CN1325840A - Process for preparing ethyl acetate - Google Patents
Process for preparing ethyl acetate Download PDFInfo
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- CN1325840A CN1325840A CN 01115328 CN01115328A CN1325840A CN 1325840 A CN1325840 A CN 1325840A CN 01115328 CN01115328 CN 01115328 CN 01115328 A CN01115328 A CN 01115328A CN 1325840 A CN1325840 A CN 1325840A
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- ethyl acetate
- extraction agent
- esterification
- esterification column
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 89
- 230000032050 esterification Effects 0.000 claims abstract description 87
- 239000002904 solvent Substances 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000895 extractive distillation Methods 0.000 claims abstract description 35
- 238000011084 recovery Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000011973 solid acid Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims description 58
- 239000003795 chemical substances by application Substances 0.000 claims description 57
- 241000282326 Felis catus Species 0.000 claims description 41
- 150000003839 salts Chemical class 0.000 claims description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 238000011049 filling Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 9
- FQKMILFVTQADHR-CYBMUJFWSA-N (2r)-6,8-dichloro-7-(2-methylpropoxy)-2-(trifluoromethyl)-2h-chromene-3-carboxylic acid Chemical compound C1=C(C(O)=O)[C@H](C(F)(F)F)OC2=C(Cl)C(OCC(C)C)=C(Cl)C=C21 FQKMILFVTQADHR-CYBMUJFWSA-N 0.000 claims description 6
- 239000002131 composite material Chemical class 0.000 claims description 6
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 5
- MMKNOJATXTZICP-KKLWWLSJSA-N (2r,3r)-2-(carboxymethoxy)-3-(5-naphthalen-2-ylpentoxy)-4-(5-naphthalen-2-ylpentylamino)-4-oxobutanoic acid Chemical compound C1=CC=CC2=CC(CCCCCNC(=O)[C@H](OCCCCCC=3C=C4C=CC=CC4=CC=3)[C@@H](OCC(=O)O)C(O)=O)=CC=C21 MMKNOJATXTZICP-KKLWWLSJSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 229960004249 sodium acetate Drugs 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 72
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000012423 maintenance Methods 0.000 abstract description 3
- 229960000583 acetic acid Drugs 0.000 description 27
- 238000010992 reflux Methods 0.000 description 27
- 239000012362 glacial acetic acid Substances 0.000 description 18
- 229960004756 ethanol Drugs 0.000 description 13
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- 238000007865 diluting Methods 0.000 description 9
- 230000000977 initiatory effect Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 aluminum alkoxide Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种生产乙酸乙酯的方法,首先在溶剂回收塔的塔釜配制萃取剂,在酯化塔釜中预置乙酸及固体酸催化剂,在预反应器内装填固体酸催化剂,使乙酸与乙醇完成预反应后,进入酯化塔下段进料口;向酯化塔内通入乙醇和乙酸,在酯化塔塔顶得到乙酸乙酯与水的二元共沸物进入精馏塔下段进料口,同时使萃取剂进入萃取精馏塔上段进料口,塔顶即得到本发明的乙酸乙酯。本发明环境污染少,设备维修与维护成本低;反应与分离流程简单,热利用率高。
The invention relates to a method for producing ethyl acetate. Firstly, an extractant is prepared in the tank of a solvent recovery tower, acetic acid and a solid acid catalyst are preset in the tank of the esterification tower, and a solid acid catalyst is filled in the pre-reactor to make the acetic acid After completing the pre-reaction with ethanol, it enters the feed port of the lower section of the esterification tower; feeds ethanol and acetic acid into the esterification tower, and obtains a binary azeotrope of ethyl acetate and water at the top of the esterification tower and enters the lower section of the rectification tower The feed inlet, and at the same time, the extractant enters the feed inlet of the upper section of the extractive distillation column, and the ethyl acetate of the present invention is obtained at the top of the tower. The invention has less environmental pollution, low equipment repair and maintenance costs, simple reaction and separation process, and high heat utilization rate.
Description
The present invention relates to a kind of method of production ethyl acetate, belong to chemical technology field.
