CN101306994A - Technological process for producing high-purity methyl acetate and device - Google Patents
Technological process for producing high-purity methyl acetate and device Download PDFInfo
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- CN101306994A CN101306994A CNA2008100535542A CN200810053554A CN101306994A CN 101306994 A CN101306994 A CN 101306994A CN A2008100535542 A CNA2008100535542 A CN A2008100535542A CN 200810053554 A CN200810053554 A CN 200810053554A CN 101306994 A CN101306994 A CN 101306994A
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Abstract
The invention relates to a process method and a device for producing high-purity methyl acetate, in particular to a process for preparing the high-purity methyl acetate by adopting a reaction rectifying tower with a combination of a solid mass transfer column plate and a catalyzer. The process method comprises the following steps of separation, extraction, rectification and methanol reclaiming of the methyl acetate; acetic acid is added from the upper part of the reaction rectifying tower; methanol is added from the bottom of the reaction rectifying tower; the methyl acetate with high purity is obtained from the top of the reaction rectifying tower and added into a refining tower from the middle part of the refining tower; material in the top of the reaction rectifying tower returns to the reaction rectifying tower; and a finished product of the methyl acetate is extracted from the bottom of the reaction rectifying tower; the material in the bottom of the reaction rectifying tower enters the middle lower part of a reclaiming tower; and the material in the top of the reclaiming tower returns to the reaction rectifying tower. In the invention, the liquid holdup amount of the column plate is obviously improved; the height of a supernatant liquid layer of the column plate can be arbitrarily adjusted in a range of between 20 and 400 mm in order to meet the requirement of the reaction rectifying tower on the liquid holdup amount. Simultaneously, in the height range of the liquid layer, the pressure drop of a monolayer column plate is less than 0.6 KPa. As the conversion rate of a single tower is obviously improved, the methyl acetate with the purity more than or equal to 99.5 percent can be obtained in the bottom of the refining tower.
Description
Technical field
The present invention relates to produce the processing method and the device of high-purity methyl acetate, the reaction fractionating tower that is specifically related to adopt combined trapezoid spray tray to combine with catalyzer prepares the technology of high-purity methyl acetate.
Technical background
High-purity methyl acetate is the important intermediate of producing multiple polyester product, is the important source material that carbonylation is produced aceticanhydride simultaneously.Reaction with methyl alcohol and the acetic acid synthesized methyl esters of acetic acid is reversible reaction, and ritalin, first alcohol and water can form binary or ternary azeotrope, so obtain very difficulty of highly purified ritalin.Conventional production process adopts 1 reactor and 9 rectifying tower, and the main drawback of this technology is: reaction equilibrium constant less (being 5.20), and transformation efficiency is low, and the separation system complexity needs a plurality of rectifying tower just can obtain pure component; And there are a large amount of unreacted methanol and acetic acid to circulate, add complicated separation process, so facility investment is big, the separating energy consumption height.
Reactive distillation is a kind of novel separating technology with wide application prospect.Chemical reaction and rectifying separation process are finished in reaction fractionating tower simultaneously, the liquid holdup decision reaction times of liquid in tower on the column plate.Because processing requirement liquid has enough residence time in tower, all need to improve height of weir plate when adopting common column plate, make height of liquid layer on the plate reach the requirement in reaction times, but this moment, there were shortcomings such as pressure drop is big, turndown ratio is little, processing power is low, plate efficiency is low in column plate.
Summary of the invention
The object of the invention is to provide a kind of processing method and device of producing high-purity methyl acetate, this method is the production method of high-purity methyl acetate and the reactive distillation tower apparatus that adopts big liquid holdup, combined trapezoid spray tray to combine with catalyzer, to overcome the defective of prior art.
The processing method of production high-purity methyl acetate provided by the invention is acetic acid synthesized methyl ester solution under the effect of catalyzer with methyl alcohol and acetic acid, passes through separation, extraction, rectifying, Methanol Recovery step then:
1) acetic acid adds from reaction fractionating tower top, and methyl alcohol adds from reactive distillation section bottom, and the reactive distillation top of tower obtains the ritalin of higher degree;
2) ritalin that will obtain higher degree adds treating tower from the middle part, treating tower bottom extraction finished product ritalin (purity 〉=99.5%), and top material returns reaction fractionating tower;
3) reactive distillation tower bottom material enters the middle and lower part of recovery tower, and the recovery tower top material returns reaction fractionating tower, the water discharging of recovery tower bottom.
