CN102814195B - Load type acidic ionic liquid catalyst and preparation method and application thereof and preparation method of ethyl acetate and methyl oleate - Google Patents

Load type acidic ionic liquid catalyst and preparation method and application thereof and preparation method of ethyl acetate and methyl oleate Download PDF

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CN102814195B
CN102814195B CN201110160867.XA CN201110160867A CN102814195B CN 102814195 B CN102814195 B CN 102814195B CN 201110160867 A CN201110160867 A CN 201110160867A CN 102814195 B CN102814195 B CN 102814195B
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catalyst
hollow ball
ionic liquid
titanium dioxide
acidic
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CN102814195A (en
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谢伦嘉
郭顺
亢宇
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention provides a load type acidic ionic liquid catalyst and a preparation method and an application thereof, wherein the catalyst comprises hollow spherical mesoporous silica carriers and an acidic ionic liquid loaded on the hollow spherical mesoporous silica carriers, the average particle diameter of the hollow spherical mesoporous silica carriers is 3 micrometers to 20 micrometers, the specific surface area is 200 square meters per gram, the pore volume is 0.5 to 1.5 milliliters per gram, and the most probable pore size is 3 micrometers to 20 micrometers. Esterification reaction of acetic acid and ethanol and oleic acid and methanol can be effectively catalyzed by using the load type acidic ionic liquid catalyst; and the catalyst can be recycled through simple recovery processing, and a high catalytic efficiency is maintained.

Description

The preparation method of support type acidic ionic liquid catalysts and its preparation method and application and ethyl acetate and methyl oleate
Technical field
The present invention relates to a kind of support type acidic ionic liquid catalysts and preparation method thereof, also relate to application and a kind of preparation method of ethyl acetate and a kind of preparation method of methyl oleate of this catalyst in esterification.
Background technology
Ethyl acetate claims again ethyl acetate.Pure ethyl acetate is the liquid that water white transparency has aromatic odor, it is a kind of broad-spectrum fine chemical product, there is excellent dissolubility, quick-drying, of many uses, be a kind of very important Organic Chemicals and fabulous industrial solvent, be widely used in the production process of acetate fiber, ethyl cellulose, vinyl, acetate fiber resin, chlorinated rubber, synthetic rubber, coating and paint etc.Its main application has: as industrial solvent, for products such as coating, adhesive, ethyl cellulose, artificial leather, malthoid colouring agent, staple fibres; As adhesive, for the production of printing-ink, olivet; As extractant, for the production of the products such as medicine, organic acid.
Mesoporous material has larger specific area, larger aperture and a large amount of high activity surface hydroxyls, be conducive to organic active group fully contacting between assembling and reactant and active sites in its hole, do carrier so multiplex, as the people such as Udayshankar G.Singh with rear synthetic Graft Method on Si-MCM 41 mesoporous materials load copper (referring to Udayshankar G.Singh, Ruth T.Williams, Keith R.Hallam, et a1.Exploring the distribution of copper-Schiff base complexcovalently anchored onto the surface of mesoporous MCM 41 silica.J Solid StateChem, 2005, 178 (11): 3405-3413).
Ionic liquid is at first because its unique physicochemical properties are as green reaction medium, and it is applied far beyond this category now, they more and more come into one's own (referring to Zhang Qinghua as the catalyst of controlling reaction, Wang Ruifeng, Li Zuopeng etc. ionic liquid is in the progress of green catalysis and application in clean synthesizing. petrochemical industry, 2007,36 (10): 975-984).Wan Hui etc. adopt bonding Graft Method, vinyl imidazole class acidic ion liquid is linked in silica gel, synthesize butyl acetate using it as catalyst (referring to ten thousand brightness, Zhang Jishen, Guan Guofeng. bonding Graft Method is prepared immobilized acidic ion liquid and is catalyzed and synthesized butyl acetate. petrochemical industry, 2009,38 (2): 134-138).
The prior synthesizing method of ethyl acetate adopts following several modes conventionally: (1) is under the catalysis of homogeneous catalyst (sulfuric acid), synthesize by esterification process, but the shortcoming such as the shortcoming that the method exists is that sulfuric acid is serious to the erosion of equipment corruption, side reaction is many and discharging of waste liquid amount is large; (2) use separately the polymerization of presence of acidic ionic liquid catalyst ethyl acetate, have acidic ion liquid consumption greatly and the shortcoming of separation difficulty; (3) acidic ion liquid bonding is grafted to catalysis ethyl acetate polymerization on the carriers such as silica gel, by chemical bond grafting acidic ion liquid, has that reagent cost is high, the longer problem of synthesis step.
In addition, the catalyst take silica gel as carrier loaded ionic liquid in prior art, because little carboxylic acid and the alcohol that is unfavorable for that molecular weight is larger in aperture of silica-gel carrier carries out esterification.For example, be unfavorable for the esterification of oleic acid and alcohol.
Summary of the invention
First object of the present invention is to overcome the existing shortcoming existing for catalyzing and synthesizing the catalyst of ethyl acetate, and a kind of a kind of support type acidic ionic liquid catalysts that back loading legal system standby not etching apparatus, side reaction are few, aftertreatment technology is simple and catalyst can be recycled of utilizing is provided.
Second object of the present invention is to provide the preparation method of this support type acidic ionic liquid catalysts.
The 3rd object of the present invention is to provide this application of support type acidic ionic liquid catalysts in esterification.
The 4th object of the present invention is to provide a kind of preparation method of ethyl acetate.
The 5th object of the present invention is to provide a kind of preparation method of methyl oleate.
