CN102039178B - Catalyst prepared by loading zinc trifluoromethanesulfonate on macroporous-mesoporous material, and preparation method and use thereof - Google Patents
Catalyst prepared by loading zinc trifluoromethanesulfonate on macroporous-mesoporous material, and preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to a macroporous-mesoporous material SBA-15 loaded with zinc trifluoromethanesulfonate and a preparation method and use thereof. A novel catalyst is synthesized by loading zinc trifluoromethanesulfonate onto the mesoporous material SBA-15 with aperture between 10 and 14 nanometers. In the invention, macroporous-mesoporous material SBA-15 supported zinc trifluoromethanesulfonate is used as a catalyst for use in the methyl oleate synthesis reaction of oleic acid and methanol, the macropores in the catalyst allow macromolecular oleic acid and methanol to enter mesoporous porous channels to promote a catalytic reaction, side reactions in the catalysts reaction are reduced, product purity is improved, the catalyst can be recycled with high acid conversion rate and little pollution to the environment. The invention also provides a process for preparing a methyl oleate important chemical raw material by using the macroporous-mesoporous material to catalyze the reaction of oleic acid and methanol.
Description
Technical field
The present invention relates to the catalytic synthetic techniques field, be specifically related to macroporous/mesoporous material and the application thereof of load TFMS zinc.
Background technology
Methyl oleate is a kind of important industrial chemicals, the esterification under effect of sulfuric acid of present industrial employing oleic acid and methyl alcohol synthetic (Esterification of oleic acid by methanol catalyzed by p-toluenesulfoicacid and the cation-ex-change resins K241 and K1481 in supercritical carbondioxide[J] .Vieville C, Mouloungui Z, Gaset A.Ind Eng Chem Res, 1993,32 (9): 2065-2068.).Because sulfuric acid and product are all liquid phase, thoroughly separate very difficult, and sulfuric acid corrosion instrument, and environment is also had larger pollution, therefore the new catalyst that substitutes sulfuric acid is being developed at present a lot of scientific researches.
the east people such as grade of unit Zhao synthesized a kind of new material-mesoporous material SBA-15 in 1998, this material has the large aperture (6-30nm) of high-sequential, pore volume large (1.0cm3/g), the high mechanical properties that thicker hole wall (4-6nm) keeps and good catalytic adsorption performance, see Triblock Copolymer Syntheses ofMesoporous Silica with Periodic 50to 300Angstrom Pores[J] .D.Y.Zhao, J.L.Feng, Q.S.Huo, N.Melosh, G.H.Fredrickson, B.F.Chmelka, G.D.Stucky, Science 279 (1998) 548-550, Zhao Dongyuan, Yu Chengzhong, Yu Yonghao. a kind of preparation method of mesonic pore molecular sieve carrier material, CN1341553A.This mesoporous material is as the heterogeneous reaction catalyst, easily realizes separating of catalyst and product.Therefore substituting sulfuric acid with mesoporous material is important research direction (Shen Jian, Yuan Xingdong, Sun Mingzhu, Zhang Li, QiYu platform mesoporous molecular sieve SBA-15-SO3H catalyzes and synthesizes methyl oleate [J]. the chemistry of fuel journal, 2003,31 (2): 167-170: Yuan Xingdong, Shen Jian, sulfonic group modified and the catalytic performance [J] on the .SBA-15 mesopore molecular sieve such as Li Guohui surface. catalysis journal, 2002,23 (5): 435-438.
Yet the mesoporous material hole wall surface only has the silicon hydroxyl, causes its chemical reactivity not high, thereby has limited the actual application value of mesoporous material.In addition, at present commonly used mesoporous material aperture is less, and average pore size is at 6～9nm, if carry out the bulky molecular catalysis reaction, large molecule duct more difficult to get access is to such an extent as to affect catalytic effect.
For above-mentioned 2 points, the present invention synthesizes macroporous/mesoporous material by high temperature method, aperture 10～14nm, and with its load TFMS zinc, synthesize new catalyst, this catalyst applied in synthesizing of large molecule methyl oleate, was 50.5% according to gas chromatographic analysis methyl oleate content, and oleic acid content is 40.8%; Under the same reaction condition of catalyst, methyl oleate content is only 4.3% and do not add, and oleic acid content is 95.7%.
