CN104119225A - New technology for producing ethyl acetate through reactive distillation by taking mixed ionic liquid as catalyst - Google Patents
New technology for producing ethyl acetate through reactive distillation by taking mixed ionic liquid as catalyst Download PDFInfo
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- 238000000066 reactive distillation Methods 0.000 title claims abstract description 138
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 66
- 238000005516 engineering process Methods 0.000 title abstract description 16
- 239000003054 catalyst Substances 0.000 title abstract 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 51
- 238000004519 manufacturing process Methods 0.000 claims description 27
- 238000007600 charging Methods 0.000 claims description 14
- 238000007701 flash-distillation Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 10
- 238000012856 packing Methods 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000010168 coupling process Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000008878 coupling Effects 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 238000009834 vaporization Methods 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims description 5
- -1 monoammonium sulfate salt ion Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract description 6
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract description 3
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 238000000895 extractive distillation Methods 0.000 abstract 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 230000010354 integration Effects 0.000 abstract 1
- 230000008569 process Effects 0.000 description 18
- 239000000047 product Substances 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005316 response function Methods 0.000 description 4
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a new technology for producing ethyl acetate through three steps of reaction, double extractive distillation and distillation coupled reactive distillation by taking mixed ionic liquid as a catalyst. The new technology is characterized by comprising the following steps: by taking mixed ionic liquid as a catalyst, feeding at different heights of a reactive distillation tower through adopting a three-ply independent feeding mode to break through the binary and ternary azeotropy of the ethanol, ethyl acetate and water, to obtain a high-purity ethyl acetate product. The mixed ionic liquid discharged from the bottom of the reactive distillation tower can be directly recycled through flash evaporation for dehydration so as to achieve the continuous production of ethyl acetate, and the integration of reaction, double extractive distillation and distillation taking the ionic liquid as the catalyst can be truly realized. The technology is low in energy consumption (less than 1.2 tonnage water vapor/tonnage ester compared with the energy consumption of more than 2.5 tonnage water vapor/tonnage ester in traditional technology.
Description
Technical field
The present invention relates to a kind of ethyl acetate continuous production technique taking mixed ionic liquid as catalyzer, particularly relate to the novel process of the continuous production ethyl acetate of reactive distillation of a kind of reaction-bis-extracting rectifying-rectifying three step couplings.
Background technology
Reactive distillation is that one integrates reaction process and rectifying, and the coupling process carrying out in same equipment.It has many advantages, can substitute traditional technology and be applied to the reactions such as etherificate, hydrogenation, alkylating aromatic hydrocarbon, esterification, is quite paid attention to industrial.Ethyl acetate is a kind of broad-spectrum fine chemical product, because it has excellent solvability and quick-drying, is widely used in the chemical processs such as synthetic rubber, coating and paint.The production of current domestic ethyl acetate mainly adopts the continuous esterification traditional technology route taking the vitriol oil as catalyzer, comprising esterification, dehydration, refining and recovery four parts.But because this technical process is long, energy consumption is high, and adopt the vitriol oil to make catalyzer, cause the problems such as, equipment corrosion low such as product selectivity and spent acid exhaust emission environment and Technical Economy be poor, therefore development of new esterification novel process efficient, environmental protection seems particularly important.
Formed by zwitterion, under room temperature, be liquid ionic liquid in recent years with its good stability, non-volatile, function is adjustable etc., and feature is widely used in multiple catalyzed reaction.As green solvent and catalyzer, ionic liquid is being played the part of the dual role of separating agent and catalyzer in numerous catalyzed reactions, partial ion liquid (having lower corrodibility and good mobility) alternative solid acid and traditional inorganic acids are synthetic for low carbon chain organic acid acetic, therefore have good industrial prospect.
In recent years, the existing application about substitute traditional technology with reactive distillation process, as patent CN103429710A, CN101745245A and CN102267972A all taking reactive distillation as production technique and in adopting solid catalyst (zeolite, solid acid and molecular sieve) to be applied to the catalysis of conventional substances and separating, but due to the use of solid catalyst, the problems such as such technique easily causes process resistance to mass transfer large, the broken loss of solid catalyst.CN101745245A be novelty proposition be a kind ofly similar to high-gravity rotating bed novel reaction rectifier unit, and the absorption, purification, reactive distillation and the nano material that are applied to the industry such as chemical industry, pharmacy such as prepare at the occasion, this invention has improved mass-transfer efficiency and the separation efficiency of rectifying greatly, but because this device design is too complicated, be unfavorable for its large-scale industrialization application; US344345 has adopted the Reaction Separation technique of multistage rectification device series connection and has been applied to the production of petrochemicals and separates with US7888541B2, this method product purity is high, but complex technical process, required equipment is many, invests high.At present, patent and document that reactive distillation process taking ionic liquid as catalyzer is applied to Chemicals production have been reported, as patent CN101255111A has reported the reactive distillation process taking α～pyrrolidone hydrosulfate ionic liquid as catalyzer, but this technique belongs to the rear rectifying of first reaction, batch production, feed way is single, the lengthy and tedious complexity of subsequent disposal; Wei Zhiping etc. have reported the reactive distillation process taking 1-hexyl pyridinium tetrafluoroborate salt ion liquid as catalyzer, but this technique products obtained therefrom yield and purity are low, cannot industrial applications.And the reaction process that integrates reaction-extracting rectifying-rectifying taking ionic liquid as catalyzer has no report.
For the dual nature of catalysis and the extraction of better utilised ionic liquid, the present invention proposes a kind of novel process of reactive distillation production ethyl acetate of the reaction-bis-extracting rectifying-rectifying three steps couplings taking mixed ionic liquid as catalyzer.Three bursts of separate feeds modes charging of this process using uniqueness, reactive distillation column can be divided into four parts, each part can play respectively reaction, extracting rectifying, rectifying, propose the effect of heating up in a steamer etc. one or more, under this effect, this technique can realize a tower highly purified ethyl acetate product (purity >98%) that directly obtains.In addition, the mixed ionic liquid that this technique adopts can be through simply dewatering and recycle, and energy consumption low (be less than 1.2 tons of water vapour/ton esters, traditional technology energy consumption is greater than 2.5 tons of water vapour/ton esters) is that one has alternative traditional technology and realizes industrialized reactive distillation novel process.
Summary of the invention
The object of the present invention is to provide a kind of novel process of reactive distillation production ethyl acetate of the reaction-bis-extracting rectifying-rectifying three step couplings taking mixed ionic liquid as catalyzer.
In order to overcome the defect and the many advantages that makes full use of ionic liquid of traditional technology, the present invention proposes the novel process of the reactive distillation production ethyl acetate of a kind of reaction-bis-extracting rectifying-rectifying three step couplings taking ionic liquid as catalyzer, it is to carry out on 30～75 rectifying tower that this technique has theoretical tray one, its content mainly comprises: the catalyzer adopting is mixed ionic liquid, and the feeding manner adopting in reactive distillation column is three bursts of separate feeds, described reactive distillation column is divided into four parts (as shown in Figure 2), under upper, be respectively: the rectifying section that A is reactive distillation column, the contained theoretical plate number of this rectifying section is 5～15 column plate (theoretical plate numbers, lower same), B is secondary extracting rectifying section (not only having extraction function but also have rectifying function) 5～15 blocks of column plates of contained theoretical plate number of reactive distillation column, C is reaction-one-level extracting rectifying section (both had response function, and had again extraction function and rectifying function) of reactive distillation column, and contained theoretical plate number is 15～30 blocks of column plates, D is that the reaction-stripping section of reactive distillation column (had both had response function, have again to carry and heat up in a steamer function), contained theoretical plate number is 5～15 blocks of column plates, the conversion zone that wherein reaction-one-level extracting rectifying section C and reaction-stripping section D are this reactive distillation column, material is long at reaction-one-level extracting rectifying section C and reaction-stripping section D residence time, reaction mass can be converted into object product completely, B in reactive distillation column, two sections of C have formed the two abstraction distillation systems in system, the characteristic that the water-absorbent of the responsible ionic liquid of this system one side and acetic acid are drawn ethanol is (at the bottom of wherein mixed ionic liquid can extract and bring into reactive distillation column tower by the water in rising material, acetic acid can and be brought conversion zone C and the D of reactive distillation column into by the alcohol extraction in rising material), thereby break water, binary between ethanol and ethyl acetate three, ternary azeotropic, preliminary purification product, then association reaction rectifying tower tower top rectifying section A is further purified product, finally obtains highly purified ethyl acetate (purity >98%) product in reactive distillation column overhead.
Concrete technical scheme is as follows:
A kind of technique of reactive distillation production ethyl acetate of the reaction-bis-extracting rectifying-rectifying three step couplings taking mixed ionic liquid as catalyzer, it is characterized in that: it is to carry out on 30～75 reactive distillation column that described technique has theoretical tray one, described reactive distillation column is divided into four parts (as shown in Figure 2), under upper, be respectively: the rectifying section A of reactive distillation column, according to the difference of reactive distillation column theoretical plate number, the contained theoretical plate number of this rectifying section is 5～15 blocks of column plates; The contained theoretical plate number of secondary extracting rectifying section B (not only having extraction function but also have rectifying function) of reactive distillation column is 5～15 blocks of column plates; The contained theoretical plate number of reaction-one-level extracting rectifying section C (both had response function, and had again extraction function and rectifying function) of reactive distillation column is 15～30 blocks of column plates; Reaction-stripping section D of reactive distillation column (had both had response function, have again to carry and heat up in a steamer function), contained theoretical plate number is 5～15 blocks of column plates, the conversion zone that wherein reaction-one-level extracting rectifying section C and reaction-stripping section D are this reactive distillation column, material is long at reaction-one-level extracting rectifying section C and reaction-stripping section D residence time, reaction mass can be converted into object product completely, specifically comprises the steps:
Step 1, step 1: with reference to the accompanying drawings 1, raw acetic acid and ethanol are participated in to reaction from 5th～15 blocks of column plates of reactive distillation column and 25th～60 column plates input reactive distillation columns of reactive distillation column respectively taking acid alcohol mol ratio as 1:1;
Step 2, with reference to the accompanying drawings 1, mixes with the mixed ionic liquid of recovery fresh mix ionic liquid through mixing tank A1, participate in reaction with 50%～250% amount of quality of acetic acid from 10th～30 column plates input reactive distillation columns of reactive distillation column;
Step 3, after reactive distillation column is stable without charging, total reflux, carry out normal charging and discharging, be highly purified ethyl acetate (purity >98%) from the product of reactive distillation column overhead extraction, from extraction at the bottom of reactive distillation column tower is moisture mixed ionic liquid;
Step 4, by moisture mixed ionic liquid input hypomere flash tank, flash distillation mode can be single-action flash distillation, also can be multi-effect flashing steam, the water flashing off directly discharges, the mixed ionic liquid after flash distillation dewaters returns to reactive distillation column with pump and continues to participate in reaction.
The technique of above-mentioned reactive distillation production ethyl acetate, described mixed ionic liquid kind can be N-sulfonic group alkyl-triethyl hydrogen sulfate ammonium salt [(R
1)
3n (CH
2)
nsO
3h] [HSO
4], wherein R
1for straight chain saturated alkyl, carbonatoms is: 1～3; N=3～6; Trialkyl hydrogen sulfate ammonium salt [(R
2)
3nH] [HSO
4], wherein R
2for straight chain saturated alkyl, carbonatoms is: 2～4 or N-alkyl imidazole hydrosulfate [R
3(C
3h
3n
2h)] [HSO
4], wherein R
3for straight chain saturated alkyl, carbonatoms is: 1～4, and the mixed ionic liquid adopting is two or more mixing compositions in above three classes, wherein in mixed ionic liquid, N-sulfonic group alkyl-triethyl hydrogen sulfate ammonium salt component concentration is generally less than 10%.Their structural formula is respectively:
The technique of above-mentioned reactive distillation production ethyl acetate, mixed ionic liquid inlet amount in the reactive distillation column described in step 2, preferably 75%～150% of acetic acid feed quality.
The technique of above-mentioned reactive distillation production ethyl acetate, described reactive distillation column can be full tray column and also can be holotactic packing tower, or board-like and structured packing mixing column, in the time selecting holotactic packing tower, N-sulfonic group alkyl-triethyl monoammonium sulfate salt ion liquid ingredient content in mixed ionic liquid must be greater than 3%, is less than 10%.
The technique of above-mentioned reactive distillation production ethyl acetate, other operational conditions of described reactive distillation column are: reactive distillation column reboiler temperature is 100～120 DEG C, reactive distillation column tower top temperature is 70～80 DEG C, and reactive distillation column operating reflux ratio is 2.0～5.0.
The technique of above-mentioned reactive distillation production ethyl acetate, three bursts of described independent material feeding plate positions, according to the difference of reactive distillation column theoretical plate number, for: acetic acid is positioned at 5th～15 plate chargings of reactive distillation column, mixed ionic liquid is positioned at 10th～30 plate chargings of reactive distillation column, and ethanol is positioned at 25th～60 plate chargings of reactive distillation column (concrete feeding manner is shown in accompanying drawing 2).
The technique of above-mentioned reactive distillation production ethyl acetate, three bursts of described independent material feeding temperature are respectively: acetic acid feed temperature is 70～90 DEG C; Mixed ionic liquid feeding temperature is 80～120 DEG C; Ethanol feeding temperature is 70～80 DEG C.
The technique of above-mentioned reactive distillation production ethyl acetate, described flash distillation mode is single-action flash distillation or multi-effect flashing steam, and flashing apparatus used is flash tank or multiple-effect evaporator, and flash vaporization point is 80～160 DEG C.
The technique of above-mentioned reactive distillation production ethyl acetate, appropriate change processing parameter, organic acid acetic is produced in the esterification that can be applied to other organic acid and alcohol.
Advantage of the present invention is: this process energy consumption low (be less than 1.2 tons of water vapour/ton esters, traditional technology energy consumption is greater than 2.5 tons of water vapour/ton esters), the mixed ionic liquid adopting can be through simply dewatering and recycle.
Brief description of the drawings
Fig. 1 is the process flow sheet of the reactive distillation production ethyl acetate of reaction of the present invention-bis-extracting rectifying-rectifying three step couplings, wherein: 1 is mixed ionic liquid material, 2 is the parallel feeding of the mixed ionic liquid 8 of mixed ionic liquid 1 and recovery, 3 is ethanol charging, 4 is acetic acid feed, 5 is ethyl acetate discharging, 6 is the discharging of mixed ionic liquid and water mixture, 7 is water discharging, the 8 mixed ionic liquid materials for recovery, A1 is mixing tank, and B1 is reactive distillation column, and B2 is flash tank or multiple-effect evaporator.
Fig. 2 is three bursts of separate feeds of reactive distillation process and four regional distribution chart of reactive distillation column of reaction of the present invention-bis-extracting rectifying-rectifying three step couplings, wherein: 4 is acetic acid feed, 2 is mixed ionic liquid charging, 3 is ethanol charging, 5 is ethyl acetate discharging, and 6 is mixed ionic liquid and water mixture discharging; A is the rectifying section of reactive distillation column, the secondary extracting rectifying section that B is reactive distillation column, reaction-one-level extracting rectifying section that C is reactive distillation column, reaction-stripping section that D is reactive distillation column.
Embodiment
Further illustrate by the following examples the present invention:
Embodiment 1: ionic liquid of the present invention is mixed ionic liquid, and ionic liquid kind is mainly: N-sulfonic group alkyl-triethyl hydrogen sulfate ammonium salt [(R
1)
3n (CH
2)
nsO
3h] [HSO
4] (wherein R
1for straight chain saturated alkyl, carbonatoms is: 1～3; N=3～6), trialkyl hydrogen sulfate ammonium salt [(R
2)
3nH] [HSO
4] (wherein R
2for straight chain saturated alkyl, carbonatoms is: 2～4), and N-alkyl imidazole hydrosulfate [R
3(C
3h
3n
2h)] [HSO
4] (wherein R
3for straight chain saturated alkyl, carbonatoms is: 1～4), the mixed ionic liquid adopting is two or more mixing compositions in above three classes, and wherein in mixed ionic liquid, N-sulfonic group alkyl-triethyl hydrogen sulfate ammonium salt component concentration is generally less than 10%.Specific embodiment is in table 1
Embodiment 2: according to embodiment 1, adopt the catalyzer that formula 1,2 or 3 is this technique, reactive distillation column is selected full tray column, and concrete technology as shown in Figure 1.Reaction and rectification device parameter is as follows: the full tower theoretical plate number of reactive distillation column is 32 blocks of plates, wherein reaction-stripping section theoretical plate number of reactive distillation column is 6, reaction-one-level extracting rectifying section theoretical plate number of reactive distillation column is 14, the secondary extracting rectifying section theoretical plate number of reactive distillation column is 6, and the rectifying section theoretical plate number of reactive distillation column is 6.Reactive distillation column reboiler temperature is 105 DEG C, and reactive distillation column tower top temperature is 73 DEG C, and acetic acid feed temperature is 80 DEG C, and mixed ionic liquid feeding temperature is 90 DEG C, and ethanol feeding temperature is 75 DEG C, and flash tank temperature is 160 DEG C.Acid alcohol mol ratio is 1:1, and ionic liquid inlet amount is quality of acetic acid 130%, and reactive distillation column trim the top of column ratio is 5.0, and ethyl acetate yield is 98%, and gas phase calibration mass content is 98%.
Embodiment 3: according to embodiment 1, adopt the catalyzer that formula 4 or 5 is this technique, reactive distillation column is selected filler and board-like mixing column, wherein reaction-one-level extracting rectifying section C is tray column, all the other positions are regular packed tower, wherein structured packing is mellpak250Y, and concrete technology as shown in Figure 1.Reaction and rectification device parameter is as follows: the full tower theoretical plate number of reactive distillation column is 50 blocks of plates, wherein reaction-stripping section theoretical plate number of reactive distillation column is 11, reaction-one-level extracting rectifying section theoretical plate number of reactive distillation column is 20, the secondary extracting rectifying section theoretical plate number of reactive distillation column is 10, and the rectifying section theoretical plate number of reactive distillation column is 9.Reactive distillation column reboiler temperature is 110 DEG C, and reactive distillation column tower top temperature is 74.5 DEG C, and acetic acid feed temperature is 80 DEG C, and mixed ionic liquid feeding temperature is 90 DEG C, and ethanol feeding temperature is 75 DEG C.Flash distillation mode is secondary multi-effect flashing steam, and wherein one-level flash vaporization point is 140 DEG C, and pressure is normal pressure; Two-stage flash temperature is 110 DEG C, and pressure is 0.5bar.Acid alcohol mol ratio is 1:1, and ionic liquid inlet amount is 100%, and reactive distillation column trim the top of column ratio is 3.5, and ethyl acetate yield is 99%, and gas phase calibration mass content is 99%.
Embodiment 4: according to embodiment 1, adopt the catalyzer that formula 8 or 10 is this technique, reactive distillation column is selected holotactic packing tower, wherein the structured packing of the rectifying section of reactive distillation column is mellpak350Y or mellpak250X, the structured packing of all the other positions of reactive distillation column is mellpak250Y, and concrete technology as shown in Figure 1.Reaction and rectification device parameter is as follows: reactive distillation column theoretical plate number is 75 blocks of plates, wherein reaction-stripping section theoretical plate number of reactive distillation column is 15, reaction-one-level extracting rectifying section theoretical plate number of reactive distillation column is 30, the secondary extracting rectifying section theoretical plate number of reactive distillation column is 15, and the rectifying section theoretical plate number of reactive distillation column is 15.Reactive distillation column reboiler temperature is 115 DEG C, and reactive distillation column tower top temperature is 76 DEG C, and acetic acid feed temperature is 75 DEG C, and mixed ionic liquid feeding temperature is 85 DEG C, and ethanol feeding temperature is 75 DEG C.Flash distillation mode is three grades of multi-effect flashing steams, and wherein one-level flash vaporization point is 140 DEG C, and pressure is normal pressure; Two-stage flash temperature is 110 DEG C, and pressure is 0.5bar, and three grades of flash vaporization points are 85 DEG C, and pressure is 0.1bar.。Acid alcohol mol ratio is 1:1, and ionic liquid inlet amount is 70%, and reactive distillation column trim the top of column ratio is 2.5, and ethyl acetate yield is 99.5%, and gas phase calibration mass content is 99.5%.