The invention provides a kind of support type acidic ionic liquid catalysts, wherein, this catalyst comprises hollow ball-shape meso-porous titanium dioxide silicon carrier and loads on the acidic ion liquid on this hollow ball-shape meso-porous titanium dioxide silicon carrier, the average particulate diameter of described hollow ball-shape meso-porous titanium dioxide silicon carrier is 3-20 micron, specific area is 200-300 meters squared per gram, pore volume is 0.5-1.5 ml/g, and most probable aperture is 3-20 nanometer.
The invention provides the preparation method of above-mentioned support type acidic ionic liquid catalysts, the method comprises acidic ion liquid is loaded on hollow ball-shape meso-porous titanium dioxide silicon carrier, the average particulate diameter of described hollow ball-shape meso-porous titanium dioxide silicon carrier is 3-20 micron, specific area is 200-300 meters squared per gram, pore volume is 0.5-1.5 ml/g, and most probable aperture is 3-20 nanometer.
The invention provides the application of above-mentioned support type acidic ionic liquid catalysts in esterification.
The invention provides a kind of preparation method of ethyl acetate, wherein, the method comprises: under the existence of catalyst, under the condition of esterification, acetic acid is contacted, to obtain ethyl acetate with ethanol, wherein, described catalyst is above-mentioned support type acidic ionic liquid catalysts.
The present invention also provides a kind of preparation method of methyl oleate, and wherein, the method comprises: under the existence of catalyst, under the condition of esterification, oleic acid is contacted, to obtain methyl oleate with methyl alcohol, wherein, described catalyst is above-mentioned support type acidic ionic liquid catalysts.
Support type acidic ionic liquid catalysts provided by the invention, compared with independent use ionic liquid, can either obtain suitable catalytic activity, can make again catalyst recycling, obviously reduces the consumption of ionic liquid; Compared with being grafted to silica gel with existing ionic liquid, can either obtain higher catalytic activity, and the preparation method of catalyst is simple, easily operation.
Digital proof by experiment, support type acidic ionic liquid catalysts prepared by the present invention is the esterification of catalysis acetic acid and ethanol efficiently, and its reactant acetic acid conversion ratio approaches 100%, and side reaction is few, and ethyl acetate selectively approaches 100%; Catalyst does not produce corrosion to equipment, and this support type acidic ionic liquid catalysts can reclaim and catalyzing and synthesizing in ethyl acetate Reusability 5 times through simple process, its reactant acetic acid conversion ratio still has 98%, ethyl acetate selectively approaches 100%.
Experimental data also illustrates, support type acidic ionic liquid catalysts prepared by the present invention is the esterification of catalysis oleic acid and methyl alcohol efficiently, the conversion ratio 95% of its reactant methanol, and side reaction is few, and methyl oleate selectively approaches 100%; This support type acidic ionic liquid catalysts can reclaim and reuse catalyzing and synthesizing in methyl oleate through simple process, and its reactant methanol conversion ratio still has 92%, methyl oleate selectively approaches 100%.
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern of hollow ball-shape mesoporous silicon oxide (MS); The x-ray diffraction pattern of the hollow ball-shape mesoporous silicon oxide (MS-ILa-1) of Fig. 2 is load ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate; The hollow ball-shape mesoporous silicon oxide (MS-ILa-2a) of Fig. 3 is above-mentioned load ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate is at the reacted x-ray diffraction pattern of quadric catalysis, wherein illustrate abscissa and be 2 θ/°;
Fig. 4 is the nitrogen Adsorption and desorption isotherms of hollow ball-shape mesoporous silicon oxide (MS); The nitrogen Adsorption and desorption isotherms of the hollow ball-shape mesoporous silicon oxide of Fig. 5 is load ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate (MS-ILa-1), wherein illustrating abscissa is relative pressure p/p 0;
Fig. 6 is the stereoscan photograph of hollow ball-shape mesoporous silicon oxide (MS); The stereoscan photograph of the hollow ball-shape mesoporous silicon oxide (MS-ILa-1) of Fig. 7 is load ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate.
The specific embodiment
The invention provides a kind of support type acidic ionic liquid catalysts, wherein, this catalyst comprises hollow ball-shape meso-porous titanium dioxide silicon carrier and loads on the acidic ion liquid on this hollow ball-shape meso-porous titanium dioxide silicon carrier, the average particulate diameter of described hollow ball-shape meso-porous titanium dioxide silicon carrier can be 3-20 micron, specific area can be 200-300 meters squared per gram, pore volume can be 0.5-1.5 ml/g, and most probable aperture can be 3-20 nanometer; Preferably, the average particulate diameter of described hollow ball-shape meso-porous titanium dioxide silicon carrier can be 5-10 micron, and specific area can be 240-270 meters squared per gram, and pore volume can be 0.7-1.0 ml/g, and most probable aperture can be 8-12 nanometer.In the present invention, the specific area of carrier and catalyst, pore volume and most probable aperture record by nitrogen adsorption desorption method.
According to the present invention, although as long as described acidic ion liquid is loaded on described hollow ball-shape meso-porous titanium dioxide silicon carrier and can realize object of the present invention, but under preferable case, take the gross weight of this catalyst as benchmark, the content of described acidic ion liquid is 10-60 % by weight, and the content of described hollow ball-shape meso-porous titanium dioxide silicon carrier is 40-90 % by weight; More preferably, take the gross weight of this catalyst as benchmark, the content of described acidic ion liquid is 35-45 % by weight, and the content of described hollow ball-shape meso-porous titanium dioxide silicon carrier is 55-65 % by weight.
