CN115318232B - Device and production process for co-producing amyl alcohol and methyl acetate - Google Patents
Device and production process for co-producing amyl alcohol and methyl acetate Download PDFInfo
- Publication number
- CN115318232B CN115318232B CN202210812339.6A CN202210812339A CN115318232B CN 115318232 B CN115318232 B CN 115318232B CN 202210812339 A CN202210812339 A CN 202210812339A CN 115318232 B CN115318232 B CN 115318232B
- Authority
- CN
- China
- Prior art keywords
- tower
- methanol
- methyl acetate
- amyl alcohol
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 393
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- 229940072049 amyl acetate Drugs 0.000 claims abstract description 61
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims abstract description 61
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- 238000003860 storage Methods 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 15
- 238000007789 sealing Methods 0.000 claims description 15
- 238000000066 reactive distillation Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 11
- 238000007670 refining Methods 0.000 claims description 11
- 238000005086 pumping Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 4
- 239000002826 coolant Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims 2
- 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 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 239000002994 raw material Substances 0.000 description 15
- 238000009835 boiling Methods 0.000 description 11
- 238000005192 partition Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 238000012856 packing Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000004821 distillation 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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011084 recovery Methods 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- YFPCLQKFNXUAAK-UHFFFAOYSA-N cyclopentyl acetate Chemical compound CC(=O)OC1CCCC1 YFPCLQKFNXUAAK-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003205 fragrance Substances 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
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- MBVZEDIBUZMQOR-UHFFFAOYSA-N cyclopenten-1-yl acetate Chemical compound CC(=O)OC1=CCCC1 MBVZEDIBUZMQOR-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram 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
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000007667 floating Methods 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
- 239000010985 leather 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
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 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
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
-
- 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 co-producing amyl alcohol and methyl acetate, wherein amyl alcohol, methyl acetate and catalyst mixture obtained from the tower kettle of a reaction rectifying tower are subjected to transesterification reaction to obtain purified amyl alcohol after passing through the rectifying tower; the methyl acetate and methanol azeotrope obtained from the top of the reaction rectifying tower passes through a condenser and then enters a high-pressure tower to obtain high-purity methyl acetate. The invention has the advantages that the kinetic reaction rate of the transesterification reaction is improved by increasing the temperature, the reaction time can be shortened by increasing the temperature, and the content of methyl acetate in the reaction rectifying tower is the lowest; the amyl acetate pretreatment device is used for pretreating amyl acetate and performance, separating amyl acetate and a small amount of water contained in the amyl acetate, avoiding hydrolysis reaction of water and methanol, and reducing the production of waste salt sodium acetate and the consumption of sodium methoxide; and obtaining the methyl acetate product with the purity of 99.5-99.9% by using a methyl acetate pressurizing tower.
Description
Technical Field
The invention relates to the field of methyl acetate production, in particular to a device for co-producing amyl alcohol and methyl acetate and a production process thereof.
Background
Methyl acetate is a novel basic chemical raw material, and becomes a mature product in the world gradually, and is used for replacing acetone, butanone, ethyl acetate, cyclopentane and the like.
Chinese patent publication No. CN113493380a reports a method and a system for preparing high purity methyl acetate, in which acetic acid and methanol react in advance in a pre-reactor under the catalysis of a solid catalyst, and then continue to react in a catalytic distillation tower, wherein acetic acid is supplemented in the middle of a reaction section of the catalytic distillation tower, and an extractant is added in 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 preparation method of the high-purity methyl acetate comprises a pre-reactor and a catalytic distillation tower which are sequentially connected in the material flow direction, wherein a first light-removal rectifying tower, a second acetic acid recovery rectifying tower and a third extractant recovery rectifying tower are arranged behind the catalytic distillation tower in series. The technical scheme realizes the high-purity methyl acetate production.
The above report mentions that the preparation of methyl acetate takes acetic acid as raw material, and acetic acid is in gas state, which has high requirement for corrosion prevention of equipment, and the extraction agent is added in the separation process, which increases difficulty for the subsequent material separation.
Chinese patent publication No. CN102399132a discloses a method for preparing cyclopentanol from cyclopentene, in which refined cyclopentene acetate and methanol are subjected to transesterification reaction in a liquid phase by a fixed bed catalyst to produce cyclopentanol and methyl acetate, and the purity of methyl acetate as a by-product is about 98wt%, which 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 method for preparing methyl acetate is insufficient, and provides a device and a production process for co-producing amyl alcohol and methyl acetate.
The technical scheme of the invention is as follows: an apparatus for co-producing amyl alcohol and methyl acetate, comprising: a reactive rectifying tower; the inlet of the condenser is communicated with the top of the reactive distillation column; the inlet of the storage tank 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 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 reaction rectifying tower, and the bottom of the reboiler is communicated with the bottom of the reaction rectifying 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-amyl alcohol rectifying tower is communicated with the bottom of the methanol removing tower; and the side surface of the 2-amyl alcohol rectifying tower is communicated with the bottom of the 3-amyl alcohol rectifying tower.
The improvement of the scheme is that the amyl acetate pretreatment device is connected to the upper portion of the reaction rectifying tower and 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 buffer space communicated with the liquid inlet is formed by enclosing 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 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 extending towards the liquid inlet direction and positioned at the bottom of the cofferdam, 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 is formed at the other side of the closed cavity.
