CN115318232A - Device and production process for coproducing amyl alcohol and methyl acetate - Google Patents
Device and production process for coproducing amyl alcohol and methyl acetate Download PDFInfo
- Publication number
- CN115318232A CN115318232A CN202210812339.6A CN202210812339A CN115318232A CN 115318232 A CN115318232 A CN 115318232A CN 202210812339 A CN202210812339 A CN 202210812339A CN 115318232 A CN115318232 A CN 115318232A
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- China
- Prior art keywords
- tower
- methanol
- methyl acetate
- pentanol
- temperature
- Prior art date
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 105
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 title claims abstract description 105
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 390
- 238000006243 chemical reaction Methods 0.000 claims abstract description 100
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229940072049 amyl acetate Drugs 0.000 claims abstract description 60
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000066 reactive distillation Methods 0.000 claims abstract description 32
- 150000002148 esters Chemical group 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004821 distillation Methods 0.000 claims abstract description 12
- 239000002699 waste material Substances 0.000 claims abstract description 10
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 76
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims description 60
- 239000000463 material Substances 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 22
- 238000003860 storage Methods 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 11
- 238000007670 refining Methods 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000005192 partition Methods 0.000 claims description 10
- 238000005086 pumping Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000002826 coolant Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 5
- 239000001632 sodium acetate Substances 0.000 abstract description 5
- 235000017281 sodium acetate Nutrition 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- -1 salt sodium acetate Chemical class 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 239000002994 raw material Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 238000009835 boiling Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 3
- YFPCLQKFNXUAAK-UHFFFAOYSA-N cyclopentyl acetate Chemical compound CC(=O)OC1CCCC1 YFPCLQKFNXUAAK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- GQKZRWSUJHVIPE-UHFFFAOYSA-N 2-Pentanol acetate Chemical compound CCCC(C)OC(C)=O GQKZRWSUJHVIPE-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N n-butyl methyl carbinol Natural products CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- IFTRQJLVEBNKJK-UHFFFAOYSA-N Aethyl-cyclopentan Natural products CCC1CCCC1 IFTRQJLVEBNKJK-UHFFFAOYSA-N 0.000 description 1
- 240000005561 Musa balbisiana Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000003721 gunpowder Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/42—Regulation; Control
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
- C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a device and a production process for coproducing amyl alcohol and methyl acetate.A mixture of amyl alcohol, methanol, methyl acetate and a catalyst obtained from a tower kettle of a reactive distillation tower is subjected to ester exchange reaction on amyl acetate and methanol and is subjected to a distillation tower to obtain purified amyl alcohol; and (3) the azeotrope of methyl acetate and methanol obtained from the top of the reactive distillation column passes through a condenser and then enters a high-pressure column to obtain high-purity methyl acetate. The invention has the advantages that the dynamic reaction rate of the ester exchange reaction is improved by raising the temperature, the reaction time can be shortened by raising the temperature, and the content of methyl acetate in the reactive distillation tower is lowest; the amyl acetate and performance are pretreated by the amyl acetate pretreatment device, the amyl acetate and a small amount of water contained in the amyl acetate are separated, the hydrolysis reaction of water and methanol is avoided, and the generation of waste salt sodium acetate and the consumption of sodium methoxide are reduced; methyl acetate products with the purity of 99.5 to 99.9 percent are obtained by utilizing a methyl acetate pressurizing tower.
Description
Technical Field
The invention relates to the field of methyl acetate manufacturing, in particular to a device and a production process for coproducing amyl alcohol and methyl acetate.
Background
Methyl acetate is a novel basic chemical raw material, gradually becomes a mature product internationally, and is used for replacing acetone, butanone, ethyl acetate, cyclopentane and the like.
Chinese patent publication No. CN113493380A reports a preparation method and a preparation system of high-purity methyl acetate, acetic acid and methanol are adopted to react in a pre-reactor under the catalytic action of a solid catalyst, and then catalytic reaction is continued in a catalytic distillation tower, wherein the catalytic distillation tower supplements acetic acid in the middle of a reaction section of the catalytic distillation tower, and an extractant is added on the upper part of the reaction section, and the extractant is at least one of ethylene glycol and propylene glycol. The preparation system of the high-purity methyl acetate preparation method comprises a pre-reactor and a catalytic distillation tower which are sequentially connected in the material flow direction, wherein a first rectifying tower for removing light, a second rectifying tower for recovering acetic acid and a third rectifying tower for recovering an extracting agent are serially arranged behind the catalytic distillation tower. The technical scheme realizes the production of high-purity methyl acetate.
The above reports suggest that the preparation of methyl acetate uses acetic acid as raw material, and the acetic acid is gaseous, so that the requirement on equipment corrosion resistance is high, and the extraction agent is added in the separation process, so that the difficulty is increased for the subsequent material separation.
Chinese patent publication No. CN102399132A discloses a method for preparing cyclopentanol from cyclopentene, wherein refined cyclopentyl acetate and methanol are subjected to transesterification reaction in a liquid phase through a fixed bed catalyst to generate cyclopentanol and methyl acetate, the purity of methyl acetate as a byproduct is about 98wt%, and the purity still needs to be further improved.
Disclosure of Invention
The invention aims to solve the technical problem that the purity of a product obtained by the existing methyl acetate preparation method is not enough, and provides a device and a production process for coproducing pentanol and methyl acetate.