Ethyl acetate is colourless and dulcet liquid, and ethyl acetate is the main component of varnish, spices etc., is many resinoid efficient solvents, is a kind of purposes fine chemical product very widely.
Produce both at home and abroad at present and mainly contain two kinds of methods: be that raw material, the vitriol oil are the direct esterification method of catalyzer 1. with acetate and ethanol; 2. be catalyzer with aluminum alkoxide, acetaldehyde carried out condensation reaction generate ethyl acetate.Domestic main employing direct esterification method production ethyl acetate, there is nearly over one hundred family in manufacturer, scale from 10,000 tons/year to not waiting in 1 kiloton/year, the main drawback of its Production Flow Chart is the energy consumption height, vitriol oil corrosion production unit and spent acid emission of serious pollution of environment.
The objective of the invention is to release a kind of method of production ethyl acetate, at vitriol oil contaminate environment in the traditional technology, the shortcoming that etching apparatus and energy consumption are high, on the basis of development of new on-macromolecular solid acid catalyst PMB-II and high score subclass solid acid catalyst storng-acid cation exchange resin THNK-9, in conjunction with the high efficient separation technology-extractive distillation with salt technology of this teaching and research group, developed new green energy conservation technical process-solid acid continuous catalysis esterification reaction rectification-extractive distillation with salt integrated process.
The method of the production ethyl acetate that the present invention releases comprises following each step:
1, prepare extraction agent in advance at the tower still of solvent recovery tower, extraction agent wherein is ethylene glycol and composite salt, and composite salt accounts for 10%～15% of tower still capacity;
2, in the esterification column still, preset acetate and solid acid catalyst, ratio between two: acetate: solid acid catalyst=1: 0.005～0.01, be heated to 95 ℃～105 ℃, make tower still material enter the opening for feed of tower epimere through interchanger;
3, filling solid acid catalyst in pre-reactor, loading height is 0.8～1.2 meter, make mol ratio be 1: 1 acetate and ethanol in this reactor, under 70～85 ℃, reacted 25～35 minutes, finish pre-reaction after, enter esterification column hypomere opening for feed;
4, feeding simultaneously mol ratio continuously in esterification column is 1: 1 ethanol and acetate, and making the internal circulating load of still liquid in the esterification column is 1/3～1/5 of esterification column hypomere inlet amount, obtains the binary azeotrope of ethyl acetate and water at the esterification column cat head;
5, above-mentioned binary azeotrope steam directly enters extractive distillation with salt tower hypomere opening for feed, make extraction agent enter extractive distillation column epimere opening for feed simultaneously, wherein extraction agent is 1～2: 1 with the ratio of binary azeotrope inlet amount, and cat head promptly obtains ethyl acetate of the present invention.
Portioned product of the present invention is back to the esterification column cat head, is used for taking out of the water of ethanol and esterification generation; The diluted extraction agent of extracting rectifying Tata still extraction recycles after entering in the extraction agent recovery tower rectification under vacuum dehydration.
Composite salt in the used extraction agent of the above-mentioned the first step can be: NaOH, sodium-acetate or K
2CO
3In any; Used solid acid catalyst can be in above-mentioned the second, three step: any in D001, Phenylsulfonic acid, D72, D61, phenylformic acid or the toluene sulfonic acide, D001 wherein, D72 and D61 are provided by Tianjin resin processing plant of Nankai University.
Compared with the prior art the present invention has following characteristics:
1, optimize the esterification condition, in the past liquid-phase esterification is improved in vapour-liquid mixed phase esterification, its equilibrium constant of reaction K will exceed 4 times than reactive liquid solution equilibrium constant K under the similarity condition, has improved esterification efficient greatly;
2, developed solid acid catalyst, this new catalyst catalyzer with traditional on catalytic effect is identical, and etching apparatus is neither exempted the N-process of aftertreatment, and is free from environmental pollution;
3, introduce high efficient separation technology-extractive distillation with salt, simplified technology and equipment greatly, reduced energy consumption and working cost; This technology once was successfully applied to produces dehydrated alcohol, technology maturation.