The liquid outlet is provided with a flow sensor, an air cylinder is arranged on the outer wall of one side of the closed cavity, a piston rod of the air cylinder extends into the closed cavity, the tail end of the piston rod of the air cylinder is fixedly connected with a sealing plate, and the sealing plate is matched with the horizontal section to close or open the notch.
The production process of the device for coproducing amyl alcohol and 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 2-5:1, the catalyst is 0.2% -0.7% of the feeding amount of the methanol, and the methanol comprises circulating methanol and fresh methanol; (2) Amyl acetate and a catalyst are input from the top of a reaction rectifying tower, circulating methanol and fresh methanol are input from the middle lower part of the reaction rectifying tower for transesterification reaction, the temperature of the reaction rectifying tower is controlled at 70-85 ℃, the pressure is controlled at 0.09-0.11 MPa, an azeotrope of a reaction product methyl acetate and part of methanol is discharged from the top of the reaction rectifying tower in a gas phase, the mixture is cooled by a condenser and then is input into a storage tank, and a reaction product amyl alcohol, methanol and catalyst mixture is discharged from the bottom of the reaction rectifying tower; (3) Part of the mixed materials of amyl alcohol, methanol and catalyst enters a reaction rectifying tower through a reboiler for recycling, the other part enters 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 an evaporator in a methanol removal tower, controlling the temperature of a rectifying section at 65-80 ℃, using methanol with the purity of 99-99.5% distilled in the rectifying section as the circulating methanol in the step (2), controlling the temperature of a stripping section at 115-126 ℃, and extracting a mixture of 2-amyl alcohol and 3-amyl alcohol; (5) Pumping the mixture of 2-amyl alcohol and 3-amyl alcohol into a 3-amyl alcohol rectifying tower, controlling the operating pressure to be-0.068 kpa to-0.05 kpa, controlling the temperature of a rectifying section to be 80-95 ℃, rectifying the 3-amyl alcohol with the purity of about 99.0-99.7%, controlling the temperature of a stripping section to be 95-110 ℃, and extracting crude 2-amyl alcohol from the stripping section; (6) Pumping the crude 2-amyl alcohol into a 2-amyl alcohol refining tower, wherein the operating pressure is 25 kpa-32 kpa, the temperature of a rectifying section is controlled at 127 ℃ to 130 ℃, the temperature of a stripping section is controlled at 130 ℃ to 140 ℃, and the 2-amyl alcohol with the purity of 99.0-99.9 percent is obtained; (7) Enabling the azeotrope of methyl acetate and methanol in the storage tank to enter a methyl acetate pressurizing tower, controlling the temperature of the tower top at 124-126 ℃ and the operating pressure at 0.8MPa, controlling the temperature of the tower bottom at 135-138 ℃, and obtaining a methyl acetate product with the purity of 99.5-99.9%; (8) Materials discharged from the top of the methyl acetate pressurizing tower enter a methyl acetate atmospheric tower, the temperature of the top of the methyl acetate atmospheric tower is controlled at 50-54 ℃, the operating pressure is 0.005MPa, the methyl acetate pressurizing tower is circularly used for obtaining materials, and the temperature of the tower bottom is controlled at 64-68 ℃ to obtain methanol.
Another production process of a device for co-producing amyl alcohol and methyl acetate comprises the following steps: (1) Inputting amyl acetate into a liquid inlet of the amyl acetate pretreatment device, accumulating amyl acetate in a first buffer space until a first cover plate is jacked up, overflowing into a second buffer space, flowing into a third buffer space from the second buffer space, and finally discharging from a liquid outlet, wherein when a flow sensor detects that the fluid flow of the liquid outlet is increased, a signal is sent to a cylinder, a piston rod extends out to enable a sealing plate to be close to a horizontal section to cover a gap, when the flow sensor detects that the fluid flow of the liquid outlet is reduced, a signal is sent to the cylinder, and the piston rod contracts to enable the sealing plate to be far away from the horizontal section to expose the gap; (2) Preparing amyl acetate, methanol and a catalyst discharged from a liquid outlet, wherein the feeding ratio of the amyl acetate to the methanol is controlled within a range of 2-5:1, the catalyst is 0.2% -0.7% of the feeding amount of the methanol, and the methanol comprises circulating methanol and fresh methanol; (3) Amyl acetate and a catalyst are input from the top of a reaction rectifying tower, circulating methanol and fresh methanol are input from the middle lower part of the reaction rectifying tower for transesterification reaction, the temperature of the reaction rectifying tower is controlled at 70-85 ℃, the pressure is controlled at 0.09-0.11 MPa, an azeotrope of a reaction product methyl acetate and part of methanol is discharged from the top of the reaction rectifying tower in a gas phase, the mixture is cooled by a condenser and then is input into a storage tank, and a reaction product amyl alcohol, methanol and catalyst mixture is discharged from the bottom of the reaction rectifying tower; (4) Part of the mixed materials of amyl alcohol, methanol and catalyst enters a reaction rectifying tower through a reboiler for recycling, the other part enters 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 an evaporator in a methanol removal tower, controlling the temperature of a rectifying section at 65-80 ℃, using methanol with the purity of 99-99.5% distilled in the rectifying section as the circulating methanol in the step (2), controlling the temperature of a stripping section at 115-126 ℃, and extracting a mixture of 2-amyl alcohol and 3-amyl alcohol; (6) Pumping the mixture of 2-amyl alcohol and 3-amyl alcohol into a 3-amyl alcohol rectifying tower, controlling the operating pressure to be-0.068 kpa to-0.05 kpa, controlling the temperature of a rectifying section to be 80-95 ℃, rectifying the 3-amyl alcohol with the purity of about 99.0-99.7%, controlling the temperature of a stripping section to be 95-110 ℃, and extracting crude 2-amyl alcohol from the stripping section; (7) Pumping the crude 2-amyl alcohol into a 2-amyl alcohol refining tower, wherein the operating pressure is 25 kpa-32 kpa, the temperature of a rectifying section is controlled at 127 ℃ to 130 ℃, the temperature of a stripping section is controlled at 130 ℃ to 140 ℃, and the 2-amyl alcohol with the purity of 99.0-99.9 percent is obtained; (8) Enabling the azeotrope of methyl acetate and methanol in the storage tank to enter a methyl acetate pressurizing tower, controlling the temperature of the tower top at 124-126 ℃ and the operating pressure at 0.8MPa, controlling the temperature of the tower bottom at 135-138 ℃, and obtaining a methyl acetate product with the purity of 99.5-99.9%; (9) Materials discharged from the top of the methyl acetate pressurizing tower enter a methyl acetate atmospheric tower, the temperature of the top of the methyl acetate atmospheric tower is controlled at 50-54 ℃, the operating pressure is 0.005MPa, the methyl acetate pressurizing tower is circularly used for obtaining materials, and the temperature of the tower bottom is controlled at 64-68 ℃ to obtain methanol.
