CN102814195A - 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 PDFInfo
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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
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 is claimed ethyl acetate again.Pure ethyl acetate is the liquid that water white transparency has aromatic odor; It is a kind of broad-spectrum fine chemical product; Have 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, be used for products such as coating, adhesive, ethyl cellulose, artificial leather, malthoid colouring agent, staple fibre; As adhesive, be used for the production of printing-ink, olivet; As extractant, be used for the production of products such as medicine, organic acid.
Mesoporous material has bigger specific area, bigger aperture and a large amount of high activity surface hydroxyls; Help organic active group fully contacting between assembling and reactant and active sites in its hole; So be used as carrier more; As synthetic grafting method behind the humans such as Udayshankar G.Singh 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 at first because of its unique physicochemical properties as the green reaction medium; And it uses this category head and shoulders above now; They as the control catalyst for reaction more and more come into one's own (referring to Zhang Qinghua, Wang Ruifeng, Li Zuopeng etc. the progress of ionic liquid application in green catalysis and cleaning are synthetic. petrochemical industry; 2007,36 (10): 975-984).Wan Hui etc. adopt bonding grafting method; Vinyl imidazole class acidic ion liquid is linked in the silica gel; With its as catalyst synthesized butyl acetate (referring to ten thousand brightness, Zhang Jishen, Guan Guofeng. bonding grafting method prepares immobilized acidic ion liquid and catalysis Synthesis of n-Butyl Acetate thereof. petrochemical industry; 2009,38 (2): 134-138).
Several kinds of modes below the prior synthesizing method of ethyl acetate adopts usually: (1) is under the catalysis of homogeneous catalyst (sulfuric acid); Synthetic through esterification process, but shortcoming such as the shortcoming that this method exists is that sulfuric acid is serious to the rotten erosion of equipment, side reaction is many and the discharging of waste liquid amount is big; (2) use the polymerization of presence of acidic ionic liquid catalyst ethyl acetate separately, have the shortcoming of the big and separation difficulty of acidic ion liquid consumption; (3) the acidic ion liquid bonding is grafted to catalysis ethyl acetate polymerization on the carrier such as silica gel,, has that reagent cost is high, the longer problem of synthesis step through chemical b ` grafting acidic ion liquid.
In addition, be carrier loaded ion liquid catalyst with silica gel in the prior art, because the aperture of silica-gel carrier is unfavorable for that for a short time carboxylic acid and alcohol that molecular weight is bigger carry out esterification.For example, be unfavorable for oleic acid and pure esterification.
Summary of the invention
First purpose of the present invention is to overcome the shortcoming that the existing catalyst that is used for the catalysis synthesizing ethyl acetate exists, and a kind of a kind of support type acidic ionic liquid catalysts that not etching apparatus, side reaction are few, aftertreatment technology is simple and catalyst can be recycled of utilizing the preparation of back loading method is provided.
Second purpose of the present invention provides the preparation method of this support type acidic ionic liquid catalysts.
The 3rd purpose of the present invention provides this application of support type acidic ionic liquid catalysts in esterification.
The 4th purpose of the present invention provides a kind of preparation method of ethyl acetate.
The 5th purpose of the present invention provides a kind of preparation method of methyl oleate.
The present 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, and the average particulate diameter of said hollow ball-shape meso-porous titanium dioxide silicon carrier is the 3-20 micron, and specific area is the 200-300 meters squared per gram; Pore volume is 0.5-1.5 milliliter/gram, and the most probable aperture is the 3-20 nanometer.
The present invention provides the preparation method of above-mentioned support type acidic ionic liquid catalysts; This method comprises acidic ion liquid is loaded on the hollow ball-shape meso-porous titanium dioxide silicon carrier; The average particulate diameter of said hollow ball-shape meso-porous titanium dioxide silicon carrier is the 3-20 micron; Specific area is the 200-300 meters squared per gram, and pore volume is 0.5-1.5 milliliter/gram, and the most probable aperture is the 3-20 nanometer.
The present invention provides the application of above-mentioned support type acidic ionic liquid catalysts in esterification.
The present invention provides a kind of preparation method of ethyl acetate, and wherein, this method comprises: in the presence of catalyst; Under the condition of esterification, acetate is contacted, with ethanol to obtain ethyl acetate; Wherein, said 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, this method comprises: in the presence of catalyst; Under the condition of esterification, oleic acid is contacted, with methyl alcohol to obtain methyl oleate; Wherein, said catalyst is above-mentioned support type acidic ionic liquid catalysts.
Support type acidic ionic liquid catalysts provided by the invention is compared with independent use ionic liquid, can either obtain suitable catalytic activity, can make the catalyst recycling again, obviously reduces ion liquid consumption; Be grafted to silica gel with existing ionic liquid and compare, can either obtain higher catalytic activity, and the Preparation of catalysts method is simple, easily operation.
Prove that through experimental data the support type acidic ionic liquid catalysts of the present invention preparation is the esterification of catalysis acetate and ethanol efficiently, its reactant acetate conversion ratio is near 100%, and side reaction is few, and the ethyl acetate selectivity is near 100%; Catalyst does not produce corrosion to equipment; And this support type acidic ionic liquid catalysts can be passed through simple process and reclaimed and in the catalysis synthesizing ethyl acetate, use repeatedly 5 times, and its reactant acetate conversion ratio still has 98%, the ethyl acetate selectivity is near 100%.
Experimental data also explains, the support type acidic ionic liquid catalysts of the present invention's preparation 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 the methyl oleate selectivity is near 100%; This support type acidic ionic liquid catalysts can be passed through that simple process reclaims and in the synthetic methyl oleate of catalysis, reused, and its reactant methanol conversion ratio still has 92%, the methyl oleate selectivity is near 100%.
Description of drawings
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 desorption thermoisopleth of hollow ball-shape mesoporous silicon oxide (MS); The nitrogen adsorption desorption thermoisopleth 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 present 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, and the average particulate diameter of said hollow ball-shape meso-porous titanium dioxide silicon carrier can be the 3-20 micron, and specific area can be the 200-300 meters squared per gram; Pore volume can be 0.5-1.5 milliliter/gram, and the most probable aperture can be the 3-20 nanometer; Preferably, the average particulate diameter of said hollow ball-shape meso-porous titanium dioxide silicon carrier can be the 5-10 micron, and specific area can be the 240-270 meters squared per gram, and pore volume can be 0.7-1.0 milliliter/gram, and the most probable aperture can be the 8-12 nanometer.Among the present invention, the specific area of carrier and catalyst, pore volume and most probable aperture record through the nitrogen adsorption desorption method.
According to the present invention; Although can realize the object of the invention as long as said acidic ion liquid loaded on the said hollow ball-shape meso-porous titanium dioxide silicon carrier; But under the preferable case; Gross weight with this catalyst is a benchmark, and the content of said acidic ion liquid is 10-60 weight %, and the content of said hollow ball-shape meso-porous titanium dioxide silicon carrier is 40-90 weight %; More preferably, be benchmark with the gross weight of this catalyst, the content of said acidic ion liquid is 35-45 weight %, the content of said hollow ball-shape meso-porous titanium dioxide silicon carrier is 55-65 weight %.
According to the present invention; The average particulate diameter of said support type acidic ionic liquid catalysts (being the said hollow ball-shape mesoporous silicon oxide behind the load acidic ion liquid) can be the 5-20 micron; Specific area can be the 190-270 meters squared per gram; Pore volume can be 0.4-0.7 milliliter/gram, and the most probable aperture can be the 2.0-9.7 nanometer; Preferably, said catalyst average particulate diameter be the 5-15 micron, specific area is the 250-260 meters squared per gram, pore volume is 0.45-0.6 milliliter/gram, the most probable aperture is the 2.5-3.5 nanometer.
Said hollow ball-shape mesoporous silicon oxide can prepare through the method that may further comprise the steps: in template, 2; 2, under the existence of 4-trimethylpentane and ethanol, tetramethoxy-silicane is contacted with acidic aqueous solution; And will contact back gained mixture crystallization under crystallization condition; With the heating of gained crystallization product, removed template method, said template is polyethylene glycol oxide-PPOX-polyethylene glycol oxide triblock copolymer.
According to the present invention, said tetramethoxy-silicane contacts temperature with acidic aqueous solution can be 10-60 ℃, is preferably 15-55 ℃; Can be 10-72 hour time of contact, is preferably 10-24 hour, finally can make the structure homogeneous, spherical complete of hollow mesoporous silicon oxide with this understanding.
According to the present invention, the kind of said acidic aqueous solution has no particular limits, and its pH value can be 1-6, more preferably 3-5.Preferably; Said acidic aqueous solution is the cushioning liquid of acetate and sodium acetate; The addition of said acidic aqueous solution has no particular limits, and can under agitation disperse uniformly as long as guarantee said template, trimethylpentane, ethanol and tetramethoxy-silicane.Concrete, the pH value of the cushioning liquid of said acetate and sodium acetate is 4.4; With respect to the said template of 1 gram; The consumption of said acidic aqueous solution is the 26-30 milliliter; Said polyethylene glycol oxide-PPOX-polyethylene glycol oxide triblock copolymer, ethanol, 2,2, the weight ratio of 4-trimethylpentane and tetramethoxy-silicane are 1: 1-3: 3-10: 1-5.
The method of said crystallization and removed template method and condition have been as well known to those skilled in the art, 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.
Among the present invention, the condition of gained crystallization product heating with removed template method had no particular limits, for example, can calcine 10-80 hour down, preferably calcined 10-80 hour down at 400-600 ℃ at 200-600 ℃.
According to the present invention; Said polyethylene glycol oxide-PPOX-polyethylene glycol oxide triblock copolymer can be the conventional various polyethylene glycol oxide-PPOXs-polyethylene glycol oxide triblock copolymer template in this area; Can be commercially available; For example, the P123 type triblock copolymer of Aldrich company production.
According to the present invention; Wherein said acidic ion liquid is preferably and contains sulfonic ionic liquid, said contain in the sulfonic ionic liquid cation 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; Said 3-alkyl can be the alkyl of carbon number 1-12; Said 1-sulfonic alkyl can for hydrogen atom on the carbon by the alkyl of 1 substituted carbon number 1-12 of sulfonic group; Said 1-sulfonic acid aryl can for hydrogen atom on the carbon by the aryl of 1 substituted carbon number 6-12 of sulfonic group, said 1-sulfonic acid aralkyl can for hydrogen atom on the aromatic ring carbon by the aralkyl of 1 substituted carbon number 7-12 of sulfonic group; Preferably; Said 3-alkyl is the alkyl of carbon number 1-4; Said 1-sulfonic alkyl be on the carbon hydrogen atom by the alkyl of 1 substituted carbon number 1-4 of sulfonic group; Said 1-sulfonic acid aryl be on the carbon hydrogen atom by the aryl of 1 substituted carbon number 6-8 of sulfonic group, said 1-sulfonic acid aralkyl be on the aromatic ring carbon hydrogen atom (for example, said alkyl is selected from methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group etc. by the aralkyl of 1 substituted carbon number 7-8 of sulfonic group; Said aryl is selected from phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl etc.; Said aralkyl is selected from benzyl, phenethyl etc.); The said anion that contains in the sulfonic ionic liquid is sulfate ion, hydrogen sulfate ion, halogen ion, PF
6 -, in the borate ion, tetrafluoroborate ion, alkyl sulfonate ion, fluoroform alkyl sulfonate radical, p-methyl benzenesulfonic acid radical ion one or more; Said alkyl sulfonate ion can in methanesulfonate ions, ethylsulfonic acid radical ion, n-pro-pyl sulfonate ion, isopropyl sulfonate ion, normal-butyl sulfonate ion, the isobutyl group sulfonate ion etc. one or more.Concrete; Saidly contain sulfonic ionic liquid and 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., more preferably said to contain sulfonic ionic liquid be 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 the preparation method who is put down in writing to prepare.
The present invention provides the preparation method of above-mentioned support type acidic ionic liquid catalysts; This method comprises acidic ion liquid is loaded on the hollow ball-shape meso-porous titanium dioxide silicon carrier; The average particulate diameter of said hollow ball-shape meso-porous titanium dioxide silicon carrier is the 3-20 micron; Specific area is the 200-300 meters squared per gram, and pore volume is 0.5-1.5 milliliter/gram, and the most probable aperture is the 3-20 nanometer.Wherein, this method at first prepares said hollow ball-shape meso-porous titanium dioxide silicon carrier, and the method, condition and the preferable case that prepare said hollow ball-shape meso-porous titanium dioxide silicon carrier are not given unnecessary details at this with aforementioned identical.
Preparation method according to support type acidic ionic liquid catalysts of the present invention; Wherein, This method loads on above-mentioned acidic ion liquid on the hollow ball-shape meso-porous titanium dioxide silicon carrier, and mode of loading comprises said hollow ball-shape mesoporous silicon oxide carrier impregnation in containing the solution of acidic ion liquid.The present invention does not have special qualification to said solvent; As long as can dissolve acidic ion liquid preferably; Can be selected from methyl alcohol, ethanol, isopropyl alcohol, normal propyl alcohol, n-butanol, n-amyl alcohol, cyclohexanol, acetone and the acetate one or more, be preferably ethanol; The weight ratio that said 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 said dipping can in very large range change; For example; Can under 25-120 ℃, preferably under 25-50 ℃, the 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.
Preparation method according to support type acidic ionic liquid catalysts of the present invention; Wherein, This method also comprise dipping back to load the hollow ball-shape meso-porous titanium dioxide silicon carrier of acidic ion liquid filter and dry; Filtration and drying mode can adopt method well known in the art, for example are filtered into suction filtration; Dry is vacuum drying, and 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 makes through the method for following steps:
(1) acetate of template, ethanol, pH value 3-5 and the cushioning liquid of sodium acetate are stirred to the template dissolving under 15-35 ℃ of temperature;
(2), under 15-35 ℃ of temperature, stir 6-10h in the solution of 4-trimethylpentane adding step (1) gained with 2,2;
(3) tetramethoxy-silicane is added in the solution of step (2) gained under 15-35 ℃ of temperature, stir 10-30h;
(4) step (3) products therefrom crystallization under crystallization condition comprises crystallization temperature 45-80 ℃, crystallization time 15-40h;
(5) with step (4) gained crystallization product heating, removed template method obtains hollow ball-shape meso-porous titanium dioxide silicon carrier, heating-up temperature be 400-600 ℃, heat time heating time 15-40h;
(6), obtain the support type acidic ionic liquid catalysts after the drying with hollow ball-shape meso-porous titanium dioxide silicon carrier, ethanol behind the removed template method of step (5) gained with contain sulfonic ionic liquid and stir down 10-40h at 25-50 ℃.
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; Said support type acidic ionic liquid catalysts can catalyzed carbon atomicity 1-10 monohydric alcohol 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; 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. like said alcohol, said acid can be formic acid, acetate, 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; This method comprises: in the presence of catalyst; Under the condition of esterification, acetate is contacted, with ethanol to obtain ethyl acetate; Wherein, said catalyst is a support type acidic ionic liquid catalysts provided by the invention.
According to the present invention, in esterification, the mol ratio of acetate and ethanol can in very large range change, and for example, the mol ratio of acetate and ethanol can be 1: 0.5-10.The consumption of said 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 the preferable case, in the acidic ion liquid of load in the catalyst, with respect to the acetate of 100 weight portions; Said catalyst consumption is the 1-20 weight portion, more preferably the 5-10 weight portion.
Among the present invention, the condition of said esterification is conventionally known to one of skill in the art, for example; The condition of said 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.Keeping the temperature of esterification can carry out through the various known method in this area, for example oil bath heating, and 100 ℃ with interior available water-bath heating.
The present invention also provides a kind of preparation method of methyl oleate, and wherein, this method comprises: in the presence of said catalyst; Under the condition of esterification, oleic acid is contacted, with methyl alcohol to obtain methyl oleate; Wherein, said catalyst is a 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 said 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 the preferable case, in the acidic ion liquid of load in the catalyst, with respect to the oleic acid of 100 weight portions; Said catalyst consumption is the 1-10 weight portion, more preferably the 1-5 weight portion.
Among the present invention, the condition of said esterification is conventionally known to one of skill in the art, for example; The condition of said 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.Keeping the temperature of esterification can carry out through the various known method in this area, for example oil bath heating, and 100 ℃ with interior available water-bath heating.
According to the present invention; After esterification finishes, can final reactant mixture be centrifugalized, with the centrifugal solid formation that obtains at 25-200 ℃ of following vacuum drying 1-24 hour; Preferably at 50-80 ℃ of following vacuum drying 4-12 hour, the catalyst that can obtain reclaiming.
Below in conjunction with embodiment the present invention is carried out detailed description.
In following examples, X-ray diffraction analysis is to carry out on the X-ray diffractometer of D8Advance in the model available from German Bruker AXS company; Scanning electron microscope analysis is to carry out on the SEM of XL-30 in the model available from U.S. FEI Co..Wavelength dispersion X ray fluorescence spectra (WDXRF) analytical method is adopted in the elementary analysis of catalyst, 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 appearance, sample was 200 ℃ of degassings 4 hours.
(1) preparation of hollow ball-shape meso-porous titanium dioxide silicon carrier
With 1.0 gram polyethylene glycol oxide-PPOX-polyethylene glycol oxide triblock copolymer (Aldrich companies; P123) and 1.69 gram ethanol join in the cushioning liquid of acetate and sodium acetate of pH=4.4 of 28ml; Under 15 ℃, be stirred to polyethylene glycol oxide-PPOX-polyethylene glycol oxide and dissolve fully, afterwards with 2,2 of 6 grams; The 4-trimethylpentane joins in the above-mentioned solution; 15 ℃ were stirred after 8 hours, 2.13 gram tetramethoxy-silicanes were joined in the above-mentioned solution again, and 15 ℃ were stirred after 20 hours; Solution is transferred in the teflon-lined agitated reactor, 60 ℃ of following baking oven crystallization after 24 hours through filtering, obtaining the former powder of hollow ball-shape mesoporous silicon oxide after the distilled water washing, drying.
The former powder of hollow ball-shape mesoporous silicon oxide was calcined 24 hours in muffle furnace at 550 ℃, obtained hollow ball-shape mesoporous silicon oxide (called after MS).
(2) preparation of support type acidic ionic liquid catalysts
Under 35 ℃; 1 gram hollow ball-shape mesoporous silicon oxide and 5 gram-ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfates (ILa) were stirred 24 hours in 30ml ethanol; After filtration and drying; Obtain supported ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate hollow ball-shape mesoporous silicon oxide (called after MS-ILa-1), after the load quality be 1.72 the gram.Learning according to calculating, is benchmark with the gross weight of this catalyst, and the content of said 1-(4-sulfonic group) butyl-3-methylimidazole disulfate is 42 weight %, and the content of said hollow ball-shape meso-porous titanium dioxide silicon carrier is 58 weight %.
Come 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 have good hexagonal hole road structure.
Fig. 4 is the nitrogen adsorption desorption thermoisopleth of hollow ball-shape mesoporous silicon oxide (MS); The nitrogen adsorption desorption thermoisopleth 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 that by spectrogram sample has the IV type thermoisopleth of sharp-pointed capillary condensation speed, this thermoisopleth has the 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.Can find out by figure; Sample is the hollow ball-shape mesoporous silicon oxide before supported ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate; Particle diameter is at the 3-20 micron, behind supported ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate, and the particle diameter 5-20 micron of sample.
Table 1
Data by last table 1 can be found out; The hollow ball-shape mesoporous silicon oxide is behind the load acidic ion liquid; Specific area, pore volume and most probable aperture all reduce, and this explanation acidic ion liquid in the load-reaction process enters into the duct of hollow ball-shape mesoporous silicon oxide and the inside of ball.The content that draws element sulphur in the support type acidic ionic liquid catalysts through xrf analysis is that the content of 7.9 weight %, carbon is 11.8 weight %.
Method according to embodiment 1 prepares the support type acidic ionic liquid catalysts; Different is; Acidic ion liquid is 5 gram 1-(4-sulfonic group) butyl-3-methylimidazole metilsulfates, obtains support type acidic ionic liquid catalysts (called after MS-ILb-1), and dry back quality is 1.61 grams.Learning according to calculating, is benchmark with the gross weight of this catalyst, and the content of said 1-(4-sulfonic group) butyl-3-methylimidazole metilsulfate is 38 weight %, and the content of said hollow ball-shape meso-porous titanium dioxide silicon carrier is 62 weight %.
Come this support type acidic ionic liquid catalysts is characterized with XRD, nitrogen adsorption-desorption experiment and ESEM; The result obtains: the x-ray diffraction pattern of catalyst MS-ILb-1, nitrogen adsorption desorption thermoisopleth and stereoscan photograph are all similar with catalyst MS-ILa-1, and structural parameters are as above shown in the table 1; The content that draws element sulphur in the support type acidic ionic liquid catalysts through xrf analysis is that the content of 7.1 weight %, carbon is 13.4 weight %.
Comparative Examples 1
Method according to embodiment 1 prepares the support type acidic ionic liquid catalysts; Different is; 1 gram hollow ball-shape mesoporous silicon oxide is replaced by 1 gram industrial silicone ES955, obtains reference support type acidic ionic liquid catalysts (called after GJ-ILa-1), and dry back quality is 1.22 grams.Learning according to calculating, is benchmark with the gross weight of this catalyst, and the content of said 1-(4-sulfonic group) butyl-3-methylimidazole disulfate is 18 weight %, and the content of said silica supports is 82 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.
With MS-ILa-1 75 ℃ of following vacuum drying 6 hours, be cooled to room temperature after, take by weighing 1.5 the gram; Take by weighing 23 gram ethanol and 15 gram acetate again, and put into successively in the there-necked flask of 100ml, 90 ℃ of oil bath heating; Reflux down stirring reaction 4 hours, be cooled to room temperature after, centrifugation; After filtration and drying, reclaim solid catalyst wherein.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
EXPERIMENTAL EXAMPLE 2
After the catalyst recovery with used load-type ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate in the EXPERIMENTAL EXAMPLE 1; In 75 ℃ of following vacuum drying 6 hours (called after MS-ILa-2a); Method according to EXPERIMENTAL EXAMPLE 1 is carried out the catalysis synthesizing ethyl acetate; Different is that MS-ILa-1 is replaced by MS-ILa-2a, utilizes gas chromatographic analysis reaction product liquid composition, and 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.
With MS-ILa-1 75 ℃ of following vacuum drying 6 hours, be cooled to room temperature after, take by weighing 0.5 the gram; Take by weighing 4.6 gram ethanol and 6.0 gram acetate again, and put into successively in the there-necked flask of 50ml, 100 ℃ of oil bath heating; Reflux down stirring reaction 1 hour, be cooled to room temperature after, centrifugation; After filtration and drying, reclaim solid catalyst wherein.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
EXPERIMENTAL EXAMPLE 4
After the catalyst recovery with used load-type ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate in the EXPERIMENTAL EXAMPLE 3; Again in 75 ℃ of following vacuum drying 6 hours (called after MS-ILa-2b); Method according to EXPERIMENTAL EXAMPLE 3 is carried out the catalysis synthesizing ethyl acetate, and different is that MS-ILa-1 is replaced by the MS-ILa-2b catalyst.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
Experiment Comparative Examples 1
Method according to EXPERIMENTAL EXAMPLE 3 prepares ethyl acetate, and different is the GJ-ILa-1 replacement of MS-ILa-1 by Comparative Examples 1 preparation of identical weight.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
Experiment Comparative Examples 2
To test the catalyst recovery of used load-type ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate in the Comparative Examples 1; And 75 ℃ of following vacuum drying 6 hours (called after GJ-ILa-2a); Method according to experiment Comparative Examples 1 prepares ethyl acetate, and different is that GJ-ILa-1 is replaced by the GJ-ILa-2a catalyst.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
Experiment Comparative Examples 3
Method according to EXPERIMENTAL EXAMPLE 3 prepares ethyl acetate, and different is MS-ILa-1 is that the concentrated sulfuric acid of 98 weight % replaces by the concentration of 0.1 gram.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 2.
The blank example 1 of experiment
Method according to EXPERIMENTAL EXAMPLE 3 prepares 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 explained according to load of the present invention the catalytic activity of ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole pyrovinic acid salt catalyst.
Method according to EXPERIMENTAL EXAMPLE 1 is carried out, and is not all the MS-ILb-1 that uses identical weight and replaces MS-ILa-1, utilizes gas chromatographic analysis reaction product liquid composition, and experimental data is as shown in table 2.
EXPERIMENTAL EXAMPLE 6-9
Catalyst recovery with used load-type ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole metilsulfate in the EXPERIMENTAL EXAMPLE 5; Before each esterification; At 6 hours (reusable number of times after according to catalyst recovery of 75 ℃ of following vacuum drying; Naming catalyst respectively is MS-ILb-2, MS-ILb-3, MS-ILb-4 and MS-ILb-5); Method according to EXPERIMENTAL EXAMPLE 5 is carried out the catalysis synthesizing ethyl acetate, utilizes gas chromatographic analysis reaction product liquid composition, and experimental data is as shown in table 2.
EXPERIMENTAL EXAMPLE 10
This EXPERIMENTAL EXAMPLE is used for having explained according to load of the present invention the catalytic activity of ionic liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate catalyst.
With MS-ILa-1 75 ℃ of following vacuum drying 6 hours, be cooled to room temperature after, take by weighing 0.5 the gram, take by weighing again 3.2 the gram methyl alcohol and 28.2 the gram oleic acid; And put into successively in the there-necked flask of 100ml, 100 ℃ of oil bath heating, stirring reaction is 6 hours under refluxing; After being cooled to room temperature, centrifugation is after filtration and drying; Reclaim solid catalyst wherein, utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 3.
EXPERIMENTAL EXAMPLE 11
After the catalyst recovery with used load-type ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate in the EXPERIMENTAL EXAMPLE 10; In 75 ℃ of following vacuum drying 6 hours (called after MS-ILa-2c); Carry out the synthetic methyl oleate of catalysis according to the method for EXPERIMENTAL EXAMPLE 10; Different is that MS-ILa-1 is replaced by MS-ILa-2c, utilizes gas chromatographic analysis reaction product liquid composition, and experimental data is as shown in table 3.
Experiment Comparative Examples 4
Method according to EXPERIMENTAL EXAMPLE 10 prepares methyl oleate, and different is the GJ-ILa-1 replacement of MS-ILa-1 by Comparative Examples 1 preparation of identical weight.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 3.
Experiment Comparative Examples 5
To test the catalyst recovery of used load-type ion liquid 1-(4-sulfonic group) butyl-3-methylimidazole disulfate in the Comparative Examples 4; And 75 ℃ of following vacuum drying 6 hours (called after GJ-ILa-2b); Method according to experiment Comparative Examples 4 prepares methyl oleate; Different is that GJ-ILa-1 is replaced by the GJ-ILa-2b catalyst.Utilize gas chromatographic analysis reaction product liquid composition, experimental data is as shown in table 3.
The blank example 2 of experiment
Method according to EXPERIMENTAL EXAMPLE 10 prepares 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
Table 3
Data through above embodiment can find out that through acidic ion liquid being carried on the 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; Compare with the data of testing Comparative Examples 1-3 and the blank example 1 of experiment through EXPERIMENTAL EXAMPLE 1-9; In the time of can finding out that using the different catalyst that contains sulfonic acidic ion liquid of load provided by the invention comes the esterification of catalysis acetate and ethanol; Improved the conversion ratio of acetate in the esterification significantly, effectively utilized reactant acetate, side reaction does not simultaneously produce corrosion to equipment less yet; And this catalyst can pass through and reclaim and use repeatedly, and aftertreatment technology is simple.Compare with the data of experiment Comparative Examples 1-2 through EXPERIMENTAL EXAMPLE 3-4; Though the catalyst GJ-ILa-1 of catalyst MS-ILa-1 provided by the invention and contrast is under identical esterification condition first when catalysis acetate and ethanol synthesis; Can obtain the conversion ratio of suitable acetate; But after catalyst recovery is utilized again, the catalyst GJ-ILa-2a that catalyst MS-ILa-2b provided by the invention is superior to contrasting.
Learn from table 3; Compare with the data of testing Comparative Examples 4-5 and the blank example 2 of experiment through EXPERIMENTAL EXAMPLE 10-11; Can find out when the catalyst that uses load provided by the invention to contain sulfonic acidic ion liquid comes the esterification of catalysis oleic acid and methyl alcohol; Can improve conversion of methanol in the esterification significantly, utilize reactant methanol fully, and this catalyst can use after reclaiming repeatedly.Compare with the data of experiment Comparative Examples 4-5 through EXPERIMENTAL EXAMPLE 10-11; Though the catalyst GJ-ILa-1 of catalyst MS-ILa-1 provided by the invention and contrast is under identical esterification condition during catalysis oleic acid and methyl alcohol reaction first; Can obtain the conversion ratio of suitable formic acid; But after catalyst recovery is utilized again, the catalyst GJ-ILa-2b that catalyst MS-ILa-2c provided by the invention is superior to contrasting.
Claims (13)
1. 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, and the average particulate diameter of said hollow ball-shape meso-porous titanium dioxide silicon carrier is the 3-20 micron, and specific area is the 200-300 meters squared per gram; Pore volume is 0.5-1.5 milliliter/gram, and the most probable aperture is the 3-20 nanometer.
2. catalyst according to claim 1 wherein, is a benchmark with the gross weight of this catalyst; The content of said acidic ion liquid is 10-60 weight %; The content of said hollow ball-shape meso-porous titanium dioxide silicon carrier is 40-90 weight %, preferably, is benchmark with the gross weight of this catalyst; The content of said acidic ion liquid is 35-45 weight %, and the content of said hollow ball-shape meso-porous titanium dioxide silicon carrier is 55-65 weight %.
3. catalyst according to claim 1 and 2, wherein, the average particulate diameter of said catalyst is the 5-20 micron, and specific area is the 190-270 meters squared per gram, and pore volume is 0.4-0.7 milliliter/gram, and the most probable aperture is the 2-9.7 nanometer; Preferably, the average particulate diameter of said catalyst is the 5-15 micron, and specific area is the 250-260 meters squared per gram, and pore volume is 0.45-0.6 milliliter/gram, and the most probable aperture is the 2.5-3.5 nanometer.
4. catalyst according to claim 1 and 2, wherein, said hollow ball-shape meso-porous titanium dioxide silicon carrier is prepared by the method that comprises the steps: in template, 2; 2, under the existence of 4-trimethylpentane and ethanol, tetramethoxy-silicane is contacted with acidic aqueous solution; And will contact back gained mixture crystallization under crystallization condition; With the heating of gained crystallization product, removed template method, said template is polyethylene glycol oxide-PPOX-polyethylene glycol oxide triblock copolymer; The condition of said contact comprises: 10-60 ℃ of contact temperature, 10-72 hour time of contact; Said acidic aqueous solution is the cushioning liquid of acetate and sodium acetate, and the pH value of said cushioning liquid is 1-6; With respect to the said template of 1 gram, the consumption of said acidic aqueous solution is the 26-30 milliliter; The condition of said crystallization comprises: crystallization temperature is 30-150 ℃, and crystallization time is 10-72 hour; Said polyethylene glycol oxide-PPOX-polyethylene glycol oxide triblock copolymer, ethanol, 2,2, the weight ratio of 4-trimethylpentane and tetramethoxy-silicane are 1: 1-3: 3-10: 1-5.
5. catalyst according to claim 1 and 2; Wherein, Said acidic ion liquid is for containing sulfonic ionic liquid, the said cation that contains in the 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 said anion that contains in the sulfonic ionic liquid is sulfate ion, hydrogen sulfate ion, halogen ion, PF
6 -, in the borate ion, tetrafluoroborate ion, alkyl sulfonate ion, fluoroform alkyl sulfonate radical, p-methyl benzenesulfonic acid radical ion one or more; It is more preferably said that to contain sulfonic ionic liquid be 1-(4-sulfonic group) butyl-3-methylimidazole disulfate and/or 1-(4-sulfonic group) butyl-3-methylimidazole metilsulfate.
6. the preparation method of any described support type acidic ionic liquid catalysts among the claim 1-5; This method comprises acidic ion liquid is loaded on the hollow ball-shape meso-porous titanium dioxide silicon carrier; The average particulate diameter of said hollow ball-shape meso-porous titanium dioxide silicon carrier is the 3-20 micron; Specific area is the 200-300 meters squared per gram, and pore volume is 0.5-1.5 milliliter/gram, and the most probable aperture is the 3-20 nanometer.
7. method according to claim 6; Wherein, The said mode that acidic ion liquid is loaded on the hollow ball-shape meso-porous titanium dioxide silicon carrier comprises said hollow ball-shape mesoporous silicon oxide carrier impregnation in containing the solution of acidic ion liquid; Contain solvent in the solution of acidic ion liquid and be in methyl alcohol, ethanol, isopropyl alcohol, normal propyl alcohol, n-butanol, n-amyl alcohol, cyclohexanol, acetone and the acetate one or more, be preferably ethanol; The weight ratio that said 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.
8. method according to claim 6, wherein, the condition of said dipping comprises: dipping temperature is 25-120 ℃, is preferably 25-50 ℃, dip time is 5-80 hour, is preferably 10-40 hour.
9. the application of any described support type acidic ionic liquid catalysts in esterification among the claim 1-5.
10. the preparation method of an ethyl acetate, wherein, this method comprises: in the presence of catalyst; Under the condition of esterification, acetate is contacted, with ethanol to obtain ethyl acetate; It is characterized in that said catalyst is any described catalyst among the claim 1-5.
11. method according to claim 10; Wherein, the mol ratio of acetate and ethanol is 1: 0.5-10, and in the acidic ion liquid of load in the catalyst; Acetate with respect to 100 weight portions; The amount of said catalyst is the 1-20 weight portion, and preferably, the amount of said catalyst is the 5-10 weight portion.
12. the preparation method of a methyl oleate, wherein, this method comprises: in the presence of catalyst; Under the condition of esterification, oleic acid is contacted, with methyl alcohol to obtain methyl oleate; It is characterized in that said catalyst is any described catalyst among the claim 1-5.
13. method according to claim 12, wherein, the mol ratio of oleic acid and methyl alcohol is 1: 0.5-10; And in the acidic ion liquid of load in the catalyst, with respect to the oleic acid of 100 weight portions, the amount of said catalyst is the 1-10 weight portion; Preferably, the amount of said catalyst is the 1-5 weight portion.
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