Advantage of the present invention is: improved esterification reaction rate to greatest extent; Develop the novel ester catalysts, reduced environmental pollution, saved maintenance of equipment and maintenance cost; Simplify reaction and separation process, improved heat utilization efficiency, reduced energy consumption, reduced facility investment expense and working cost, reduced production cost; The production equipment operability is good, stable process conditions; Quality product can reach the standard of GB top grade product.All be better than domestic original technology at aspects such as technical indicator, economic benefit, operations.
Description of drawings:
Fig. 1 is the process flow sheet of the inventive method.
Below introduce embodiments of the invention.
Embodiment 1:
At internal diameter is Φ 30mm, stripping section is 500mm, the esterification section is 1000m, rectifying section is Glacial acetic acid and catalyzer Phenylsulfonic acid 50 grams of the interior 500ml of adding of esterification column still of 300m, 95% (volume ratio) ethanol and Glacial acetic acid were mixed back speed with 5ml/min in 1: 1 in molar ratio to be entered in the fixed bed pre-reactor of filling 270 gram D001 catalyzer, 80 ℃ of temperature through behind the initial action, enter esterification column underfeed mouth and enter esterification column; The circulation acetic acid that contains catalyzer in the tower still is mixed into esterification column top opening for feed and enters in the esterification column, tower still internal circulating load is 1/5 of charging, cat head obtains the binary azeotrope steam of ethyl acetate and water, tower top temperature is 71.5 ℃, reflux ratio is 1.5, do not need condensation to enter extractive distillation with salt tower bottom, the extraction agent that enters with cat head extractant feed mouth contacts, cat head obtain the ethyl acetate partial reflux to the esterification column cat head as trim the top of column, remainder is a product, purity is greater than more than 99.5%, product ethyl acetate yield is greater than 90%, the solvent ratio of extractive distillation with salt tower is 1.2, and tower top temperature is 77 ℃, about 110 ℃ of tower still temperature, extraction agent is ethylene glycol+NaOH, the stripping section 500mm of extractive distillation with salt tower, the extracting rectifying section is 1000mm, the extraction agent washing section is 200mm; The extraction agent that the tower still obtains diluting, enter solvent recovery tower and carry out rectification under vacuum, removed overhead moisture content, obtain the extraction agent that can be recycled at the bottom of the tower, the top vacuum degree of solvent recovery tower is 700mmHg, and tower top temperature is 40 ℃～50 ℃, tower still temperature is about 120 ℃, reflux ratio is 2, solvent recovery tower stripping section 600mm, rectifying section 1000mm.
Embodiment 2:
At internal diameter is Φ 30mm, stripping section is 500mm, the esterification section is 1000m, rectifying section is Glacial acetic acid and catalyzer Phenylsulfonic acid 50 grams of the interior 500ml of adding of esterification column still of 300m, 95% (volume ratio) ethanol and Glacial acetic acid were mixed back speed with 5ml/min in 1: 1 in molar ratio to be entered in the fixed bed pre-reactor of filling 300 gram D72 catalyzer, 85 ℃ of temperature through behind the initial action, enter esterification column underfeed mouth and enter esterification column; The circulation acetic acid that contains catalyzer in the tower still is mixed into esterification column top opening for feed and enters in the esterification column, tower still internal circulating load is 1/4 of charging, cat head obtains the binary azeotrope steam of ethyl acetate and water, tower top temperature is 71.5 ℃, reflux ratio is 1.5, do not need condensation to enter extractive distillation with salt tower bottom, the extraction agent that enters with cat head extractant feed mouth contacts, cat head obtain the ethyl acetate partial reflux to the esterification column cat head as trim the top of column, remainder is a product, purity is greater than more than 99.5%, product ethyl acetate yield is greater than 89%, the solvent ratio of extractive distillation with salt tower is 1.2, and tower top temperature is 77 ℃, about 110 ℃ of tower still temperature, extraction agent is ethylene glycol+NaOH, the stripping section 500mm of extractive distillation with salt tower, the extracting rectifying section is 1000mm, the extraction agent washing section is 200mm; The extraction agent that the tower still obtains diluting, enter solvent recovery tower and carry out rectification under vacuum, removed overhead moisture content, obtain the extraction agent that can be recycled at the bottom of the tower, the top vacuum degree of solvent recovery tower is 700mmHg, and tower top temperature is 40 ℃～50 ℃, tower still temperature is about 120 ℃, reflux ratio is 2, solvent recovery tower stripping section 600mm, rectifying section 1000mm.