The catalyst in the step (2) in the scheme is a 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 reaction rectifying tower is controlled at 75-80 ℃ and the pressure is controlled at 0.095-0.1 MPa.
In the scheme, the cooling medium of the condenser is circulating water at the temperature of 25-33 ℃, the reaction rectifying tower comprises a reaction section, a stripping section and a rectifying section, and steam in the rectifying section is supercooled to 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 0.2 MPa-0.3 MPa, and the temperature is 135-145 ℃.
In the scheme, the reflux ratio of the reaction rectifying tower is 1-3.
The invention has the advantages that the kinetic reaction rate of the transesterification reaction is improved by increasing the temperature, the reaction time can be shortened by increasing the temperature, and the content of methyl acetate in the reaction rectifying tower is the lowest; the amyl acetate pretreatment device is used for pretreating amyl acetate and performance, separating amyl acetate and a small amount of water contained in the amyl acetate, avoiding hydrolysis reaction of water and methanol, and reducing the production of waste salt sodium acetate and the consumption of sodium methoxide; and obtaining the methyl acetate product with the purity of 99.5-99.9% by using a methyl acetate pressurizing tower.
Drawings
FIG. 1 is a schematic illustration of reactive distillation in accordance with the present invention;
FIG. 2 is a process flow diagram of the present invention;
FIG. 3 is a schematic view of an amyl acetate pretreatment apparatus of 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, a 3-amyl alcohol rectifying tower, 10, 2-amyl alcohol 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 solutions in the embodiments of the present invention are clearly and completely described below with reference to the accompanying drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. Based on the embodiments of the present invention, all other embodiments of the invention are within the scope of the present invention for those of ordinary skill in the art without making any inventive effort.
The technical route of the invention is that amyl alcohol, methanol, methyl acetate and catalyst mixture obtained from the tower kettle of a reaction rectifying tower are purified after amyl acetate and methanol are subjected to transesterification reaction, and the purified amyl alcohol is obtained after passing through the rectifying tower; methyl acetate and methanol azeotrope obtained from the top of the reactive rectifying tower pass through a condenser and then enter a high-pressure tower to obtain methyl acetate with the purity of 99.5-99.9%.
Raw material 1 amyl acetate. Also known as "amyl acetate", "banana oil". Is one of esters, is an esterification product of acetic acid and amyl alcohol, is colorless transparent liquid at normal temperature, has fruit fragrance, is inflammable, is slightly soluble in water, and is mutually soluble with ethanol and diethyl ether. Amyl acetate is used as a solvent, diluent, for the manufacture of fragrances, cosmetics, imitation leather, film, gunpowder, and the like. Amyl acetate has no optical activity. 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 explosion limit% (V/V): 1.0.
raw material 2 methanol (recycle methanol, fresh methanol)
The raw material methanol of the reactive distillation section comprises fresh methanol and recycled methanol (a methanol removal tower).
Methanol (Methanol) is the saturated monohydric alcohol with the simplest structure. The appearance is colorless, transparent, inflammable and volatile poisonous liquid. The relative density is 0.792 (20/4 ℃), the melting point is-97.8 ℃, the boiling point is 64.5 ℃, the flash point is 12.22 ℃, the self-ignition point is 463.89 ℃, the vapor density is 1.11, the vapor pressure is 13.33kPa (100 mmHg21.2 ℃), the explosion limit of the vapor-air mixture is 6-36.5% (volume ratio), and the mixture can be mixed with water, ethanol, diethyl ether, benzene, ketone, halogenated hydrocarbon and a plurality of other organic solvents.