The technical scheme of the invention is as follows: an apparatus for coproducing amyl alcohol and methyl acetate comprises: a reactive distillation column; the inlet of the condenser is communicated with the top of the reaction rectifying tower; an inlet of the storage tank is communicated with an outlet of the condenser, and an outlet of the storage tank is communicated with the upper part of the reactive distillation column; the side surface of the methyl acetate pressurizing tower is communicated with the outlet of the storage tank; the top of the methyl acetate atmospheric tower is communicated with the side surface of the methyl acetate pressurizing tower; the side surface of the methyl acetate atmospheric tower is communicated with the top of the methyl acetate pressurizing tower, and the bottom of the methyl acetate atmospheric tower is communicated with the lower part of the reaction rectifying tower; the outlet of the reboiler is communicated with the lower part of the reactive distillation tower, and the bottom of the reboiler is communicated with the bottom of the reactive distillation tower; the side surface of the evaporator is communicated with the bottom of the reboiler; the side surface of the methanol removing tower is communicated with the top of the evaporator, and the top of the methanol removing tower is communicated with the bottom of the methyl acetate atmospheric tower; the side surface of the 3-pentanol rectifying tower is communicated with the bottom of the methanol removing tower; the side surface of the 2-pentanol rectifying tower is communicated with the bottom of the 3-pentanol rectifying tower.
The improvement of the scheme is that the upper part of the reaction rectifying tower is connected with a amyl acetate pretreatment device, the amyl acetate pretreatment device comprises a closed cavity, a liquid inlet is formed in the middle of one side of the closed cavity, an electromagnetic valve is arranged on the liquid inlet, a cofferdam is arranged in the closed cavity, a first cache space communicated with the liquid inlet is defined by the cofferdam and the closed cavity, a first cover plate is hinged in the closed cavity and matched with the top of the cofferdam, an L-shaped partition plate is installed at the top of the closed cavity and comprises a vertical section fixedly connected with the top of the closed cavity and a horizontal section which is positioned at the bottom of the cofferdam and extends towards the liquid inlet, a notch is reserved between the free end of the horizontal section and one side of the closed cavity, a second cache space is formed between the L-shaped partition plate and the cofferdam, a third cache space is formed between the partition plate and the other side of the closed cavity, and a liquid outlet is formed in the other side of the closed cavity.
The further improvement of the scheme is that a flow sensor is arranged on the liquid outlet, a cylinder is installed on the outer wall of one side of the sealed cavity, a piston rod of the cylinder extends into the sealed cavity and is fixedly connected with a sealing plate at the tail end of the sealed cavity, and the sealing plate is matched with the horizontal section to seal or open the notch.
The production process of the device for coproducing the amyl alcohol and the methyl acetate comprises the following steps: (1) Preparing amyl acetate, methanol and a catalyst, wherein the feeding ratio of the amyl acetate to the methanol is controlled within the range of 2-5, the catalyst is 0.2-0.7% of the feeding amount of the methanol, and the methanol comprises circulating methanol and fresh methanol; (2) Inputting amyl acetate and a catalyst from the top of a reaction rectifying tower, inputting circulating methanol and fresh methanol from the middle lower part of the reaction rectifying tower for ester exchange reaction, controlling the temperature of the reaction rectifying tower at 70-85 ℃ and the pressure at 0.09-0.11 MPa, discharging an azeotrope of a reaction product methyl acetate and part of methanol from the top of the reaction rectifying tower in a gas phase, cooling the azeotrope by a condenser and inputting the cooled azeotrope into a storage tank, and discharging a mixed material of the reaction product amyl alcohol, the methanol and the catalyst from the bottom of the reaction rectifying tower; (3) Part of mixed materials of amyl alcohol, methanol and catalyst enter a reaction rectifying tower through a reboiler for cyclic utilization, the other part of mixed materials enter an evaporator for evaporation, the temperature is 100-120 ℃, the pressure is less than or equal to 0.05MPa, and waste salt is intermittently discharged from the bottom of the evaporator; (4) Continuously rectifying the gas phase obtained by evaporation in the evaporator in a methanol removing tower, controlling the temperature of a rectifying section at 65-80 ℃, using the methanol with the purity of 99-99.5% distilled from the rectifying section as the circulating methanol in the step (2), controlling the temperature of a stripping section at 115-126 ℃, and extracting the mixture of 2-pentanol and 3-pentanol; (5) Pumping the mixture of 2-pentanol and 3-pentanol to a 3-pentanol rectifying tower, wherein the operating pressure is-0.068 kpa to-0.05 kpa, the temperature of a rectifying section is controlled at 80-95 ℃, 3-pentanol with the purity of about 99.0-99.7% is rectified, the temperature of a stripping section is controlled at 95-110 ℃, and crude 2-pentanol is extracted from the stripping section; (6) Pumping the crude 2-pentanol into a 2-pentanol refining tower, wherein the operating pressure is 25-32 kpa, the temperature of a rectifying section is controlled at 127-130 ℃, and the temperature of a stripping section is controlled at 130-140 ℃ to obtain the 2-pentanol with the purity of 99.0-99.9 percent; (7) The azeotrope of methyl acetate and methanol in the storage tank enters a methyl acetate pressurizing tower, the temperature of the top of the tower is controlled to be 124-126 ℃, the operating pressure is 0.8MPa, the temperature of the bottom of the tower is controlled to be 135-138 ℃, and a methyl acetate product with the purity of 99.5-99.9 percent is obtained in the bottom of the tower; (8) And feeding the material discharged from the top of the methyl acetate pressurizing tower into a methyl acetate atmospheric tower, controlling the temperature at the top of the methyl acetate atmospheric tower to be 50-54 ℃ and the operating pressure to be 0.005MPa, feeding the obtained material into the methyl acetate pressurizing tower for circulation, and controlling the temperature at the bottom of the tower to be 64-68 ℃ to obtain the methanol.