Claims (9)
1. the technique of the reactive distillation production ethyl acetate of the reaction-bis-extracting rectifying-rectifying three step couplings taking mixed ionic liquid as catalyzer, it is characterized in that: it is to carry out on 30～75 reactive distillation column that described technique has theoretical tray at one, described reactive distillation column is divided into four parts, under upper, be respectively: the rectifying section A of reactive distillation column, according to the difference of reactive distillation column theoretical plate number, the contained theoretical plate number of this rectifying section is 5～15 blocks of column plates; The secondary extracting rectifying section B of reactive distillation column, contained theoretical plate number is 5～15 blocks of column plates; Reaction-one-level extracting rectifying section C of reactive distillation column, contained theoretical plate number is 15～30 blocks of column plates; Reaction-stripping section D of reactive distillation column, contained theoretical plate number is 5～15 blocks of column plates, the conversion zone that wherein reaction-one-level extracting rectifying section C and reaction-stripping section D are this reactive distillation column, material is long at reaction-one-level extracting rectifying section C and reaction-stripping section D residence time, reaction mass can be converted into object product completely, specifically comprises the steps:
Step 1, raw acetic acid and ethanol are participated in to reaction from 5th～15 blocks of column plates of reactive distillation column and 25th～60 column plates input reactive distillation columns of reactive distillation column respectively taking acid alcohol mol ratio as 1:1;
Step 2, fresh mix ionic liquid is mixed through mixing tank A1 with the mixed ionic liquid of recovery, participate in reaction with 50%～250% amount of quality of acetic acid from 10th～30 column plates input reactive distillation columns of reactive distillation column;
Step 3, after reactive distillation column is stable without charging, total reflux, carry out normal charging and discharging, be highly purified ethyl acetate from the product of reactive distillation column overhead extraction, from extraction at the bottom of reactive distillation column tower is moisture mixed ionic liquid;
Step 4, by moisture mixed ionic liquid input hypomere flash tank, flash distillation mode can be single-action flash distillation, also can be multi-effect flashing steam, the water flashing off directly discharges, the mixed ionic liquid after flash distillation dewaters returns to reactive distillation column with pump and continues to participate in reaction.
2. the technique of reactive distillation production ethyl acetate according to claim 1, is characterized in that: described mixed ionic liquid kind is N-sulfonic group alkyl-triethyl hydrogen sulfate ammonium salt [(R
1)
3n (CH
2)
nsO
3h] [HSO
4], wherein R
1for straight chain saturated alkyl, carbonatoms is: 1～3; N=3～6; Trialkyl hydrogen sulfate ammonium salt [(R
2)
3nH] [HSO
4], wherein R
2for straight chain saturated alkyl, carbonatoms is: 2～4 or N-alkyl imidazole hydrosulfate [R
3(C
3h
3n
2h)] [HSO
4], wherein R
3for straight chain saturated alkyl, carbonatoms is: 1～4, the mixed ionic liquid adopting is two or more mixing compositions in above three classes, and wherein in mixed ionic liquid, N-sulfonic group alkyl-triethyl hydrogen sulfate ammonium salt component concentration is generally less than 10%, and their structural formula is respectively:
3. the technique of reactive distillation production ethyl acetate according to claim 1, is characterized in that: in the reactive distillation column described in step 2, mixed ionic liquid inlet amount is 75%～150% of acetic acid feed quality.
4. the technique of reactive distillation production ethyl acetate according to claim 1, it is characterized in that: described reactive distillation column is full tray column or is holotactic packing tower, or be board-like and structured packing mixing column, in the time selecting holotactic packing tower, N-sulfonic group alkyl-triethyl monoammonium sulfate salt ion liquid ingredient content in mixed ionic liquid must be greater than 3%, is less than 10%.
5. the technique of reactive distillation production ethyl acetate according to claim 1, it is characterized in that: other operational conditions of described reactive distillation column are: reactive distillation column reboiler temperature is 100～120 DEG C, reactive distillation column tower top temperature is 70～80 DEG C, and reactive distillation column operating reflux ratio is 2.0～5.0.
6. the technique of reactive distillation production ethyl acetate according to claim 1, it is characterized in that: three bursts of described independent material feeding plate positions, according to the difference of reactive distillation column theoretical plate number, for: acetic acid is positioned at 5th～15 plate chargings of reactive distillation column, mixed ionic liquid is positioned at 10th～30 plate chargings of reactive distillation column, and ethanol is positioned at 25th～60 plate chargings of reactive distillation column.
7. the technique of reactive distillation production ethyl acetate according to claim 1, is characterized in that: three bursts of described independent material feeding temperature are respectively: acetic acid feed temperature is 70～90 DEG C; Mixed ionic liquid feeding temperature is 80～120 DEG C; Ethanol feeding temperature is 70～80 DEG C.
8. the technique of reactive distillation production ethyl acetate according to claim 1, is characterized in that: described flash distillation mode is single-action flash distillation or multi-effect flashing steam, and flashing apparatus used is flash tank or multiple-effect evaporator, and flash vaporization point is 80～160 DEG C.
9. the technique of reactive distillation production ethyl acetate according to claim 1, is characterized in that: change processing parameter, described technique can be applied to the esterification of other organic acid and alcohol and produce organic acid acetic.
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