Embodiment 3:
At internal diameter is Φ 30mm, stripping section is 500mm, the esterification section is 1000m, rectifying section is Glacial acetic acid and catalyzer Phenylsulfonic acid 50 grams of the interior 500ml of adding of esterification column still of 300m, 95% (volume ratio) ethanol and Glacial acetic acid were mixed back speed with 5ml/min in 1: 1 in molar ratio to be entered in the fixed bed pre-reactor of filling 320 gram D61 catalyzer, 91 ℃ of temperature through behind the initial action, enter esterification column underfeed mouth and enter esterification column; The circulation acetic acid that contains catalyzer in the tower still is mixed into esterification column top opening for feed and enters in the esterification column, tower still internal circulating load is 1/4.5 of charging, cat head obtains the binary azeotrope steam of ethyl acetate and water, tower top temperature is 71.5 ℃, reflux ratio is 1.5, do not need condensation to enter extractive distillation with salt tower bottom, the extraction agent that enters with cat head extractant feed mouth contacts, cat head obtain the ethyl acetate partial reflux to the esterification column cat head as trim the top of column, remainder is a product, purity is greater than more than 99.5%, product ethyl acetate yield is greater than 87%, the solvent ratio of extractive distillation with salt tower is 1.2, and tower top temperature is 77 ℃, about 110 ℃ of tower still temperature, extraction agent is ethylene glycol+NaOH, the stripping section 500mm of extractive distillation with salt tower, the extracting rectifying section is 1000mm, the extraction agent washing section is 200mm; The extraction agent that the tower still obtains diluting, enter solvent recovery tower and carry out rectification under vacuum, removed overhead moisture content, obtain the extraction agent that can be recycled at the bottom of the tower, the top vacuum degree of solvent recovery tower is 700mmHg, and tower top temperature is 40 ℃～50 ℃, tower still temperature is about 120 ℃, reflux ratio is 2, solvent recovery tower stripping section 600mm, rectifying section 1000mm.
Embodiment 4:
At internal diameter is Φ 30mm, stripping section is 500mm, the esterification section is 1000m, rectifying section is Glacial acetic acid and catalyzer phenylformic acid 75 grams of the interior 500ml of adding of esterification column still of 300m, 95% (volume ratio) ethanol and Glacial acetic acid were mixed back speed with 5ml/min in 1: 1 in molar ratio to be entered in the fixed bed pre-reactor of filling 270 gram D72 catalyzer, 85 ℃ of temperature through behind the initial action, enter esterification column underfeed mouth and enter esterification column; The circulation acetic acid that contains catalyzer in the tower still is mixed into esterification column top opening for feed and enters in the esterification column, tower still internal circulating load is 1/3 of charging, cat head obtains the binary azeotrope steam of ethyl acetate and water, tower top temperature is 71.5 ℃, reflux ratio is 1.5, do not need condensation to enter extractive distillation with salt tower bottom, the extraction agent that enters with cat head extractant feed mouth contacts, cat head obtain the ethyl acetate partial reflux to the esterification column cat head as trim the top of column, remainder is a product, purity is greater than more than 99.5%, product ethyl acetate yield is greater than 90%, the solvent ratio of extractive distillation with salt tower is 1.2, and tower top temperature is 77 ℃, about 110 ℃ of tower still temperature, extraction agent is ethylene glycol+NaOH, the stripping section 500mm of extractive distillation with salt tower, the extracting rectifying section is 1000mm, the extraction agent washing section is 200mm; The extraction agent that the tower still obtains diluting, enter solvent recovery tower and carry out rectification under vacuum, removed overhead moisture content, obtain the extraction agent that can be recycled at the bottom of the tower, the top vacuum degree of solvent recovery tower is 700mmHg, and tower top temperature is 40 ℃～50 ℃, tower still temperature is about 120 ℃, reflux ratio is 2, solvent recovery tower stripping section 600mm, rectifying section 1000mm.