According to the present invention, the average particulate diameter of described support type acidic ionic liquid catalysts (being the described hollow ball-shape mesoporous silicon oxide after load acidic ion liquid) can be 5-20 micron, specific area can be 190-270 meters squared per gram, pore volume can be 0.4-0.7 ml/g, and most probable aperture can be 2.0-9.7 nanometer; Preferably, described catalyst average particulate diameter be 5-15 micron, specific area is 250-260 meters squared per gram, pore volume is 0.45-0.6 ml/g, most probable aperture is 2.5-3.5 nanometer.
Described hollow ball-shape mesoporous silicon oxide can prepare by the method comprising the following steps: at template, 2,2, under the existence of 4-trimethylpentane and ethanol, tetramethoxy-silicane is contacted with acidic aqueous solution, and gained mixture crystallization under crystallization condition after contacting, by the heating of gained crystallization product, removed template method, described template is polyethylene glycol oxide-PPOX-polyethylene glycol oxide triblock copolymer.
According to the present invention, described tetramethoxy-silicane and acidic aqueous solution Contact Temperature can be 10-60 ℃, are preferably 15-55 ℃; Can be 10-72 hour time of contact, is preferably 10-24 hour, finally can make with this understanding the structure homogeneous, spherical complete of hollow mesoporous silicon oxide.
According to the present invention, the kind of described acidic aqueous solution has no particular limits, and its pH value can be 1-6, more preferably 3-5.Preferably, described acidic aqueous solution is the cushioning liquid of acetic acid and sodium acetate, the addition of described acidic aqueous solution has no particular limits, as long as guarantee that described template, trimethylpentane, ethanol and tetramethoxy-silicane can under agitation disperse uniformly.Concrete, the pH value of the cushioning liquid of described acetic acid and sodium acetate is 4.4; With respect to 1 gram of described template, the consumption of described acidic aqueous solution is 26-30 milliliter, described polyethylene glycol oxide-PPOX-polyethylene glycol oxide triblock copolymer, ethanol, 2,2, the weight ratio of 4-trimethylpentane and tetramethoxy-silicane is 1: 1-3: 3-10: 1-5.
Method and the condition of described crystallization and removed template method are known to the skilled person, and for example, the temperature of crystallization can be 30-150 ℃, the time of crystallization can be 10-72 hour, preferably, the temperature of crystallization is 50-80 ℃, and the time of crystallization is 20-26 hour.
In the present invention, the heating of gained crystallization product is had no particular limits with the condition of removed template method, for example, can at 200-600 ℃, calcine 10-80 hour, preferably at 400-600 ℃, calcine 10-80 hour.
According to the present invention, described polyethylene glycol oxide-PPOX-polyethylene glycol oxide triblock copolymer can be various polyethylene glycol oxide-PPOXs-polyethylene glycol oxide triblock copolymer template of this area routine, can be commercially available, for example, the P123 type triblock copolymer that Aldrich company produces.
According to the present invention, wherein said acidic ion liquid is preferably and contains sulfonic ionic liquid, described in contain cation in sulfonic ionic liquid can for 1-sulfonic alkyl-3-alkyl imidazole cation, 1-sulfonic acid aryl-3-alkyl imidazole cation, 1-sulfonic acid aralkyl-3-alkyl imidazole cationic one or more; Described 3-alkyl can be the alkyl of carbon number 1-12, described 1-sulfonic alkyl can be the alkyl of the carbon number 1-12 that on carbon, hydrogen atom is replaced by 1 sulfonic group, described 1-sulfonic acid aryl can be the aryl of the carbon number 6-12 that on carbon, hydrogen atom is replaced by 1 sulfonic group, and described 1-sulfonic acid aralkyl can be the aralkyl of the carbon number 7-12 that on aromatic ring carbon, hydrogen atom is replaced by 1 sulfonic group; Preferably, described 3-alkyl is the alkyl of carbon number 1-4, described 1-sulfonic alkyl is the alkyl of the carbon number 1-4 that on carbon, hydrogen atom is replaced by 1 sulfonic group, described 1-sulfonic acid aryl is the aryl of the carbon number 6-8 that on carbon, hydrogen atom is replaced by 1 sulfonic group, described 1-sulfonic acid aralkyl is that (for example, described alkyl is selected from methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group etc. for the aralkyl of the carbon number 7-8 that on aromatic ring carbon, hydrogen atom is replaced by 1 sulfonic group; Described aryl is selected from phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl etc.; Described aralkyl is selected from benzyl, phenethyl etc.); The described anion containing in sulfonic ionic liquid is sulfate ion, hydrogen sulfate ion, halogen ion, PF 6 -, one or more in borate ion, tetrafluoroborate ion, alkyl sulfonate ion, fluoroform alkyl sulfonate radical, p-methyl benzenesulfonic acid radical ion; Described alkyl sulfonate ion can be in methanesulfonate ions, ethylsulfonic acid radical ion, n-pro-pyl sulfonate ion, isopropyl sulfonate ion, normal-butyl sulfonate ion, isobutyl group sulfonate ion etc. one or more.Concrete, described to contain sulfonic ionic liquid can be 1-(4-sulfonic group) butyl-3-methylimidazole disulfate, 1-(4-sulfonic group) butyl-3-methylimidazole metilsulfate, 1-(4-sulfonic group) butyl-3-methylimidazole fluoroform sulphonate, 1-(4-sulfonic group) butyl-3-methylimidazole tosilate etc., and containing sulfonic ionic liquid described in is more preferably 1-(4-sulfonic group) butyl-3-methylimidazole disulfate and/or 1-(4-sulfonic group) butyl-3-methylimidazole metilsulfate.Above-describedly contain sulfonic ionic liquid and can prepare by means commonly known in the art, for example, according to document J.of Am.Chem.Soc., 2002,124 (21), 5962-5963; Journal of MolecularCatalysis A:Chemical.2005,225 (1), 27-31; " petrochemical industry ", 2007,36 (10), 975-984; " chemical industry progress ", 2008 (27), 438-441; " petrochemical industry " 2009,38 (1), 20-29; The Gao Lei work master thesis " SO of Dalian University of Technology 3synthetic and the catalytic performance research of H-functionalized ion liquid ", 2009, wait recorded preparation method to prepare.
The invention provides the preparation method of above-mentioned support type acidic ionic liquid catalysts, the method comprises acidic ion liquid is loaded on hollow ball-shape meso-porous titanium dioxide silicon carrier, the average particulate diameter of described hollow ball-shape meso-porous titanium dioxide silicon carrier is 3-20 micron, specific area is 200-300 meters squared per gram, pore volume is 0.5-1.5 ml/g, and most probable aperture is 3-20 nanometer.Wherein, first the method prepares described hollow ball-shape meso-porous titanium dioxide silicon carrier, prepares method, condition and the preferable case of described hollow ball-shape meso-porous titanium dioxide silicon carrier as hereinbefore, and therefore not to repeat here.
According to the preparation method of support type acidic ionic liquid catalysts of the present invention, wherein, the method loads on above-mentioned acidic ion liquid on hollow ball-shape meso-porous titanium dioxide silicon carrier, and mode of loading comprises described hollow ball-shape mesoporous silicon oxide carrier impregnation in the solution that contains acidic ion liquid.To described solvent, there is no particular limitation in the present invention, as long as can dissolve preferably acidic ion liquid, can be selected from one or more in methyl alcohol, ethanol, isopropyl alcohol, normal propyl alcohol, n-butanol, n-amyl alcohol, cyclohexanol, acetone and acetic acid, be preferably ethanol; The weight ratio that described hollow ball-shape meso-porous titanium dioxide silicon carrier, solvent and acidic ion liquid add is 1: 2-200: 0.1-10, is preferably 1: 15-30: 2-8.
According to the preparation method of support type acidic ionic liquid catalysts of the present invention, wherein, the condition of described dipping can in very large range change, for example, can, at 25-120 ℃, preferably, at 25-50 ℃, hollow ball-shape mesoporous silicon oxide be immersed in the solution that contains acidic ion liquid, the time of dipping can be 5-80 hour, is preferably 10-40 hour.
According to the preparation method of support type acidic ionic liquid catalysts of the present invention, wherein, the method has also comprised after dipping that to load the hollow ball-shape meso-porous titanium dioxide silicon carrier of acidic ion liquid filters and is dried, filtration and drying mode can adopt method well known in the art, for example, be filtered into suction filtration; Be dried as vacuum drying, baking temperature can be 60-100 ℃, and can be 4-8h drying time.
According to one embodiment of the present invention, support type acidic ionic liquid catalysts of the present invention method as follows makes:
(1) template, ethanol, the acetic acid of pH value 3-5 and the cushioning liquid of sodium acetate being stirred at 15-35 ℃ of temperature to template dissolves;
(2) 2,2,4-trimethylpentane is added in the solution of step (1) gained and stir 6-10h at 15-35 ℃ of temperature;
(3) tetramethoxy-silicane is added in the solution of step (2) gained and stir 10-30h at 15-35 ℃ of temperature;
(4) step (3) products therefrom crystallization under crystallization condition, comprises crystallization temperature 45-80 ℃, crystallization time 15-40h;
(5) by the heating of step (4) gained crystallization product, removed template method, obtains hollow ball-shape meso-porous titanium dioxide silicon carrier, and heating-up temperature is 400-600 ℃, heat time 15-40h;
(6) at 25-50 ℃, stir 10-40h by the hollow ball-shape meso-porous titanium dioxide silicon carrier after the removed template method of step (5) gained, ethanol with containing sulfonic ionic liquid, obtain support type acidic ionic liquid catalysts after dry.
The consumption of each composition is described above, no longer repeats at this.
In addition, the present invention also provides the application of above-mentioned support type acidic ionic liquid catalysts in esterification, described support type acidic ionic liquid catalysts can the monohydric alcohol of catalyzed carbon atomicity 1-10 and the monacid esterification of carbon number 1-18, the preferably monacid esterification of the monohydric alcohol of catalyzed carbon atomicity 1-4 and carbon number 1-18; As described in alcohol can be methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, n-amyl alcohol, n-hexyl alcohol, ring propyl alcohol, cyclohexanol or phenmethylol etc., described acid can be formic acid, acetic acid, propionic acid, isopropyl acid, butyric acid, valeric acid, caproic acid, oleic acid or benzoic acid etc.; The condition of esterification can be selected according to alcohol, acid constituents by those skilled in the art.
In addition, the present invention also provides a kind of preparation method of ethyl acetate, wherein, the method comprises: under the existence of catalyst, under the condition of esterification, acetic acid is contacted, to obtain ethyl acetate with ethanol, wherein, described catalyst is support type acidic ionic liquid catalysts provided by the invention.
According to the present invention, in esterification, the mol ratio of acetic acid and ethanol can in very large range change, and for example, the mol ratio of acetic acid and ethanol can be 1: 0.5-10.The consumption of described support type acidic ionic liquid catalysts has no particular limits, those skilled in the art can carry out suitable adjustment according to the needs of reaction, but under preferable case, in the acidic ion liquid of load in catalyst, with respect to the acetic acid of 100 weight portions, the consumption of described catalyst is 1-20 weight portion, more preferably 5-10 weight portion.
In the present invention, the condition of described esterification is conventionally known to one of skill in the art, for example, the condition of described esterification can comprise: the temperature of reaction is 60-150 ℃, and the time of reaction is 1-72 hour, preferably, the temperature of reaction is 65-100 ℃, and the time of reaction is 3-8 hour.The temperature that maintains esterification can be undertaken by the various known methods in this area, for example oil bath heating, and 100 ℃ with interior available heating water bath.
The present invention also provides a kind of preparation method of methyl oleate, and wherein, the method comprises: under the existence of described catalyst, under the condition of esterification, oleic acid is contacted, to obtain methyl oleate with methyl alcohol, wherein, described catalyst is support type acidic ionic liquid catalysts provided by the invention.
According to the present invention, in esterification, the mol ratio of oleic acid and methyl alcohol can in very large range change, and for example, the mol ratio of oleic acid and methyl alcohol can be 1: 0.5-10.The consumption of described support type acidic ionic liquid catalysts has no particular limits, those skilled in the art can carry out suitable adjustment according to the needs of reaction, but under preferable case, in the acidic ion liquid of load in catalyst, with respect to the oleic acid of 100 weight portions, the consumption of described catalyst is 1-10 weight portion, more preferably 1-5 weight portion.
In the present invention, the condition of described esterification is conventionally known to one of skill in the art, for example, the condition of described esterification can comprise: the temperature of reaction is 60-150 ℃, and the time of reaction is 1-72 hour, preferably, the temperature of reaction is 65-100 ℃, and the time of reaction is 3-8 hour.The temperature that maintains esterification can be undertaken by the various known methods in this area, for example oil bath heating, and 100 ℃ with interior available heating water bath.
According to the present invention, after esterification finishes, can carry out centrifugation to final reactant mixture, by the centrifugal solid formation obtaining vacuum drying 1-24 hour at 25-200 ℃, preferably vacuum drying 4-12 hour at 50-80 ℃, the catalyst that can be recycled.
Below in conjunction with embodiment, the present invention is described in detail.
In following examples, X-ray diffraction analysis carries out on the X-ray diffractometer that is D8Advance purchased from the model of German Bruker AXS company; In the SEM that scanning electron microscope analysis is XL-30 in the model purchased from FEI Co. of the U.S., carry out.The elementary analysis of catalyst adopts wavelength dispersion X ray fluorescence spectra (WDXRF) analytical method, on the Axios-Advanced wavelength dispersion X-ray fluorescence spectrometer of Dutch PANalytical BV company, carries out.
Nitrogen adsorption-desorption experiment condition comprises: the U.S. Autosorb-1 of Kang Ta company nitrogen adsorption desorption instrument, sample is degassed 4 hours at 200 ℃.
Embodiment 1
(1) preparation of hollow ball-shape meso-porous titanium dioxide silicon carrier
By 1.0 grams of polyethylene glycol oxide-PPOX-polyethylene glycol oxide triblock copolymer (Aldrich companies, P123) and 1.69 grams of ethanol join in the acetic acid of pH=4.4 and the cushioning liquid of sodium acetate of 28ml, at 15 ℃, being stirred to polyethylene glycol oxide-PPOX-polyethylene glycol oxide dissolves completely, afterwards by 6 grams 2, 2, 4-trimethylpentane joins in above-mentioned solution, 15 ℃ were stirred after 8 hours, again 2.13 grams of tetramethoxy-silicanes are joined in above-mentioned solution, 15 ℃ were stirred after 20 hours, solution is transferred in teflon-lined reactor, at 60 ℃ baking oven crystallization after 24 hours through filtration, distilled water washing, after dry, obtain the former powder of hollow ball-shape mesoporous silicon oxide.
Former hollow ball-shape mesoporous silicon oxide powder is calcined 24 hours at 550 ℃ in muffle furnace, obtained hollow ball-shape mesoporous silicon oxide (called after MS).
(2) preparation of support type acidic ionic liquid catalysts
At 35 ℃, 1 gram of hollow ball-shape mesoporous silicon oxide and 5 gram-ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfates (ILa) are stirred 24 hours in 30ml ethanol, after filtering and being dried, obtain supported ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate hollow ball-shape mesoporous silicon oxide (called after MS-ILa-1), after load, quality is 1.72 grams.Learn according to calculating, take the gross weight of this catalyst as benchmark, the content of described 1-(4-sulfonic group) butyl-3-methylimidazole disulfate is 42 % by weight, and the content of described hollow ball-shape meso-porous titanium dioxide silicon carrier is 58 % by weight.
This support type acidic ionic liquid catalysts is characterized with XRD, nitrogen adsorption-desorption experiment and ESEM.
Fig. 1 is the x-ray diffraction pattern of hollow ball-shape mesoporous silicon oxide (MS); The x-ray diffraction pattern of the hollow ball-shape mesoporous silicon oxide (MS-ILa-1) of Fig. 2 is load ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate; The hollow ball-shape mesoporous silicon oxide (MS-ILa-2a) of Fig. 3 is load ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate is at the reacted x-ray diffraction pattern of quadric catalysis.From XRD spectra, can find out significantly, hollow ball-shape mesoporous silicon oxide (Fig. 1), load the hollow ball-shape mesoporous silicon oxide (Fig. 2) of ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate, the reacted load of quadric catalysis the collection of illustrative plates of hollow ball-shape mesoporous silicon oxide (Fig. 3) of ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate, all there is good hexagonal hole road structure.
Fig. 4 is the nitrogen Adsorption and desorption isotherms of hollow ball-shape mesoporous silicon oxide (MS); The nitrogen Adsorption and desorption isotherms of the hollow ball-shape mesoporous silicon oxide (MS-ILa-1) of Fig. 5 is load ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate.Can be found out by spectrogram, sample has the IV type thermoisopleth of sharp-pointed capillary condensation speed, and this thermoisopleth has H1 hysteresis loop, and this shows that sample has the aperture size distribution of homogeneous (concrete data provide in table 1).