The production process of the other device for coproducing the amyl alcohol and the methyl acetate comprises the following steps: (1) Inputting amyl acetate into a liquid inlet of a amyl acetate pretreatment device, accumulating amyl acetate in a first cache space until a first cover plate is jacked up, overflowing to a second cache space, then flowing to a third cache space from the second cache space, and finally discharging from a liquid outlet; (2) Preparing amyl acetate, methanol and a catalyst which are discharged from a liquid outlet, wherein the feeding ratio of the amyl acetate to the methanol is controlled within the range of 2-5, the catalyst is 0.2-0.7% of the feeding amount of the methanol, and the methanol comprises circulating methanol and fresh methanol; (3) Inputting amyl acetate and a catalyst from the top of a reaction rectifying tower, inputting circulating methanol and fresh methanol from the middle lower part of the reaction rectifying tower for ester exchange reaction, controlling the temperature of the reaction rectifying tower at 70-85 ℃ and the pressure at 0.09-0.11 MPa, discharging an azeotrope of a reaction product methyl acetate and part of methanol from the top of the reaction rectifying tower in a gas phase, cooling the azeotrope by a condenser and inputting the cooled azeotrope into a storage tank, and discharging a mixed material of the reaction product amyl alcohol, the methanol and the catalyst from the bottom of the reaction rectifying tower; (4) Part of mixed materials of amyl alcohol, methanol and catalyst enter a reaction rectifying tower through a reboiler for cyclic utilization, the other part of mixed materials enter an evaporator for evaporation, the temperature is 100-120 ℃, the pressure is less than or equal to 0.05MPa, and waste salt is intermittently discharged from the bottom of the evaporator; (5) Continuously rectifying the gas phase obtained by evaporation in the evaporator in a methanol removing tower, controlling the temperature of a rectifying section at 65-80 ℃, using the methanol with the distillation purity of 99-99.5% in the rectifying section as the circulating methanol in the step (2), controlling the temperature of a stripping section at 115-126 ℃, and extracting the mixture of 2-pentanol and 3-pentanol; (6) Pumping the mixture of 2-pentanol and 3-pentanol to a 3-pentanol rectifying tower, wherein the operating pressure is-0.068 kpa to-0.05 kpa, the temperature of a rectifying section is controlled at 80-95 ℃, 3-pentanol with the purity of about 99.0-99.7% is rectified, the temperature of a stripping section is controlled at 95-110 ℃, and crude 2-pentanol is extracted from the stripping section; (7) Pumping the crude 2-pentanol into a 2-pentanol refining tower, wherein the operating pressure is 25-32 kpa, the temperature of a rectifying section is controlled at 127-130 ℃, and the temperature of a stripping section is controlled at 130-140 ℃ to obtain the 2-pentanol with the purity of 99.0-99.9 percent; (8) The azeotrope of methyl acetate and methanol in the storage tank enters a methyl acetate pressurizing tower, the temperature of the top of the tower is controlled to be 124-126 ℃, the operating pressure is 0.8MPa, the temperature of the bottom of the tower is controlled to be 135-138 ℃, and the methyl acetate product with the purity of 99.5-99.9 percent is obtained from the bottom of the tower; (9) And feeding the material discharged from the top of the methyl acetate pressurizing tower into a methyl acetate atmospheric tower, controlling the temperature at the top of the methyl acetate pressurizing tower to be 50-54 ℃ and the operating pressure to be 0.005MPa, feeding the obtained material into the methyl acetate pressurizing tower for circulation, and controlling the temperature at the bottom of the tower to be 64-68 ℃ to obtain the methanol.
In the scheme, the catalyst in the step (2) is methanol solution of sodium methoxide, and the dosage of the catalyst is 0.4-0.6% of the feeding amount of methanol.
In the scheme, the temperature of the reactive distillation tower is controlled to be 75-80 ℃, and the pressure is controlled to be 0.095-0.1 MPa.
In the scheme, the cooling medium of the condenser is circulating water at the temperature of 25-33 ℃, the reactive distillation column comprises a reaction section, a stripping section and a distillation section, and steam in the distillation section is supercooled to the temperature of 35-50 ℃ for extraction and reflux.
In the scheme, the heating medium of the reboiler is low-pressure steam, the pressure in the reboiler is 0.2MPa to 0.3MPa, and the temperature is 135 ℃ to 145 ℃.
In the scheme, the reflux ratio of the reactive distillation column is 1-3.
The invention has the advantages that the dynamic reaction rate of the ester exchange reaction is improved by raising the temperature, the reaction time can be shortened by raising the temperature, and the content of methyl acetate in the reactive distillation tower is lowest; the amyl acetate pretreatment device is used for pretreating amyl acetate and performance, and separating amyl acetate and a small amount of water contained in the amyl acetate, so that hydrolysis reaction of water and methanol is avoided, and the generation of waste salt sodium acetate and the consumption of sodium methoxide are reduced; methyl acetate products with the purity of 99.5 to 99.9 percent are obtained by utilizing a methyl acetate pressurizing tower.
Drawings
FIG. 1 is a schematic reactive distillation diagram of the present invention;
FIG. 2 is a process flow diagram of the present invention;
FIG. 3 is a schematic view of a pretreatment apparatus for amyl acetate in accordance with the present invention;
FIG. 4 is a schematic view of another amyl acetate pretreatment apparatus of the present invention;
in the figure, 1, a reaction rectifying tower, 2, a condenser, 3, a storage tank, 4, a methyl acetate pressurizing tower, 5, a methyl acetate atmospheric tower, 6, a reboiler, 7, an evaporator, 8, a methanol removing tower, 9, 3-pentanol rectifying tower, 10, 2-pentanol rectifying tower, 11, a closed cavity, 12, a liquid inlet, 13, a cofferdam, 14, a first cover plate, 15, a partition plate, 16, a sealing plate, 17 and a liquid outlet.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below with reference to the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments based on the embodiments in the present invention, without any inventive work, will be apparent to those skilled in the art from the following description.
After the amyl acetate and the methanol are subjected to ester exchange reaction, amyl alcohol, methanol, methyl acetate and a catalyst mixture obtained from a tower bottom of a reactive distillation tower are subjected to distillation to obtain purified amyl alcohol; the azeotrope of methyl acetate and methanol obtained from the top of the reactive distillation column passes through a condenser and then enters a high-pressure column to obtain methyl acetate with the purity of 99.5-99.9%.
