-10-30 | 2024-06-04 | 烟台国邦化工机械科技有限公司 | Device for producing cyanoacetic acid ester and malonic acid ester by batch reaction rectification and production process thereof |
| CN110357779A (en) * | 2018-04-10 | 2019-10-22 | 山东华鲁恒升化工股份有限公司 | Prepare acetic acid esters technique and its equipment |
| CN110449097A (en) * | 2019-08-16 | 2019-11-15 | 泰兴金江化学工业有限公司 | A kind of Intubaction device for butyl acetate reaction kettle |
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