The stereoscan photograph of Fig. 6 hollow ball-shape mesoporous silicon oxide (MS); The stereoscan photograph of the hollow ball-shape mesoporous silicon oxide (MS-ILa-1) of Fig. 7 is load ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate.As seen from the figure, sample is hollow ball-shape mesoporous silicon oxide before supported ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate, particle diameter is at 3-20 micron, after supported ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate, the particle diameter 5-20 micron of sample.
Table 1
Figure BSA00000518357600121
Data by upper table 1 can be found out, hollow ball-shape mesoporous silicon oxide is after load acidic ion liquid, specific area, pore volume and most probable aperture all reduce, and this explanation acidic ion liquid in load-reaction process enters into the duct of hollow ball-shape mesoporous silicon oxide and the inside of ball.Show that by xrf analysis the content of element sulphur in support type acidic ionic liquid catalysts is that the content of 7.9 % by weight, carbon is 11.8 % by weight.
Embodiment 2
Prepare support type acidic ionic liquid catalysts according to the method for embodiment 1, different is, acidic ion liquid is 5 grams of 1-(4-sulfonic group) butyl-3-methylimidazole metilsulfate, obtain support type acidic ionic liquid catalysts (called after MS-ILb-1), dry rear quality is 1.61 grams.Learn according to calculating, take the gross weight of this catalyst as benchmark, the content of described 1-(4-sulfonic group) butyl-3-methylimidazole metilsulfate is 38 % by weight, and the content of described hollow ball-shape meso-porous titanium dioxide silicon carrier is 62 % by weight.
This support type acidic ionic liquid catalysts is characterized with XRD, nitrogen adsorption-desorption experiment and ESEM, result obtains: x-ray diffraction pattern, nitrogen Adsorption and desorption isotherms and the stereoscan photograph of catalyst MS-ILb-1 are all similar to catalyst MS-ILa-1, and structural parameters as shown in Table 1; Show that by xrf analysis the content of element sulphur in support type acidic ionic liquid catalysts is that the content of 7.1 % by weight, carbon is 13.4 % by weight.
Comparative example 1
Prepare support type acidic ionic liquid catalysts according to the method for embodiment 1, different is, 1 gram of hollow ball-shape mesoporous silicon oxide is replaced by 1 gram of industrial silicone ES955, obtains reference support type acidic ionic liquid catalysts (called after GJ-ILa-1), and dry rear quality is 1.22 grams.Learn according to calculating, take the gross weight of this catalyst as benchmark, the content of described 1-(4-sulfonic group) butyl-3-methylimidazole disulfate is 18 % by weight, and the content of described silica supports is 82 % by weight.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE be used for explanation according to load of the present invention the catalytic activity of catalyst of ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate.
By MS-ILa-1 vacuum drying 6 hours at 75 ℃, be cooled to after room temperature, take 1.5 grams, then take 23 grams of ethanol and 15 grams of acetic acid, and put into successively in the there-necked flask of 100ml, 90 ℃ of oil bath heating, under refluxing, stirring reaction 4 hours, is cooled to after room temperature centrifugation, after filtering and being dried, reclaim solid catalyst wherein.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
EXPERIMENTAL EXAMPLE 2
By after the catalyst recovery of used load-type ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate in EXPERIMENTAL EXAMPLE 1, vacuum drying 6 hours (called after MS-ILa-2a) at 75 ℃, method according to EXPERIMENTAL EXAMPLE 1 catalyzes and synthesizes ethyl acetate, different is that MS-ILa-1 is replaced by MS-ILa-2a, utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE be used for explanation according to load of the present invention the catalytic activity of catalyst of ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate.
By MS-ILa-1 vacuum drying 6 hours at 75 ℃, be cooled to after room temperature, take 0.5 gram, then take 4.6 grams of ethanol and 6.0 grams of acetic acid, and put into successively in the there-necked flask of 50ml, 100 ℃ of oil bath heating, under refluxing, stirring reaction 1 hour, is cooled to after room temperature centrifugation, after filtering and being dried, reclaim solid catalyst wherein.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
EXPERIMENTAL EXAMPLE 4
By after the catalyst recovery of used load-type ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate in EXPERIMENTAL EXAMPLE 3, vacuum drying 6 hours (called after MS-ILa-2b) at 75 ℃ again, method according to EXPERIMENTAL EXAMPLE 3 catalyzes and synthesizes ethyl acetate, and different is that MS-ILa-1 is replaced by MS-ILa-2b catalyst.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
Experiment comparative example 1
Method according to EXPERIMENTAL EXAMPLE 3 is prepared ethyl acetate, and different is that the GJ-ILa-1 that MS-ILa-1 is prepared by the comparative example 1 of identical weight replaces.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
Experiment comparative example 2
To test the catalyst recovery of used load-type ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate in comparative example 1, and vacuum drying 6 hours (called after GJ-ILa-2a) at 75 ℃, method according to experiment comparative example 1 is prepared ethyl acetate, and different is that GJ-ILa-1 is replaced by GJ-ILa-2a catalyst.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
Experiment comparative example 3
Method according to EXPERIMENTAL EXAMPLE 3 is prepared ethyl acetate, and different is that the concentrated sulfuric acid that MS-ILa-1 is 98 % by weight by the concentration of 0.1 gram replaces.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
Test blank example 1
Method according to EXPERIMENTAL EXAMPLE 3 is prepared ethyl acetate, and different is not use catalyst.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
EXPERIMENTAL EXAMPLE 5
This EXPERIMENTAL EXAMPLE is used for having illustrated according to load of the present invention the catalytic activity of ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole pyrovinic acid salt catalyst.