Starting material 1 amyl acetate. Also named as amyl acetate and banana oil. Is one kind of ester, is esterification product of acetic acid and amyl alcohol, is colorless transparent liquid at normal temperature, has fruit fragrance, is flammable, is slightly soluble in water, and is mutually soluble with ethanol and diethyl ether. Amyl acetate is used as solvent and diluent for making essence, cosmetics, artificial leather, film, gunpowder, etc. Amyl acetate is not optically active. Melting point: -78.5 ℃, boiling point: 149.3 ℃, relative density: 0.88, relative vapor density: 4.5, saturated vapor pressure (148 ℃): 98.24kPa, flash point: 25 ℃, ignition point: 360 ℃, upper explosion limit% (V/V): 7.5, lower explosive limit% (V/V): 1.0.
The raw material methanol of the reactive distillation section comprises fresh methanol and circulating methanol (a methanol removing tower).
Methanol (Methanol) is the most structurally simple saturated monoalcohol. The appearance is colorless, transparent, inflammable and volatile toxic liquid. Relative density 0.792 (20/4 deg.C), melting point-97.8 deg.C, boiling point 64.5 deg.C, flash point 12.22 deg.C, self-ignition point 463.89 deg.C, vapor density 1.11, vapor pressure 13.33kPa (100mmHg21.2 deg.C), explosion limit of vapor and air mixture 6-36.5% (volume ratio), and can be mixed with water, ethanol, ether, benzene, ketone, halogenated hydrocarbon and many other organic solvents.
Catalyst and process for producing the same
The catalyst is one or more of sodium methoxide, lithium hydroxide, lithium carbonate, potassium hydroxide, potassium carbonate, zinc oxide, tetrabutyl titanate and dibutyltin oxide, and the sodium methoxide is selected as the catalyst in the project: sodium methoxide is dissolved in methanol and is used in a concentration range of 10-30%, preferably 20-30%.
The process flow of the invention comprises a reactive distillation tower 1, a condenser 2, a storage tank 3, a methyl acetate pressurized tower 4, a methyl acetate atmospheric tower 5, a reboiler 6, an evaporator 7, a demethanizer 8, a 3-pentanol refining tower 9 and a 2-pentanol refining tower 10, as shown in fig. 1-2, the process sequence for producing pentanol and methyl acetate is as follows:
(II) ester exchange step
The charging ratio of the raw materials of amyl acetate and methanol in the ester exchange reaction process is controlled within the range of 2-5, and the preferable charging ratio is 3-4: the feeding amount of the methanol solution of sodium methoxide catalyst is determined by simulation calculation, and the methanol solution of sodium methoxide is about 0.2-0.7%, preferably 0.4-0.6% of the feeding amount of the raw material methanol for transesterification reaction. The temperature of the reaction rectifying tower is controlled between 70 ℃ and 85 ℃, preferably between 75 ℃ and 80 ℃, and the pressure is controlled between 0.09MPa and 0.11MPa, preferably between 0.095MPa and 0.1MPa. The methanol solution of amyl acetate and sodium methoxide is fed from the top of the reaction section of the reaction rectifying tower, the retention time of raw materials and catalysts in the reaction section of the reaction rectifying tower is increased, and fresh methanol and circulating methanol are fed at multiple points and are both fed at the middle lower part of the reaction section, wherein the circulating methanol is arranged at the middle part, and the fresh methanol is added to the bottom of the reaction section of the reaction rectifying tower. The ester exchange reaction is a reversible reaction, methyl acetate generated by the reaction is separated out in a gas phase form on a tower plate of a reaction rectifying tower, and the concentration of reactants can be increased by replenishing methanol to promote the forward progress of the ester exchange reaction. And the azeotrope of the reaction product methyl acetate and partial methanol is discharged from the top of the reactive distillation tower in a gas phase, and the mixed material of the amyl alcohol, the methanol and the catalyst which are the reaction product of the reactive distillation tower is discharged from the bottom of the reactive distillation tower.
The reactive distillation tower comprises a reaction section, a stripping section and a rectifying section. Wherein the column type is a combined column for reaction and separation, the column plate structure of the reaction section is a plate column structure, the column plate can be a sieve plate column, a float valve column, a bubble column or the like, the rectifying section is a filler, and the filler is a regular filler. The continuous reaction rectifying tower is provided with a condenser, the cooling medium is circulating water (25-33 ℃), the steam in the rectifying section is supercooled to (35-50 ℃) for extraction and reflux, and the heating medium of the reboiler is low-pressure steam (0.2-0.3 MPa, 135-145 ℃).
The amyl acetate and the methanol react to obtain a reaction solution with 2-amyl alcohol and 3-amyl alcohol as main components. The present application increases the rate of the kinetic reaction of the transesterification reaction by increasing the temperature. The increase in temperature can shorten the reaction time. Goal of transesterification: the method has the advantages that the amyl acetate is completely converted into methyl acetate and amyl alcohol in the shortest time, the thermodynamic equilibrium is changed by continuously removing the generated methyl acetate by adopting a reactive distillation technology, the forward reaction is promoted, and the depth of the ester exchange reaction or the residual amount of the amyl acetate in the ester exchange reaction is determined by the content of the methyl acetate in a reaction tower kettle. That is, the lower the methyl acetate content in the tower bottom, the lower the residual amyl acetate concentration, compared with the prior art, for example, the content of Chinese patent publication No. CN102399132A "the refined cyclopentyl acetate obtained by the method and the methanol are subjected to ester exchange reaction in liquid phase through a fixed bed catalyst to generate the cyclopentyl alcohol and the methyl acetate, the feeding molar ratio of the cyclopentyl acetate to the methanol is 1 to (2-5), and the liquid mass space velocity is 0.8-2 hr -1 The reaction temperature is 40-60 ℃, and the dynamic reaction rate of the ester exchange reaction is improved by increasing the temperature. The increase in temperature can shorten the reaction time to 70% of the original time.