Embodiment 5:
At internal diameter is Φ 30mm, stripping section is 500mm, the esterification section is 1000m, rectifying section is Glacial acetic acid and catalyzer phenylformic acid 75 grams of the interior 500ml of adding of esterification column still of 300m, 95% (volume ratio) ethanol and Glacial acetic acid were mixed back speed with 5ml/min in 1: 1 in molar ratio to be entered in the fixed bed pre-reactor of filling 270 gram D001 catalyzer, 80 ℃ of temperature through behind the initial action, enter esterification column underfeed mouth and enter esterification column; The circulation acetic acid that contains catalyzer in the tower still is mixed into esterification column top opening for feed and enters in the esterification column, tower still internal circulating load is 1/4.3 of charging, cat head obtains the binary azeotrope steam of ethyl acetate and water, tower top temperature is 71.5 ℃, reflux ratio is 1.5, do not need condensation to enter extractive distillation with salt tower bottom, the extraction agent that enters with cat head extractant feed mouth contacts, cat head obtain the ethyl acetate partial reflux to the esterification column cat head as trim the top of column, remainder is a product, purity is greater than more than 99.5%, product ethyl acetate yield is greater than 90%, the solvent ratio of extractive distillation with salt tower is 1.2, and tower top temperature is 77 ℃, about 110 ℃ of tower still temperature, extraction agent is ethylene glycol+NaOH, the stripping section 500mm of extractive distillation with salt tower, the extracting rectifying section is 1000mm, the extraction agent washing section is 200mm; The extraction agent that the tower still obtains diluting, enter solvent recovery tower and carry out rectification under vacuum, removed overhead moisture content, obtain the extraction agent that can be recycled at the bottom of the tower, the top vacuum degree of solvent recovery tower is 700mmHg, and tower top temperature is 40 ℃～50 ℃, tower still temperature is about 120 ℃, reflux ratio is 2, solvent recovery tower stripping section 600mm, rectifying section 1000mm.
Embodiment 6:
At internal diameter is Φ 30mm, stripping section is 500mm, the esterification section is 1000m, rectifying section is Glacial acetic acid and catalyzer toluene sulfonic acide 65 grams of the interior 500ml of adding of esterification column still of 300m, 95% (volume ratio) ethanol and Glacial acetic acid were mixed back speed with 5ml/min in 1: 1 in molar ratio to be entered in the fixed bed pre-reactor of filling 282 gram D001 catalyzer, 80 ℃ of temperature through behind the initial action, enter esterification column underfeed mouth and enter esterification column; The circulation acetic acid that contains catalyzer in the tower still is mixed into esterification column top opening for feed and enters in the esterification column, tower still internal circulating load is 1/4.6 of charging, cat head obtains the binary azeotrope steam of ethyl acetate and water, tower top temperature is 71.5 ℃, reflux ratio is 1.5, do not need condensation to enter extractive distillation with salt tower bottom, the extraction agent that enters with cat head extractant feed mouth contacts, cat head obtain the ethyl acetate partial reflux to the esterification column cat head as trim the top of column, remainder is a product, purity is greater than more than 99.5%, product ethyl acetate yield is greater than 90%, the solvent ratio of extractive distillation with salt tower is 1.2, and tower top temperature is 77 ℃, about 110 ℃ of tower still temperature, extraction agent is ethylene glycol+NaOH, the stripping section 500mm of extractive distillation with salt tower, the extracting rectifying section is 1000mm, the extraction agent washing section is 200mm; The extraction agent that the tower still obtains diluting, enter solvent recovery tower and carry out rectification under vacuum, removed overhead moisture content, obtain the extraction agent that can be recycled at the bottom of the tower, the top vacuum degree of solvent recovery tower is 700mmHg, and tower top temperature is 40 ℃～50 ℃, tower still temperature is about 120 ℃, reflux ratio is 2, solvent recovery tower stripping section 600mm, rectifying section 1000mm.