Summary of the invention
For the deficiencies in the prior art, the invention provides macroporous/mesoporous material of a kind of load TFMS zinc and preparation method thereof, with this macroporous/mesoporous material as catalyst, large aperture is conducive to large molecule oleic acid and the methanol oxidation reaction is carried out, and not only can reduce side reaction in catalytic reaction, improve product purity, still keep sour conversion ratio preferably after Reusability, environmental pollution is less.Another object of the present invention is to provide the technique of utilizing this macroporous/mesoporous material catalysis oleic acid and methyl alcohol reaction to obtain important industrial chemicals methyl oleate.
The present invention a kind of on macroporous/mesoporous material SBA-15 the catalyst (SBA-Zn (OTf) of load TFMS zinc
2), described macroporous/mesoporous material is that the aperture is at the SBA-15 of 10nm～14nm mesoporous material, at outer surface and the inner duct load TFMS zinc of described macroporous/mesoporous material SBA-15.
After load, the catalyst of gained load TFMS zinc on macroporous/mesoporous material SBA-15 is designated as SBA-Zn (OTf)
2Wherein-Zn (OTf)
2Representative loads on the outer surface of macroporous/mesoporous material SBA-15 and the TFMS zinc of inner hole wall; Zn (OTf)
2Represent TFMS zinc; SBA represents macroporous/mesoporous material SBA-15; SBA-Zn (OTf)
2Represent Zn (OTf)
2Load on outer surface and the inner hole wall of macroporous/mesoporous material SBA-15, also namely load on part or all of exposed surface of SBA-15.
The preparation method of the catalyst of the upper load TFMS zinc of macroporous/mesoporous material SBA-15 of the present invention comprises the steps:
(1) with triblock copolymer polyethylene glycol oxide-PPOX-polyethylene glycol oxide, join in aqueous hydrochloric acid solution, by a mole rate of charge, triblock copolymer polyethylene glycol oxide-PPOX-polyethylene glycol oxide: water: hydrogen chloride=1: 9000～15000: 100～500 are stirred to dissolving at 25～60 ℃ of temperature; The material that the preferred U.S. chemical abstract registration number of described triblock copolymer polyethylene glycol oxide-PPOX-polyethylene glycol oxide is 9003-11-6, its average molecular mass Mn=5800.
(2) add ethyl orthosilicate in previous step gained solution, stir more than 25 minutes at 25～60 ℃ of temperature; By a mole rate of charge, triblock copolymer polyethylene glycol oxide-PPOX-polyethylene glycol oxide: the ethyl orthosilicate rate of charge is 1: 30～70;
(3) gained solution of upper step is placed in closed reaction vessel, crystallization is 10～40 hours at 90～180 ℃ of temperature;
(4) with the filtration of crystallization afterproduct, washing, drying, obtain the former powder of macroporous/mesoporous material;
(5) the former powder of gained macroporous/mesoporous material was washed 10～40 hours at 90～120 ℃ of temperature with ethanol, remove the masterplate agent, obtain macroporous/mesoporous material;
(6) macroporous/mesoporous material and acetone, the TFMS zinc of gained of upper step are put into closed reaction vessel jointly, by the quality rate of charge, mesoporous material: acetone: TFMS zinc=1: 10～50: 0.1～10, stirred 1～72 hour under 25～150 ℃ of conditions;
(7) product is cooled to room temperature, after Separation of Solid and Liquid, solid obtains the macroporous/mesoporous material solid catalyst of load TFMS zinc 25～200 ℃ of lower vacuum drying 1～24 hour.
The present invention comprises the steps: in the application of catalyst in the preparation methyl oleate of load TFMS zinc on macroporous/mesoporous material SBA-15
(1) add oleic acid and methyl alcohol in reactor, and add the catalyst of the upper load TFMS zinc of macroporous/mesoporous material SBA-15, by the quality rate of charge, oleic acid: methyl alcohol: catalyst=1: 0.1～2: 0.1～0.3;
(2) adding under the condition of hot reflux stirring reaction 0.1～72 hour, after being cooled to room temperature, centrifugal solid-liquid separates;
(3) the liquid product rectifying that obtains is separated, obtain the product methyl oleate, rectifying separates adopts conventional known technology.
To the solid product that (2) step centrifugation obtains, vacuum drying is 1～24 hour at 25～200 ℃ of temperature, the catalyst that is recycled, and the catalyst of recovery can continue to use in preparation methyl oleate technique.
Utilizing the catalyst that the present invention prepares to carry out catalytic reaction to oleic acid and methyl alcohol, is 50.5% with gas chromatographic analysis methyl oleate content, and oleic acid content is 40.8%; After the catalyst recovery recycling, methyl oleate content is 18.2%, and oleic acid content is 81.8%.Under the catalyst condition, methyl oleate content is only 4.3% and do not add, and oleic acid content is 95.7%.Quadric catalysis post catalyst reaction SBA-Zn (OTf)
2Still keep the distinctive orderly hexagonal hole road structure (seeing Fig. 1 and Fig. 3) of mesoporous material SBA-15.
The invention has the beneficial effects as follows:
The macroporous/mesoporous material of load TFMS zinc of the present invention, with this macroporous/mesoporous material as catalyst, be applied to the reaction of the synthetic methyl oleate of oleic acid and methyl alcohol, in catalyst, large aperture is conducive to large molecule oleic acid and methyl alcohol enters in mesopore orbit, catalytic reaction is carried out better, and not only can reduce side reaction in catalytic reaction, improve product purity, still keep sour conversion ratio preferably after the catalyst recovery Reusability, environmental pollution is less.
Description of drawings
Fig. 1 is macropore SBA-15 and SBA-Zn of the present invention (OTf)
2XRD comparison diagram before and after the quadric catalysis reaction.
Fig. 2 is macropore SBA-15 and SBA-Zn of the present invention (OTf)
2Nitrogen adsorption desorption curve and pore size distribution curve.
Fig. 3 is macropore SBA-15 and SBA-Zn of the present invention (OTf)
2Quadric catalysis reaction front and rear gaps structural representation (adopting the TEM transmission electron microscope to characterize).
Fig. 4 is macropore SBA-15 and SBA-Zn of the present invention (OTf)
2Quadric catalysis reaction before and after microscopic appearance figure (adopting the SEM ESEM to characterize).
The specific embodiment
The content of the various materials of the following example is to calculate according to the result that gas chromatography-mass spectrography is analyzed to get.
The macroporous/mesoporous material of embodiment 1 preparation load TFMS zinc
(1) 4.0 gram P123 (registration number at U.S. chemical abstract is the material of 9003-11-6, its average molecular mass Mn=5800) are joined in the solution of 37% 16.4ml hydrochloric acid and 128ml water, be stirred to P123 at 40 ℃ and dissolve fully;
(2) again 8.86 gram ethyl orthosilicates are joined in mentioned solution, stirred 24 hours at 40 ℃;
(3) gained solution is transferred in the teflon-lined reactor, 150 ℃ of crystallization 24 hours;
(4) through obtaining former powder mesoporous material after filtration, washing, drying;
(5) former powder mesoporous material was under refluxad washed 24 hours with ethanol, remove the masterplate agent, obtain macroporous/mesoporous material;
(6) with the above-mentioned macroporous/mesoporous material of 1g 150 ℃ of lower vacuum drying 6 hours, after being cooled to room temperature, again 50ml acetone and 1g TFMS zinc are put into 100ml teflon-lined reactor together, the capping still stirred 24 hours under 45 ℃ of conditions;
(7) be cooled to room temperature after, obtain solid product after the centrifugation filter liquide, with its 150 ℃ of vacuum drying 4 hours to remove impurity.Obtain product SBA-Zn (OTf)
2
Figure (1) a is the XRD spectra of macropore SBA-15, and figure (1) b is SBA-Zn (OTf)
2XRD spectra, figure (1) c be the reacted SBA-Zn of quadric catalysis (OTf)
2XRD spectra.By above-mentioned three XRD spectras as can be known, macropore SBA-15 and SBA-Zn (OTf)
2All has the peculiar sequential 2 D hexagonal hole of mesoporous material SBA-15 road structure before and after quadric catalysis reaction.
Take 1 gram macroporous/mesoporous material catalyst S BA-Zn (OTf)
2Take again 7.05 gram oleic acid, 5.6 gram methyl alcohol are put into the 100ml there-necked flask together, add condenser pipe, stirred 4 hours under 60 ℃ of conditions that add hot reflux, after being cooled to room temperature, gc analysis reaction product liquid composition is adopted in centrifugation, wherein methyl oleate content is 50.5%, and oleic acid content is 40.8%.Macroporous/mesoporous material catalyst S BA-Zn (OTf)
2150 ℃ of lower vacuum drying 6 hours, after being cooled to room temperature, recycling after reclaiming.
The catalyst that embodiment 3 use reclaim prepares methyl oleate
1 gram macroporous/mesoporous material catalyst S BA-Zn (OTf) with embodiment 2 recyclings
2Take again 7.05 gram oleic acid, 5.6 gram methyl alcohol are put into the 100ml there-necked flask together, add condenser pipe, stirred 4 hours under 60 ℃ of conditions that add hot reflux, after being cooled to room temperature, centrifugation utilizes gc analysis reaction product liquid composition, wherein methyl oleate content is 18.2%, and oleic acid content is 81.8%.Macroporous/mesoporous material catalyst S BA-Zn (OTf)
2150 ℃ of lower vacuum drying 6 hours, after being cooled to room temperature, recycling after reclaiming.
Comparative Examples 1
Take 7.05 gram oleic acid and 5.6 gram methyl alcohol are put into the 100ml there-necked flask, add condenser pipe, stirred 4 hours under 60 ℃ of conditions that add hot reflux, after being cooled to room temperature, centrifugation, utilize gas chromatographic analysis reaction product liquid composition, methyl oleate content is 4.3%, and oleic acid content is 95.7%.
Fig. 1 is macropore SBA-15 and SBA-Zn of the present invention (OTf)
2Structure Comparison figure before and after the quadric catalysis reaction.Wherein figure (1) a is the XRD spectra of macropore SBA-15, and figure (1) b is SBA-Zn (OTf)
2XRD spectra, figure (1) c be the reacted SBA-Zn of quadric catalysis (OTf)
2XRD spectra.Compose the peak as can be known by the low-angle that XRD spectra occurs, the SBA-Zn (OTf) before and after SBA-15 and quadric catalysis reaction
2The hexagonal hole road structure that still keeps the peculiar sequential 2 D of mesoporous material SBA-15.The abscissa of figure is 2 θ (degree).
The a of Fig. 2 is macropore SBA-15 and SBA-Zn of the present invention (OTf)
2Nitrogen adsorption desorption curve, the abscissa of figure is relative pressure.The nitrogen adsorption desorption class of a curve of the shape of curve and the SBA-15 of bibliographical information seemingly shows the SBA-15 and the SBA-Zn of the present invention (OTf) that synthesize
2Be mesoporous material.By SBA-15 and SBA-Zn of the present invention (OTf)
2Pore size distribution curve (b) (abscissa of figure is aperture (0.1nm)) finds out, the aperture curve distribution of two samples is even, and the peak shape symmetry is better.Recording sample macropore SBA-15 aperture by the full-automatic materialization adsorption analysis of ASAP2020-M+C instrument is 12nm, SBA-Zn (OTf)
2The aperture is 12.4nm.
Fig. 3 is macropore SBA-15 and SBA-Zn of the present invention (OTf)
2Pore structure schematic diagram (TEM transmission electron microscope).Wherein figure (3) a is the pore structure schematic diagram of macropore SBA-15, and figure (3) b is SBA-Zn (OTf)
2The pore structure schematic diagram, figure (3) c be SBA-Zn (OTf)
2The pore structure schematic diagram of quadric catalysis.As seen from the figure, macropore SBA-15 and SBA-Zn (OTf)
2Still keep the hexagonal hole road structure of the peculiar sequential 2 D of mesoporous material SBA-15, this result is consistent with the result of XRD.
Fig. 4 is macropore SBA-15 and SBA-Zn of the present invention (OTf)
2Microscopic appearance figure (SEM ESEM) before and after the quadric catalysis reaction.Wherein figure (4) a is the microscopic appearance figure of macropore SBA-15, and figure (4) b is SBA-Zn (OTf)
2Microscopic appearance figure, figure (4) c be SBA-Zn (OTf)
2The microscopic appearance figure of quadric catalysis.As seen from the figure, the SBA-Zn (OTf) before and after the reaction of macropore SBA-15 and quadric catalysis
2Microstructure is consistent with the result of bibliographical information.
Table 1 is macropore SBA-15 and SBA-Zn (OTf)
2Pore structure parameter and x fluorescence analysis, wherein sample a is macropore SBA-15, sample b is SBA-Zn of the present invention (OTf)
2As seen from table, macropore SBA-15 is after load TFMS zinc, and pore volume and specific area all reduce to some extent.The x fluorescence analysis shows SBA-Zn (OTf)
2Really contain metal ion zinc in the product that obtains after carrying out load.
Table 1 pore structure parameter and x fluorescence analysis
| Sample | Specific area (m 2/g) | Pore volume (ml/g) | Aperture (nm) | Sample Zn content (%) |
| a | 351 | 1.0 | 12.0 | 0 |
| b | 306 | 0.9 | 12.4 | 0.9 |
Claims (5)
1. the catalyst S BA-Zn (OTf) of a load TFMS zinc on macroporous/mesoporous material SBA-15
2, it is characterized in that, described macroporous/mesoporous material is that the aperture is at the SBA-15 of 10nm～14nm mesoporous material, at outer surface and the inner duct load TFMS zinc of described macroporous/mesoporous material SBA-15;
The catalyst of the upper load TFMS zinc of described macroporous/mesoporous material SBA-15 prepares by following method:
(1) with triblock copolymer polyethylene glycol oxide-PPOX-polyethylene glycol oxide, join in aqueous hydrochloric acid solution, by a mole rate of charge, triblock copolymer polyethylene glycol oxide-PPOX-polyethylene glycol oxide: water: hydrogen chloride=1:9000～15000:100～500 are stirred to dissolving at 25 ℃～60 ℃ temperature;
(2) add ethyl orthosilicate in previous step gained solution, stir more than 25 minutes at 25 ℃～60 ℃ temperature; By a mole rate of charge, triblock copolymer polyethylene glycol oxide-PPOX-polyethylene glycol oxide: the ethyl orthosilicate rate of charge is 1:30～70;
(3) gained solution of upper step is placed in closed reaction vessel, crystallization is 10 hours～40 hours at 90 ℃～180 ℃ temperature;
(4) with the filtration of crystallization afterproduct, washing, drying, obtain the former powder of macroporous/mesoporous material;
(5) the former powder of gained macroporous/mesoporous material was washed 10 hours～40 hours at 90 ℃～120 ℃ temperature with ethanol, remove the masterplate agent, obtain macroporous/mesoporous material;
(6) macroporous/mesoporous material and acetone, the TFMS zinc of gained of upper step are put into closed reaction vessel jointly, by the quality rate of charge, the macroporous/mesoporous material that obtains in (5): acetone: TFMS zinc=1:10～50:0.1～10, stirred 1 hour～72 hours under 25 ℃～150 ℃ conditions;
(7) product is cooled to room temperature, after Separation of Solid and Liquid, solid obtains the macroporous/mesoporous material solid catalyst of load TFMS zinc 25 ℃～200 ℃ lower vacuum drying 1～24 hour.
2. the preparation method of the catalyst of the upper load TFMS zinc of the described macroporous/mesoporous material SBA-15 of claim 1, is characterized in that, comprises the steps:
(1) with triblock copolymer polyethylene glycol oxide-PPOX-polyethylene glycol oxide, join in aqueous hydrochloric acid solution, by a mole rate of charge, triblock copolymer polyethylene glycol oxide-PPOX-polyethylene glycol oxide: water: hydrogen chloride=1:9000～15000:100～500 are stirred to dissolving at 25 ℃～60 ℃ temperature;
(2) add ethyl orthosilicate in previous step gained solution, stir more than 25 minutes at 25 ℃～60 ℃ temperature; By a mole rate of charge, triblock copolymer polyethylene glycol oxide-PPOX-polyethylene glycol oxide: the ethyl orthosilicate rate of charge is 1:30～70;
(3) gained solution of upper step is placed in closed reaction vessel, crystallization is 10 hours～40 hours at 90 ℃～180 ℃ temperature;
(4) with the filtration of crystallization afterproduct, washing, drying, obtain the former powder of macroporous/mesoporous material;
(5) the former powder of gained macroporous/mesoporous material was washed 10 hours～40 hours at 90 ℃～120 ℃ temperature with ethanol, remove the masterplate agent, obtain macroporous/mesoporous material;
(6) macroporous/mesoporous material and acetone, the TFMS zinc of gained of upper step are put into closed reaction vessel jointly, by the quality rate of charge, the macroporous/mesoporous material that obtains in (5): acetone: TFMS zinc=1:10～50:0.1～10, stirred 1 hour～72 hours under 25 ℃～150 ℃ conditions;
(7) product is cooled to room temperature, after Separation of Solid and Liquid, solid obtains the macroporous/mesoporous material solid catalyst of load TFMS zinc 25 ℃～200 ℃ lower vacuum drying 1～24 hour.
According to claim 2 on macroporous/mesoporous material SBA-15 the preparation method of the catalyst of load TFMS zinc, it is characterized in that, that the U.S. chemical abstract registration number is the material of 9003-11-6 at (1) step described triblock copolymer polyethylene glycol oxide-PPOX-polyethylene glycol oxide, its average molecular mass Mn=5800.
4. the application of the catalyst of the upper load TFMS zinc of the described macroporous/mesoporous material SBA-15 of claim 1 in the preparation methyl oleate is characterized in that, comprises the steps:
(1) add oleic acid and methyl alcohol in reactor, and add the catalyst of the upper load TFMS zinc of the described macroporous/mesoporous material SBA-15 of claim 1, by the quality rate of charge, oleic acid: methyl alcohol: catalyst=1:0.1～2:0.1～0.3;
(2) adding under the condition of hot reflux stirring reaction 0.1 hour～72 hours, after being cooled to room temperature, centrifugal solid-liquid separates;
(3) the liquid product rectifying that obtains is separated, obtain the product methyl oleate.
5. the application of the catalyst of the upper load TFMS zinc of macroporous/mesoporous material SBA-15 in the preparation methyl oleate according to claim 4, it is characterized in that, go on foot to (2) solid product that centrifugation obtains, vacuum drying is 1～24 hour at 25～200 ℃ of temperature, the catalyst that is recycled.
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| CN112169835A (en) * | 2020-10-27 | 2021-01-05 | 山东益丰生化环保股份有限公司 | Catalyst for synthesizing mercaptocarboxylic ester compound and preparation method and application thereof |
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| CN101371990A (en) * | 2008-07-15 | 2009-02-25 | 大连理工大学 | Method for preparing phosphine ligand SBA-15 functional material with modification on external surface and grafting on interior surface |
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| CN101371990A (en) * | 2008-07-15 | 2009-02-25 | 大连理工大学 | Method for preparing phosphine ligand SBA-15 functional material with modification on external surface and grafting on interior surface |
Non-Patent Citations (2)
| Title |
|---|
| Nature of the acid sites in the metal triflates immobilized in SBA-15 and their role in the Friedel–Crafts acylation of naphthalene;S.Selvakumar et al;《Applied Catalysis A: General》;20091021;第372卷;130-137 * |
| S.Selvakumar et al.Nature of the acid sites in the metal triflates immobilized in SBA-15 and their role in the Friedel–Crafts acylation of naphthalene.《Applied Catalysis A: General》.2009,第372卷130-137. |
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