CN103406146A - Preparation method of immobilized alkaline ionic liquid catalyst - Google Patents
Preparation method of immobilized alkaline ionic liquid catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of an immobilized alkaline ionic liquid catalyst for ester exchange reaction. According to the method, by using pure silicon molecular sieves or silicon dioxide microbeads as a support and chloracetyl chloride, 1-alkyliminazole and tetramethylammonium hydroxide as raw materials, the ionic liquid can be effectively immobilized on the surface of the pure silicon molecular sieves or silicon dioxide microbeads by three reaction steps. The method is simple; and the obtained immobilized alkaline ionic liquid catalyst after reaction can be recycled for cyclic utilization after simple treatment, and thus, has the advantages of long service life and no pollution, thereby greatly lowering the reaction cost. The catalyst has favorable effect when being used in the ester exchange reaction of synthesizing methylethyl carbonate from dimethyl carbonate and diethyl carbonate.
Description
Technical field
The present invention relates to the preparation field of immobilized alkali ionic liquid, particularly a kind of preparation method of the immobilized alkaline ionic liquid catalyst for ester exchange reaction.
Background technology
Ester exchange reaction catalyst used is mostly alkalescence at present, as NaOH, KOH, NaOCH
3, KOCH
3Deng, these catalyst activities are higher, but this class catalyst of discovery is poorly soluble in reactant liquor in actual application, easily precipitates, and easily fouling, reuse rear active decline very fast, affected catalyst life, and easily in destilling tower, separated out, blocking pipe.And these catalyst are difficult to from product, separating, the heterogeneous catalysis that this just impels people to study high activity and be easy to separate.
There is bibliographical information to cross several heterogeneous catalysis, as quaternary amine type strong alkali resin, the sulfonic acid type strong resin, the carboxylic acid type weak acid resin, flooded the SiO of alkali metal, alkaline-earth-metal silicate
2, wherein quaternary amine type strong alkali resin activity is the highest, and there is not the later separation problem in this class catalyst, but general activity is not high.
Ionic liquid, owing to having the advantages such as low-vapor pressure, good heat endurance and chemical stability, has caused numerous scientific research personnel's concern in recent years at catalytic field.Bao Guirong (Chinese oil, 2010,8:47-50) use respectively alkali ionic liquid [BmIm] OH, [BmIm] Im be catalyst for ester-interchange method biodiesel synthesis and dipropyl carbonate, obtained good effect.Yet these catalyst are difficult to from product, separating, the heterogeneous catalysis that this just impels people to study high activity and be easy to separate.Therefore, how to realize the immobilized focus that becomes current research of ionic-liquid catalyst.
The method of solid-loaded ionic-liquid catalyst has at present:
(1) infusion process
Ionic liquid is added drop-wise on solid carrier, fully moistening to carrier, or carrier is immersed in excessive ionic liquid; After dipping, with the Soxhlet extractor washing, remove the ionic liquid be not adsorbed on carrier and get final product; Finally immobilized ionic liquid being carried out to drying processes.Such as (Green Chemistry such as Valkenberg, 2002,4:88-93) ionic liquid is joined in Bio-sil all wetted to silica gel, then utilize Soxhlet extractor by unnecessary ion liquid abstraction out, although it is very high that the ionic-liquid catalyst obtained is estimated activity first, active decline significantly in reusing process.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 is serious in application intermediate ion fluid loss, poor stability, and have a strong impact on product quality.
(2) bonding method
When immobilized by anion in above-mentioned infusion process in order to overcome, destroy carrier structure, reduce acidity, be confined to the shortcoming such as Lewis acids ionic liquid, people work out again by bonding method by ionic liquid supported to carrier, refer to that namely carrier mode by covalent bond between ionic liquid is combined.Adopt at present the method for silane coupler to come 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, catalyst recovery and recycle the preparation method of the immobilized ionic-liquid catalyst simple, that catalytic activity is high significant.
Summary of the invention
The technical problem to be solved in the present invention is that the catalyst activity occurred in ester exchange reaction for current ionic-liquid catalyst is low, recovery is difficult, the high in cost of production defect.In order to address the above problem, the invention provides a kind of preparation method of immobilized ionic-liquid catalyst, can realize high catalytic activity, the high selectivity of ionic-liquid catalyst in ester exchange reaction, and catalyst recovery and recycle simply, reaction cost reduced.
The technical solution adopted for the present invention to solve the technical problems is to take pure silicon molecular sieve or silica bead to be carrier, at first with chloracetyl chloride, react, and then react with the 1-alkyl imidazole, last and TMAH carries out anion exchange, can obtain described immobilized alkaline ionic liquid catalyst.
Concrete steps are as follows:
(1) in round-bottomed flask, add successively toluene, chloracetyl chloride and pure silicon molecular sieve or silica bead, at-10～30 ℃ of lower magnetic force stirring reaction 6h, can realize the esterification of chloracetyl chloride and pure silicon molecular sieve or silica bead surface hydroxyl, reaction equation is as follows:
(2) reaction system step (1) obtained after filtration, washing and dry, the solid obtained is put into to dry round-bottomed flask, add successively again toluene and 1-alkyl imidazole, be heated to 60～100 ℃ of magnetic agitation reaction 6h, can obtain immobilized ionic-liquid catalyst, reaction equation is as follows:
Wherein R is C
nH
2n+1(n=1～4)
(3) the immobilized ionic liquid obtained in step (2) is carried out to anion exchange with TMAH in methanol solution, the room temperature lower magnetic force stirs 8h, obtains immobilized alkaline ionic liquid catalyst, and reaction equation is as follows.
As limitation of the invention, pure silicon molecular sieve of the present invention is MCM-41, MCM-48 or SBA-15.
As limitation of the invention further, the mass ratio of the pure silicon molecular sieve described in step (1) or silica bead and toluene is 1:30; The mass ratio of pure silicon molecular sieve or silica bead and chloracetyl chloride is 8:1～10:1; In step (2), the mass ratio of toluene and solid is 10:1; The mass ratio of 1-alkyl imidazole and solid is 0.2:1～0.5:1; In step (3), the mass ratio of methyl alcohol and immobilized ionic liquid is 10:1, and the mass ratio of TMAH and immobilized ionic liquid is 0.2:1～0.5:1.
The present invention adopts chloracetyl chloride to substitute silane coupler can successfully realize the effectively immobilized of ionic liquid.Chloracetyl chloride is the chemical products of large-scale production, and therefore cheap, this can reduce the preparation cost of immobilized ionic-liquid catalyst greatly.Traditional silane coupler two to three silicon hydroxyls often just can instead be given birth to esterification and realize the immobilized of ionic liquid with a coupling agent molecule, and the chloracetyl chloride that the present invention uses only needs to realize the immobilized of ionic liquid with a silicon hydroxyl generation etherification reaction, therefore can significantly improve the quantity of the immobilized ionic liquid in pure silicon molecular sieve surface, this is conducive to improve the activity of immobilized ionic-liquid catalyst in ester exchange reaction.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, has successfully overcome the drawback of conventional method.
The ester exchange reaction that immobilized ionic-liquid catalyst of the present invention is applied to dimethyl carbonate and diethyl carbonate has obtained good effect.Not only catalytic activity is high for immobilized ionic-liquid catalyst in course of reaction, and through simple process, is that recyclable the continuation recycles after reaction, and the life-span is long, without any pollution, greatly reduces the preparation cost of catalyst for ester exchange reaction.
The specific embodiment
The present invention will be described further with regard to following examples, but will be appreciated that, these embodiment are the use for illustrating only, and should not be interpreted as restriction of the invention process.
Embodiment 1
(1) in round-bottomed flask, add successively toluene, pure silicon molecular sieve MCM-41 and chloracetyl chloride, wherein the mass ratio of pure silicon molecular sieve MCM-41 and toluene is 1:30, and the mass ratio of pure silicon molecular sieve MCM-41 and chloracetyl chloride is 8:1.At-10 ℃ of lower magnetic force stirring reaction 6h, obtain the pure silicon molecular sieve of surface hydroxyl esterification.
(2) reaction system step (1) obtained after filtration, after washing and drying, the solid obtained is put into to dry round-bottomed flask, add successively again toluene and 1-methylimidazole, wherein the mass ratio of toluene and solid is 10:1, the mass ratio of 1-methylimidazole and solid is 0.2:1, be heated to 60 ℃ of magnetic agitation reaction 6h, can obtain take the immobilized ionic liquid of pure silicon molecular sieve as carrier.
(3) will be added in round-bottomed flask by the immobilized ionic liquid that step (2) obtain, add successively again methyl alcohol and TMAH, wherein the mass ratio of methyl alcohol and immobilized ionic liquid is 10:1, the mass ratio of TMAH and immobilized ionic liquid is 0.2:1, the room temperature lower magnetic force stirs 8h, obtain immobilized alkaline ionic liquid catalyst, be designated as Cat1.
Embodiment 2
(1) in round-bottomed flask, add successively toluene, pure silicon MCM-48 and chloracetyl chloride, wherein the mass ratio of pure silicon MCM-48 and toluene is 1:30, and the mass ratio of pure silicon MCM-48 and chloracetyl chloride is 8:1.At 30 ℃ of lower magnetic force stirring reaction 6h, obtain the pure silicon molecular sieve of surface hydroxyl esterification.
(2) reaction system step (1) obtained after filtration, after washing and drying, the solid obtained is added in round-bottomed flask, add successively again toluene and 1-methylimidazole, wherein the mass ratio of toluene and solid is 10:1, the mass ratio of 1-ethyl imidazol(e) and solid is 0.5:1, be heated to 100 ℃ of magnetic agitation reaction 6h, can obtain take the immobilized ionic liquid of pure silicon molecular sieve as carrier.
(3) the immobilized ionic liquid obtained in step (2) is added in round-bottomed flask, add successively again methyl alcohol and TMAH, wherein the mass ratio of methyl alcohol and immobilized ionic liquid is 10:1, the mass ratio of TMAH and immobilized ionic liquid is 0.2:1, the room temperature lower magnetic force stirs 8h, obtain immobilized alkaline ionic liquid catalyst, be designated as Cat2.
Embodiment 3
(1) in round-bottomed flask, add successively toluene, pure silicon molecular sieve SBA-15 and chloracetyl chloride, wherein the mass ratio of pure silicon molecular sieve SBA-15 and toluene is 1:30, and the mass ratio of pure silicon molecular sieve SBA-15 and chloracetyl chloride is 8:1.At 10 ℃ of lower magnetic force stirring reaction 6h, obtain the pure silicon molecular sieve of surface hydroxyl esterification.
(2) reaction system step (1) obtained after filtration, after washing and drying, the solid obtained is added in round-bottomed flask, add successively again toluene and 1-propyl imidazole, wherein the mass ratio of toluene and solid is 10:1, the mass ratio of 1-propyl imidazole and solid is 0.3:1, be heated to 100 ℃ of magnetic agitation reaction 6h, can obtain take the immobilized ionic liquid of pure silicon molecular sieve as carrier.
(3) the immobilized ionic liquid obtained in step (2) is added in round-bottomed flask, add successively again methyl alcohol and TMAH, wherein the mass ratio of methyl alcohol and immobilized ionic liquid is 10:1, the mass ratio of TMAH and immobilized ionic liquid is 0.4:1, the room temperature lower magnetic force stirs 8h, obtain immobilized alkaline ionic liquid catalyst, be designated as Cat3.
Embodiment 4
(1) in round-bottomed flask, add successively toluene, silica bead and chloracetyl chloride, wherein the mass ratio of silica bead and toluene is 1:30, and the mass ratio of silica bead and chloracetyl chloride is 8:1.At 10 ℃ of lower magnetic force stirring reaction 6h, obtain the pure silicon molecular sieve of surface hydroxyl esterification.
(2) reaction system step (1) obtained after filtration, after washing and drying, the solid obtained is added in round-bottomed flask, add successively again toluene and 1-methylimidazole, wherein the mass ratio of toluene and solid is 10:1, the mass ratio of 1-methylimidazole and solid is 0.5:1, be heated to 80 ℃ of magnetic agitation reaction 6h, can obtain take the immobilized ionic liquid of pure silicon molecular sieve as carrier.
(3) the immobilized ionic liquid obtained in step (2) is added in round-bottomed flask, add successively again methyl alcohol and TMAH, wherein the mass ratio of methyl alcohol and immobilized ionic liquid is 10:1, the mass ratio of TMAH and immobilized ionic liquid is 0.5:1, the room temperature lower magnetic force stirs 8h, obtain immobilized alkaline ionic liquid catalyst, be designated as Cat4.
Embodiment 5
(1) in round-bottomed flask, add successively toluene, silica bead and chloracetyl chloride, wherein the mass ratio of silica bead and toluene is 1:30, and the mass ratio of silica bead and chloracetyl chloride is 10:1.At 10 ℃ of lower magnetic force stirring reaction 6h, obtain the pure silicon molecular sieve of surface hydroxyl esterification.
(2) reaction system step (1) obtained after filtration, after washing and drying, the solid obtained is added in round-bottomed flask, add successively again toluene and 1-methylimidazole, wherein the mass ratio of toluene and solid is 10:1, the mass ratio of 1-butyl imidazole and solid is 0.5:1, be heated to 80 ℃ of magnetic agitation reaction 6h, can obtain take the immobilized ionic liquid of pure silicon molecular sieve as carrier.
(3) the immobilized ionic liquid obtained in step (2) is added in round-bottomed flask, add successively again methyl alcohol and TMAH, wherein the mass ratio of methyl alcohol and immobilized ionic liquid is 10:1, the mass ratio of TMAH and immobilized ionic liquid is 0.5:1, the room temperature lower magnetic force stirs 8h, obtain immobilized alkaline ionic liquid catalyst, be designated as Cat5.
By the ester exchange reaction of above-mentioned immobilized alkaline ionic liquid catalyst for dimethyl carbonate and diethyl carbonate, reaction condition is:
The mol ratio of dimethyl carbonate and diethyl carbonate is 1:1, and the consumption of immobilized ionic-liquid catalyst is 2% of dimethyl carbonate quality, and reaction temperature is 120 ℃, and the reaction time is 6h;
Product adopts gas chromatographic analysis, and the condition of chromatography is: the OV-101 capillary chromatographic column, and 250 ℃ of vaporizer and detector temperatures, 80～180 ℃ of temperature programmings of column oven temperature, determine that the yield of product is with selective, concrete outcome is as shown in table 1.
The catalytic activity of table 1 catalyst
| Catalyst | Methyl ethyl carbonate selective (%) | Methyl ethyl carbonate yield (%) |
| Cat1 | 100% | 42.7% |
| Cat2 | 100% | 48.3% |
| Cat3 | 100% | 52.8% |
| Cat4 | 100% | 59.4% |
| Cat5 | 100% | 56.7% |
Visible from table 1 result, the immobilized alkaline ionic liquid catalyst that the present invention obtains reveals good catalytic activity and selective to the reaction table of the ester exchange Catalysts of Preparing Methyl Ethyl Carbonate of dimethyl carbonate and diethyl carbonate.
The method of adopt filtering reclaims the immobilized alkaline ionic liquid catalyst in reactant liquor, reuse after drying, catalyst Cat4 to reuse result as shown in table 2.
The recycling of table 2 catalyst
| Cycle-index | Methyl ethyl carbonate selective (%) | Methyl ethyl carbonate yield (%) |
| 1 | 100% | 59.1% |
| 2 | 100% | 58.6% |
| 3 | 100% | 58.1% |
As can be seen from Table 2, after this catalyst was recycled through three times, the selective and yield of methyl ethyl carbonate was basicly stable, illustrates that this catalyst can reuse and not reduce its catalytic activity, has good effect.
The above-mentioned foundation desirable embodiment of the present invention of take is enlightenment, and by above-mentioned description, the relevant staff can, in the scope that does not depart from this invention technological thought, carry out various change and modification fully.The technical scope of this invention is not limited to the content on specification, must determine its technical scope according to the claim scope.
Claims (7)
1. preparation method for the immobilized alkaline ionic liquid catalyst of ester exchange reaction, it is characterized in that the method is to take pure silicon molecular sieve or silica bead to be carrier, at first with chloracetyl chloride, react, and then react with the 1-alkyl imidazole, last and TMAH carries out anion exchange, can obtain described immobilized alkaline ionic liquid catalyst.
2. the preparation method of the immobilized alkaline ionic liquid catalyst for ester exchange reaction according to claim 1 is characterized in that what the method was specifically carried out according to following steps:
(1) in round-bottomed flask, add successively toluene, chloracetyl chloride and pure silicon molecular sieve or silica bead, at-10～30 ℃ of lower magnetic force stirring reaction 6h, can realize the esterification of chloracetyl chloride and pure silicon molecular sieve or silica bead surface hydroxyl, reaction equation is as follows:
(2) reaction system step (1) obtained after filtration, washing and dry, the solid that then will obtain is put into dry round-bottomed flask, add successively again toluene and 1-alkyl imidazole, be heated to 60～100 ℃ of magnetic agitation reaction 6h, can obtain immobilized ionic-liquid catalyst, reaction equation is as follows:
(3) the immobilized ionic liquid obtained in step (2) is carried out to anion exchange with TMAH in methanol solution, the room temperature lower magnetic force stirs 8h, obtains immobilized alkaline ionic liquid catalyst, and reaction equation is as follows.
3. the preparation method of the immobilized alkali ionic liquid for ester exchange reaction according to claim 1 and 2, is characterized in that described pure silicon molecular sieve is MCM-41, MCM-48 or SBA-15.
4. the preparation method of the immobilized alkali ionic liquid for ester exchange reaction according to claim 1 and 2, is characterized in that described 1-alkyl imidazole is 1-methylimidazole, 1-ethyl imidazol(e), 1-propyl imidazole or 1-butyl imidazole.
5. the preparation method of the immobilized alkali ionic liquid for ester exchange reaction according to claim 2, the mass ratio that it is characterized in that the pure silicon molecular sieve described in step (1) or silica bead and toluene is 1:30; The mass ratio of pure silicon molecular sieve or silica bead and chloracetyl chloride is 8:1～10:1.
6. the preparation method of the immobilized alkali ionic liquid for ester exchange reaction according to claim 2, is characterized in that the mass ratio of the middle toluene of step (2) and solid is 10:1; The mass ratio of 1-alkyl imidazole and solid is 0.2:1～0.5:1.
7. the preparation method of the immobilized alkali ionic liquid for ester exchange reaction according to claim 2, the mass ratio that it is characterized in that the middle methyl alcohol of step (3) and immobilized ionic liquid is 10:1, and the mass ratio of TMAH and immobilized ionic liquid is 0.2:1～0.5:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104707651A (en) * | 2013-12-16 | 2015-06-17 | 中国科学院大连化学物理研究所 | Catalyst for catalyzing efficient conversion of silane to silanol, preparation and application thereof |
| CN112442387A (en) * | 2020-11-02 | 2021-03-05 | 烟台大学 | Method for improving yield of biodiesel prepared from palm oil |
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| PL212217B1 (en) * | 2010-04-06 | 2012-08-31 | Inst Ciężkiej Syntezy Organicznej Blachownia | Alkaline ionic liquids |
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| PL212217B1 (en) * | 2010-04-06 | 2012-08-31 | Inst Ciężkiej Syntezy Organicznej Blachownia | Alkaline ionic liquids |
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| CN104707651A (en) * | 2013-12-16 | 2015-06-17 | 中国科学院大连化学物理研究所 | Catalyst for catalyzing efficient conversion of silane to silanol, preparation and application thereof |
| CN104707651B (en) * | 2013-12-16 | 2017-04-05 | 中国科学院大连化学物理研究所 | Catalyst and its preparation and application of a kind of catalysis silane to silanol Efficient Conversion |
| CN112442387A (en) * | 2020-11-02 | 2021-03-05 | 烟台大学 | Method for improving yield of biodiesel prepared from palm oil |
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