Carry out according to the method for EXPERIMENTAL EXAMPLE 1, be not all and use the MS-ILb-1 of identical weight to replace MS-ILa-1, utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
EXPERIMENTAL EXAMPLE 6-9
By the catalyst recovery of used load-type ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole metilsulfate in EXPERIMENTAL EXAMPLE 5, before each esterification, at 75 ℃, vacuum drying 6 hours is (according to reusable number of times after catalyst recovery, naming respectively catalyst is MS-ILb-2, MS-ILb-3, MS-ILb-4 and MS-ILb-5), method according to EXPERIMENTAL EXAMPLE 5 catalyzes and synthesizes ethyl acetate, utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
EXPERIMENTAL EXAMPLE 10
This EXPERIMENTAL EXAMPLE is used for having illustrated according to load of the present invention the catalytic activity of ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate catalyst.
By MS-ILa-1 vacuum drying 6 hours at 75 ℃, be cooled to after room temperature, take 0.5 gram, take again 3.2 grams of methyl alcohol and 28.2 grams of oleic acid, and put into successively in the there-necked flask of 100ml, 100 ℃ of oil bath heating, stirring reaction 6 hours under refluxing, be cooled to after room temperature, centrifugation, after filtering and being dried, reclaims solid catalyst wherein, utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 3.
EXPERIMENTAL EXAMPLE 11
By after the catalyst recovery of used load-type ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate in EXPERIMENTAL EXAMPLE 10, vacuum drying 6 hours (called after MS-ILa-2c) at 75 ℃, method according to EXPERIMENTAL EXAMPLE 10 catalyzes and synthesizes methyl oleate, different is that MS-ILa-1 is replaced by MS-ILa-2c, utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 3.
Experiment comparative example 4
Method according to EXPERIMENTAL EXAMPLE 10 is prepared methyl oleate, and different is that the GJ-ILa-1 that MS-ILa-1 is prepared by the comparative example 1 of identical weight replaces.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 3.
Experiment comparative example 5
To test the catalyst recovery of used load-type ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate in comparative example 4, and vacuum drying 6 hours (called after GJ-ILa-2b) at 75 ℃, method according to experiment comparative example 4 is prepared methyl oleate, different, GJ-ILa-1 is replaced by GJ-ILa-2b catalyst.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 3.
Test blank example 2
Method according to EXPERIMENTAL EXAMPLE 10 is prepared methyl oleate, and different is not use catalyst.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 3.
Table 2
Figure BSA00000518357600181
Table 3
Figure BSA00000518357600182
Data by above embodiment can find out, by acidic ion liquid being carried on hollow ball-shape meso-porous titanium dioxide silicon carrier, the catalytic performance of the support type acidic ionic liquid catalysts of acquisition is better.
Learn from table 2, embodiment 1-9 and experiment comparative example 1-3 and the data comparison of testing blank example 1 by experiment, can find out when the different catalyst containing sulfonic acidic ion liquid of application load provided by the invention carrys out the esterification of catalysis acetic acid and ethanol, improve significantly the conversion ratio of acetic acid in esterification, effectively utilize reactant acetic acid, simultaneously side reaction does not also produce corrosion to equipment less, and this catalyst can be through reclaiming Reusability, aftertreatment technology is simple.The data comparison of embodiment 3-4 and experiment comparative example 1-2 by experiment, although the catalyst GJ-ILa-1 of catalyst MS-ILa-1 provided by the invention and contrast is under identical esterification condition first when catalysis acetic acid and ethanol synthesis, can obtain the conversion ratio of suitable acetic acid, but after catalyst recovery recycling, catalyst MS-ILa-2b provided by the invention is better than the catalyst GJ-ILa-2a of contrast.
Learn from table 3, embodiment 10-11 and experiment comparative example 4-5 and the data comparison of testing blank example 2 by experiment, can find out while carrying out the esterification of catalysis oleic acid and methyl alcohol with load provided by the invention containing the catalyst of sulfonic acidic ion liquid, can improve significantly the conversion ratio of methyl alcohol in esterification, utilize fully reactant methanol, and this catalyst can Reusability after reclaiming.The data comparison of embodiment 10-11 and experiment comparative example 4-5 by experiment, although the catalyst GJ-ILa-1 of catalyst MS-ILa-1 provided by the invention and contrast is under identical esterification condition when catalysis oleic acid and methyl alcohol reaction first, can obtain the conversion ratio of suitable formic acid, but after catalyst recovery recycling, catalyst MS-ILa-2c provided by the invention is better than the catalyst GJ-ILa-2b of contrast.

Claims (20)

1. a support type acidic ionic liquid catalysts, it is characterized in that, this catalyst comprises hollow ball-shape meso-porous titanium dioxide silicon carrier and loads on the acidic ion liquid on this hollow ball-shape meso-porous titanium dioxide silicon carrier, the average particulate diameter of described hollow ball-shape meso-porous titanium dioxide silicon carrier is 3-20 micron, specific area is 200-300 meters squared per gram, pore volume is 0.5-1.5 ml/g, and most probable aperture is 3-20 nanometer; Take the gross weight of this catalyst as benchmark, the content of described acidic ion liquid is 10-60 % by weight, and the content of described hollow ball-shape meso-porous titanium dioxide silicon carrier is 40-90 % by weight.
2. catalyst according to claim 1, wherein, take the gross weight of this catalyst as benchmark, the content of described acidic ion liquid is 35-45 % by weight, the content of described hollow ball-shape meso-porous titanium dioxide silicon carrier is 55-65 % by weight.