Catalyst
The catalyst is one or more of sodium methoxide, lithium hydroxide, lithium carbonate, potassium hydroxide, potassium carbonate, zinc oxide, tetrabutyl titanate and dibutyl tin 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 reaction rectifying tower 1, the condenser 2, the storage tank 3, the methyl acetate pressurizing tower 4, the methyl acetate atmospheric tower 5, the reboiler 6, the evaporator 7, the methanol removal tower 8, the 3-amyl alcohol refining tower 9 and the 2-amyl alcohol refining tower 10 which are used in the process flow of the invention are shown in the figures 1-2, and the specific process sequence for producing amyl alcohol and methyl acetate is as follows:
(one) transesterification Process
The raw material amyl acetate and methanol feed ratio in the transesterification reaction process is controlled within the range of 2-5:1, and the feed ratio is preferably 3-4: 1, the feeding amount of the methanol solution catalyst of sodium methoxide is determined according to simulation calculation, and the feeding amount of the methanol solution of sodium methoxide is about 0.2-0.7%, preferably 0.4-0.6% of the feeding amount of the methanol serving as a raw material for transesterification. The temperature of the transesterification 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 methyl alcohol solution of amyl acetate and sodium methoxide is selectively fed from the top of the reaction section of the reaction rectifying tower, the residence time of raw materials and catalysts in the reaction section of the reaction rectifying tower is increased, and the fresh methyl alcohol and the circulating methyl alcohol are selectively fed at multiple points and are respectively fed at the middle and lower parts of the reaction section, wherein the circulating methyl alcohol is in the middle part, and the fresh methyl alcohol is added to the bottom of the reaction section of the reaction rectifying tower. The transesterification is a reversible reaction, methyl acetate generated by the reaction is separated in a gas phase mode from a tower plate of a reaction rectifying tower, and the concentration of a reactant can be increased by adding methanol, so that the forward progress of the transesterification is promoted. The azeotrope of methyl acetate and partial methanol as reaction product is discharged from the top of the reactive rectifying tower in gas phase, and the mixture of amyl alcohol, methanol and catalyst as reaction product is discharged from the bottom of the reactive rectifying tower.
The reactive rectifying tower comprises a reaction section, a stripping section and a rectifying section. The tower type is a reaction and separation combined tower, a plate tower structure is selected as a tower plate structure of a reaction section, a sieve plate tower, a floating valve tower, a bubble cap tower and other structures can be selected as tower plates, and a packing is selected as a rectifying section, and the packing is recommended to select structured packing. The continuous reaction rectifying tower is provided with a condenser, the cooling medium is circulating water (25-33 ℃), the rectifying section steam is supercooled to (35-50 ℃) to be extracted and refluxed, and the reboiler heating medium is low-pressure steam (0.2-0.3 MPa, 135-145 ℃).
The amyl acetate and the methanol react to obtain the reaction liquid with 2-amyl alcohol and 3-amyl alcohol as main components. The present application increases the kinetic reaction rate of transesterification by increasing the temperature. The increase in temperature shortens the reaction time. Target of transesterification: the amyl acetate is completely converted into methyl acetate and amyl alcohol in the shortest time possible, the thermodynamic equilibrium is changed by continuously removing the generated methyl acetate by adopting the reaction rectification technology, the forward reaction is promoted, and the methyl acetate in the reaction tower kettle is promotedThe content determines the depth of the transesterification reaction or the residual amount of amyl acetate in the transesterification reaction. Namely, the lower the methyl acetate content in the tower kettle is, the lower the concentration of residual amyl acetate is, compared with the prior art, for example, the refined cyclopentyl acetate obtained by the disclosure of Chinese patent publication No. CN102399132A and methanol are subjected to transesterification reaction in liquid phase through a fixed bed catalyst to generate cyclopentanol and methyl acetate, the feeding mole ratio of the cyclopentyl acetate and the methanol is 1:2-5, and the liquid mass space velocity is 0.8-2 hr -1 The reaction temperature is 40-60 ℃, and the kinetic reaction rate of the transesterification reaction is improved by increasing the temperature. The increase in temperature shortens the reaction time to 70% of the original.
Since water existing in the reaction system can cause hydrolysis of sodium methoxide to generate NaOH, and the existence of NaOH and water can cause saponification of amyl acetate, naOH is converted into sodium acetate with weaker alkalinity, so that the consumption of the catalyst sodium methoxide is increased, and more waste sodium acetate is generated. Since the saponification process is continuously carried out, the pH of the reaction system is gradually reduced in the transesterification reaction process, and in actual production, it is found that the transesterification reaction rate is significantly reduced when the pH is as low as 8 or less. Therefore, the less residual moisture of the raw material amyl acetate, the better, otherwise, the more sodium methoxide is consumed, the larger the amount of sodium methoxide is, the larger the amount of waste salt is produced, and the main component of the waste salt is sodium acetate.
In order to ensure that amyl acetate entering a reactive distillation column does not contain moisture, the prior art practice is to dehydrate with molecular sieves, but molecular sieves are expensive and cannot ensure complete dehydration, so the application does not adopt, but rather uses a new way to design an amyl acetate pretreatment device by utilizing the characteristic that amyl acetate is lighter than water and slightly soluble in water, and 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 enclosing the cofferdam and the closed cavity, a first cover plate 14 is hinged in the closed cavity and matched with the top of the cofferdam, an L-shaped partition 15 is mounted on the top of the closed cavity, the L-shaped partition comprises a vertical section fixedly connected with the top of the closed cavity and a horizontal section extending towards the liquid inlet and positioned at the bottom of the cofferdam, 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 and the cofferdam, a third buffer space is formed between the partition and the other side of the closed cavity, and a liquid outlet 17 is formed on the other side of the closed cavity.
