CN101602012A - Contain mesoporous material of aromatic hydrocarbon sulfonic acid groups and its production and application - Google Patents

Contain mesoporous material of aromatic hydrocarbon sulfonic acid groups and its production and application Download PDF

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CN101602012A
CN101602012A CNA2008101147614A CN200810114761A CN101602012A CN 101602012 A CN101602012 A CN 101602012A CN A2008101147614 A CNA2008101147614 A CN A2008101147614A CN 200810114761 A CN200810114761 A CN 200810114761A CN 101602012 A CN101602012 A CN 101602012A
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mesoporous material
aromatic hydrocarbon
sulfonic acid
acid groups
temperature
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CN101602012B (en
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谢伦嘉
亢宇
王伟
赵思源
田宇
冯华升
冯再兴
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Sinopec Baling Co
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The present invention relates to the catalyst synthesis technical field, a kind of mesoporous material that contains aromatic hydrocarbon sulfonic acid groups and preparation method thereof is provided, outer surface and inner hole wall grafting aromatic hydrocarbon sulfonic acid groups at the SBA-15 mesoporous material, utilize one-step method directly synthetic, make that this mesoporous material pore volume is big, specific area is big, more help catalytic reaction and carry out.In replacing the reaction of sulfuric acid as catalyst, have very high reactivity, reduce side reaction, improve product purity, and can use repeatedly, there are not the three wastes fully, environmental pollution is little.The present invention is used for chemical field.

Description

Contain mesoporous material of aromatic hydrocarbon sulfonic acid groups and its production and application
Technical field
The present invention relates to the catalyst synthesis technical field, be specifically related to mesoporous material that contains aromatic hydrocarbon sulfonic acid groups and its production and application.
Background technology
Butanone-ethylene ketal has peat-reek, can be used in the essence, also can be used as the intermediate of organic synthesis or solvent (flavor chemistry. Beijing: the .1984.250 of light industry publishing house, NH Bo Latusi; Silico-tungstic acid doped polyaniline catalyst synthesizes butanone ethylene ketal, chemical reagent, 2005,27 (2), 121～123, Yang Shuijin; Tong Wenlong; Sun Jutang).Its traditional synthetic method is synthetic under the catalysis of homogeneous catalyst inorganic acid, but this method exists side reaction many, and product purity is not high, and equipment corrosion is serious, contains a large amount of acid waste water in the post processing, causes shortcomings such as environmental pollution.Therefore, as select for use the heterogeneous catalysis of excellent catalytic effect to replace the homogeneous catalyst inorganic acid, not only can avoid above-mentioned defective, also can make heterogeneousization of homogeneous catalysis.
Synthesized a kind of new material-mesoporous material SBA-15 in 1998, this material has large aperture (6-30nm), the pore volume (1.0cm of high-sequential 3/ g), the high mechanical properties that keeps of thicker hole wall (4-6nm) and good catalysis absorption property (Triblock Copolymer Syntheses ofMesoporous Silica with Periodic 50 to 300 Angstrom Pores.D.Y.Zhao, J.L.Feng, Q.S.Huo, N.Melosh, G.H.Fredrickson, B.F.Chmelka, G.D.Stucky, Science 279 (1998) 548; Zhao Dongyuan, Yu Chengzhong, Yu Yonghao. a kind of preparation method of mesonic pore molecular sieve carrier material, CN1341553A).Yet the mesoporous material hole wall surface has only the silicon hydroxyl, causes its chemical reactivity not high, thereby has limited the actual application value of mesoporous material greatly.Along with going deep into to the mesopore molecular sieve application study, people begin to utilize the modifiability on mesoporous material surface gradually, the surface nature of mesoporous material is carried out organically-modified, improve its catalytic reaction activity, so that develop the application of mesoporous material in catalytic field to a greater extent.
At present, existing a lot of research and report about the mesopore molecular sieve surface modification method.Modify the difference of mode according to mesoporous material being carried out organo-functional group, these methods mainly are divided into two kinds, i.e. grafting method (but also claiming the method for grafting afterwards) behind coprecipitation (claim not only in-situ synthesis) and the covalent bond.The in-situ modification that wherein utilizes silane coupler to carry out the mesoporous material surface is the more problem of research in the mesoporous material research field.Employing in-situ synthesis such as Lim will contain sulfydryl, amino, in the preparation of the organically-modified mesoporous material of silane coupler such as epoxy alkyl and imidazole radicals (Synthesis andcharacterization of a reactive vinyl-functionalized MCM-41:probing theinternal pore structure by a bromination reaction[J] .J.Am.Chem.Soc., 1997,119 (17): 4090-4091.Lim M H, Blanford C F, Stein A.Stucky) research group adopts in-situ synthesis will contain (Direct syntheses of ordered SBA-15 mesoporous silica containing sulfonicacid groups in the preparation of organically-modified mesoporous material of sulfonic silane coupler, Chem.Mater.2000,12,2448-2459 D.Margolese, J.A.Melero, S.C.Christiansen, B.F.Chmelka, G.D.Stucky).
In homogeneous catalyst, the concentrated sulfuric acid is acid commonly used, is a kind of homogeneous catalyst preferably, is used for catalysis ethylene glycol and butanone and obtains the spices 2-ethyl-2-methyl isophthalic acid of food industry, the reaction process of 3-ring butyl oxide link (butanone-ethylene ketal).But use sulfuric acid that the problem of environmental protection aspect is arranged.
Summary of the invention
The technical problem to be solved in the present invention is:
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of mesoporous material that contains aromatic hydrocarbon sulfonic acid groups and preparation method thereof, make that this mesoporous material specific area is big, pore volume is big, more help catalytic reaction and carry out; In replacing the reaction of sulfuric acid as catalyst, reduce side reaction, improve product purity, help environmental protection.
Product technology scheme of the present invention is:
A kind of mesoporous material that contains aromatic hydrocarbon sulfonic acid groups, described mesoporous material are at the outer surface of SBA-15 mesoporous material and/or inner hole wall grafting aromatic hydrocarbon sulfonic acid groups;
The pore volume of described mesoporous material is 1cm 3/ g～1.5cm 3/ g.
The expression formula of mesoporous material product of the present invention is SBA-Ar-SO 3H.Ar-SO wherein 3H represents aromatic hydrocarbon sulfonic acid groups, Ar-SO 3H is grafted on the outer surface and/or the inner hole wall of mesoporous material SBA-15, also promptly is grafted on part or all of exposed surface of SBA-15.In the present invention, the outer surface of mesoporous material SBA-15 and other groups of not grafting of inner hole wall.SBA represents mesoporous material SBA-15.
Particularly, the specific area of described mesoporous material is 630m 2/ g～800m 2/ g, the aperture is 5nm～6nm.
Particularly, described mesoporous material is outer surface and/or inner hole wall grafting 2-(the 4-sulfonic group phenyl) ethyl group at the SBA-15 mesoporous material.This moment, expression formula was
Figure S2008101147614D00031
Preparation method's technical scheme of the present invention is:
May further comprise the steps:
The 1st step is with three camphane section copolymer EO 20PO 70EO 20, join mass concentration and be in 1%～37% the aqueous hydrochloric acid solution, in molar ratio,
Three camphane section copolymer EO 20PO 70EO 20: hydrochloric acid=1: 100～500,
Under 25 ℃～60 ℃ temperature, be stirred to dissolving;
Described three camphane section copolymer EO 20PO 70EO 20, i.e. a kind of in three camphane section copolymer polyethylene glycol-glycerine-polyethylene glycol.
The 2nd step added ethyl orthosilicate in previous step gained solution, stir more than 25 minutes under 25 ℃～80 ℃ temperature; Add 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silane again, under 25 ℃～80 ℃ temperature, stir more than 10 hours; In molar ratio,
Ethyl orthosilicate: 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silane=10～40: 1;
The 3rd step, will go up step gained solution and place closed reaction vessel, crystallization is 10 hours～72 hours under 90 ℃～150 ℃ temperature;
In the 4th step,, obtain mesoporous material raw powder with the filtration of crystallization afterproduct, washing, drying;
The 5th step, the gained mesoporous material raw powder was washed 10 hours～80 hours under 90 ℃～120 ℃ temperature with ethanol, remove the masterplate agent, obtain the mesoporous material product of the aforesaid 2-of containing (4-sulfonic group phenyl) ethyl group.
With document " Direct synthesis of ordered SBA-15 mesoporous materialscontaining arenesulfonic acid groups.Melero, J.A; Stucky, G.D.; Van Grieken, R.; Morales, G.J.Mater.Chem.9 (2002) 1664 " to compare; the novel mesoporous material that the present invention proposes is in the organic decoration process; use the amount of silane coupler 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silane to have only half that report in the document; after carrying out organic decoration; have bigger pore volume and bigger specific area, because of the mesoporous material catalytic reaction mainly occurs in the hole, to carry out so big pore structure parameter more helps catalytic reaction.
Application process technical scheme of the present invention is: be used for 2-ethyl-2-methyl isophthalic acid, as catalyst, replace sulfuric acid of the prior art in the preparation feedback process of 3-ring butyl oxide link.
This reaction is a reaction raw materials with ethylene glycol and butanone, in molar ratio,
Ethylene glycol: butanone=1: 1～10,
Mesoporous material with the above-mentioned 2-of containing (4-sulfonic group phenyl) ethyl group is a catalyst,
Under 120 ℃～150 ℃ temperature, stirring reaction 1 hour～72 hours, after reactant liquor was cooled to room temperature, centrifugation obtained liquid product: 2-ethyl-2-methyl isophthalic acid, 3-encircles butyl oxide link;
The vacuum drying 1 hour～24 hours under 25 ℃～200 ℃ temperature of the solid product of centrifugation, the catalyst that obtains reclaiming.
2-ethyl-2-methyl isophthalic acid, 3-encircles butyl oxide link, also can claim butanone-ethylene ketal, has peat-reek, can be used in the essence of food industry, also can be used as the intermediate or the solvent of organic synthesis.Prior art uses sulfuric acid as Preparation of Catalyst butanone-ethylene ketal, and sulfuric acid constantly is consumed, and can not recycle.
Utilize of the present invention
Figure S2008101147614D00051
As catalyst butanone and ethylene glycol are carried out catalytic reaction, butanone conversion ratio 95%, 2-ethyl-2-methyl isophthalic acid, the selectivity 100% of 3-ring butyl oxide link (butanone-ethylene ketal), yield 95%.
When the catalyst that reclaims after the above-mentioned reaction reuses, butanone conversion ratio 96%, 2-ethyl-2-methyl isophthalic acid, 3-ring butyl oxide link (butanone-ethylene ketal) 100%, yield 96%.And the quadric catalysis post catalyst reaction
Figure S2008101147614D00052
Still keep the distinctive orderly hexagonal hole road structure of mesoporous material SBA-15, see Fig. 1 and Fig. 2.
The technical scheme that another kind of product of the present invention contains the macroporous/mesoporous material of aromatic hydrocarbon sulfonic acid groups is:
Described mesoporous material is at the outer surface of SBA-15 mesoporous material and/or inner hole wall grafting aromatic hydrocarbon sulfonic acid groups;
The pore volume of described mesoporous material is 1cm 3/ g～1.5cm 3/ g, specific area is 500m 2/ g～650m 2/ g, the aperture is 7nm～13nm.
Macroporous/mesoporous material product and aforementioned mesoporous material product have common trait aspect grafting aromatic hydrocarbon sulfonic acid groups and the pore volume, and difference is that the aperture is bigger.