Embodiment 7:
At internal diameter is Φ 30mm, stripping section is 500mm, the esterification section is 1000m, rectifying section is Glacial acetic acid and catalyzer toluene sulfonic acide 65 grams of the interior 500ml of adding of esterification column still of 300m, 95% (volume ratio) ethanol and Glacial acetic acid were mixed back speed with 5ml/min in 1: 1 in molar ratio to be entered in the fixed bed pre-reactor of filling 282 gram D001 catalyzer, 80 ℃ of temperature through behind the initial action, enter esterification column underfeed mouth and enter esterification column; The circulation acetic acid that contains catalyzer in the tower still is mixed into esterification column top opening for feed and enters in the esterification column, tower still internal circulating load is 1/4.6 of charging, cat head obtains the binary azeotrope steam of ethyl acetate and water, tower top temperature is 71.5 ℃, reflux ratio is 1.5, do not need condensation to enter extractive distillation with salt tower bottom, the extraction agent that enters with cat head extractant feed mouth contacts, cat head obtain the ethyl acetate partial reflux to the esterification column cat head as trim the top of column, remainder is a product, purity is greater than more than 99.5%, product ethyl acetate yield is greater than 90%, the solvent ratio of extractive distillation with salt tower is 2.0, and tower top temperature is 77 ℃, about 110 ℃ of tower still temperature, extraction agent is ethylene glycol+sodium-acetate, the stripping section 500mm of extractive distillation with salt tower, the extracting rectifying section is 1000mm, the extraction agent washing section is 200mm; The extraction agent that the tower still obtains diluting, enter solvent recovery tower and carry out rectification under vacuum, removed overhead moisture content, obtain the extraction agent that can be recycled at the bottom of the tower, the top vacuum degree of solvent recovery tower is 700mmHg, and tower top temperature is 40 ℃～50 ℃, tower still temperature is about 120 ℃, reflux ratio is 1.8, solvent recovery tower stripping section 600mm, rectifying section 1000mm.
Embodiment 8:
At internal diameter is Φ 30mm, stripping section is 500mm, the esterification section is 1200m, rectifying section is Glacial acetic acid and catalyzer toluene sulfonic acide 65 grams of the interior 500ml of adding of esterification column still of 300m, 95% (volume ratio) ethanol and Glacial acetic acid were mixed back speed with 5ml/min in 1: 1 in molar ratio to be entered in the fixed bed pre-reactor of filling 300 gram D72 catalyzer, 85 ℃ of temperature through behind the initial action, enter esterification column underfeed mouth and enter esterification column; The circulation acetic acid that contains catalyzer in the tower still is mixed into esterification column top opening for feed and enters in the esterification column, tower still internal circulating load is 1/4.6 of charging, cat head obtains the binary azeotrope steam of ethyl acetate and water, tower top temperature is 71.5 ℃, reflux ratio is 1.5, do not need condensation to enter extractive distillation with salt tower bottom, the extraction agent that enters with cat head extractant feed mouth contacts, cat head obtain the ethyl acetate partial reflux to the esterification column cat head as trim the top of column, remainder is a product, purity is greater than more than 99.5%, product ethyl acetate yield is greater than 90%, and the solvent ratio of extractive distillation with salt tower is 1.4, and tower top temperature is 77 ℃, about 110 ℃ of tower still temperature, extraction agent is ethylene glycol+K
2CO
3, the stripping section 500mm of extractive distillation with salt tower, the extracting rectifying section is 1000mm, the extraction agent washing section is 200mm; The extraction agent that the tower still obtains diluting, enter solvent recovery tower and carry out rectification under vacuum, removed overhead moisture content, obtain the extraction agent that can be recycled at the bottom of the tower, the top vacuum degree of solvent recovery tower is 700mmHg, and tower top temperature is 40 ℃～50 ℃, tower still temperature is about 120 ℃, reflux ratio is 1.6, solvent recovery tower stripping section 800mm, rectifying section 1000mm.