The use method of the amyl acetate pretreatment device is as follows: the amyl acetate is input into a liquid inlet of the amyl acetate pretreatment device, the amyl acetate accumulates in the first buffer space until the first cover plate is jacked up, overflows into the second buffer space, flows into the third buffer space through a gap in the second buffer space, is finally discharged from a liquid outlet, and is subjected to standing separation through the first buffer space and the third buffer space in the process, so that only the amyl acetate is ensured to flow out from the liquid outlet.
Example 2: as shown in fig. 4, as the deformation of the amyl acetate pretreatment device, a flow sensor is arranged on the liquid outlet, a cylinder is arranged on the outer wall of one side of the closed cavity, a piston rod of the cylinder extends into the closed cavity, the tail end of the piston rod is fixedly connected with a sealing plate 16, and the sealing plate is matched with the horizontal section to seal or open the notch.
The use method of the amyl acetate pretreatment device is as follows: when the flow sensor detects that the fluid flow of the liquid outlet becomes larger, 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 buffer space and the third buffer space are separated by the sealing plate, when the flow sensor detects that the fluid flow of the liquid outlet becomes smaller, 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 buffer space and the third buffer space are communicated through the notch.
Compared with the embodiment 1, the embodiment 2 can quickly sense the change of the flow and make adjustment in time, the gap is covered or exposed by the movement of the sealing plate, the flow in the second buffer space is controlled, and the part of the second buffer space above the first buffer space can be used for temporarily storing the redundant amyl acetate when the flow becomes large, and the part is also indispensable for realizing the flow adjustment.
(II) Evaporation
The materials at the tower bottom enter an evaporator, the evaporator can be a kettle type evaporator, a scraper evaporator, a thin film evaporator and the like, the transesterification reaction liquid in the transesterification product is pumped to the evaporator for evaporation, the temperature is 100-120 ℃, the pressure is less than or equal to 0.05MPa, the gas phase generated by evaporation enters a methanol removing tower for continuous rectification, and waste salt is intermittently discharged from the bottom of the evaporator.
(III) methanol recovery
The gas phase of the evaporator enters a methanol removal tower for continuous rectification, the temperature of a rectifying section is controlled at 65-80 ℃, methanol with the purity of 99-99.5% is distilled out from the rectifying section, and the methanol can be recovered and continuously used as a raw material for transesterification, so that the utilization rate of materials is improved. The temperature of the stripping section is controlled between 115 ℃ and 126 ℃ and the mixture of 2-amyl alcohol and 3-amyl alcohol is extracted.
The main principle of the process is as follows: the boiling point of the methanol is 64 ℃, the lowest boiling point of the mixed material is 115 ℃ (3-amyl alcohol), and the methanol is separated from the mixed material through rectification operation by utilizing the property that the boiling point of the methanol is lower than that of other materials, so that the pure methanol which can be recycled is obtained.
(IV) 3-amyl alcohol rectifying and separating tower
2-amyl alcohol and 3-amyl alcohol are pumped into a rectifying tower, the operating pressure is-0.068 to-0.05 kpa, preferably-0.06 to-0.058 kpa, the temperature of a rectifying section is controlled at 80 ℃ to 95 ℃, preferably 85 ℃ to 92 ℃, 3-amyl alcohol with the purity of about 99.0% to 99.7% is rectified, the temperature of a stripping section is controlled at 95 ℃ to 110 ℃, preferably 97 ℃ to 104 ℃, and crude 2-amyl alcohol is extracted from the stripping section.
The main principle of the process is as follows: the boiling point of the 3-amyl alcohol is 115.6 ℃, the lowest boiling point of the mixed material is 119 ℃ (2-amyl alcohol), and the 3-amyl alcohol is separated from the mixed material by rectification operation by utilizing the property that the boiling point of the mixed material is lower than that of other materials, so as to obtain the 3-amyl alcohol product.
(V) 2-pentanol refining tower
Feeding the crude 2-amyl alcohol into a 2-amyl alcohol refining tower, wherein the operating 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-amyl alcohol with the purity of 99.0-99.9% is obtained.
The main principle of the process is as follows: the boiling point of 2-amyl alcohol is 126 ℃, the lowest boiling point of the mixed material is 130 ℃ (sec-amyl acetate), and the 2-amyl alcohol is separated from the mixed material by rectification operation by utilizing the property that the boiling point of the mixed material is lower than that of other materials, so as to obtain the 2-amyl alcohol product.
(6) Refining methyl acetate
The azeotrope of methyl acetate and methanol, which are the transesterification reaction products, enters a methyl acetate pressurizing tower, the temperature of the top of the tower is controlled between 124 ℃ and 126 ℃, the operation pressure is 0.8MPa, and the temperature of the tower kettle is controlled between 135 ℃ and 138 ℃. Methyl acetate product with purity of 99.5% -99.9% is obtained at the tower bottom, the material at the tower top enters an atmospheric tower, the temperature at the tower top of the atmospheric tower is controlled at 50-54 ℃, the operating pressure is 0.005MPa, the temperature at the tower bottom of the atmospheric tower is controlled at 64-68 ℃, methanol can be recovered at the tower bottom of the atmospheric tower, and the material at the tower top of the atmospheric tower is recycled by removing the material from the pressurizing tower, 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 containing a packing layer, the type of a tower plate of a reaction section adopts a large liquid holdup and a high-efficiency mass transfer tower plate, the type of a rectifying section adopts a high-efficiency structured packing, the selection basis is that the plate tower has a larger reaction liquid holdup than the packing tower, and the separation effect of the packing is better when the reaction is not involved. According to the design of 10-15 plates (5-6 meters of filler layer) of rectifying section and 28-33 plates of reaction section. The operating pressure of the reactive distillation column is determined according to the reactive temperature (temperature of the reaction section) of the catalyst;
the temperature of the reactive distillation column is controlled to be 70-85 ℃, preferably 75-80 ℃, and the pressure is controlled to be 0.09-0.11 MPa, preferably 0.095-0.1 MPa in consideration of the versatility of the reactive distillation column.