3. catalyst according to claim 1 and 2, wherein, the average particulate diameter of described catalyst is 5-20 micron, and specific area is 190-270 meters squared per gram, and pore volume is 0.4-0.7 ml/g, and most probable aperture is 2-9.7 nanometer.
4. catalyst according to claim 3, wherein, the average particulate diameter of described catalyst is 5-15 micron, and specific area is 250-260 meters squared per gram, and pore volume is 0.45-0.6 ml/g, and most probable aperture is 2.5-3.5 nanometer.
5. catalyst according to claim 1 and 2, wherein, described hollow ball-shape meso-porous titanium dioxide silicon carrier is prepared by the method comprising the steps: at template, 2, under the existence of 2,4-trimethylpentane and ethanol, tetramethoxy-silicane is contacted with acidic aqueous solution, and gained mixture crystallization under crystallization condition after contacting, by the heating of gained crystallization product, removed template method, described template is polyethylene glycol oxide-PPOX-polyethylene glycol oxide triblock copolymer; The condition of described contact comprises: Contact Temperature 10-60 ℃, time of contact 10-72 hour; Described acidic aqueous solution is the cushioning liquid of acetic acid and sodium acetate, and the pH value of described cushioning liquid is 1-6; With respect to 1 gram of described template, the consumption of described acidic aqueous solution is 26-30 milliliter; The condition of described crystallization comprises: crystallization temperature is 30-150 ℃, and crystallization time is 10-72 hour; Described polyethylene glycol oxide-PPOX-polyethylene glycol oxide triblock copolymer, ethanol, 2,2, the weight ratio of 4-trimethylpentane and tetramethoxy-silicane is 1:1-3:3-10:1-5.
6. catalyst according to claim 1, wherein, described acidic ion liquid is for containing sulfonic ionic liquid, described in contain cation in sulfonic ionic liquid be 1-sulfonic alkyl-3-alkyl imidazole cation, 1-sulfonic acid aryl-3-alkyl imidazole cation, 1-sulfonic acid aralkyl-3-alkyl imidazole cationic one or more; The described anion containing in sulfonic ionic liquid is sulfate ion, hydrogen sulfate ion, halogen ion, PF 6 -, one or more in borate ion, tetrafluoroborate ion, alkyl sulfonate ion, fluoroform alkyl sulfonate radical, p-methyl benzenesulfonic acid radical ion.
7. catalyst according to claim 6, wherein, described in to contain sulfonic ionic liquid be 1-(4-sulfonic group) butyl-3-methylimidazole disulfate and/or 1-(4-sulfonic group) butyl-3-methylimidazole metilsulfate.
8. the preparation method of the support type acidic ionic liquid catalysts described in any one in claim 1-7, the method comprises acidic ion liquid is loaded on hollow ball-shape meso-porous titanium dioxide silicon carrier, the average particulate diameter of described hollow ball-shape meso-porous titanium dioxide silicon carrier is 3-20 micron, specific area is 200-300 meters squared per gram, pore volume is 0.5-1.5 ml/g, and most probable aperture is 3-20 nanometer.
9. method according to claim 8, wherein, the described mode that acidic ion liquid is loaded on hollow ball-shape meso-porous titanium dioxide silicon carrier comprises that by described hollow ball-shape mesoporous silicon oxide carrier impregnation the solvent in the solution that contains acidic ion liquid is one or more in methyl alcohol, ethanol, isopropyl alcohol, normal propyl alcohol, n-butanol, n-amyl alcohol, cyclohexanol, acetone and acetic acid in the solution that contains acidic ion liquid; The weight ratio that described hollow ball-shape meso-porous titanium dioxide silicon carrier, solvent and acidic ion liquid add is 1:2-200:0.1-10.
10. method according to claim 9, wherein, described in contain acidic ion liquid solution in solvent be ethanol.
11. methods according to claim 9, wherein, the weight ratio that described hollow ball-shape meso-porous titanium dioxide silicon carrier, solvent and acidic ion liquid add is 1:15-30:2-8.
12. methods according to claim 8, wherein, the condition of described dipping comprises: dipping temperature is 25-120 ℃, dip time is 5-80 hour.
13. methods according to claim 12, wherein, the condition of described dipping comprises: dipping temperature is 25-50 ℃, dip time is 10-40 hour.
The application of support type acidic ionic liquid catalysts in 14. claim 1-7 described in any one in esterification.
The preparation method of 15. 1 kinds of ethyl acetate, wherein, the method comprises: under the existence of catalyst, under the condition of esterification, acetic acid is contacted, to obtain ethyl acetate with ethanol, it is characterized in that, described catalyst is the catalyst described in any one in claim 1-7.
16. methods according to claim 15, wherein, the mol ratio of acetic acid and ethanol is 1:0.5-10, and in the acidic ion liquid of load in catalyst, with respect to the acetic acid of 100 weight portions, the amount of described catalyst is 1-20 weight portion.
17. methods according to claim 16, wherein, with respect to the acetic acid of 100 weight portions, the amount of described catalyst is 5-10 weight portion.
The preparation method of 18. 1 kinds of methyl oleates, wherein, the method comprises: under the existence of catalyst, under the condition of esterification, oleic acid is contacted, to obtain methyl oleate with methyl alcohol, it is characterized in that, described catalyst is the catalyst described in any one in claim 1-7.
19. methods according to claim 18, wherein, the mol ratio of oleic acid and methyl alcohol is 1:0.5-10, and in the acidic ion liquid of load in catalyst, with respect to the oleic acid of 100 weight portions, the amount of described catalyst is 1-10 weight portion.
20. methods according to claim 19, wherein, in the acidic ion liquid of load in catalyst, with respect to the oleic acid of 100 weight portions, the amount of described catalyst is 1-5 weight portion.
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