Methyl alcohol and acetic acid generate ritalin in the reactive distillation section reaction of reaction fractionating tower, and acetic acid destroys the binary and the ternary azeotrope (making ritalin, first alcohol and water can not form binary or ternary azeotrope) of ritalin, methyl alcohol, water formation in the extraction section of reaction fractionating tower; Acetic acid separates at the rectifying section of reaction fractionating tower top of tower to acetic acid with ritalin; Methyl alcohol, ritalin separate with the stripping section of water at reaction fractionating tower.
Described catalyzer is a C100 type storng-acid cation exchange resin.
Described reaction fractionating tower 101 reflux ratios are 0.8～2: 1.
The mol ratio of described methyl alcohol and acetic acid is 0.5～1.5: 1.
The condition of described reaction fractionating tower operating process is: 0.1～0.2Mpa (absolute pressure), and 30～150 ℃, and preferred 0.1～0.15Mpa (absolute pressure), 50～95 ℃.
The device of the processing method of production high-purity methyl acetate of the present invention mainly comprises reaction fractionating tower 101, treating tower 102, recovery tower 103;
Described reaction fractionating tower 101 comprises tower body, column plate, liquid discharging plate, overflow weir, jet cover, catalyst filling; Described column plate is horizontal column plate, has the air rising hole of rule on the horizontal column plate, and riser is housed on the air rising hole, each riser matches a jet cover is installed, have jet hole on the jet cover, the gas-liquid separation plate is installed in the top of jet cover, is referred to as injection unit; The filler frame is housed between the injection unit; Described catalyst filling is contained in the filler frame; Described liquid discharging plate is vertical with column plate to be installed, and overflow weir is the part that liquid discharging plate exceeds column plate.
Described reaction fractionating tower (101) comprises rectifying section, extraction section, reactive distillation section and stripping section; It is rectifying section that the rectifying tower top adds section to acetic acid, and it is extraction section that acetic acid adds the topmost that enters the mouth to catalyst filling, and the part that catalyst filling is housed is the reactive distillation section, and it is stripping section that methyl alcohol adds inlet following.
The column plate of described reaction fractionating tower (101) rectifying section is 5～20 layers, and the column plate of extraction section is 10～30 layers, and the column plate of reactive distillation section is 5～50 layers, and the column plate of stripping section is 5～20 layers.
Have regularly arranged rectangle, circular plate hole on the described column plate, wherein, row's number in hole is 1-20; Corresponding rectangle or circular riser are installed on each plate hole on the column plate, and folded angle is 60-85 ° between riser and the column plate.
Described height of weir plate 20～400mm, preferred 100～400mm.
The present invention carries out catalyzed reaction by the reaction fractionating tower that acetic acid and methyl alcohol combine with catalyzer at big liquid holdup, combined trapezoid spray tray to generate ritalin solution, the column plate liquid holdup obviously improves, column plate supernatant layer height can be adjusted arbitrarily in the 20-400mm scope, to satisfy the requirement of reactive distillation to liquid holdup.Evidence is in this height of liquid layer scope, and individual layer column plate pressure falls less than 0.6KPa.The transformation efficiency of single tower obviously improves, and treating tower 102 bottoms can obtain the ritalin of purity 〉=99.5%.The present invention has that facility investment is few, cost is low, simple to operate, characteristics such as turndown ratio is big, processing power height, uses catalyzer renewable simultaneously, and environmentally safe is practical.
Description of drawings
Fig. 1 is the combined trapezoid spray tray of the present invention tower plate structure synoptic diagram that combines with catalyzer.
Fig. 2 is Fig. 1 vertical view of the present invention.
Fig. 3 is technological process device figure of the present invention.
Embodiment
As shown in the figure, 1 liquid discharging plate, 2 column plates, 3 riseies, 4 jet covers, 5 spacer plates, 6 tower bodies, 7 seal pots, 8 filler frames.
The present invention mainly comprises reaction fractionating tower 101, treating tower 102, recovery tower 103; Reaction fractionating tower 101 comprises tower body, column plate, liquid discharging plate, overflow weir, jet cover, catalyst filling; Catalyzer is contained on the combined trapezoid spray tray.The structure of injection unit is the riser 3 of regular arrangement on column plate 2, riser 3 highly can be adjusted as required, each riser 3 matches a jet cover 4 is installed, leave the slit between jet cover 4 and the riser 3, have jet hole on the jet cover, gas-liquid separation plate 5 is installed in the top of jet cover 4; The filler frame is housed between jet cover, and catalyst filling is contained in the filler frame and is installed between the injection unit then; Column plate 2 levels are installed; Liquid discharging plate 1 and column plate 2 vertical installations; Have regularly arranged rectangle, circular plate hole on the column plate 2, row's number in hole is 1-20.
5～20 layers of described reaction fractionating tower 101 rectifying section column plates, 10～30 layers of extraction section column plates, 5～50 layers of reactive distillation section column plates, 5～20 layers of stripping section column plates.
Corresponding rectangle or circular riser are installed on described each plate hole, and folded angle is 60-85 ° between riser and the column plate.
Described device tray outlet height of weir degree 100～400mm.
The step of this processing method:
1) Glacial acetic acid adds from reaction fractionating tower 101 tops, and methyl alcohol (99%) adds from reactive distillation section bottom, and reaction fractionating tower 101 tops obtain the ritalin (99%) of higher degree;
2) ritalin of the higher degree that obtains of rectifying tower top adds treating tower 102 from the middle part, treating tower 102 bottoms obtain the ritalin of purity 〉=99.5%, and top material (water and the acetic acid of ritalin, trace) returns reaction fractionating tower 101 (treating tower 102 adopts common rectifying tower to get final product).
3) reaction fractionating tower 101 bottom materials (unreacted methanol, water and a spot of ritalin) enter the middle and lower part of recovery tower 103, recovery tower 103 top materials (methyl alcohol and a spot of ritalin) return reaction fractionating tower 101, the water discharging of recovery tower 103 bottoms (recovery tower 103 adopts common rectifying tower to get final product).
Described catalyzer is that C100 type storng-acid cation exchange resin (floats Lai Te (China) company limited, C100/6100H).
Described reaction fractionating tower 101 reflux ratios are 0.8～2: 1.
The mol ratio of described methyl alcohol and acetic acid is 0.5～1.5: 1.
The condition of described reaction fractionating tower 101 operating process is: 0.1～0.2Mpa (absolute pressure), 30～150 ℃; And preferred 0.1～0.15Mpa (absolute pressure), 50～95 ℃.
It is rectifying section that reaction fractionating tower 101 tops of tower add section to acetic acid, and acetic acid separates in this section with ritalin;
Reaction fractionating tower 101 acetic acid add enter the mouth to the topmost of catalyst filling be extraction section, destroy binary and the ternary azeotrope (making ritalin, first alcohol and water can not form binary or ternary azeotrope) that ritalin, methyl alcohol, water form at this regional acetic acid;
The part that reaction fractionating tower 101 is equipped with catalyst filling is the reactive distillation section, and methyl alcohol and acetic acid reaction generate the reaction of ritalin mainly to carry out in this zone;
Reaction fractionating tower 101 methyl alcohol add that inlet is following to be stripping section, finish methyl alcohol, ritalin separates with water.
Described reaction fractionating tower 101 is liquid phase feedings.
5～20 layers of described reaction fractionating tower 101 rectifying section column plates, 10～30 layers of extraction section column plates, 35～50 layers of reactive distillation section column plates, 5～20 layers of stripping section column plates.
Corresponding rectangle or circular riser are installed on described each plate hole, and folded angle is 60-85 ° between riser and the column plate.
Application Example:
Adopt Fig. 3 technical process, tower 101 adopt the combined trapezoid spray tray of Fig. 1, Fig. 2 and catalyzer [C100 type storng-acid cation exchange resin. float Lai Te (China) company limited, C100/6100H] column plate that combines.
10 layers of reaction fractionating tower 101 rectifying section column plates, 20 layers of extraction section column plates, 40 layers of conversion zone column plates, 10 layers of stripping section column plates;
Reaction fractionating tower 101 heights of weir plate=200mm;
10 layers for the treatment of tower 102 rectifying section column plates, 20 layers of column plate of stripping section;
25 layers of recovery tower 103 rectifying section column plates, 15 layers of stripping section column plates;
The condition of reaction fractionating tower 101 operating process is: tower top pressure 0.1Mpa (absolute pressure), tower still pressure 0.14Mpa (absolute pressure), 57.2 ℃ of tower top temperatures; 85 ℃ of tower still temperature.
Reaction fractionating tower 101 raw materials components mole ratio methyl alcohol: acetic acid=1.2;
Reaction fractionating tower 101 reflux ratios=1.2;
Treating tower 102 reflux ratios=2.0;
Result such as following table 1:
Adopt above-mentioned example, it is 99.6% ritalin that treating tower 102 bottoms can obtain purity, acetic acid conversion＞99.9%.
Claims (10)
1, a kind of processing method of producing high-purity methyl acetate is characterized in that this processing method is acetic acid synthesized methyl ester solution under the effect of catalyzer with methyl alcohol and acetic acid, passes through separation, extraction, rectifying, Methanol Recovery step then:
1) acetic acid adds from reaction fractionating tower top, and methyl alcohol adds from reactive distillation section bottom, and the reactive distillation top of tower obtains the ritalin of higher degree;
2) ritalin that will obtain higher degree adds treating tower from the middle part, treating tower bottom extraction finished product ritalin, and top material returns reaction fractionating tower;
3) reactive distillation tower bottom material enters the middle and lower part of recovery tower, and the recovery tower top material returns reaction fractionating tower, the water discharging of recovery tower bottom.
2, processing method according to claim 1, it is characterized in that: methyl alcohol and acetic acid generate ritalin in the reactive distillation section reaction of reaction fractionating tower, and acetic acid destroys the binary and the ternary azeotrope of ritalin, methyl alcohol, water formation in the extraction section of reaction fractionating tower; Acetic acid separates at the rectifying section of reaction fractionating tower top of tower to acetic acid with ritalin; Methyl alcohol, ritalin separate with the stripping section of water at reaction fractionating tower.
3, processing method according to claim 1 is characterized in that described catalyzer is a C100 type storng-acid cation exchange resin.
4, processing method according to claim 1 is characterized in that described reaction fractionating tower reflux ratio is 0.8～2: 1; The mol ratio of described methyl alcohol and acetic acid is 0.5～1.5: 1.
5, processing method according to claim 1 is characterized in that the condition of described reaction fractionating tower operating process is: 0.1～0.2Mpa, 30～150 ℃.
6, the device of the processing method of the described production high-purity methyl acetate of a kind of claim 1 is characterized in that mainly comprising reaction fractionating tower (101), treating tower (102), recovery tower (103);
Described reaction fractionating tower (101) comprises tower body, column plate, liquid discharging plate, overflow weir, jet cover, catalyst filling; Described column plate is horizontal column plate; Have the air rising hole of rule on the horizontal column plate, riser is housed on the air rising hole, each riser matches a jet cover is installed, and has jet hole on the jet cover, and the gas-liquid separation plate is installed in the top of jet cover, is referred to as injection unit; The filler frame is housed between the injection unit; Described catalyst filling is contained in the filler frame; Described liquid discharging plate is vertical with column plate to be installed, and overflow weir is the part that liquid discharging plate exceeds column plate.
7, device according to claim 6 is characterized in that: described reaction fractionating tower (101) comprises rectifying section, extraction section, reactive distillation section and stripping section; It is rectifying section that the rectifying tower top adds section to acetic acid, and it is extraction section that acetic acid adds the topmost that enters the mouth to catalyst filling, and the part that catalyst filling is housed is the reactive distillation section, and it is stripping section that methyl alcohol adds inlet following.
8, device according to claim 7 is characterized in that the column plate of described reaction fractionating tower (101) rectifying section is 5～20 layers, and the column plate of extraction section is 10～30 layers, and the column plate of reactive distillation section is 5～50 layers, and the column plate of stripping section is 5～20 layers.
9, device according to claim 6 is characterized in that corresponding rectangle or circular riser are installed on each plate hole on the described column plate, and folded angle is 60-85 ° between riser and the column plate.
10, device according to claim 6 is characterized in that described height of weir plate 20～400mm.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008100535542A CN101306994A (en) | 2008-06-18 | 2008-06-18 | Technological process for producing high-purity methyl acetate and device |
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| CNA2008100535542A CN101306994A (en) | 2008-06-18 | 2008-06-18 | Technological process for producing high-purity methyl acetate and device |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757342A (en) * | 2012-07-19 | 2012-10-31 | 安徽皖维高新材料股份有限公司 | Method for purifying by-product methyl acetate generated during production of PVA (polyvinyl acetate) |
| CN102766044A (en) * | 2012-08-07 | 2012-11-07 | 天津凯赛特科技有限公司 | Reaction and rectification system and method for recycling acetic acid from diluted acetic acid solution |
| CN101691325B (en) * | 2009-09-28 | 2012-11-28 | 中国石化集团南京设计院 | Preparation method and device of raw materials needed in preparing acetic anhydride by carbonylation |
| CN103408454A (en) * | 2013-08-16 | 2013-11-27 | 兰州大学 | Preparation method of hydrazide compound |
| CN103787832A (en) * | 2014-01-22 | 2014-05-14 | 天津普莱化工技术有限公司 | Process method for preparing ethanol by hydrogenating methyl acetate |
| CN104644572A (en) * | 2015-01-27 | 2015-05-27 | 华北制药股份有限公司 | High purity clindamycin phosphate powder-injection and preparation process thereof |
| CN105669445A (en) * | 2015-12-29 | 2016-06-15 | 天津普莱化工技术有限公司 | Production technology of ethyl acetate |
| CN105968007A (en) * | 2016-07-06 | 2016-09-28 | 湖北三里枫香科技有限公司 | High-purity methyl acetate production process device and method |
| CN114014755A (en) * | 2021-12-07 | 2022-02-08 | 江苏省瑞丰高分子材料有限公司 | Organic chemical methyl acetate and production process thereof |
| CN114253130A (en) * | 2021-12-21 | 2022-03-29 | 南通大学 | Active-disturbance-rejection control structure and control method for binary rectification process |
| CN116444367A (en) * | 2023-03-15 | 2023-07-18 | 珠海谦信新材料有限公司 | Process for producing high-purity methyl acetate by reactive distillation |
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2008
- 2008-06-18 CN CNA2008100535542A patent/CN101306994A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101691325B (en) * | 2009-09-28 | 2012-11-28 | 中国石化集团南京设计院 | Preparation method and device of raw materials needed in preparing acetic anhydride by carbonylation |
| CN102757342A (en) * | 2012-07-19 | 2012-10-31 | 安徽皖维高新材料股份有限公司 | Method for purifying by-product methyl acetate generated during production of PVA (polyvinyl acetate) |
| CN102766044A (en) * | 2012-08-07 | 2012-11-07 | 天津凯赛特科技有限公司 | Reaction and rectification system and method for recycling acetic acid from diluted acetic acid solution |
| CN103408454B (en) * | 2013-08-16 | 2015-09-23 | 兰州大学 | A kind of preparation method of hydrazide kind compound |
| CN103408454A (en) * | 2013-08-16 | 2013-11-27 | 兰州大学 | Preparation method of hydrazide compound |
| CN103787832B (en) * | 2014-01-22 | 2016-08-31 | 天津普莱化工技术有限公司 | The process of methyl acetate preparation of ethanol through hydrogenation |
| CN103787832A (en) * | 2014-01-22 | 2014-05-14 | 天津普莱化工技术有限公司 | Process method for preparing ethanol by hydrogenating methyl acetate |
| CN104644572A (en) * | 2015-01-27 | 2015-05-27 | 华北制药股份有限公司 | High purity clindamycin phosphate powder-injection and preparation process thereof |
| CN104644572B (en) * | 2015-01-27 | 2017-10-03 | 华北制药股份有限公司 | A kind of high-purity clindamycin phosphate powder and its preparation technology |
| CN105669445A (en) * | 2015-12-29 | 2016-06-15 | 天津普莱化工技术有限公司 | Production technology of ethyl acetate |
| CN105669445B (en) * | 2015-12-29 | 2018-11-06 | 天津普莱化工技术有限公司 | The production technology of ethyl acetate |
| CN105968007A (en) * | 2016-07-06 | 2016-09-28 | 湖北三里枫香科技有限公司 | High-purity methyl acetate production process device and method |
| CN114014755A (en) * | 2021-12-07 | 2022-02-08 | 江苏省瑞丰高分子材料有限公司 | Organic chemical methyl acetate and production process thereof |
| CN114253130A (en) * | 2021-12-21 | 2022-03-29 | 南通大学 | Active-disturbance-rejection control structure and control method for binary rectification process |
| CN114253130B (en) * | 2021-12-21 | 2022-12-16 | 南通大学 | Active disturbance rejection control structure and control method for binary rectification process |
| CN116444367A (en) * | 2023-03-15 | 2023-07-18 | 珠海谦信新材料有限公司 | Process for producing high-purity methyl acetate by reactive distillation |
| CN116444367B (en) * | 2023-03-15 | 2023-10-20 | 珠海谦信新材料有限公司 | Process for producing high-purity methyl acetate by reactive distillation |
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Open date: 20081119 |