Determination of reflux ratio (energy consumption index) of reactive distillation column
Adopting reflux ratio to represent the flow rate and energy consumption index of the gas and liquid phase in the tower, and determining the reflux ratio range according to the simulation result;
the larger the reflux ratio is, the shorter the residence time of the material in the reaction section is, and the lower the single-pass conversion rate of 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 catalyst on the tray;
the larger the reflux ratio is, the larger the energy consumption is;
reflux ratio range: 1 to 3.
The feeding amount of the catalyst has great influence on the reactive distillation process, and is related to the reaction rate of amyl acetate, the generation amount of products and the like, and the higher the feeding amount is, the higher the reaction rate of amyl acetate is; the catalyst feed is determined by simulation calculations to be about 0.2% to about 0.7%, preferably about 0.4% to about 0.6% of the methanol feed. In view of operational flexibility, the catalyst is dissolved in the methanol solution to form a sodium methoxide methanol solution, and the apparatus is designed with the catalyst fed separately, such as by a metering pump.
In the invention, one of the raw materials of the methanol consists of two parts, wherein 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 transesterification again, so that the utilization rate of the raw material of the methanol is improved, and the damage to the environment is reduced. The reaction rectification technology is adopted in the project, the thermodynamic equilibrium is changed by continuously removing the generated methyl acetate, the forward reaction is promoted, and the reaction time is reduced. And the methyl alcohol solution of the reaction raw material amyl acetate and the catalyst sodium methoxide is fed from the top of the reaction section of the reaction rectifying tower, so that the residence time of the raw material in the reaction section is increased, the fresh methyl alcohol and the circulating methyl alcohol are fed at 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 transesterification reaction is promoted. In the invention, the amyl acetate which is an upstream product is taken as one of raw materials for producing the methyl acetate product, acetic acid is not needed to be taken as the raw material, the requirement of equipment on corrosion resistance is reduced, an extractant is not needed to be added in the subsequent methyl acetate refining process, and the separation difficulty of materials in the methyl acetate and amyl alcohol refining process is reduced.
Claims (9)
1. A device for co-producing amyl alcohol and methyl acetate is characterized in that: comprising the following steps: a reactive rectifying tower (1); the inlet of the condenser (2) is communicated with the top of the reaction rectifying tower; the inlet of the storage tank 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; a methyl acetate pressurizing tower (4), the side surface of which is communicated with the outlet of the storage tank; a methyl acetate atmospheric tower (5), wherein 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 reactive distillation tower; a reboiler (6), wherein the outlet of the reboiler is communicated with the lower part of the reaction rectifying tower, and the bottom of the reboiler is communicated with the bottom of the reaction rectifying tower; an evaporator (7), the side surface of which is communicated 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; a 3-amyl alcohol rectifying tower (9), wherein the side surface of the 3-amyl alcohol rectifying tower is communicated with the bottom of the methanol removing tower; a 2-amyl alcohol rectifying tower (10), wherein the side surface of the 2-amyl alcohol rectifying tower is communicated with the bottom of the 3-amyl alcohol rectifying tower; the upper portion of reaction rectifying column is connected with amyl acetate preprocessing device, amyl acetate preprocessing device includes airtight cavity (11), inlet (12) have been seted up at airtight cavity one side middle part, be equipped with the solenoid valve on the inlet, be equipped with cofferdam (13) in the airtight cavity, cofferdam and airtight cavity enclose into the first buffer space with the inlet intercommunication, articulated in the airtight cavity have first apron (14), first apron cooperates with cofferdam top, L type baffle (15) are installed at airtight cavity top, L type baffle includes the vertical section with airtight cavity top rigid coupling and is located the horizontal segment that cofferdam bottom extends to the inlet direction, leave the breach between free end of horizontal segment and the airtight cavity one side, form the second buffer space between L type baffle and the cofferdam, form the third buffer space between baffle and the opposite side of airtight cavity, liquid outlet (17) have been seted up to airtight cavity opposite side.
2. The apparatus for co-producing amyl alcohol and methyl acetate as recited in claim 1, wherein: the liquid outlet is provided with a flow sensor, an air cylinder is arranged on the outer wall of one side of the closed cavity, a piston rod of the air cylinder stretches into the closed cavity, the tail end of the piston rod of the air cylinder is fixedly connected with a sealing plate (16), and the sealing plate is matched with the horizontal section to close or open the notch.
