CN102773118B - 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
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- CN102773118B CN102773118B CN201210289335.0A CN201210289335A CN102773118B CN 102773118 B CN102773118 B CN 102773118B CN 201210289335 A CN201210289335 A CN 201210289335A CN 102773118 B CN102773118 B CN 102773118B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000000605 extraction Methods 0.000 title claims abstract description 33
- 230000008569 process Effects 0.000 title claims abstract description 33
- 150000007524 organic acids Chemical class 0.000 title claims abstract description 24
- 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
- 238000010168 coupling process Methods 0.000 title abstract description 6
- 230000008878 coupling Effects 0.000 title abstract description 4
- 238000005859 coupling reaction Methods 0.000 title abstract description 4
- 239000002608 ionic liquid Substances 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- -1 organic acid ester Chemical class 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000741 silica gel Substances 0.000 claims description 13
- 229910002027 silica gel Inorganic materials 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 230000010354 integration Effects 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 8
- 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
- 239000006096 absorbing agent Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 229940093499 ethyl acetate Drugs 0.000 claims description 3
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 3
- 239000012535 impurity Substances 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
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 238000001704 evaporation 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
- 238000004064 recycling Methods 0.000 claims description 2
- 238000001179 sorption measurement 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
- 239000002253 acid Substances 0.000 abstract description 12
- 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
- 239000012071 phase Substances 0.000 description 15
- 238000007599 discharging Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 0 *[n]1cncc1 Chemical compound *[n]1cncc1 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 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
- 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
- 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
- BSKHPKMHTQYZBB-UHFFFAOYSA-O Cc1[nH+]cccc1 Chemical compound Cc1[nH+]cccc1 BSKHPKMHTQYZBB-UHFFFAOYSA-O 0.000 description 1
- 230000002378 acidificating effect Effects 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
- 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
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 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
- 238000009776 industrial production Methods 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
- 239000000155 melt Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 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
- 230000007420 reactivation Effects 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
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
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- 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 a class ionic liquid compositions catalyst and the application in the organic acid esters metallization processes of integration of reaction and extraction strengthening thereof.
Background technology
Organic acid esters is the very important organic compound raw material of a class, has industrial use very widely in fields such as paint, coating, adhesives.Particularly in recent years in the face of environmental protection problem; people try hard to reduce toluene, dimethylbenzene, the use of the high toxicities such as ketone, non-environment-friendly type solvent; and Devoting Major Efforts To Developing and utilize hypotoxicity, environmentally friendly organic acid ester containing oxygen organic coating, to replace volatility ketone and aromatic hydrocarbons.Its traditional esterification technique adopts the inorganic acids such as the concentrated sulfuric acid as catalyst mostly, but this technique exists shortcomings.As easily caused equipment corrosion, catalyst is difficult to recovery, side reaction is many, product separation is difficult.And solid catalyst (as solid acid, ion-exchange resin etc.) though have some superiority in product separation and catalyst recovery etc., but there is the shortcomings such as catalyst melts, loss, inefficacy, temperature tolerance difference, and also there is power and the mass transfer restricted problem of catalytic inner, have impact on its commercial Application.Therefore, select new catalyst, efficient, the green esterification technique tool of development of new is of great significance.
Ionic liquid is a kind of green solvent and catalyst that receive much concern in recent years also known as ionic liquid at room temperature (Room Temperature Ionic Liquids is called for short RTILs).It is a kind of fusing point lower than the organic fuse salt of liquid state of 100 DEG C.Because it is made up of zwitterion completely, therefore ionic liquid has the much character being different from conventional organic solvent, and as: " zero " vapour pressure, heat endurance is high, solvability is strong and structure and fuction can design.Ionic liquid is applied in the esterification of acid alcohol catalysis in recent years, and its distinctive fixedness makes ionic liquid in catalytic reaction, be conducive to the recovery of being separated of product and catalyst with unique dissolubility.Therefore, be used for the industrial production of organic acid esters with the ionic liquid replacement concentrated sulfuric acid or solid acid as catalyst, there is huge application potential.
At present, the Patents bibliographical information of existing ionic liquid-catalyzed esterification, mainly containing application number is: CN101863855A, CN1405140A, CN1405140A, CN101007760A, CN1554638A, the patents such as CN101147877A, CN101024613A, CN101172949A.The component of ionic-liquid catalyst and function singleness in these patents, and have the defects such as the highly corrosive that highly acid causes, high consumption cost and the conveying inconvenience that causes because of lazy flow because of it, limits its application in the industry.This is also the main reason that above patented technology there is not yet commercial Application.
Summary of the invention
In order to overcome the defect of more than ionic-liquid catalyst and better commercial Application, the present invention proposes the scheme of mixed ionic liquid composition as esterification catalyst first, and its main contents comprise the design of ionic liquid compositions catalyst and coupling of reaction and extraction technique two parts supporting with it.Contain a small amount of high activity strong acidic ion liquid and make major catalyst in the ionic liquid compositions catalyst of design, then be aided with noncorrosive ionic liquid and make co-catalyst.This formula Design has taken into account kinetics and the performance of thermodynamics two aspect that is separated, wherein the highly acid of major catalyst gives composition solution high catalytic activity, reaction can be made to obtain good catalytic kinetics effect, in the short time, very high reaction conversion ratio can be reached; And co-catalyst rises except catalytic action except assistance major catalyst, be that it can also play liquid-liquid phase separation effect more, product ester can be driven away to another phase, to make molecular balance move to product direction more, until reaction reaches complete.In addition co-catalyst can also play performance modification to composition solution, as reduced viscosity, reducing fusing point, regulating amphipathic property etc., being more suitable for industrial applications to make ionic liquid compositions catalyst.At Reaction Separation process aspect, in view of current reactive distillation coupling technique universality is poor, the defect that energy consumption is still larger; The present invention proposes integration of reaction and extraction technical scheme first to replace the reaction rectification coupling scheme of existing commercial Application.Integration of reaction and extraction technique is compared with 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 the purity of product more easily ensures, 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 that the integration of reaction and extraction of a class ionic liquid compositions catalyst and catalysis thereof is strengthened.
Technical scheme of the present invention is as follows:
One class ionic liquid compositions catalyst, it is mixed by two class ionic liquid constituents A and B component and forms, wherein mass content scope shared by component A is 2% ~ 10%, mass content scope shared by B component is 90% ~ 98%, wherein, the ionic liquid that can be used for component A is: N-sulfonic group alkyl-triethyl ammonium disulfate ([(Et)
3n (CH
2) nSO
3h] [HSO
4] (wherein n=3-6)), N-sulfonic group alkyl-N-methylimidazolium hydrogen sulphate salt ([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] wherein R
1containing C:1 ~ 4), alkyl pyridine disulfate ([R
2py] [HSO
4] wherein R
2containing C:0 ~ 4), 2-picoline disulfate ([Hmpy] [HSO
4]) or tetraalkyl quaternary ammonium hydrogensulfates ([(R
3)
3r
4[HSO
4] wherein R
3containing C:1 ~ 4; R
4containing C:1 ~ 4) one or both, their structural formula is respectively:
The mechanism of catalytic reaction of the esterifying organic acid new technology of integration of reaction and extraction strengthening of the present invention as shown in Figure 1.
Reactant organic acid and alcohol and ionic liquid compositions catalyst dissolve each other before the reaction, and just produce ester very soon after reaction starts and be divided into two-phase, upper is ester phase mutually, wherein reactant organic acid and alcohol be present in a large number ester mutually in, lower is ionic liquid phase mutually.Because reactant organic acid and alcohol have good compatibility to ionic liquid compositions catalyst, reactant enters ionic liquid phase reaction endlessly, generate water be then retained in catalyst ion fluid composition mutually in, then by ionic liquid, middle the disengaging enters ester phase to the ester generated mutually at once, and this separation can reach and impel molecular balance to generate the effect of direction movement to product.When reaction reaches balance, a small amount of remaining unreacted reactant organic acid and alcohol are then because the effect of balancing each other is present in ester phase and ionic liquid phase two-phase.Because of the present invention's employing is excessive acid technique, therefore the alcohol in system almost transforms completely.Ionic liquid mutually in only there is a large amount of water and excessive organic acid that reaction produces, moisture and organic acid ionic liquid ionic liquid compositions catalyst after flash distillation process can continue to recycle.
According to above catalysis-phase transfer theory, the present invention devises corresponding integration of reaction and extraction esterifying organic acid new technology, and is realized by following process program:
More than one state the organic acid esters metallization processes of the integration of reaction and extraction of ionic liquid compositions catalyst, and it comprises the steps:
Raw material is that 1:1 ~ 1.5:1 inputs in pre-reactor and carries out pre-reaction together with 50% ~ 100% ionic liquid compositions catalyst of organic acid quality by acid alcohol mol ratio by step 1: according to Fig. 1;
Step 2: the system after pre-reaction is sent into turntable extracting tower, 50% ~ 200% formula ionic-liquid catalyst adding organic acid quality reacts further;
Step 3: extraction ionic liquid phase at the bottom of turntable extracting tower tower also inputs evaporimeter, the isolated ionic liquid compositions catalyst of base of evaporator, return in pre-reactor carry out pre-reaction through shunting a part, another part returns turntable extracting tower and participates in reaction, keeps the recycling circulation of formula ionic-liquid catalyst with this; The isolated organic acid in evaporimeter top and water mixed liquid enter rectifying column, and the water outlet of rectifying column side line is directly discharged, and the azeotropic mixture of tower top water outlet and a small amount of ester enters turntable extracting tower, and acid at the bottom of tower returns pre-reactor and reacts;
Step 4: from turntable extracting tower overhead extraction ester phase, a part return to do bottom turntable extracting tower extractant extracting ionic liquid composition mutually in a small amount of unreacted reactant continue to participate in reaction, to make reaction carry out completely, another part obtains pure organic acid esters through silica gel absorption tower absorption removing trace impurity.
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 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, the carbon number such as ethyl butyrate or propyl butyrate is no more than the organic acid ester of 8.
Above-mentioned organic acid esters metallization processes, described pre-reactor operating condition is: acid alcohol molar ratio is 1:1 ~ 1.5:1, and pre-reaction ionic liquid compositions catalyst amount used is 50% ~ 100% of sour quality, and reaction temperature is 60 DEG C ~ 115 DEG C, 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 (in tower, one deck mixed plate and one deck divide phase-plate to consist of one-level), ionic liquid compositions catalyst amount used is 50% ~ 200% of organic acid quality, mechanical agitation, reaction temperature is 60 DEG C ~ 115 DEG C, and extraction ester returns tower bottom, and to divide with the volume ratio entering silica gel absorption tower section be 1:2 ~ 1:5.
Above-mentioned organic acid esters metallization processes, described evaporator operation condition is: ionic liquid phase mixture evaporating temperature is 145 DEG C ~ 195 DEG C.
Above-mentioned organic acid esters metallization processes, described rectifying column operating condition is: theoretical cam curve is 50 ~ 70, feedboard position is 27th ~ 35 blocks of column plates, side take-off water plate position is 9th ~ 12 blocks of column plates, operating reflux ratio is 3.0 ~ 4.0, feeding temperature is 60 DEG C ~ 115 DEG C, and tower top temperature is 100 DEG C ~ 105 DEG C, and reboiler temperature is 115 DEG C ~ 175 DEG C.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.Adsorbent reactivation scheme is: first use water as eluant, eluent is with 2 ~ 10BV/h flow velocity process adsorbent, to remove alcohol, ester and the ionic liquid compositions catalyst etc. that adsorb in silica gel, silica gel absorber after process, again by hot dry air process regeneration, regenerates complete can continuation and uses.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of mechanism of catalytic reaction of the present invention.
Fig. 2 is the esterifying organic acid new technological flow schematic diagram of integration of reaction and extraction of the present invention strengthening, wherein: 1 is alcohol charging, 2 and 4 is sour charging, 3 and 5 is the charging of formula ionic-liquid catalyst, 6 is the discharging of pre-reaction reactor, 7 is pre-reaction mixture system and the mixed feeding of recovery azeotropic mixture, 8 is ionic liquid phase discharging at the bottom of turntable extracting tower tower, 9 is the discharging of turntable extracting tower tower top ester phase, 10 is the discharging of evaporimeter formula ionic liquid, 11 enter turntable extracting tower part for shunting formula ionic-liquid catalyst, 12 enter pre-reactor part for shunting formula ionic-liquid catalyst, 13 is the discharging of evaporator overhead sour water mixture, 14 and 15 is formula ionic-liquid catalyst (turntable extracting tower) charging, 16 is discharging at the bottom of rectifying tower (acid recovery), 17 is rectifying column overhead water and the discharging of ester azeotropic mixture, 18 is rectifying column side line water outlet (directly discharging), 19 divide for shunting extraction ester is back to tower bottom, 20 enter subordinate's ester purification part for shunting extraction ester, 21 is silica gel absorption tower discharging (product ester).
Fig. 3 is turntable extracting tower schematic diagram.
Detailed description of the invention
Further illustrate the present invention by the following examples
Embodiment 1 ~ 20: recipe ingredient of the present invention is recipe ingredient A+ recipe ingredient B, wherein mass percent shared by recipe ingredient A is 2% ~ 10%, mass percent shared by recipe ingredient B is 90% ~ 98%, and the total consumption of mixing formula ionic-liquid catalyst is 100% ~ 300% of acetic acid quality.Wherein a
1for N-sulfonic group alkyl-triethyl ammonium disulfate, a
2for N-sulfonic group alkyl-N-methylimidazolium hydrogen sulphate salt, a
3for sulfonic alkyl pyridine disulfate, b
1for N-alkyl imidazole disulfate, b
2for pyridine disulfate, b
3for 2-picoline disulfate, b
4for tetraalkyl quaternary ammonium hydrogensulfates.Specific embodiment is in table 1:
Table 1
Embodiment 29: according to embodiment 1 ~ 28, esterification novel process of the present invention is as shown in Figure 1: in pre-reactor, add certain proportioning acid and alcohol (condition 1), add a certain amount of ionic liquid compositions catalyst (condition 2), react (condition 3) at a certain temperature, stay for some time (condition 4) input turntable extracting tower afterwards, a certain amount of formula ionic liquid of the same race (condition 6) is added again in the turntable extracting tower of certain progression (condition 5: in extraction tower, one deck mixed plate and one deck divide phase-plate to be one-level), in tower, mixture system reacts (condition 7) at a certain temperature, at the bottom of tower, extraction ionic liquid compositions enters evaporimeter mutually, ionic liquid is separated with atmospheric flashing under uniform temperature (condition 8) in evaporimeter, extraction ionic liquid compositions at the bottom of tower enters pre-reactor respectively and turntable extracting tower participates in reaction, overhead extraction acetic acid and aqueous mixtures system enter the rectifying column of certain theoretical cam curve (condition 10) with certain plate position (condition 9), the operating condition of rectifying column comprises tower top temperature (condition 11), reboiler temperature (condition 12), reflux ratio (condition 13), with the side take-off water of certain plate position (condition 14) (directly discharging), the azeotropic mixture of overhead extraction water and a small amount of ester enters turntable extracting tower, extraction acetic acid at the bottom of tower then returns pre-reactor and participates in reaction.The ester of turntable extracting tower overhead extraction distributes (condition 15: return tower bottom and divide and the volume ratio entering subordinate's purification part) by a certain percentage, a part enter to do bottom turntable extracting tower extractant extracting ionic liquid mutually in a small amount of unreacted reactant continue to participate in reaction, another part enters absorption tower adsorbs removal of impurities with certain flow rate (condition 16), finally obtain the ester (condition 17) of certain yield, the regeneration of adsorbent is then with the water of certain flow rate (condition 18) and hot dry air regeneration.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, the carbon number such as ethyl butyrate or propyl butyrate is no more than the organic acid ester of 8.Concrete implementation and operation condition is in table 2:
Table 2
Embodiment 30: according to embodiment 29, changes condition 2, the ionic liquid compositions catalyst type of condition 5, and change product species, concrete implementation condition is in table 3:
Table 3
Embodiment 31: according to embodiment 29, change condition 2 and condition 5 are filled a prescription ionic liquid kind, and change product species, concrete implementation condition is in table 4:
Table 4
Claims (8)
1. the organic acid esters metallization processes strengthened with the integration of reaction and extraction of ionic liquid compositions catalyst, described ionic liquid compositions catalyst forms for being mixed by two class ionic liquid constituents A and B component, wherein mass content scope shared by component A is 2% ~ 10%, mass content scope shared by 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-methylimidazolium hydrogen sulphate salt 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: N-alkyl imidazole disulfate, pyridine disulfate, alkyl pyridine disulfate, one or both of 2-picoline disulfate or tetraalkyl quaternary ammonium hydrogensulfates, wherein alkyl is the alkyl of 1 ~ 4 carbon, it is characterized in that it comprises the steps:
Step 1: be that 1:1 ~ 1.5:1 adds in pre-reactor and carries out pre-reaction together with 50% ~ 100% ionic liquid compositions catalyst of organic acid quality by organic acid and alcohol mol ratio by raw material;
Step 2: the system after pre-reaction is passed into turntable extracting tower, 50% ~ 200% ionic liquid compositions catalyst adding organic acid quality reacts further;
Step 3: extraction ionic liquid compositions catalyst phase at the bottom of turntable extracting tower tower also inputs evaporimeter, isolated ionic liquid compositions catalyst at the bottom of evaporimeter tower, return in pre-reactor through a flow divider shunting part and carry out pre-reaction, another part returns turntable extracting tower and participates in reaction, keeps the recycling circulation of formula ionic liquid compositions catalyst with this; The isolated organic acid of evaporator overhead and water mixed liquid enter rectifying column, and the water outlet of rectifying column side line is directly discharged, and the azeotropic mixture that rectifying tower ejects water and a small amount of ester enters turntable extracting tower, and organic acid at the bottom of rectifying tower returns pre-reactor and reacts;
Step 4: from turntable extracting tower overhead extraction ester phase, a part return to do bottom turntable extracting tower extractant extracting ionic liquid composition catalyst mutually in a small amount of unreacted reactant continue to participate in reaction, to make reaction carry out completely, another part obtains pure organic acid esters through silica gel absorption tower absorption removing trace impurity.
2. organic acid esters metallization processes according to claim 1, is characterized in that: described organic acid is acetic acid, propionic acid or butyric acid.
3. organic acid esters metallization processes according to claim 1, is characterized in that: described organic acid esters 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, ethyl butyrate or propyl butyrate.
4. organic acid esters metallization processes according to claim 1, is characterized in that: described pre-reactor operating condition is: reaction temperature is 60 DEG C ~ 115 DEG C, mechanical agitation, and the time of staying is 10 ~ 30min.
5. organic acid esters metallization processes according to claim 1, it is characterized in that: described turntable extracting tower operating condition is: turntable extracting tower progression is 6 ~ 10 grades, mechanical agitation, reaction temperature is 60 DEG C ~ 115 DEG C, and extraction ester returns turntable extracting tower tower bottom, and to divide with the volume ratio entering silica gel absorption tower section be 1:2 ~ 1:5.
6. organic acid esters metallization processes according to claim 1, is characterized in that: described evaporator operation condition is: ionic liquid compositions catalyst phase mixture evaporating temperature is 145 DEG C ~ 195 DEG C.
7. organic acid esters metallization processes according to claim 1, it is characterized in that: described rectifying column operating condition is: theoretical cam curve is 50 ~ 70, feedboard position is 27th ~ 35 blocks of column plates, rectifying column side take-off water plate position is 9th ~ 12 blocks of column plates, operating reflux ratio is 3.0 ~ 4.0, and feeding temperature is 60 DEG C ~ 115 DEG C, and rectifying column tower top temperature is 100 DEG C ~ 105 DEG C, reboiler temperature is 115 DEG C ~ 175 DEG C, and rectifying column is packed tower or plate column.
8. organic acid esters metallization processes according to claim 1, it is characterized in that: described silica gel absorption tower operating condition is: the rate of adsorption 5 ~ 25BV/h, silica gel absorber regeneration scheme is: first use water as eluant, eluent is with 2 ~ 10BV/h flow velocity process silica gel absorber, to remove the alcohol, ester and the ionic liquid compositions catalyst that adsorb in silica gel absorber, silica gel absorber after process, again by hot dry air process regeneration, regenerates complete can continuation and uses.
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| 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 |
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| 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 |
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