Embodiment 9:
At internal diameter is Φ 30mm, stripping section is 500mm, the esterification section is 1200m, rectifying section is Glacial acetic acid and catalyzer toluene sulfonic acide 65 grams of the interior 500ml of adding of esterification column still of 300m, 95% (volume ratio) ethanol and Glacial acetic acid were mixed back speed with 5ml/min in 1: 1 in molar ratio to be entered in the fixed bed pre-reactor of filling 275 gram D001 catalyzer, 80 ℃ of temperature through behind the initial action, enter esterification column underfeed mouth and enter esterification column; The circulation acetic acid that contains catalyzer in the tower still is mixed into esterification column top opening for feed and enters in the esterification column, tower still internal circulating load is 1/4.6 of charging, cat head obtains the binary azeotrope steam of ethyl acetate and water, tower top temperature is 71.5 ℃, reflux ratio is 1.5, do not need condensation to enter extractive distillation with salt tower bottom, the extraction agent that enters with cat head extractant feed mouth contacts, cat head obtain the ethyl acetate partial reflux to the esterification column cat head as trim the top of column, remainder is a product, purity is greater than more than 99.5%, product ethyl acetate yield is greater than 90%, and the solvent ratio of extractive distillation with salt tower is 1.4, and tower top temperature is 77 ℃, about 110 ℃ of tower still temperature, extraction agent is ethylene glycol+K
2CO
3, the stripping section 500mm of extractive distillation with salt tower, the extracting rectifying section is 1000mm, the extraction agent washing section is 200mm; The extraction agent that the tower still obtains diluting, enter solvent recovery tower and carry out rectification under vacuum, removed overhead moisture content, obtain the extraction agent that can be recycled at the bottom of the tower, the top vacuum degree of solvent recovery tower is 700mmHg, and tower top temperature is 40 ℃～50 ℃, tower still temperature is about 120 ℃, reflux ratio is 1.6, solvent recovery tower stripping section 800mm, rectifying section 1000mm.
Claims (3)
1, a kind of method of production ethyl acetate is characterized in that this method comprises following each step:
(1) prepare extraction agent in advance at the tower still of solvent recovery tower, extraction agent wherein is ethylene glycol and composite salt, and composite salt accounts for 10%～15% of tower still capacity;
(2) in the esterification column still, preset acetate and solid acid catalyst, ratio between two: acetate: solid acid catalyst=1: 0.005～0.01, be heated to 95 ℃～105 ℃, make tower still material enter the opening for feed of tower epimere through interchanger;
(3) filling solid acid catalyst in pre-reactor, loading height is 0.8～1.2 meter, make mol ratio be 1: 1 acetate and ethanol in this reactor, under 70～85 ℃, reacted 25～35 minutes, finish pre-reaction after, enter esterification column hypomere opening for feed;
(4) feeding simultaneously mol ratio continuously in esterification column is 1: 1 ethanol and acetate, and making the internal circulating load of still liquid in the esterification column is 1/3～1/5 of esterification column hypomere inlet amount, obtains the binary azeotrope of ethyl acetate and water at the esterification column cat head;
(5) above-mentioned binary azeotrope steam directly enters extractive distillation with salt tower hypomere opening for feed, make extraction agent enter extractive distillation column epimere opening for feed simultaneously, wherein extraction agent is 1～2: 1 with the ratio of binary azeotrope inlet amount, and cat head promptly obtains ethyl acetate of the present invention.
2, preparation method as claimed in claim 1 is characterized in that the composite salt in the used extraction agent of the first step wherein is NaOH, sodium-acetate or K
2CO
3In any.
3, preparation method as claimed in claim 1 is characterized in that wherein used solid acid catalyst is in second and third step: any in D001, Phenylsulfonic acid, D72, D61, phenylformic acid or the toluene sulfonic acide.
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| CN 01115328 CN1325840A (en) | 2001-04-20 | 2001-04-20 | Process for preparing ethyl acetate |
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|---|---|---|---|
| CN 01115328 CN1325840A (en) | 2001-04-20 | 2001-04-20 | Process for preparing ethyl acetate |
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| CN1325840A true CN1325840A (en) | 2001-12-12 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294114C (en) * | 2004-05-21 | 2007-01-10 | 河北科技大学 | Method for producing acetic ether |
| CN102399130A (en) * | 2011-12-13 | 2012-04-04 | 西南化工研究设计院 | Method for simplifying rectification process for preparing ethanol through hydrogenation of acetic acid |
| CN103539663A (en) * | 2013-10-28 | 2014-01-29 | 江苏理工学院 | Method for separating ethyl acetate from cyclohexane |
| CN106693434A (en) * | 2015-08-05 | 2017-05-24 | 南通鸿志化工有限公司 | Salting extractive rectification device |
| 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 |
| CN108083978A (en) * | 2017-12-25 | 2018-05-29 | 万华化学集团股份有限公司 | The preparation process and device of cyclohexanedimethanol |
| CN108675929A (en) * | 2018-03-23 | 2018-10-19 | 广西金茂生物化工有限公司 | A kind of production technology of ethyl acetate |
| CN109942358A (en) * | 2019-04-16 | 2019-06-28 | 营创三征(营口)精细化工有限公司 | A kind of solid acid catalyzed continuous esterification process of low boiling point alcohol |
| CN113493380A (en) * | 2020-04-01 | 2021-10-12 | 丹东明珠特种树脂有限公司 | Preparation method and preparation system of high-purity methyl acetate |
-
2001
- 2001-04-20 CN CN 01115328 patent/CN1325840A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294114C (en) * | 2004-05-21 | 2007-01-10 | 河北科技大学 | Method for producing acetic ether |
| CN102399130B (en) * | 2011-12-13 | 2014-07-02 | 西南化工研究设计院 | Method for simplifying rectification process for preparing ethanol through hydrogenation of acetic acid |
| CN102399130A (en) * | 2011-12-13 | 2012-04-04 | 西南化工研究设计院 | Method for simplifying rectification process for preparing ethanol through hydrogenation of acetic acid |
| CN104829408B (en) * | 2013-10-28 | 2017-03-08 | 江苏理工学院 | Method for separating ethyl acetate and cyclohexane |
| CN103539663B (en) * | 2013-10-28 | 2015-05-13 | 江苏理工学院 | Method for separating ethyl acetate from cyclohexane |
| CN104829408A (en) * | 2013-10-28 | 2015-08-12 | 江苏理工学院 | Method for separating ethyl acetate and cyclohexane |
| CN103539663A (en) * | 2013-10-28 | 2014-01-29 | 江苏理工学院 | Method for separating ethyl acetate from cyclohexane |
| CN106693434A (en) * | 2015-08-05 | 2017-05-24 | 南通鸿志化工有限公司 | Salting extractive rectification device |
| 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 |
| CN108083978A (en) * | 2017-12-25 | 2018-05-29 | 万华化学集团股份有限公司 | The preparation process and device of cyclohexanedimethanol |
| CN108083978B (en) * | 2017-12-25 | 2021-01-29 | 万华化学集团股份有限公司 | Process and apparatus for the preparation of cyclohexanedimethanol |
| CN108675929A (en) * | 2018-03-23 | 2018-10-19 | 广西金茂生物化工有限公司 | A kind of production technology of ethyl acetate |
| CN109942358A (en) * | 2019-04-16 | 2019-06-28 | 营创三征(营口)精细化工有限公司 | A kind of solid acid catalyzed continuous esterification process of low boiling point alcohol |
| CN113493380A (en) * | 2020-04-01 | 2021-10-12 | 丹东明珠特种树脂有限公司 | Preparation method and preparation system of high-purity methyl acetate |
| CN113493380B (en) * | 2020-04-01 | 2024-09-13 | 丹东明珠特种树脂有限公司 | Methyl acetate preparation method |
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