The water existing in the reaction system can cause the hydrolysis of sodium methoxide to generate NaOH, and the existence of the NaOH and the water can cause the saponification reaction of amyl acetate to convert the NaOH into sodium acetate with weak alkalinity, so that the consumption of the catalyst sodium methoxide is increased, and more waste salt sodium acetate is generated. Since the saponification process is continued, the pH of the reaction system is gradually lowered during the transesterification reaction, and it is found in actual production that the transesterification reaction rate is significantly lowered when the pH is as low as 8 or less. Therefore, the less the residual moisture of the raw material amyl acetate, the better, otherwise, sodium methoxide should be consumed, and the more sodium methoxide is used, the larger the amount of waste salt is generated, and the main component of the waste salt is sodium acetate.
In order to ensure that the amyl acetate entering a reaction and rectification tower does not contain moisture, the method in the prior art is to dehydrate by using a molecular sieve, but the molecular sieve is expensive and cannot ensure complete dehydration, so that the application is not adopted but made a new way, and a amyl acetate pretreatment device is designed by utilizing the characteristics that amyl acetate is lighter than water and is slightly soluble in water, and the embodiment 1: as shown in fig. 3, the amyl acetate pretreatment device comprises a closed cavity 11, a liquid inlet 12 is formed in the middle of one side of the closed cavity, a cofferdam 13 is arranged in the closed cavity, a first buffer space communicated with the liquid inlet is formed by the cofferdam and the closed cavity in a surrounding manner, a first cover plate 14 is hinged in the closed cavity and matched with the top of the cofferdam, an L-shaped partition plate 15 is mounted at the top of the closed cavity and comprises a vertical section fixedly connected with the top of the closed cavity and a horizontal section located at the bottom of the cofferdam and extending towards the liquid inlet, a gap is reserved between the free end of the horizontal section and one side of the closed cavity, a second buffer space is formed between the L-shaped partition plate and the cofferdam, a third buffer space is formed between the partition plate and the other side of the closed cavity, and a liquid outlet 17 is formed in the other side of the closed cavity.
The use method of the amyl acetate pretreatment device comprises the following steps: inputting amyl acetate into a liquid inlet of the amyl acetate pretreatment device, accumulating amyl acetate in the first cache space until jacking the first cover plate, overflowing to the second cache space, flowing to the third cache space through the gap in the second cache space, and finally discharging from the liquid outlet, wherein only amyl acetate flows out from the liquid outlet through the standing separation of the first cache space and the third cache space in the process.
Example 2: as shown in fig. 4, as the deformation of the acetic acid amyl ester pretreatment device, a flow sensor is arranged on the liquid outlet, an air cylinder is installed on the outer wall of one side of the closed cavity, a piston rod of the air cylinder extends into the closed cavity, a sealing plate 16 is fixedly connected to the tail end of the piston rod, and the sealing plate is matched with the horizontal section to seal or open the gap.
The use method of the amyl acetate pretreatment device comprises the following steps: when the flow sensor detects that the fluid flow of the liquid outlet becomes large, a signal is sent to the air cylinder, the piston rod stretches out to enable the sealing plate to be close to the horizontal section to cover the notch, the second cache space and the third cache space are separated by the sealing plate, when the flow sensor detects that the fluid flow of the liquid outlet becomes small, the signal is sent to the air cylinder, the piston rod contracts to enable the sealing plate to be far away from the horizontal section to expose the notch, and the second cache space and the third cache space are communicated through the notch.
Compared with the embodiment 1, the embodiment 2 can quickly sense the change of the flow rate, timely make adjustment, cover or expose the gap by moving the sealing plate, control the flow rate in the second buffer space, and temporarily store the surplus amyl acetate when the flow rate is increased in the second buffer space above the first buffer space, wherein the part is also indispensable for realizing the flow rate adjustment.
(II) Evaporation
The materials in the tower bottom enter an evaporator, the evaporator can be a kettle type evaporator, a scraper evaporator, a thin film evaporator and the like, ester exchange reaction liquid in the ester exchange products is pumped into the evaporator to be evaporated, the temperature is 100-120 ℃, the pressure is less than or equal to 0.05MPa, gas phase generated by evaporation enters a methanol removing tower to be continuously rectified, and waste salt is intermittently discharged from the bottom of the evaporator.
(III) methanol recovery
The gas phase of the evaporator enters a methanol removing tower for continuous rectification, the temperature of a rectification section is controlled to be 65-80 ℃, the methanol with the purity of 99-99.5% is distilled out of the rectification section and can be recycled and continuously used as a raw material for ester exchange reaction, and the utilization rate of the material is improved. The temperature of the stripping section is controlled between 115 ℃ and 126 ℃, and a mixture of 2-pentanol and 3-pentanol is extracted.
The main principle of the process is as follows: the boiling point of the methanol is 64 ℃, the boiling point of the lowest material in the mixed material is 115 ℃ (3-pentanol), and the methanol is separated from the mixed material by using the property that the boiling point of the methanol is lower than that of other materials through rectification operation, so that the recyclable pure methanol is obtained.
(IV) 3-pentanol rectification separation tower
Pumping the 2-pentanol and the 3-pentanol to a rectifying tower at an operating pressure of-0.068 to-0.05 kpa, preferably-0.06 to-0.058 kpa, rectifying to obtain 3-pentanol with the purity of about 99.0 to 99.7 percent at a temperature of between 80 and 95 ℃ and preferably between 85 and 92 ℃, and extracting to obtain crude 2-pentanol at a temperature of between 95 and 110 ℃ and preferably between 97 and 104 ℃.
The main principle of the process is as follows: the boiling point of the 3-pentanol is 115.6 ℃, the boiling point of the lowest material in the mixed material is 119 ℃ (2-pentanol), and the 3-pentanol is separated from the mixed material by rectification operation by utilizing the property that the boiling point of the 3-pentanol is lower than that of other materials, so that the 3-pentanol product is obtained.
(V) 2-pentanol refining tower
The crude 2-pentanol enters a 2-pentanol refining tower, the operation pressure is 25-32 kpa, the temperature of a rectifying section is controlled at 127-130 ℃, the temperature of a stripping section is controlled at 130-140 ℃, and the 2-pentanol with the purity of 99.0-99.9% is obtained.
The main principle of the process is as follows: the boiling point of the 2-pentanol is 126 ℃, the boiling point of the lowest material in the mixed material is 130 ℃ (sec-amyl acetate), and the 2-pentanol is separated from the mixed material by rectification operation by utilizing the property that the boiling point of the mixture is lower than that of other materials to obtain the 2-pentanol product.
(6) Refining of methyl acetate
The azeotrope of methyl acetate and methanol as the ester exchange reaction product is fed into methyl acetate pressurizing tower with tower top temperature of 124-126 deg.c, operation pressure of 0.8MPa and tower kettle temperature of 135-138 deg.c. The methyl acetate product with the purity of 99.5-99.9% is obtained in the tower kettle, the material at the tower top enters an atmospheric tower, the temperature at the tower top of the atmospheric tower is controlled to be 50-54 ℃, the operating pressure is 0.005MPa, the temperature at the tower kettle of the atmospheric tower is controlled to be 64-68 ℃, the methanol can be recovered in the tower kettle of the atmospheric tower, and the material at the tower top of the atmospheric tower is sent to a pressurizing tower for circulation, so that the material utilization rate is improved.
The reaction rectifying tower is a general reaction rectifying tower comprising a rectifying section and a reaction section. The type is a plate tower comprising a packing layer, the reaction section tower plate type adopts a large liquid holdup and high-efficiency mass transfer tower plate, the rectification section type adopts high-efficiency structured packing, and the type selection is based on that the plate tower has a larger reaction liquid holdup than a packed tower, and the separation effect of the packing is better when the reaction is not involved. The design is that 10-15 plates (5-6 m packing layer) in the rectifying section and 28-33 plates in the reaction section are used. The operation pressure of the reactive distillation column is determined according to the reactive temperature (the temperature of the reaction section) of the catalyst;
the temperature of the reactive distillation column is controlled to be 70 to 85 ℃, preferably 75 to 80 ℃, and the pressure is controlled to be 0.09 to 0.11MPa, preferably 0.095 to 0.1MPa in view of the universality of the reactive distillation column.
Determination of reflux ratio (energy consumption index) of reactive distillation column
The reflux ratio is adopted to represent the flow of vapor and liquid phases in the tower and the energy consumption index, and the reflux ratio range is determined according to the simulation result;
the larger the reflux ratio is, the shorter the material retention time in the reaction section is, and the lower the conversion per pass of the amyl acetate is;
reflux ratio has an effect on the hydrodynamic behavior of the column;
the reflux ratio has an effect on the concentration of the catalyst on the tray;
the larger the reflux ratio is, the larger the energy consumption is;
the reflux ratio range is as follows: 1 to 3.
The feeding amount of the catalyst has great influence on the reaction rectification process and is related to the reaction rate of the amyl acetate, the generation amount of the product and the like, and the higher the feeding amount is, the higher the reaction rate of the amyl acetate is; the feed rate of the catalyst is determined by simulation and is about 0.2% to 0.7%, preferably 0.4% to 0.6% of the feed rate of methanol. In view of the flexibility of operation, the catalyst is dissolved in methanol solution to form sodium methoxide methanol solution, and the apparatus is designed to feed the catalyst separately, for example by means of a metering pump.
One of the raw materials in the invention is composed of two parts, one part is from outsourcing fresh methanol, the other part is methanol with the purity of 99-99.5% recovered in the methanol removing process, the recovered methanol accounts for 50-60% of the fed methanol, and the recovered methanol participates in the ester exchange reaction again, thus improving the utilization rate of the raw material methanol and reducing the harm to the environment. The reaction rectification technology is adopted in the project, and thermodynamic equilibrium is changed by continuously removing the generated methyl acetate, so that the forward reaction is promoted, and the reaction time is reduced. And the reaction raw materials of amyl acetate and the methanol solution of catalyst sodium methoxide are selectively fed from the top of the reaction section of the reaction rectifying tower, so that the retention time of the raw materials in the reaction section is increased, fresh methanol and circulating methanol are fed in the middle lower part of the reaction section of the reaction rectifying tower, the concentration of reactants is increased, and the forward progress of the ester exchange reaction is promoted. In addition, the invention takes the upstream product of amyl acetate as one of the raw materials for producing methyl acetate products, does not need acetic acid as the raw material, reduces the requirement of equipment on corrosion resistance, does not need to add an extracting agent in the subsequent refining process of methyl acetate, and reduces the separation difficulty of materials in the refining process of methyl acetate and amyl alcohol.
Claims (10)
1. The utility model provides a device of coproduction amyl alcohol and methyl acetate which characterized by: the method comprises the following steps: a reactive distillation column (1); the inlet of the condenser (2) is communicated with the top of the reaction rectifying tower; the inlet of the storage tank (3) is communicated with the outlet of the condenser, and the outlet of the storage tank is communicated with the upper part of the reactive distillation column; the side surface of the methyl acetate pressurizing tower (4) is communicated with the outlet of the storage tank; the top of the methyl acetate atmospheric tower is communicated with the side surface of the methyl acetate pressurizing tower, the side surface of the methyl acetate atmospheric tower is communicated with the top of the methyl acetate pressurizing tower, and the bottom of the methyl acetate atmospheric tower is communicated with the lower part of the reaction rectifying tower; a reboiler (6), the outlet of the reboiler is communicated with the lower part of the reactive distillation column, and the bottom of the reboiler is communicated with the bottom of the reactive distillation column; an evaporator (7) having a side surface communicating with the bottom of the reboiler; a methanol removing tower (8), wherein the side surface of the methanol removing tower is communicated with the top of the evaporator, and the top of the methanol removing tower is communicated with the bottom of the methyl acetate atmospheric tower; the side surface of the 3-pentanol rectifying tower (9) is communicated with the bottom of the methanol removing tower; the side surface of the 2-amyl alcohol rectifying tower (10) is communicated with the bottom of the 3-amyl alcohol rectifying tower.
2. The device for coproduction of amyl alcohol and methyl acetate as claimed in claim 1, wherein: the reaction rectifying tower is characterized in that the upper part of the reaction rectifying tower is connected with an acetic acid amyl ester pretreatment device, the acetic acid amyl ester pretreatment device comprises an airtight cavity (11), a liquid inlet (12) is formed in the middle of one side of the airtight cavity, an electromagnetic valve is arranged on the liquid inlet, a cofferdam (13) is arranged in the airtight cavity, a first cache space communicated with the liquid inlet is formed by the cofferdam and the airtight cavity in a surrounding mode, a first cover plate (14) is hinged in the airtight cavity and matched with the top of the cofferdam, an L-shaped partition plate (15) is installed at the top of the airtight cavity and comprises a vertical section fixedly connected with the top of the airtight cavity and a horizontal section extending towards the liquid inlet at the bottom of the cofferdam, a notch is reserved between the free end of the horizontal section and one side of the airtight cavity, a second cache space is formed between the L-shaped partition plate and the cofferdam, a third cache space is formed between the partition plate and the other side of the airtight cavity, and a liquid outlet (17) is formed in the other side of the airtight cavity.
3. The device for coproducing pentanol and methyl acetate as claimed in claim 2, wherein: be equipped with flow sensor on the liquid outlet, the cylinder is installed to airtight cavity one side outer wall, the piston rod of cylinder stretches into in the airtight cavity and its terminal rigid coupling has closing plate (16), the closing plate realizes closing or opening the breach with the horizontal segment cooperation.
4. A production process of the device for coproducing amyl alcohol and methyl acetate according to claim 1, which is characterized in that: the method comprises the following steps: (1) Preparing amyl acetate, methanol and a catalyst, wherein the feeding ratio of the amyl acetate to the methanol is controlled within the range of 2-5, the catalyst is 0.2-0.7% of the feeding amount of the methanol, and the methanol comprises circulating methanol and fresh methanol; (2) Inputting amyl acetate and a catalyst from the top of a reaction rectifying tower, inputting circulating methanol and fresh methanol from the middle lower part of the reaction rectifying tower for ester exchange reaction, controlling the temperature of the reaction rectifying tower to be 70-85 ℃, controlling the pressure to be 0.09-0.11 MPa, discharging an azeotrope of a reaction product of methyl acetate and part of methanol from the top of the reaction rectifying tower in a gas phase, cooling the azeotrope by a condenser, inputting the cooled azeotrope into a storage tank, and discharging a mixed material of the reaction product of amyl alcohol, methanol and the catalyst from the bottom of the reaction rectifying tower; (3) Part of mixed materials of amyl alcohol, methanol and catalyst enter a reaction rectifying tower through a reboiler for cyclic utilization, the other part of mixed materials enter an evaporator for evaporation, the temperature is 100-120 ℃, the pressure is less than or equal to 0.05MPa, and waste salt is intermittently discharged from the bottom of the evaporator; (4) Continuously rectifying the gas phase obtained by evaporation in the evaporator in a methanol removing tower, controlling the temperature of a rectifying section at 65-80 ℃, using the methanol with the purity of 99-99.5% distilled from the rectifying section as the circulating methanol in the step (2), controlling the temperature of a stripping section at 115-126 ℃, and extracting the mixture of 2-pentanol and 3-pentanol; (5) Pumping the mixture of 2-pentanol and 3-pentanol to a 3-pentanol rectifying tower, wherein the operating pressure is-0.068 kpa to-0.05 kpa, the temperature of a rectifying section is controlled at 80-95 ℃, 3-pentanol with the purity of about 99.0-99.7% is rectified, the temperature of a stripping section is controlled at 95-110 ℃, and crude 2-pentanol is extracted from the stripping section; (6) Pumping the crude 2-pentanol into a 2-pentanol refining tower, wherein the operating pressure is 25-32 kpa, the temperature of a rectifying section is controlled at 127-130 ℃, and the temperature of a stripping section is controlled at 130-140 ℃ to obtain the 2-pentanol with the purity of 99.0-99.9 percent; (7) The azeotrope of methyl acetate and methanol in the storage tank enters a methyl acetate pressurizing tower, the temperature of the top of the tower is controlled to be 124-126 ℃, the operating pressure is 0.8MPa, the temperature of the bottom of the tower is controlled to be 135-138 ℃, and the methyl acetate product with the purity of 99.5-99.9 percent is obtained from the bottom of the tower; (8) And feeding the material discharged from the top of the methyl acetate pressurizing tower into a methyl acetate atmospheric tower, controlling the temperature at the top of the methyl acetate pressurizing tower to be 50-54 ℃ and the operating pressure to be 0.005MPa, feeding the obtained material into the methyl acetate pressurizing tower for circulation, and controlling the temperature at the bottom of the tower to be 64-68 ℃ to obtain the methanol.
5. The production process of the device for coproducing amyl alcohol and methyl acetate as claimed in claim 3, which is characterized in that: the method comprises the following steps: (1) Inputting amyl acetate into a liquid inlet of a amyl acetate pretreatment device, accumulating amyl acetate in a first cache space until a first cover plate is jacked up, overflowing to a second cache space, then flowing to a third cache space from the second cache space, and finally discharging from a liquid outlet; (2) Preparing amyl acetate, methanol and a catalyst which are discharged from a liquid outlet, wherein the feeding ratio of the amyl acetate to the methanol is controlled within the range of 2-5, the catalyst is 0.2-0.7% of the feeding amount of the methanol, and the methanol comprises circulating methanol and fresh methanol; (3) Inputting amyl acetate and a catalyst from the top of a reaction rectifying tower, inputting circulating methanol and fresh methanol from the middle lower part of the reaction rectifying tower for ester exchange reaction, controlling the temperature of the reaction rectifying tower at 70-85 ℃ and the pressure at 0.09-0.11 MPa, discharging an azeotrope of a reaction product methyl acetate and part of methanol from the top of the reaction rectifying tower in a gas phase, cooling the azeotrope by a condenser and inputting the cooled azeotrope into a storage tank, and discharging a mixed material of the reaction product amyl alcohol, the methanol and the catalyst from the bottom of the reaction rectifying tower; (4) Part of mixed materials of amyl alcohol, methanol and catalyst enter a reaction rectifying tower through a reboiler for cyclic utilization, the other part of mixed materials enter an evaporator for evaporation, the temperature is 100-120 ℃, the pressure is less than or equal to 0.05MPa, and waste salt is intermittently discharged from the bottom of the evaporator; (5) Continuously rectifying the gas phase obtained by evaporation in the evaporator in a methanol removing tower, controlling the temperature of a rectifying section at 65-80 ℃, using the methanol with the purity of 99-99.5% distilled from the rectifying section as the circulating methanol in the step (2), controlling the temperature of a stripping section at 115-126 ℃, and extracting the mixture of 2-pentanol and 3-pentanol; (6) Pumping the mixture of 2-pentanol and 3-pentanol to a 3-pentanol rectifying tower, wherein the operating pressure is-0.068 kpa to-0.05 kpa, the temperature of a rectifying section is controlled at 80-95 ℃, 3-pentanol with the purity of about 99.0-99.7% is rectified, the temperature of a stripping section is controlled at 95-110 ℃, and crude 2-pentanol is extracted from the stripping section; (7) Pumping the crude 2-pentanol into a 2-pentanol refining tower, wherein the operating pressure is 25-32 kpa, the temperature of a rectifying section is controlled at 127-130 ℃, and the temperature of a stripping section is controlled at 130-140 ℃ to obtain the 2-pentanol with the purity of 99.0-99.9 percent; (8) The azeotrope of methyl acetate and methanol in the storage tank enters a methyl acetate pressurizing tower, the temperature of the top of the tower is controlled to be 124-126 ℃, the operating pressure is 0.8MPa, the temperature of the bottom of the tower is controlled to be 135-138 ℃, and a methyl acetate product with the purity of 99.5-99.9 percent is obtained in the bottom of the tower; (9) And feeding the material discharged from the top of the methyl acetate pressurizing tower into a methyl acetate atmospheric tower, controlling the temperature at the top of the methyl acetate atmospheric tower to be 50-54 ℃ and the operating pressure to be 0.005MPa, feeding the obtained material into the methyl acetate pressurizing tower for circulation, and controlling the temperature at the bottom of the tower to be 64-68 ℃ to obtain the methanol.
6. The production process of the device for coproducing pentanol and methyl acetate as claimed in claim 4 or 5, wherein the production process comprises the following steps: the catalyst in the step (2) is sodium methoxide, and the dosage of the sodium methoxide is 0.4-0.6 percent of the feeding quantity of methanol.
7. The production process of the device for coproducing pentanol and methyl acetate as claimed in claim 4 or 5, wherein the production process comprises the following steps: the temperature of the reactive distillation tower is controlled to be 75-80 ℃, and the pressure is controlled to be 0.095-0.1 MPa.
8. The production process of the device for coproducing pentanol and methyl acetate as claimed in claim 4 or 5, wherein the production process comprises the following steps: the cooling medium of the condenser is circulating water with the temperature of 25-33 ℃, the reactive distillation column comprises a reaction section, a stripping section and a distillation section, and steam in the distillation section is overcooled to the temperature of 35-50 ℃ for extraction and reflux.
9. The production process of the device for coproducing pentanol and methyl acetate as claimed in claim 4 or 5, wherein the production process comprises the following steps: the heating medium of the reboiler is low pressure steam, the pressure in the reboiler is 0.2MPa to 0.3MPa, and the temperature is 135 ℃ to 145 ℃.
10. The production process of the device for coproducing the pentanol and the methyl acetate as claimed in claim 4 or 5, wherein the production process comprises the following steps: the reflux ratio of the reactive distillation column is 1-3.
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| CN109369340A (en) * | 2018-11-14 | 2019-02-22 | 常州大学 | A kind of device and method of reactive distillation transesterification preparing isopropanol |
| WO2021047393A1 (en) * | 2019-09-10 | 2021-03-18 | 上海浦景化工技术股份有限公司 | Rectification device and rectification method for oxo synthesis of acetic acid |
| CN113443990A (en) * | 2021-06-02 | 2021-09-28 | 天津大学 | Methyl acetate dividing wall tower extraction-reaction rectification hydrolysis process and device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102795961A (en) * | 2012-08-07 | 2012-11-28 | 临海市联盛化学有限公司 | Device and method for synthesizing sec-butyl alcohol by continuous reaction-rectification |
| CN102875328A (en) * | 2012-09-20 | 2013-01-16 | 福州大学 | Catalyzing rectifying technology for synthesizing sec-butyl alcohol through ester exchange method and production equipment of catalyzing rectifying technology |
| CN105461515A (en) * | 2015-12-07 | 2016-04-06 | 上海派尔科化工材料股份有限公司 | Method for preparing cyclopentanol from cyclopentene |
| CN109369340A (en) * | 2018-11-14 | 2019-02-22 | 常州大学 | A kind of device and method of reactive distillation transesterification preparing isopropanol |
| WO2021047393A1 (en) * | 2019-09-10 | 2021-03-18 | 上海浦景化工技术股份有限公司 | Rectification device and rectification method for oxo synthesis of acetic acid |
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