3. A production process of a device for co-producing amyl alcohol and methyl acetate by using the method in 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 2-5:1, the catalyst is 0.2% -0.7% of the feeding amount of the methanol, and the methanol comprises circulating methanol and fresh methanol; (2) Amyl acetate and a catalyst are input from the top of a reaction rectifying tower, circulating methanol and fresh methanol are input from the middle lower part of the reaction rectifying tower for transesterification reaction, the temperature of the reaction rectifying tower is controlled at 70-85 ℃, the pressure is controlled at 0.09-0.11 MPa, an azeotrope of a reaction product methyl acetate and part of methanol is discharged from the top of the reaction rectifying tower in a gas phase, the mixture is cooled by a condenser and then is input into a storage tank, and a reaction product amyl alcohol, methanol and catalyst mixture is discharged from the bottom of the reaction rectifying tower; (3) Part of the mixed materials of amyl alcohol, methanol and catalyst enters a reaction rectifying tower through a reboiler for recycling, the other part enters 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 an evaporator in a methanol removal tower, controlling the temperature of a rectifying section at 65-80 ℃, using methanol with the purity of 99-99.5% distilled in the rectifying section as the circulating methanol in the step (2), controlling the temperature of a stripping section at 115-126 ℃, and extracting a mixture of 2-amyl alcohol and 3-amyl alcohol; (5) Pumping the mixture of 2-amyl alcohol and 3-amyl alcohol into a 3-amyl alcohol rectifying tower, controlling the operating pressure to be-0.068 kpa to-0.05 kpa, controlling the temperature of a rectifying section to be 80-95 ℃, rectifying the 3-amyl alcohol with the purity of 99.0-99.7%, controlling the temperature of a stripping section to be 95-110 ℃, and extracting crude 2-amyl alcohol from the stripping section; (6) Pumping the crude 2-amyl alcohol into a 2-amyl alcohol refining tower, wherein the operating pressure is 25 kpa-32 kpa, the temperature of a rectifying section is controlled at 127 ℃ to 130 ℃, the temperature of a stripping section is controlled at 130 ℃ to 140 ℃, and the 2-amyl alcohol with the purity of 99.0-99.9 percent is obtained; (7) Enabling the azeotrope of methyl acetate and methanol in the storage tank to enter a methyl acetate pressurizing tower, controlling the temperature of the tower top at 124-126 ℃ and the operating pressure at 0.8MPa, controlling the temperature of the tower bottom at 135-138 ℃, and obtaining a methyl acetate product with the purity of 99.5-99.9%; (8) Materials discharged from the top of the methyl acetate pressurizing tower enter a methyl acetate atmospheric tower, the temperature of the top of the methyl acetate atmospheric tower is controlled at 50-54 ℃, the operating pressure is 0.005MPa, the methyl acetate pressurizing tower is circularly used for obtaining materials, and the temperature of the tower bottom is controlled at 64-68 ℃ to obtain methanol.
4. The production process of the device for co-producing amyl alcohol and methyl acetate as recited in claim 2, which is characterized in that: the method comprises the following steps: (1) Inputting amyl acetate into a liquid inlet of the amyl acetate pretreatment device, accumulating amyl acetate in a first buffer space until a first cover plate is jacked up, overflowing into a second buffer space, flowing into a third buffer space from the second buffer space, and finally discharging from a liquid outlet, wherein when a flow sensor detects that the fluid flow of the liquid outlet is increased, a signal is sent to a cylinder, a piston rod extends out to enable a sealing plate to be close to a horizontal section to cover a gap, when the flow sensor detects that the fluid flow of the liquid outlet is reduced, a signal is sent to the cylinder, and the piston rod contracts to enable the sealing plate to be far away from the horizontal section to expose the gap; (2) Preparing amyl acetate, methanol and a catalyst discharged from a liquid outlet, wherein the feeding ratio of the amyl acetate to the methanol is controlled within a range of 2-5:1, the catalyst is 0.2% -0.7% of the feeding amount of the methanol, and the methanol comprises circulating methanol and fresh methanol; (3) Amyl acetate and a catalyst are input from the top of a reaction rectifying tower, circulating methanol and fresh methanol are input from the middle lower part of the reaction rectifying tower for transesterification reaction, the temperature of the reaction rectifying tower is controlled at 70-85 ℃, the pressure is controlled at 0.09-0.11 MPa, an azeotrope of a reaction product methyl acetate and part of methanol is discharged from the top of the reaction rectifying tower in a gas phase, the mixture is cooled by a condenser and then is input into a storage tank, and a reaction product amyl alcohol, methanol and catalyst mixture is discharged from the bottom of the reaction rectifying tower; (4) Part of the mixed materials of amyl alcohol, methanol and catalyst enters a reaction rectifying tower through a reboiler for recycling, the other part enters 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 an evaporator in a methanol removal tower, controlling the temperature of a rectifying section at 65-80 ℃, using methanol with the purity of 99-99.5% distilled in the rectifying section as the circulating methanol in the step (2), controlling the temperature of a stripping section at 115-126 ℃, and extracting a mixture of 2-amyl alcohol and 3-amyl alcohol; (6) Pumping the mixture of 2-amyl alcohol and 3-amyl alcohol into a 3-amyl alcohol rectifying tower, controlling the operating pressure to be-0.068 kpa to-0.05 kpa, controlling the temperature of a rectifying section to be 80-95 ℃, rectifying the 3-amyl alcohol with the purity of 99.0-99.7%, controlling the temperature of a stripping section to be 95-110 ℃, and extracting crude 2-amyl alcohol from the stripping section; (7) Pumping the crude 2-amyl alcohol into a 2-amyl alcohol refining tower, wherein the operating pressure is 25 kpa-32 kpa, the temperature of a rectifying section is controlled at 127 ℃ to 130 ℃, the temperature of a stripping section is controlled at 130 ℃ to 140 ℃, and the 2-amyl alcohol with the purity of 99.0-99.9 percent is obtained; (8) Enabling the azeotrope of methyl acetate and methanol in the storage tank to enter a methyl acetate pressurizing tower, controlling the temperature of the tower top at 124-126 ℃ and the operating pressure at 0.8MPa, controlling the temperature of the tower bottom at 135-138 ℃, and obtaining a methyl acetate product with the purity of 99.5-99.9%; (9) Materials discharged from the top of the methyl acetate pressurizing tower enter a methyl acetate atmospheric tower, the temperature of the top of the methyl acetate atmospheric tower is controlled at 50-54 ℃, the operating pressure is 0.005MPa, the methyl acetate pressurizing tower is circularly used for obtaining materials, and the temperature of the tower bottom is controlled at 64-68 ℃ to obtain methanol.