The expression formula of macroporous/mesoporous material product of the present invention is SBA-Ar-SO 3H.Ar-SO wherein 3H represents aromatic hydrocarbon sulfonic acid groups, Ar-SO 3H is grafted on the outer surface and/or the inner hole wall of mesoporous material SBA-15.SBA represents mesoporous material SBA-15.
Usually, macroporous/mesoporous material is outer surface and/or inner hole wall grafting 2-(the 4-sulfonic group phenyl) ethyl group at the SBA-15 mesoporous material.This moment, expression formula was
Figure S2008101147614D00053
Preparation method's technical scheme of macroporous/mesoporous material of the present invention is:
May further comprise the steps:
The 1st step is with three camphane section copolymer EO 20PO 70EO 20, join mass concentration and be in 1%～37% the aqueous hydrochloric acid solution, in molar ratio,
Three camphane section copolymer EO 20PO 70EO 20: hydrochloric acid=1: 100～500,
Under 25 ℃～60 ℃ temperature, be stirred to dissolving;
Described three camphane section copolymer EO 20PO 70EO 20, i.e. a kind of in three camphane section copolymer polyethylene glycol-glycerine-polyethylene glycol.
The 2nd step added 1 gram～5 grams, 1,3,5 mesitylene in previous step gained solution, stir more than 25 minutes under 25 ℃～80 ℃ temperature;
The 3rd step added ethyl orthosilicate in previous step gained solution, stir more than 25 minutes under 25 ℃～80 ℃ temperature;
The 4th step placed closed reaction vessel with previous step gained solution, and crystallization is 10 hours～72 hours under 90 ℃～150 ℃ temperature;
In the 5th step,, obtain the former powder of macroporous/mesoporous material with the filtration of crystallization afterproduct, washing, drying;
The 6th step, the former powder of gained macroporous/mesoporous material was washed 10 hours～80 hours under 90 ℃～120 ℃ temperature with ethanol, remove the masterplate agent;
The 7th step, the former powder of gained macroporous/mesoporous material was washed 10 hours～80 hours under 90 ℃～120 ℃ temperature with acetone and 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silane, obtain the macroporous/mesoporous material product of the described 2-of containing (4-sulfonic group phenyl) ethyl group
The invention has the beneficial effects as follows:
The mesoporous material that contains aromatic hydrocarbon sulfonic acid groups of the present invention has the big and big characteristics of specific area of pore volume, more helping catalytic reaction carries out, in the butanone-ethylene ketal course of reaction of preparation, has high reaction activity, can reduce side reaction, improve product purity, and can use repeatedly, do not have the three wastes fully, environmental pollution is little.Preparation method of the present invention utilizes one-step method directly to synthesize to contain the mesoporous material of 2-(4-sulfonic group phenyl) ethyl group, and dosage of silane coupling agent is few.
Description of drawings
Fig. 1 is the XRD spectra of mesoporous material of the present invention before and after catalytic reaction.
Fig. 2 is the pore structure figure of mesoporous material of the present invention before and after catalytic reaction.
Fig. 3 is a mesoporous material of the present invention 29Si CPMAS NMR spectrogram.
Fig. 4 is the graph of pore diameter distribution of mesoporous material of the present invention before and after catalytic reaction.
Fig. 5 is the XRD spectra of macroporous/mesoporous material of the present invention.
Fig. 6 is a macroporous/mesoporous material of the present invention 29Si CPMAS NMR spectrogram.
The specific embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Conversion ratio of the following example and selectivity, result's calculating of analyzing according to gas chromatography-mass spectrography gets.In the computational process, determining of each concrete material is to compare with the standard spectrogram in being input to computer according to providing according to given mass spectrogram.
Embodiment 1, a kind of preparation that contains the mesoporous material of 2-(4-sulfonic group phenyl) ethyl group:
With 4.0 grams, three camphane section copolymer EO 20PO 70EO 20(commercial goods, abbreviate P123 as) join in the solution of 120ml hydrochloric acid (mass concentration 37%) and 6ml water, being stirred to P123 under 40 ℃ of temperature dissolves fully, again the 8.2ml ethyl orthosilicate is joined in the above-mentioned solution, under 40 ℃ of temperature, stirred 45 minutes, in solution, add 1.3 gram 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silanes again, after stirring 24 hours under 40 ℃ of temperature, solution is transferred in the teflon-lined reactor, crystallization was filtered solution after 24 hours under 100 ℃ of temperature, washing, obtain mesoporous material raw powder after the drying.Mesoporous material raw powder was under refluxad washed 24 hours with ethanol, obtain containing in the skeleton mesoporous material product of 2-(4-sulfonic group phenyl) ethyl group
Figure S2008101147614D00081
Embodiment 2,2-ethyl-2-methyl isophthalic acid, and the preparation of 3-ring butyl oxide link:
With mesoporous material
Figure S2008101147614D00082
150 ℃ of following vacuum drying 6 hours, after being cooled to room temperature, take by weighing 0.3 gram, take by weighing again 21.6 the gram butanone and 22.3 the gram ethylene glycol put into the 100ml there-necked flask successively, add water knockout drum and condenser pipe, under the condition of heating reflux water-dividing, stirred 4 hours, after being cooled to room temperature, with the solid-liquid centrifugation, utilize gas chromatographic analysis product liquid phase ingredient, butanone conversion ratio 95%, 2-ethyl-2-methyl isophthalic acid, the selectivity 100% of 3-ring butyl oxide link (butanone-ethylene ketal), yield 95%, solid catalyst mesoporous material
Figure S2008101147614D00083
150 ℃ of following vacuum drying 6 hours, be cooled to room temperature after, utilize again after the recovery.
Embodiment 3,2-ethyl-2-methyl isophthalic acid, and the preparation of 3-ring butyl oxide link:
With the mesoporous material of recycling
Figure S2008101147614D00084
150 ℃ of following vacuum drying 6 hours, after being cooled to room temperature, take by weighing 0.3g, take by weighing again 21.6 the gram butanone and 22.3 the gram ethylene glycol put into the 100ml there-necked flask successively, add water knockout drum and condenser pipe, under the condition of heating reflux water-dividing, stirred 4 hours, after being cooled to room temperature, with the solid-liquid centrifugation, utilize gas chromatographic analysis product liquid phase ingredient, butanone conversion ratio 96%, 2-ethyl-2-methyl isophthalic acid, the selectivity 100% of 3-ring butyl oxide link (butanone-ethylene ketal), yield 96%.
Embodiment 4, a kind of preparation that contains the macroporous/mesoporous material of 2-(4-sulfonic group phenyl) ethyl group:
4.0 grams, three camphane section copolymer ps 123 are joined in the solution of 120ml hydrochloric acid (mass concentration 37%) and 6ml water, being stirred to P123 under 40 ℃ dissolves fully, with 1 of 1.5g, 3,5 mesitylene join in the above-mentioned solution, after 40 ℃ are stirred 2 hours down, again the 8.2ml ethyl orthosilicate is joined in the above-mentioned solution, after 40 ℃ are stirred 24 hours down, solution is transferred in the teflon-lined reactor, 100 ℃ of following crystallization are after 24 hours, through obtaining the former powder of macroporous/mesoporous material after filtration, washing, the drying in baking oven.The former powder of macroporous/mesoporous material was under refluxad washed 24 hours with ethanol, obtain macroporous/mesoporous material.At last macroporous/mesoporous material was under refluxad washed 24 hours with acetone and 1.3 gram 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silanes, after filtration and drying, obtain containing in the skeleton macroporous/mesoporous material product of phenylbenzimidazole sulfonic acid base.
Comparative Examples 1:
Take by weighing 21.6 the gram butanone and 22.3 the gram ethylene glycol put into the 100ml there-necked flask successively, add water knockout drum and condenser pipe, under the condition of heating reflux water-dividing, stirred 4 hours, after being cooled to room temperature, with the solid-liquid centrifugation, utilize gas chromatographic analysis product liquid phase ingredient, do not see to measure other products.
Fig. 1 provides
Figure S2008101147614D00091
Carry out the XRD spectra of catalytic reaction front and back as catalyst.A is XRD spectra, b is that quadric catalysis is reacted XRD spectra.Compose the peak as can be known by the low-angle that XRD spectra occurs,
Figure S2008101147614D00094
Hexagonal hole road structure with the peculiar sequential 2 D of mesoporous material SBA-15, and order mesoporous structure still remains unchanged after carrying out twice catalytic reaction.
Fig. 2 is before and after the catalytic reaction
Figure S2008101147614D00095
The pore structure schematic diagram, a is
Figure S2008101147614D00096
The pore structure schematic diagram, b is that quadric catalysis is reacted
Figure S2008101147614D00097
The pore structure schematic diagram.As seen from the figure,
Figure S2008101147614D00098
And carry out the reacted pore structure of quadric catalysis and still keep the distinctive hexagonal hole of mesoporous material road structure.This result is consistent with the result of XRD.
Fig. 3 is 29Si CPMAS NMR spectrogram, wherein a is that SBA-15, b be not for passing through catalytic reaction
Figure S2008101147614D00101
C is for after reclaiming once more after the catalytic reaction
Figure S2008101147614D00102
29Si CPMAS NMR spectrogram.Before and after by spectrogram as can be seen, mesoporous material of the present invention uses 29In the Si CPMAS NMR spectrogram, promptly among b and the c, (SiO) 2Si (OH) 2Go out peak position (Q among the figure 2The position), (SiO) 3Si (OH) goes out peak position (Q among the figure 3The position) and (SiO) 4Si goes out peak position (Q among the figure 4The position), i.e. three kinds of peak positions that go out that connect skeleton Si are with coincideing of SBA-15.Compare with SBA-15, except above-mentioned three peaks, the spectrogram of b and c new peak all occurs at 55ppm and 60ppm place, and these two emerging spectrum peaks can belong to T m(T m=RSi (OSi) m(OH) 3-m, m=1-3; T 2At δ=-55 and T 3δ=-60ppm).These two emerging spectrum peaks show
Figure S2008101147614D00103
Group successfully is grafted on the skeleton of SBA-15, and after the catalytic reaction
Figure S2008101147614D00104
Skeleton structure is not destroyed.
Fig. 4 is before and after the catalytic reaction
Figure S2008101147614D00105
Graph of pore diameter distribution, by graph of pore diameter distribution as can be seen Has narrow pore-size distribution, the result of this and bibliographical information is consistent, document is seen " Science 279 (1998) 548 for Triblock Copolymer Syntheses of Mesoporous Silica withPeriodic 50 to 300 Angstrom Pores.D.Y.Zhao; J.L.Feng, Q.S.Huo, N.Melosh; G.H.Fredrickson; B.F.Chmelka, G.D.Stucky ".And after the quadric catalysis reaction, sample
Figure S2008101147614D00107
Pore size distribution curve remains unchanged substantially, and peak shape is narrow and symmetrical.This explanation quadric catalysis reaction does not destroy the pore structure of sample.This and XRD diffraction result are consistent.
Fig. 5 is the XRD spectra before and after the macroporous/mesoporous material grafting.C is the XRD spectra of macropore SBA-15, and d is the macropore SBA-Ar-SO behind the graft reaction 3The XRD spectra of H.Compose the peak as can be known, macropore SBA-15 and macropore SBA-Ar-SO by the low-angle that XRD spectra occurs 3H has the hexagonal hole road structure of the peculiar sequential 2 D of mesoporous material SBA-15.
Fig. 6 is macropore SBA-15 (c) and macropore SBA-Ar-SO 3H's (d) 29Si CPMAS NMR spectrogram is by spectrogram macropore SBA-15 (c) and macropore SBA-Ar-SO as can be seen 3H's (d) 29In the Si CPMASNMR spectrogram (SiO) 2Si (OH) 2(Q 2The position), (SiO) 3Si (OH) (Q 3The position) and (SiO) 4Si (Q 4The position) three kinds connect skeleton Si go out the identical of peak position and SBA-15.SBA-15 compares with macropore, except above-mentioned three peaks, and macropore SBA-Ar-SO 3H's 29Si MAS NMR spectrogram 55 and the 60ppm place new peak all appears, these two emerging spectrum peaks can belong to T m(T m=RSi (OSi) m(OH) 3-m, m=1-3; T 2At δ=-55 and T 3δ=-60ppm).These two emerging spectrum peaks show
Figure S2008101147614D00111
Group successfully is grafted on the skeleton of macropore SBA-15.
Table 1 is
Figure S2008101147614D00112
Before the catalytic reaction (sample is the pore structure parameter of (sample b) a) and after the catalytic reaction, as seen from table, and mesoporous material
Figure S2008101147614D00113
After the quadric catalysis reaction, pore volume and specific area all reduce to some extent, and pore wall thickness increases, and this explanation reactant in catalytic reaction process enters in the duct of mesoporous material.It then is because due to the reactant that the part hole wall is entered into the mesoporous material duct in catalytic reaction process bursts that last aperture slightly increases.
Table 1 pore structure parameter table
Sample ??d 100(nm) Cell parameter (nm) Pore wall thickness (nm) Specific area (m 2/g) Pore volume (cm 3/g) Aperture (nm)
??a ??9.6 ??11.1 ??5.5 ??690 ??1.0 ??5.6
??b ??12.6 ??14.6 ??6.7 ??208 ??0.4 ??7.9
Table 2 is macropore SBA-15 (sample c) and macropore SBA-Ar-SO 3The pore structure parameter of H (sample d), as seen from table, macroporous/mesoporous material SBA-15 is behind graft reaction, and specific area and aperture reduce to some extent, and this explanation organic group in process of grafting enters into the skeleton of mesoporous material.
Table 2 pore structure parameter table
Sample Specific area (m 2/g) Pore volume (cm 3/g) Aperture (nm)
??c ??623 ??1.0 ??10
??d ??566 ??1.2 ??7.8

Claims (8)

1 one kinds of mesoporous materials that contain aromatic hydrocarbon sulfonic acid groups is characterized in that:
Described mesoporous material is at the outer surface of SBA-15 mesoporous material and/or inner hole wall grafting aromatic hydrocarbon sulfonic acid groups;
The pore volume of described mesoporous material is 1cm 3/ g～1.5cm 3/ g.
2 mesoporous materials that contain aromatic hydrocarbon sulfonic acid groups according to claim 1 is characterized in that:
The specific area of described mesoporous material is 630m 2/ g～800m 2/ g, the aperture is 5nm～6nm.
3 mesoporous materials that contain aromatic hydrocarbon sulfonic acid groups according to claim 2 is characterized in that:
Described mesoporous material is at the outer surface of SBA-15 mesoporous material and/or inner hole wall grafting 2-(4-sulfonic group phenyl) ethyl group.
4 one kinds of preparation methods that contain the mesoporous material of aromatic hydrocarbon sulfonic acid groups is characterized in that, may further comprise the steps:
The 1st step is with three down section copolymer EO 20PO 70EO 20, join mass concentration and be in 1%～37% the aqueous hydrochloric acid solution, in molar ratio,
Three down section copolymer EO 20PO 70EO 20: hydrochloric acid=1: 100～500,
Under 25 ℃～60 ℃ temperature, be stirred to dissolving;
The 2nd step added ethyl orthosilicate in previous step gained solution, stir more than 25 minutes under 25 ℃～80 ℃ temperature; Add 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silane again, under 25 ℃～80 ℃ temperature, stir more than 10 hours; In molar ratio,
Ethyl orthosilicate: 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silane=10～40: 1;
The 3rd step, will go up step gained solution and place closed reaction vessel, crystallization is 10 hours～72 hours under 90 ℃～150 ℃ temperature;
In the 4th step,, obtain mesoporous material raw powder with the filtration of crystallization afterproduct, washing, drying;
The 5th step, the gained mesoporous material raw powder was washed 10 hours～80 hours under 90 ℃～120 ℃ temperature with ethanol, remove the masterplate agent, obtain the mesoporous material product that contains aromatic hydrocarbon sulfonic acid groups as claimed in claim 3.
5 one kinds of mesoporous material application in catalytic reaction that contain aromatic hydrocarbon sulfonic acid groups is characterized in that:
With ethylene glycol and butanone is reaction raw materials, in molar ratio,
Ethylene glycol: butanone=1: 1～10,
With the described mesoporous material that contains aromatic hydrocarbon sulfonic acid groups of one of claim 2 to 3 is catalyst,
Under 120 ℃～150 ℃ temperature, stirring reaction 1 hour～72 hours after reactant liquor is cooled to room temperature, carries out centrifugation, obtains liquid product: 2-ethyl-2-methyl isophthalic acid, and 3-encircles butyl oxide link;
The vacuum drying 1 hour～24 hours under 25 ℃～200 ℃ temperature of the solid product of centrifugation, the catalyst that obtains reclaiming.
6 one kinds of macroporous/mesoporous materials that contain aromatic hydrocarbon sulfonic acid groups is characterized in that:
Described mesoporous material is at the outer surface of SBA-15 mesoporous material and/or inner hole wall grafting aromatic hydrocarbon sulfonic acid groups;
The pore volume of described mesoporous material is 1cm 3/ g～1.5cm 3/ g, specific area is 500m 2/ g～650m 2/ g, the aperture is 7nm～13nm.
7 according to the described macroporous/mesoporous material that contains aromatic hydrocarbon sulfonic acid groups of claim 1 to 6, it is characterized in that:
Described mesoporous material is at the outer surface of SBA-15 mesoporous material and/or inner hole wall grafting 2-(4-sulfonic group phenyl) ethyl group.
8 one kinds of preparation methods that contain the macroporous/mesoporous material of aromatic hydrocarbon sulfonic acid groups is characterized in that, may further comprise the steps:
The 1st step is with three down section copolymer EO 20PO 70EO 20, join mass concentration and be in 1%～37% the aqueous hydrochloric acid solution, in molar ratio,
Three down section copolymer EO 20PO 70EO 20: hydrochloric acid=1: 100～500,
Under 25 ℃～60 ℃ temperature, be stirred to dissolving;
The 2nd step added 1 gram～5 grams, 1,3,5 mesitylene in previous step gained solution, stir more than 25 minutes under 25 ℃～80 ℃ temperature;
The 3rd step added ethyl orthosilicate in previous step gained solution, stir more than 25 minutes under 25 ℃～80 ℃ temperature;
The 4th step placed closed reaction vessel with previous step gained solution, and crystallization is 10 hours～72 hours under 90 ℃～150 ℃ temperature;
In the 5th step,, obtain the former powder of macroporous/mesoporous material with the filtration of crystallization afterproduct, washing, drying;
The 6th step, the former powder of gained macroporous/mesoporous material was washed 10 hours～80 hours under 90 ℃～120 ℃ temperature with ethanol, remove the masterplate agent;
The 7th step, the former powder of gained macroporous/mesoporous material was washed 10 hours～80 hours under 90 ℃～120 ℃ temperature with acetone and 2-(4-benzene sulfonyl chloride) ethyl trimethoxy silane, obtain the macroporous/mesoporous material product that contains aromatic hydrocarbon sulfonic acid groups as claimed in claim 7.
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CN105435854A (en) * 2014-06-09 2016-03-30 中国石油化工股份有限公司 Chlorite mesoporous composite, supported catalyst and preparation method and application thereof and preparation method of cyclohexanone glyceryl ketal
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