CN103055937B - Preparation method of immobilized ionic liquid used for ester exchange reaction - Google Patents
Preparation method of immobilized ionic liquid used for ester exchange reaction Download PDFInfo
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- CN103055937B CN103055937B CN201210549843.8A CN201210549843A CN103055937B CN 103055937 B CN103055937 B CN 103055937B CN 201210549843 A CN201210549843 A CN 201210549843A CN 103055937 B CN103055937 B CN 103055937B
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Abstract
The invention relates to a preparation method of an immobilized ionic liquid used for an ester exchange reaction. The preparation method comprises the steps of: regarding a pure silicon molecular sieve as a carrier and regarding epoxy chloropropane or epoxy bromopropane and 1-alkyl imidazole as raw materials to realize efficient immobilization of the ionic liquid on the surface of the pure silicon molecular sieve through two-step reaction. The preparation method is simple; and the obtained immobilized ionic liquid catalyst after the reaction can be recycled for the continuous cyclic utilization through a simple treatment, has a long service life and no pollution, and greatly reduces the reaction cost. Very good catalysis effects can be obtained when the catalyst prepared by the preparation method is used for the ester exchange reaction, such as the ester exchange reaction of dimethyl carbonate and diethyl carbonate and the ester exchange reaction of ethylene carbonate and methanol.
Description
Technical field
The present invention relates to the preparation field of immobilized ionic liquid, particularly a kind of preparation method of the immobilized ionic-liquid catalyst for ester exchange reaction.
Background technology
Current ester exchange reaction catalyst used is mostly alkalescence, as NaOH, KOH, NaOCH
3, KOCH
3deng, these catalyst activities are higher, but in actual application, find that this kind of catalyst is poorly soluble in reactant liquor, easily precipitate, easy fouling, reuse rear activity decrease very fast, have impact on catalyst life, and easily separate out in a distillation column, blocking pipe.Further, these catalyst are difficult to separate from product, and this just impels people to study high activity and is easy to the heterogeneous catalysis of separation.
Have bibliographical information to cross several heterogeneous catalysis, as quaternary amine type strong alkali resin, sulfonic acid type strong resin, carboxylic acid type weak acid resin, impregnated of the SiO of alkali metal, alkaline-earth-metal silicate
2, wherein quaternary amine type strong alkali resin activity is the highest, and this kind of catalyst does not exist later separation problem, but general activity is not high.
Ionic liquid, owing to having the advantages such as low-vapor pressure, good heat endurance and chemical stability, causes the concern of numerous scientific research personnel in recent years at catalytic field.Bao Guirong (Chinese oil, 2010,8:47 ~ 50) uses alkali ionic liquid [BmIm] OH respectively, [BmIm] Im be catalyst for ester-interchange method biodiesel synthesis and dipropyl carbonate, achieve good effect.But these catalyst are difficult to separate from product, this just impels people to study high activity and is easy to the heterogeneous catalysis of separation.Therefore, the immobilized focus becoming current research of ionic-liquid catalyst how is realized.
The method of current solid-loaded ionic-liquid catalyst has:
(1) infusion process
Ionic liquid is added drop-wise on solid carrier, completely moistening to carrier, or carrier is immersed in excessive ionic liquid; After dipping, remove on carrier not by the ionic liquid adsorbed with Soxhlet extractor washing; Finally immobilized ionic liquid is carried out drying process.Such as ionic liquid joins in Bio-sil all wetted to silica gel by Valkenberg etc. (Green Chemistry, 2002,4:88-93), then utilizes Soxhlet extractor by unnecessary ion liquid abstraction out.Although it is very high that the ionic-liquid catalyst obtained evaluates activity first, reusing, activity decrease in process is remarkable.Therefore, although infusion process is the preparation method of the most frequently used load-type ion liquid catalyst, the solid-carrying type ionic-liquid catalyst that this method obtains in the application ionic liquid runs off serious, poor stability, and has a strong impact on product quality.
(2) bonding method
In order to destroy when overcoming immobilized by anion in above-mentioned infusion process carrier structure, reduce acidity, be confined to the shortcomings such as Lewis acidic ionic liquids, people to work out ionic liquid supported again by bonding method on carrier, namely refer to that the mode by covalent bond between carrier with ionic liquid is combined.The method of current employing silane coupler carrys out solid-loaded ionic-liquid research also a lot, but coupling agent is mostly expensive, is difficult to realize large-scale production.
In sum, find a kind of with low cost, to reclaim and recycle the immobilized ionic-liquid catalyst simple, catalytic activity is high significant.
Summary of the invention
The technical problem to be solved in the present invention is the catalyst recovery difficulty, the high in cost of production defect that occur in ester exchange reaction for current ionic-liquid catalyst.In order to solve the problem, the invention provides a kind of preparation method of immobilized ionic-liquid catalyst, the high catalytic activity of ionic-liquid catalyst in ester exchange reaction, high selectivity can be realized, and catalyst recovery and recycle simple, reduce reaction cost.
The technical solution adopted for the present invention to solve the technical problems is:
Toluene, epoxychloropropane or epoxy bromopropane, pure silicon molecular sieve and catalyst is added successively in round-bottomed flask.Wherein the mass ratio of pure silicon molecular sieve and toluene is 1:20 ~ 1:50, the mass ratio of pure silicon molecular sieve and epoxychloropropane or epoxy bromopropane is 10:1 ~ 5:1, the consumption of catalyst is 2% of pure silicon molecular sieve quality, at 80 DEG C of lower magnetic force stirring reaction 6h, epoxychloropropane or epoxy bromopropane and pure silicon molecular sieve surface etherification of hydroxyl groups can be realized and react.
Wherein said pure silicon molecular sieve is MCM-41, MCM-48 or SBA-15; Described catalyst is zinc chloride or iron chloride.
By above-mentioned reaction system after filtration, washing and drying after, the solid obtained is put into dry round-bottomed flask, add toluene and 1-alkyl imidazole more successively, wherein the mass ratio of toluene and solid is 10:1, the mass ratio of 1-alkyl imidazole and solid is 1:1 ~ 2:1, be heated to 80 DEG C of magnetic agitation reaction 6h, the immobilized ionic-liquid catalyst that can to obtain with pure silicon molecular sieve be carrier.
The present invention's epoxychloropropane or epoxy bromopropane substitute silane coupler successfully can realize the effectively immobilized of ionic liquid.Epoxychloropropane or epoxy bromopropane are the chemical products of large-scale production, therefore cheap, and this can reduce the preparation cost of immobilized ionic-liquid catalyst greatly.Traditional silane coupler often two to three silicone hydroxyl just can instead be given birth to esterification with a coupling agent molecule and realize the immobilized of ionic liquid, and the epoxychloropropane that the present invention uses or epoxy bromopropane only need and a silicone hydroxyl generation etherification reaction and realize the immobilized of ionic liquid, therefore significantly can improve the quantity of the immobilized ionic liquid of pure silicon molecular sieve surface, this is conducive to improving the activity of immobilized ionic-liquid catalyst in ester exchange reaction.In addition, chemically the angle of stability is considered, the stability of ehter bond, far above ester bond, therefore adopts its stability of catalyst of the present invention's design also obviously can be better than the immobilized ionic-liquid catalyst of traditional silane coupler.Therefore the method is simple to operate, with low cost, and immobilized effective, catalyst activity is high, is a kind of effective ways of supported ionic liquids, successfully overcomes the drawback of conventional method.
Immobilized ionic-liquid catalyst of the present invention is applied to ester exchange reaction, the ester exchange reaction of the ester exchange reaction of such as dimethyl carbonate and diethyl carbonate and ethylene carbonate and methyl alcohol, all gets and obtain good effect.In course of reaction, not only catalytic activity is high for immobilized ionic-liquid catalyst, and recycles through simple process and recyclable continuation after the reaction, and the life-span is long, without any pollution, greatly reduces the preparation cost of catalyst for ester exchange reaction.
Accompanying drawing explanation
Fig. 1: the reaction equation of the etherification reaction of epoxychloropropane or epoxy bromopropane and pure silicon molecular sieve surface hydroxyl, wherein X is Br or Cl;
Fig. 2: the reaction equation that the product in step (1) and 1-alkyl imidazole react, wherein X is Br or Cl, R is C
nh
2n+1(n=1 ~ 4).
Detailed description of the invention
The present invention will be described further with regard to following examples, but it is to be understood that these embodiments are only the use illustrated, and should not be interpreted as restriction of the invention process.
Embodiment 1
Toluene, pure silicon molecular sieve MCM-41, epoxychloropropane and zinc chloride is added successively in round-bottomed flask, wherein the mass ratio of pure silicon molecular sieve MCM-41 and toluene is 1:20, the mass ratio of pure silicon molecular sieve MCM-41 and epoxychloropropane is 10:1, and the consumption of zinc chloride is 2% of pure silicon molecular sieve MCM-41 quality.At 80 DEG C of lower magnetic force stirring reaction 6h, obtain the pure silicon molecular sieve of surface hydroxyl etherificate.
The solid obtained by said process adds in round-bottomed flask, dry round-bottomed flask is put into again after washing and drying, add toluene and 1-methylimidazole more successively, wherein the mass ratio of toluene and solid is 10:1, the mass ratio of 1-methylimidazole and solid is 1:1, be heated to 80 DEG C of magnetic agitation reaction 6h, the immobilized ionic-liquid catalyst that can to obtain with pure silicon molecular sieve be carrier, is designated as Cat1.
Embodiment 2
Toluene, pure silicon MCM-48, epoxy bromopropane and iron chloride is added successively in round-bottomed flask, wherein the mass ratio of pure silicon MCM-48 and toluene is 1:50, the mass ratio of pure silicon MCM-48 and epoxy bromopropane is 5:1, and the consumption of iron chloride is 2% of pure silicon MCM-48 quality.At 80 DEG C of lower magnetic force stirring reaction 6h, obtain the pure silicon molecular sieve of surface hydroxyl etherificate.
The solid obtained by said process adds in round-bottomed flask, dry round-bottomed flask is put into again after washing and drying, add toluene and 1-ethyl imidazol(e) more successively, wherein the mass ratio of toluene and solid is 10:1, the mass ratio of 1-ethyl imidazol(e) and solid is 2:1, be heated to 80 DEG C of magnetic agitation reaction 6h, the immobilized ionic-liquid catalyst that can to obtain with pure silicon molecular sieve be carrier, is designated as Cat2.
Embodiment 3
Toluene, pure silicon molecular sieve SBA-15, epoxy bromopropane and iron chloride is added successively in round-bottomed flask, wherein the mass ratio of pure silicon molecular sieve SBA-15 and toluene is 1:30, the mass ratio of pure silicon molecular sieve SBA-15 and epoxy bromopropane is 6:1, and the consumption of iron chloride is 2% of pure silicon molecular sieve SBA-15 quality.At 80 DEG C of lower magnetic force stirring reaction 6h, obtain the pure silicon molecular sieve of surface hydroxyl etherificate.
The solid obtained by said process adds in round-bottomed flask, dry round-bottomed flask is put into again after washing and drying, add toluene and 1-propyl imidazole more successively, wherein the mass ratio of toluene and solid is 10:1, the mass ratio of 1-propyl imidazole and solid is 1:1, be heated to 80 DEG C of magnetic agitation reaction 6h, the immobilized ionic-liquid catalyst that can to obtain with pure silicon molecular sieve be carrier, is designated as Cat3.
Embodiment 4
Toluene, pure silicon molecular sieve MCM-41, epoxychloropropane and zinc chloride is added successively in round-bottomed flask, wherein the mass ratio of pure silicon molecular sieve MCM-41 and toluene is 1:30, the mass ratio of pure silicon molecular sieve MCM-41 and epoxychloropropane is 10:1, and the consumption of zinc chloride is 2% of pure silicon molecular sieve MCM-41 quality.At 80 DEG C of lower magnetic force stirring reaction 6h, obtain the pure silicon molecular sieve of surface hydroxyl etherificate.
The solid obtained by said process adds in round-bottomed flask, dry round-bottomed flask is put into again after washing and drying, add toluene and 1-butyl imidazole more successively, wherein the mass ratio of toluene and solid is 10:1, the mass ratio of 1-butyl imidazole and solid is 1:1, be heated to 80 DEG C of magnetic agitation reaction 6h, the immobilized ionic-liquid catalyst that can to obtain with pure silicon molecular sieve be carrier, is designated as Cat4.
Above-mentioned immobilized ionic-liquid catalyst is respectively used to the ester exchange reaction of dimethyl carbonate and diethyl carbonate and the ester exchange reaction of ethylene carbonate and methyl alcohol, reaction condition is respectively:
(1) mol ratio of dimethyl carbonate and diethyl carbonate is 1:1, and the consumption of catalyst is 2% of dimethyl carbonate quality, and reaction temperature is 120 DEG C, and the reaction time is 6h;
(2) mol ratio of ethylene carbonate and methyl alcohol is 1:8, and the consumption of catalyst is 2% of dimethyl carbonate quality, and reaction temperature is 80 DEG C, and the reaction time is 6h.
Product adopts gas chromatographic analysis, the condition of chromatography is: OV-101 capillary chromatographic column, vaporizer and detector temperature 250 DEG C, 80 ~ 180 DEG C of temperature programmings of column oven temperature, determine the yield of product and selective, concrete outcome as shown in Table 1 and Table 2.
The catalytic activity of table 1 catalyst
| Catalyst | Methyl ethyl carbonate selective (%) | Methyl ethyl carbonate yield (%) |
| Cat1 | 100％ | 47.9％ |
| Cat2 | 100％ | 50.2％ |
| Cat3 | 100％ | 53.7％ |
| Cat4 | 100％ | 55.9％ |
The catalytic activity of table 2 catalyst
| Catalyst | Dimethyl carbonate selective (%) | Dimethyl carbonate yield (%) |
| Cat1 | 99.2％ | 80.5％ |
| Cat2 | 99.5％ | 82.4％ |
| Cat3 | 99.1％ | 83.7％ |
| Cat4 | 99.4％ | 85.2％ |
As can be seen from Table 1 and Table 2, by catalyst application of the present invention in ester exchange reaction, catalyst all has higher activity.
Adopt the method for filtering to be reclaimed by the immobilized ionic-liquid catalyst in reactant liquor, reuse after drying, catalyst CAT4 in the ester exchange reaction of ethylene carbonate and methyl alcohol to reuse result as shown in table 3.
The recycling of table 3 catalyst
| Cycle-index | Dimethyl carbonate selective (%) | Dimethyl carbonate yield (%) |
| 1 | 99.4％ | 85.2％ |
| 2 | 99.5％ | 84.7％ |
| 3 | 99.1％ | 84.6％ |
As can be seen from Table 3, this catalyst is after three times are recycled, and the selective and yield of methyl ethyl carbonate is basicly stable, illustrates that this catalyst can reuse and not reduce its catalytic activity, has good effect.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on description, must determine its technical scope according to right.
Claims (6)
1. for a preparation method for the immobilized ionic liquid of ester exchange reaction, it is characterized in that specifically carrying out according to following steps of the method:
(1) in round-bottomed flask, toluene, epoxychloropropane, pure silicon molecular sieve and catalyst is added successively, or in round-bottomed flask, add toluene, epoxy bromopropane, pure silicon molecular sieve and catalyst successively, then at 80 DEG C of lower magnetic force stirring reaction 6h, can realize the etherification reaction of epoxychloropropane or epoxy bromopropane and pure silicon molecular sieve surface hydroxyl, reaction equation is:
wherein X is Cl or Br;
(2) by above-mentioned reaction system after filtration, washing and dry, the solid obtained is put into dry round-bottomed flask, then add toluene and 1-alkyl imidazole successively, be heated to 80 DEG C of magnetic agitation reaction 6h, can obtain described immobilized ionic liquid, reaction equation is:
wherein R is C
nh
2n+1, n=1 ~ 4.
2. the preparation method of the immobilized ionic liquid for ester exchange reaction according to claim 1, is characterized in that the pure silicon molecular sieve described in step (1) is MCM-41, MCM-48 or SBA-15.
3. the preparation method of the immobilized ionic liquid for ester exchange reaction according to claim 1, is characterized in that the catalyst described in step (1) is zinc chloride or iron chloride, and its consumption is 2% of pure silicon molecular sieve quality.
4. the preparation method of the immobilized ionic liquid for ester exchange reaction according to claim 1, is characterized in that the mass ratio of the pure silicon molecular sieve described in step (1) and toluene is 1:20 ~ 1:50; The mass ratio of pure silicon molecular sieve and epoxychloropropane or epoxy bromopropane is 10:1 ~ 5:1.
5. the preparation method of the immobilized ionic liquid for ester exchange reaction according to claim 1, is characterized in that the 1-alkyl imidazole described in step (2) is 1-methylimidazole, 1-ethyl imidazol(e), 1-propyl imidazole or 1-butyl imidazole.
6. the preparation method of the immobilized ionic liquid for ester exchange reaction according to claim 1, is characterized in that the mass ratio of toluene and solid in step (2) is 10:1; The mass ratio of 1-alkyl imidazole and solid is 1:1 ~ 2:1.
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| CN103406146B (en) * | 2013-07-16 | 2016-03-09 | 常州大学 | A kind of preparation method of immobilized alkaline ionic liquid catalyst |
| CN103537318B (en) * | 2013-09-24 | 2015-07-01 | 常州大学 | Solid catalyst for process of preparing ethylene glycol by hydrolyzing ethylene carbonate and preparation method thereof |
| CN103537319B (en) * | 2013-09-26 | 2015-07-01 | 常州大学 | Solid catalyst for ester exchange reactions and preparation method thereof |
| CN103506157B (en) * | 2013-09-26 | 2015-08-12 | 常州大学 | A kind of solid catalyst for the synthesis of methyl ethyl carbonate and preparation method thereof |
| CN103816937B (en) * | 2014-03-11 | 2015-11-25 | 江南大学 | The preparation method of the immobilized ionic-liquid catalyst of a kind of urea alcoholysis synthesizing diethyl carbonate |
| CN104646055B (en) * | 2014-11-21 | 2017-01-18 | 常州大学 | Method for preparing immobilized ionic liquid catalyst |
| TWI781785B (en) * | 2021-10-07 | 2022-10-21 | 南亞塑膠工業股份有限公司 | Preparation method of ion catalyst material for pet chemical recycling and pet chemical recycling method |
| CN115322098B (en) * | 2022-09-21 | 2023-09-26 | 胜华新材料集团股份有限公司 | Method for synthesizing dimethyl carbonate by ionic liquid catalysis |
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