5. The production process of the device for co-producing amyl alcohol and methyl acetate as recited in claim 3 or 4, which is characterized in that: the catalyst in the step (2) is sodium methoxide, and the dosage of the catalyst is 0.4-0.6% of the feeding amount of methanol.
6. The production process of the device for co-producing amyl alcohol and methyl acetate as recited in claim 3 or 4, which is characterized in that: the temperature of the reaction rectifying tower is controlled at 75-80 ℃ and the pressure is controlled at 0.095-0.1 MPa.
7. The production process of the device for co-producing amyl alcohol and methyl acetate as recited in claim 3 or 4, which is characterized in that: the cooling medium of the condenser is circulating water at the temperature of 25-33 ℃, the reaction rectifying tower comprises a reaction section, a stripping section and a rectifying section, and the rectifying section steam is supercooled to 35-50 ℃ for extraction and reflux.
8. The production process of the device for co-producing amyl alcohol and methyl acetate as recited in claim 3 or 4, which is characterized in that: the heating medium of the reboiler is low-pressure steam, the pressure in the reboiler is 0.2 MPa-0.3 MPa, and the temperature is 135-145 ℃.
9. The production process of the device for co-producing amyl alcohol and methyl acetate as recited in claim 3 or 4, which is characterized in that: the reflux ratio of the reaction rectifying tower is 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210812339.6A CN115318232B (en) | 2022-07-12 | 2022-07-12 | Device and production process for co-producing amyl alcohol and methyl acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210812339.6A CN115318232B (en) | 2022-07-12 | 2022-07-12 | Device and production process for co-producing amyl alcohol and methyl acetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115318232A CN115318232A (en) | 2022-11-11 |
| CN115318232B true CN115318232B (en) | 2024-02-23 |
Family
ID=83918509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210812339.6A Active CN115318232B (en) | 2022-07-12 | 2022-07-12 | Device and production process for co-producing amyl alcohol and methyl acetate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115318232B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113443990A (en) * | 2021-06-02 | 2021-09-28 | 天津大学 | Methyl acetate dividing wall tower extraction-reaction rectification hydrolysis process and device |
-
2022
- 2022-07-12 CN CN202210812339.6A patent/CN115318232B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113443990A (en) * | 2021-06-02 | 2021-09-28 | 天津大学 | Methyl acetate dividing wall tower extraction-reaction rectification hydrolysis process and device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115318232A (en) | 2022-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1125915B1 (en) | Process for simultaneous production of ethylene glycol and carbonate ester | |
| CN104725203B (en) | Process unit and the method for the synthetic polymethoxy dimethyl ether of a kind of gas formaldehyde and depickling | |
| US7531688B2 (en) | Method for recovering unreacted alcohol from biodiesel product streams by flash purification | |
| CN103980124B (en) | The synthetic method of ionic liquid-catalyzed propylene carbonate Synthesis of dimethyl carbonate | |
| CN101389587A (en) | A process for reactive distillation of a carboxylic acid | |
| JP2010159212A (en) | Method for separating alcohol | |
| NO340209B1 (en) | Process for the preparation of carboxylate alkyl esters | |
| CN104262152A (en) | Production method of methyl glycolate | |
| CN101723834A (en) | Method for continuously producing carbonate mixed ester | |
| CN102399130A (en) | Method for simplifying rectification process for preparing ethanol through hydrogenation of acetic acid | |
| CN102548950B (en) | Process for preparing alkanediol and dialkyl carbonate | |
| CN113354540A (en) | Method for efficiently and continuously preparing methyl ethyl carbonate | |
| CN101948383B (en) | Device and method for preparing medium-high carbon fatty acid ester by continuous alcoholysis method | |
| WO2020029753A1 (en) | Production process of 2,2-dimethyl-1,3-propanediol | |
| CN114315767A (en) | Preparation method and preparation device of 5-hydroxymethylfurfural | |
| CN111377802A (en) | Preparation method and system of sec-butyl alcohol | |
| CN115318232B (en) | Device and production process for co-producing amyl alcohol and methyl acetate | |
| US20100281763A1 (en) | Unit, Method, And Renewable Material | |
| CN103159591B (en) | Technique of synthesizing ethanol with acetic acid | |
| CN101092365A (en) | Technical method for associated producing carbonic allyl ester, methyl carbonate, and propylene glycol | |
| CN102304048A (en) | Method and equipment for refining high-purity diethyl carbonate | |
| CN102559393B (en) | Method for preparing biodiesel with low acid value | |
| CN102992930B (en) | Recovery process and separation device of toluene solvent in production process of alpha-acetyl-gamma butyrolactone | |
| CN109569488A (en) | A kind of method continuous rectification production ten two system of alcohol ester and its produce alcohol ester 12 | |
| CN107827746A (en) | A kind of method of catalytic distillation synthesis mixed ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |