CN102773118A - Ion-like liquid composition catalyst and application thereof in organic acid esterification process for reaction-extraction coupling - Google Patents
Ion-like liquid composition catalyst and application thereof in organic acid esterification process for reaction-extraction coupling Download PDFInfo
- Publication number
- CN102773118A CN102773118A CN2012102893350A CN201210289335A CN102773118A CN 102773118 A CN102773118 A CN 102773118A CN 2012102893350 A CN2012102893350 A CN 2012102893350A CN 201210289335 A CN201210289335 A CN 201210289335A CN 102773118 A CN102773118 A CN 102773118A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- organic acid
- tower
- reaction
- catalyst
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 238000000605 extraction Methods 0.000 title claims abstract description 33
- 230000008569 process Effects 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 27
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 21
- 238000010168 coupling process Methods 0.000 title claims abstract description 16
- 230000008878 coupling Effects 0.000 title claims abstract description 11
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 11
- 239000007788 liquid Substances 0.000 title claims abstract description 7
- 230000032050 esterification Effects 0.000 title abstract description 8
- 238000005886 esterification reaction Methods 0.000 title abstract description 8
- 239000002608 ionic liquid Substances 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- -1 organic acid ester Chemical class 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002148 esters Chemical class 0.000 claims description 24
- 238000001465 metallisation Methods 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000741 silica gel Substances 0.000 claims description 11
- 229910002027 silica gel Inorganic materials 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 241000282326 Felis catus Species 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 3
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 3
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- UQLUUJQJCQIVKJ-UHFFFAOYSA-N S(=O)(=O)(O)OS(=O)(=O)O.N1=C(C=CC=C1)C Chemical compound S(=O)(=O)(O)OS(=O)(=O)O.N1=C(C=CC=C1)C UQLUUJQJCQIVKJ-UHFFFAOYSA-N 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 229940072049 amyl acetate Drugs 0.000 claims description 3
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 3
- 229940043232 butyl acetate Drugs 0.000 claims description 3
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 3
- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 claims description 3
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 3
- 229940117955 isoamyl acetate Drugs 0.000 claims description 3
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 3
- 229940011051 isopropyl acetate Drugs 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 230000008676 import Effects 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- AJTWAFXXIGBVRF-UHFFFAOYSA-N pyridine;sulfo hydrogen sulfate Chemical compound C1=CC=NC=C1.OS(=O)(=O)OS(O)(=O)=O AJTWAFXXIGBVRF-UHFFFAOYSA-N 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 230000007420 reactivation Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims 1
- 239000004615 ingredient Substances 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000009972 noncorrosive effect Effects 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WSCXJWXISTXXCV-UHFFFAOYSA-N N,N-diethylethanamine sulfo hydrogen sulfate Chemical compound CCN(CC)CC.CCN(CC)CC.OS(=O)(=O)OS(O)(=O)=O WSCXJWXISTXXCV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Images
Classifications
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an ion-like liquid composition catalyst which is composed of an ingredient A and an ingredient B, wherein the mass content of the ingredient A ranges from 2% to 10%; the mass content of the ingredient B ranges from 90% to 98%; the ingredient A is a high-activity storng-acid ionic liquid; and the ingredient B is a non-corrosive ionic liquid. An organic acid esterification process in which the ionic liquid composition catalyst is used for catalysis for reaction-extraction coupling comprises the following steps of: adding the acid, the alcohol and the ionic liquid composition catalyst into a preaction kettle together for prereaction; adding the ingredients into a rotary disc extraction tower; adding the ionic liquid composition catalyst of which the content is 50wt%-200wt% of the organic acid for further reaction; extracting the ionic liquid from the bottom of the rotary disc extraction tower and performing phase-flashing on the ionic liquid; returning one part of the flashed ionic liquid composition catalyst to the preaction kettle for preaction, and returning the other part of the flashed ionic liquid composition catalyst to the rotary disc extraction tower to participate in the reaction; feeding the flashed acid and water mixture liquid into a rectification tower; and extracting the organic acid ester from the top of the rotary disc extraction tower. The process is low in energy consumption; and the product is easy to separate.
Description
Technical field
The present invention relates to one type of ionic liquid compositions catalyst and the application in the organic acid esters metallization processes of reaction-extraction coupling and intensifying thereof.
Background technology
Organic acid esters is one type of crucial organic compound raw material, has very wide industrial purposes in fields such as paint, coating, adhesives.Particularly in recent years in the face of environmental protection problem; People try hard to reduce toluene, xylenes, the use of high toxicities such as ketone, non-environment-friendly type solvent; And development and utilization hypotoxicity, environmentally friendly organic acid ester contain the oxygen organic coating energetically, to replace volatility ketone and aromatic hydrocarbons.Its traditional esterification technology adopts inorganic acids such as the concentrated sulfuric acid as catalyst mostly, but there are many shortcomings in this technology.As be prone to cause equipment corrosion, catalyst to be difficult to reclaim, side reaction is many, product separation difficulty etc.And solid catalyst (like solid acid, ion-exchange resin etc.) is though have certain advantage at aspects such as product separation and catalyst recovery; But there are shortcomings such as catalyst thawing, loss, inefficacy, temperature tolerance difference; And also there are catalyst inner power and mass transfer limit problem, influenced its commercial Application.Therefore, select new catalyst for use, efficient, the green esterification technique of development of new has crucial meaning.
Ionic liquid claims that again ionic liquid at room temperature (Room Temperature Ionic Liquids is called for short RTILs) is a kind of green solvent and the catalyst that receives much concern in recent years.It is that a kind of fusing point is lower than liquid organic fuse salt of 100 ℃.Because it is made up of zwitterion fully, so ionic liquid has many character that are different from conventional organic solvent, as: " zero " vapour pressure, heat endurance height, solvability reach structure and function by force and can design etc.Ionic liquid is applied in the esterification of acid alcohol catalysis in recent years, and its distinctive fixedness makes ionic liquid in catalytic reaction, help the recovery of separating of product and catalyst with unique dissolubility.Therefore, replace the concentrated sulfuric acid or solid acid with ionic liquid and be used for the commercial production of organic acid esters, have huge application potential as catalyst.
At present, the related patent U.S. Patent No. bibliographical information of existing ionic liquid-catalyzed esterification mainly contains application number and is: CN101863855A, CN1405140A; CN1405140A, CN101007760A, CN1554638A; CN101147877A, CN101024613A, patents such as CN101172949A.In the component and the function singleness of these patent intermediate ion liquid catalysts, and, limited it in Industrial Application because of it has the highly corrosive that highly acid causes, high consumption cost, and the defectives such as conveying inconvenience that cause because of lazy flow.This also is the main reason that above patented technology is not seen commercial Application as yet.
Summary of the invention
In order to overcome the defective and better commercial Application more than the ionic-liquid catalyst; The present invention has proposed the scheme of mixed ionic liquid composition as esterification catalyst first, and its main contents comprise ionic liquid compositions catalyst design and supporting with it reaction, extraction coupling technique two parts.Comprised a spot of high activity highly acid ionic liquid in the ionic liquid compositions catalyst of design and made major catalyst, be aided with noncorrosive ionic liquid again and make co-catalyst.This prescription design has taken into account the performance of kinetics with thermodynamics two aspects that are separated; Wherein the highly acid of major catalyst gives composition solution high catalytic activity; Can make reaction obtain good catalytic kinetics effect, can reach very high reaction conversion ratio in the short time; And co-catalyst is that it can also play the liquid-liquid phase separation effect except that assisting major catalyst to rise the catalytic action more, can the product ester be driven away to another phase, so that molecular balance moves to the product direction more, reaches complete until reaction.Co-catalyst can also play the performance modification to composition solution in addition, as reducing viscosity, reduces fusing point, regulates amphipathic property etc., so that the ionic liquid compositions catalyst is more suitable for industrial applications.At the Reaction Separation process aspect, seeing that present reactive distillation coupling technique universality is poor, the defective that energy consumption is still bigger; The present invention has proposed reaction-extraction coupling technique scheme first to replace the reaction rectification coupling scheme of existing commercial Application.Reaction-extraction coupling technique is compared with the reaction rectification coupling technique, and the universality of this process program is strong, can be applicable to the catalytic reaction-isolation integral process of various organic acid esters.In addition, this process energy consumption is lower, and the separation of product is easier, and the Costco Wholesale of catalyst is lower and utilization rate is higher, and degree of purity of production more is prone to guarantee, is the cleaning procedure of a real green low-carbon.
The object of the present invention is to provide the esterifying organic acid new technology of the reaction-extraction coupling and intensifying of one type of ionic liquid compositions catalyst and catalysis thereof.
Technical scheme of the present invention is following:
One type of ionic liquid compositions catalyst; It is mixed by two types of ionic liquid constituents A and B component and forms; Wherein the shared mass content scope of component A is 2% ~ 10%; The shared mass content scope of B component is 90% ~ 98%, and wherein, the ionic liquid that can be used for component A is: N-sulfonic group alkyl-the triethyl ammonium disulfate ([(Et)
3N (CH
2) nSO
3H] [HSO
4] (wherein n=3-6)), N-sulfonic group alkyl-N-methylimidazole disulfate ([CH
3(C
3H
3N
2) (CH
2)
nSO
3H] [HSO
4] (wherein n=3-6)), sulfonic alkyl pyridine disulfate ([C
5NH
4(CH
2) nSO
3H] [HSO
4] (wherein n=3-6)) their structural formula is respectively:
Wherein, the ionic liquid that can be used for B component mainly contains: N-alkyl imidazole disulfate ([R
1Im] [HSO
4] R wherein
1Contain C:1 ~ 4), alkyl pyridine disulfate ([R
2Py] [HSO
4] R wherein
2Contain C:0 ~ 4), 2-picoline disulfate ([Hmpy] [HSO
4]) or tetraalkyl quaternary ammonium hydrogensulfates ([(R
3)
3R
4[HSO
4] R wherein
3Contain C:1 ~ 4; R
4Contain C:1 ~ 4) one or both, their structural formula is respectively:
The mechanism of catalytic reaction of the esterifying organic acid new technology of reaction of the present invention-extraction coupling and intensifying is as shown in Figure 1.
The reactant organic acid dissolves each other with the ionic liquid compositions catalyst with alcohol before reaction, just produce ester very soon and be divided into two phases after the reaction beginning, on be the ester phase mutually, wherein reactant organic acid and alcohol be present in a large number ester mutually in, under be the ionic liquid phase mutually.Because the reactant organic acid has good compatibility with alcohol to the ionic liquid compositions catalyst; Reactant constantly gets into the ionic liquid phase reaction in a steady stream; The water that generates then be retained in the catalyst ion fluid composition mutually in; The ester that generates then gets into the ester phase by middle mutually disengaging of ionic liquid at once, and this separation can reach and impel molecular balance to generate the effect that direction moves to product.When reaction reaches balance, a small amount of remaining unreacted reactant organic acid and alcohol then since the effect of balancing each other be present in ester mutually with ionic liquid mutually two mutually in.What adopt because of the present invention is excessive acid technology, so the alcohol in the system almost completely transforms.Ionic liquid only exists a large amount of water that reaction produces and excessive organic acid in mutually, moisturely can continue to recycle with ionic liquid compositions catalyst after the organic acid ionic liquid is handled through flash distillation mutually.
According to above catalysis-phase transfer theory, the present invention has designed corresponding reaction-extraction coupling esterifying organic acid new technology, and realizes through following process program:
More than one state the organic acid esters metallization processes of the reaction-extraction coupling of ionic liquid compositions catalyst, and it comprises the steps:
Step 1:, be that 50% ~ 100% ionic liquid compositions catalyst of 1:1 ~ 1.5:1 and organic acid quality is imported together and carried out pre-reaction in the pre-reactor by the acid alcohol mol ratio with raw material according to Fig. 1;
Step 2: the system after the pre-reaction is sent into turntable extracting tower, and 50% ~ 200% prescription ionic-liquid catalyst that adds the organic acid quality further reacts;
Step 3: the extraction ionic liquid mutually and import evaporimeter at the bottom of the turntable extracting tower tower; The isolated ionic liquid compositions catalyst of base of evaporator; A warp shunting part is returned and is carried out pre-reaction in the pre-reactor; Another part returns turntable extracting tower and participates in reaction, with the recycling circulation of this ionic-liquid catalyst that keeps filling a prescription; The isolated organic acid in evaporimeter top and water mixed liquid get into rectifying column, and the water outlet of rectifying column side line is directly discharged, and the azeotropic mixture of cat head water outlet and a small amount of ester gets into turntable extracting tower, and acid is returned pre-reactor and reacted at the bottom of the tower;
Step 4: from turntable extracting tower cat head extraction ester phase; A part is returned turntable extracting tower bottom and is done a small amount of unreacted reactant of extractant extracting ionic liquid composition in mutually and continue to participate in reaction; So that reaction is carried out fully, the absorption of another part process silica gel absorption tower is removed trace impurity and is obtained pure organic acid esters.
Above-mentioned organic acid esters metallization processes, described organic acid can be acetic acid, propionic acid or butyric acid.
Above-mentioned organic acid esters metallization processes, described organic acid esters can be to comprise methyl acetate, ethyl acetate, propyl acetate; Isopropyl acetate, butyl acetate, amyl acetate, isoamyl acetate; Capryl acetate, methyl propionate, ethyl propionate, propyl propionate; Butyl propionate, methyl butyrate, carbon numbers such as ethyl butyrate or propyl butyrate are no more than 8 organic acid ester.
Above-mentioned organic acid esters metallization processes; Described pre-reactor operating condition is: the acid alcohol molar ratio is 1:1 ~ 1.5:1, and the used ionic liquid compositions catalyst amount of pre-reaction is 50% ~ 100% of a sour quality, and reaction temperature is 60 ℃ ~ 115 ℃; Mechanical agitation, the time of staying is 10 ~ 30min.
Above-mentioned organic acid esters metallization processes; Described turntable extracting tower operating condition is: extraction tower progression is 6 ~ 10 grades (layer of mixing plate and one deck divide phase-plate to consist of one-level in the tower); Used ionic liquid compositions catalyst amount is 50% ~ 200% of an organic acid quality; Mechanical agitation, reaction temperature are 60 ℃ ~ 115 ℃, and it is 1:2 ~ 1:5 with the volume ratio that gets into the silica gel absorption tower section that the extraction ester returns the tower bottom branch.
Above-mentioned organic acid esters metallization processes, described evaporator operation condition is: ionic liquid phase mixture evaporating temperature is 145 ℃ ~ 195 ℃.
Above-mentioned organic acid esters metallization processes; Described rectifying column operating condition is: theoretical cam curve is 50 ~ 70, and the feedboard position is the 27th ~ 35 a block of column plate, and side line recovered water plate position is the 9th ~ 12 a block of column plate; Operating reflux ratio is 3.0 ~ 4.0; Feeding temperature is 60 ℃ ~ 115 ℃, and tower top temperature is 100 ℃ ~ 105 ℃, and reboiler temperature is 115 ℃ ~ 175 ℃.Rectifying column can be packed tower, also can be plate column, preferably uses packed tower.
Above-mentioned organic acid esters metallization processes, described silica gel absorption tower operating condition is: the rate of adsorption 5 ~ 25BV/h.The adsorbent reactivation scheme is: first water is handled adsorbent as eluant, eluent with 2 ~ 10BV/h flow velocity; To remove the alcohol that adsorbs in the silica gel, ester, and ionic liquid compositions catalyst etc.; Silica gel absorber after the processing is handled regeneration through hot dry air again, and regeneration finishes and can continue to use.
Description of drawings
Fig. 1 is the sketch map of mechanism of catalytic reaction of the present invention.
Fig. 2 is the esterifying organic acid new technological flow sketch map of reaction of the present invention-extraction coupling and intensifying, and wherein: 1 is pure charging, and 2 and 4 is sour charging; 3 and 5 is the charging of prescription ionic-liquid catalyst, and 6 are the discharging of pre-reaction agitated reactor, and 7 are pre-reaction mixture system and the mixed feeding of recovery azeotropic mixture; 8 is ionic liquid phase discharging at the bottom of the turntable extracting tower tower, and 9 is the discharging of turntable extracting tower cat head ester phase, and 10 is the discharging of evaporimeter prescription ionic liquid; 11 are shunting prescription ionic-liquid catalyst entering turntable extracting tower part; 12 for shunting prescription ionic-liquid catalyst gets into the pre-reactor part, and 13 is the discharging of evaporimeter cat head sour water mixture, and 14 and 15 are the charging of prescription ionic-liquid catalyst (turntable extracting tower); 16 are discharging (acid recovery) at the bottom of the rectifying Tata; 17 is rectifying column overhead water and the discharging of ester azeotropic mixture, and 18 is rectifying column side line water outlet (directly discharging), and 19 is that shunting extraction ester is back to the tower bottom branch; 20 for shunting extraction ester gets into subordinate's ester purification part, and 21 are silica gel absorption tower discharging (product ester).
Fig. 3 is the turntable extracting tower sketch map.
The specific embodiment
Below further specify the present invention through embodiment
Embodiment 1 ~ 20: recipe ingredient of the present invention is recipe ingredient A+ recipe ingredient B; Wherein the shared mass percent of recipe ingredient A is 2% ~ 10%; The shared mass percent of recipe ingredient B is 90% ~ 98%, and the total consumption of mixing formula ionic-liquid catalyst is 100% ~ 300% of an acetic acid quality.A wherein
1Be N-sulfonic group alkyl-triethyl ammonium disulfate, a
2Be N-sulfonic group alkyl-N-methylimidazole disulfate, a
3Be sulfonic alkyl pyridine disulfate, b
1Be N-alkyl imidazole disulfate, b
2Be pyridine disulfate, b
3Be 2-picoline disulfate, b
4Be the tetraalkyl quaternary ammonium hydrogensulfates.Specific embodiment is seen table 1:
Table 1
Embodiment 29: according to embodiment 1 ~ 28; The esterification novel process that the present invention adopted is shown in accompanying drawing 1: the acid and the alcohol (condition 1) that in pre-reactor, add certain proportioning; Add a certain amount of ionic liquid compositions catalyst (condition 2), reaction (condition 3) at a certain temperature, (condition 4) back input turntable extracting tower stays for some time; In the turntable extracting tower of certain progression (condition 5: in the extraction tower layer of mixing plate and one deck to divide phase-plate be one-level), add a certain amount of prescription ionic liquid of the same race (condition 6) again; Mixture series is reacted (condition 7) at a certain temperature in the tower, and the extraction ionic liquid compositions gets into evaporimeter mutually at the bottom of the tower, ionic liquid in evaporimeter with uniform temperature (condition 8) down atmospheric flashing separate; The extraction ionic liquid compositions gets into pre-reactor and turntable extracting tower participation reaction respectively at the bottom of the tower; Cat head extraction acetic acid and aqueous mixtures system get into the rectifying column of certain theoretical cam curve (condition 10) with certain plate position (condition 9), and the operating condition of rectifying column comprises tower top temperature (condition 11), reboiler temperature (condition 12); Reflux ratio (condition 13); With the side line recovered water (directly discharging) of certain plate position (condition 14), the azeotropic mixture of cat head recovered water and a small amount of ester gets into turntable extracting tower, and extraction acetic acid then returns pre-reactor and participates in reaction at the bottom of the tower.The ester of turntable extracting tower cat head extraction distributes (condition 15: return tower bottom and divide and the volume ratio that gets into subordinate's purification part) by a certain percentage; A part get into the turntable extracting tower bottom do the extractant extracting ionic liquid mutually in a small amount of unreacted reactant continue to participate in reaction; Another part gets into the adsorption tower adsorption-edulcoration with certain flow rate (condition 16); Finally obtain the ester (condition 17) of certain yield, the regeneration of adsorbent is then with the water and the hot dry air regeneration of certain flow rate (condition 18).Catalytic reaction is methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, amyl acetate, isoamyl acetate, capryl acetate, methyl propionate; Ethyl propionate; Propyl propionate; Butyl propionate, methyl butyrate, carbon numbers such as ethyl butyrate or propyl butyrate are no more than 8 organic acid ester.The practical implementation operating condition is seen table 2:
Table 2
Embodiment 30: according to embodiment 29, and change condition 2, the ionic liquid compositions catalyst type of condition 5 changes the product kind, and the practical implementation condition is seen table 3:
Table 3
Embodiment 31: according to embodiment 29, change condition 2 and condition 5 prescription ionic liquid kinds change the product kind, and the practical implementation condition is seen table 4:
Table 4
Claims (9)
1. one type of ionic liquid compositions catalyst; It is characterized in that: it is mixed by two types of ionic liquid constituents A and B component and forms; Wherein the shared mass content scope of component A is 2% ~ 10%; The shared mass content scope of B component is 90% ~ 98%; The ionic liquid that can be used for component A is: N-sulfonic group alkyl-triethyl ammonium disulfate, N-sulfonic group alkyl-N-methylimidazole disulfate or sulfonic alkyl pyridine disulfate; The alkyl of described sulfonic group alkyl is the alkyl of 3 ~ 6 carbon: the ionic liquid that can be used for B component mainly contains: one or both of N-alkyl imidazole disulfate, pyridine disulfate, alkyl pyridine disulfate, 2-picoline disulfate or tetraalkyl quaternary ammonium hydrogensulfates, wherein alkyl is the alkyl of 0 ~ 4 carbon.
2. the organic acid esters metallization processes of the reaction with the described ionic liquid compositions catalyst of claim 1-extraction coupling and intensifying is characterized in that it comprises the steps:
Step 1: is that 50% ~ 100% ionic liquid compositions catalyst of 1:1 ~ 1.5:1 and organic acid quality add in pre-reactor carry out pre-reaction by acid with pure mol ratio with raw material;
Step 2: the system after the pre-reaction is fed turntable extracting tower, and 50% ~ 200% ionic liquid compositions catalyst that adds the organic acid quality further reacts;
Step 3: the extraction ionic liquid mutually and import evaporimeter at the bottom of the turntable extracting tower tower; Isolated ionic liquid compositions catalyst at the bottom of the evaporimeter tower; Return through a flow divider shunting part and to carry out pre-reaction in the pre-reactor; Another part returns turntable extracting tower and participates in reaction, with the recycling circulation of this ionic-liquid catalyst that keeps filling a prescription; The isolated acid of evaporimeter cat head and water mixed liquid get into rectifying column, and the water outlet of rectifying column side line is directly discharged, and the azeotropic mixture of cat head water outlet and a small amount of ester gets into turntable extracting tower, and acid is returned pre-reactor and reacted at the bottom of the tower;
Step 4: from turntable extracting tower cat head extraction ester phase; A part is returned turntable extracting tower bottom and is done a small amount of unreacted reactant of extractant extracting ionic liquid composition in mutually and continue to participate in reaction; So that reaction is carried out fully, the absorption of another part process silica gel absorption tower is removed trace impurity and is obtained pure organic acid esters.
3. organic acid esters metallization processes according to claim 2 is characterized in that: described organic acid is acetic acid, propionic acid or butyric acid.
4. organic acid esters metallization processes according to claim 2 is characterized in that: described organic acid esters is to comprise methyl acetate, ethyl acetate, propyl acetate; Isopropyl acetate, butyl acetate, amyl acetate, isoamyl acetate; Capryl acetate, methyl propionate, ethyl propionate, propyl propionate; Butyl propionate, methyl butyrate, ethyl butyrate or propyl butyrate, carbon number are no more than 8 organic acid ester.
5. organic acid esters metallization processes according to claim 2 is characterized in that: described pre-reactor operating condition is: reaction temperature is 60 ℃ ~ 115 ℃, mechanical agitation, and the time of staying is 10 ~ 30min.
6. organic acid esters metallization processes according to claim 2; It is characterized in that: described turntable extracting tower operating condition is: extraction tower progression is 6 ~ 10 grades; Mechanical agitation; Reaction temperature is 60 ℃ ~ 115 ℃, and it is 1:2 ~ 1:5 with the volume ratio that gets into the silica gel absorption tower section that the extraction ester returns the tower bottom branch.
7. organic acid esters metallization processes according to claim 2 is characterized in that: described evaporator operation condition is: ionic liquid phase mixture evaporating temperature is 145 ℃ ~ 195 ℃.
8. organic acid esters metallization processes according to claim 2 is characterized in that: described rectifying column operating condition is: theoretical cam curve is 50 ~ 70, and the feedboard position is the 27th ~ 35 a block of column plate; Side line recovered water plate position is the 9th ~ 12 a block of column plate; Operating reflux ratio is 3.0 ~ 4.0, and feeding temperature is 60 ℃ ~ 115 ℃, and tower top temperature is 100 ℃ ~ 105 ℃; Reboiler temperature is 115 ℃ ~ 175 ℃, and rectifying column is packed tower or plate column.
9. organic acid esters metallization processes according to claim 2; It is characterized in that: described silica gel absorption tower operating condition is: the rate of adsorption 5 ~ 25BV/h; The adsorbent reactivation scheme is: first water is handled adsorbent as eluant, eluent with 2 ~ 10BV/h flow velocity; To remove the alcohol that adsorbs in the silica gel, ester, and ionic liquid compositions catalyst, the silica gel absorber after the processing is handled regeneration through hot dry air again, and regeneration finishes and can continue to use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210289335.0A CN102773118B (en) | 2012-08-14 | 2012-08-14 | Ion-like liquid composition catalyst and application thereof in organic acid esterification process for reaction-extraction coupling |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210289335.0A CN102773118B (en) | 2012-08-14 | 2012-08-14 | Ion-like liquid composition catalyst and application thereof in organic acid esterification process for reaction-extraction coupling |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102773118A true CN102773118A (en) | 2012-11-14 |
| CN102773118B CN102773118B (en) | 2015-06-10 |
Family
ID=47118359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210289335.0A Active CN102773118B (en) | 2012-08-14 | 2012-08-14 | Ion-like liquid composition catalyst and application thereof in organic acid esterification process for reaction-extraction coupling |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102773118B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119225A (en) * | 2014-07-29 | 2014-10-29 | 南京大学 | New technology for producing ethyl acetate through reactive distillation by taking mixed ionic liquid as catalyst |
| CN109400476A (en) * | 2018-12-06 | 2019-03-01 | 华东理工大学 | A kind of preparation method of long-chain ester |
| CN111116609A (en) * | 2019-12-12 | 2020-05-08 | 南京恒道医药科技有限公司 | Method and device for continuously producing and separating levofloxacin by using levofloxacin mother nucleus and 1-methylpiperazine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1554638A (en) * | 2003-12-29 | 2004-12-15 | 中国科学院过程工程研究所 | Catalytic alcohol acid esterizing method |
| CN1903824A (en) * | 2006-08-03 | 2007-01-31 | 青岛科技大学 | Clean esterification method for producing bialkyl ortho phthalate |
| CN101456813A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for synthesizing polyatomic alcohol fatty acid ester |
| WO2011012814A1 (en) * | 2009-07-31 | 2011-02-03 | Universite Pierre Et Marie Curie (Paris 6) | Method for synthesizing polyesters in an acidic ionic liquid medium |
-
2012
- 2012-08-14 CN CN201210289335.0A patent/CN102773118B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1554638A (en) * | 2003-12-29 | 2004-12-15 | 中国科学院过程工程研究所 | Catalytic alcohol acid esterizing method |
| CN1903824A (en) * | 2006-08-03 | 2007-01-31 | 青岛科技大学 | Clean esterification method for producing bialkyl ortho phthalate |
| CN101456813A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for synthesizing polyatomic alcohol fatty acid ester |
| WO2011012814A1 (en) * | 2009-07-31 | 2011-02-03 | Universite Pierre Et Marie Curie (Paris 6) | Method for synthesizing polyesters in an acidic ionic liquid medium |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119225A (en) * | 2014-07-29 | 2014-10-29 | 南京大学 | New technology for producing ethyl acetate through reactive distillation by taking mixed ionic liquid as catalyst |
| CN109400476A (en) * | 2018-12-06 | 2019-03-01 | 华东理工大学 | A kind of preparation method of long-chain ester |
| CN111116609A (en) * | 2019-12-12 | 2020-05-08 | 南京恒道医药科技有限公司 | Method and device for continuously producing and separating levofloxacin by using levofloxacin mother nucleus and 1-methylpiperazine |
| CN111116609B (en) * | 2019-12-12 | 2021-03-02 | 南京恒道医药科技有限公司 | Method and device for continuously producing and separating levofloxacin by using levofloxacin mother nucleus and 1-methylpiperazine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102773118B (en) | 2015-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1301985C (en) | Method for extracting Vitamin C and gulonic acid from Vitamin C mother liquor | |
| CN101898965B (en) | Two-step method for producing propyl lactate with high content and high optical purity | |
| CN102755759A (en) | Continuous reaction rectification process and rectification equipment for synthesizing isopropyl alcohol | |
| CN102773118B (en) | Ion-like liquid composition catalyst and application thereof in organic acid esterification process for reaction-extraction coupling | |
| CN103435445A (en) | Method for separating mixture of ethanol alcohol and water | |
| CN102584544B (en) | Process for separating ethylene glycol monomethyl ether and water with intermittent azeotropic distillation method | |
| CN104945252A (en) | Method for preparing isobutyl acetate through rectification | |
| CN110627764A (en) | Ethylene carbonate production equipment system and production method thereof | |
| CN110981721A (en) | Method for continuously producing n-propyl acetate | |
| CN102795961B (en) | Device and method for synthesizing sec-butyl alcohol by continuous reaction-rectification | |
| CN104151164A (en) | Method for preparing methyl chloroacetate | |
| CN101914022B (en) | Method for producing methyl lactate with high content and high optical purity in two steps | |
| CN106977398A (en) | A kind of synthetic method of sec-butyl acetate | |
| CN102826956A (en) | Method for separating methyl propionate-methanol-water system by integration of salt-effect extraction and rectification | |
| CN101914021A (en) | Method for producing high-content and high-optical purity butyl lactate with two-step method | |
| CN103772185B (en) | Device and method for removing moisture and heteroacids in acetic acid | |
| CN102267898A (en) | Method for preparing diethyl succinate by using pyridine ionic liquid as catalyst | |
| JP5113854B2 (en) | Method of absorbing methyl acrolein with ionic liquid | |
| CN106349473A (en) | Method for preparing dipolyethylene glycol maleate by using ionic liquid | |
| CN108689812A (en) | A kind of method of ion liquid abstraction rectifying methanol removal and water simultaneously | |
| CN112047838B (en) | Relay type ethyl acetate industrial preparation process | |
| CN104119225A (en) | New technology for producing ethyl acetate through reactive distillation by taking mixed ionic liquid as catalyst | |
| CN102731299B (en) | Liquid-liquid extraction separation method of methyl propionate-methanol-water azeotropic system | |
| CN102794185A (en) | Method, catalyst and device for prepareing 1,3-dioxolane | |
| CN105669445A (en) | Production technology of ethyl acetate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |