CN108654688A - A kind of mesoporous silica gel surface bond alkyl sulfonic acid catalyst and preparation method thereof - Google Patents
A kind of mesoporous silica gel surface bond alkyl sulfonic acid catalyst and preparation method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The present invention relates to a kind of mesoporous silica gel surface bond alkyl sulfonic acid catalyst and preparation method thereof, and preparation method is as follows：By 3 chloropropyl alkoxy silanes, absolute ethyl alcohol, water and sour wiring solution-forming according to a certain percentage, mesoporous silica gel is impregnated with this solution.Silica gel after dipping is put into Na after drying2SO3And NaHSO3Salt-mixture aqueous solution in, add absolute ethyl alcohol, carry out hydro-thermal reaction at a certain temperature.Obtained solid product is acidified through strong acid, washs, obtains catalyst of the invention after drying.The method for preparing catalyst is simple, at low cost.During catalytic esterification, which presents higher activity and excellent repeat performance, and 7 activity of reuse, which have no, to be decreased obviously, and has good prospects for commercial application.
Description
Technical field
The present invention relates to a kind of solid sulfoacid catalyst, and in particular to a kind of mesoporous silica gel surface bond alkyl sulfonic acid catalysis
Agent and preparation method thereof.
Background technology
Acid catalyzed reaction is very common in organic chemical industry, such as esterification, acylation, alkylation, isomerization.Traditional
Acid catalyst includes the concentrated sulfuric acid, hydrofluoric acid and p-methyl benzenesulfonic acid etc., although correlated response can be effectively catalyzed, there is corrosion
Equipment, pollution environment, the defects of being difficult to detach with product.To adapt to the requirement of environmentally protective and sustainable development, exploitation is efficient
The acid catalyst that can be recycled, especially solid acid catalyst becomes the inevitable choice of researcher.
Solid sulfoacid catalyst is a kind of important solid acid catalyst.Most commonly storng-acid cation exchange resin
And its trim or the like.Publication number CN1136470A, CN1590361A, CN101596464A, CN102500416A and
This kind of catalyst of the patent literatures such as CN104525260A.But resin structure disintegration caused by swelling is to be difficult to gram
Clothes, so the temperature in use of this kind of catalyst is restricted, generally at 120 DEG C or less.Another kind of typical solid sulfoacid is urged
Agent is sulfonation carbon material catalyst.Preparation method is by the organic principles such as resin, glycerine, biomass high temperature carbonization or in acid
Property under the conditions of carbonize after carry out again sulfonation or other modification.Publication number CN101289629A, CN101918523A,
The such catalyst of the document reports such as CN103611569A and CN103623863A.Influence factor in its preparation process is extremely more,
Cause to be difficult to control its final duct and surface texture, so not having high activity and stability as expected still, especially
Stability.
In recent years, the exploitation of inorganic carrier load alkyl sulfonic acid catalyst attracts attention.Relevant document has Energy＆
Fuels 2009,23,539–547、Journal of Catalysis 229(2005)365–373、Journal of
Catalysis 193,283–294(2000)、Journal of Catalysis 193,295–302(2000)、Journal of
Catalysis 219(2003)329–336、Journal of Catalysis 182,156–164(1999)、Chemistry
of Materials 2000,12,2448-2459、Chemical Engineering Journal,174(2011)668-676、
Microporous and Mesoporous Materials 80(2005)33–42、Applied Catalysis A:
General 242(2003)161–169、Applied Catalysis A:General 205 (2001) 19-30 and
Applied Catalysis A:General 254 (2003) 173-188 etc..Its preparation principle is：Pass through so-called rear grafting
The means such as method or direct synthesis technique, by silane coupling agent (3-mercaptopropyi trimethoxy silane etc.) and carrier key with sulfydryl
Close, then again by sulfhydryl oxidase be sulfonic group.Carrier with mesoporous silica zeolite (also referred to as mesoporous silica gel) such as MCM-41 and
Based on SBA-15 etc..Above-mentioned catalyst is typical solid proton acid catalyst, can the effectively reactions such as catalytic esterification, represent
A developing direction of solid acid catalyst.But it prepares the complicated hydrothermal synthesis process that generally requires, and needs to have strong
The mercaptan compound of strong stink participates in；The oxidation of sulfydryl is often incomplete, causes Surface acidity relatively low, and catalyst activity is difficult again
It improves；The recycling performance of catalyst is undesirable.
Invention content
Based on the above shortcoming, a kind of mesoporous silica gel surface bond alkyl sulfonic acid catalyst of present invention offer and its preparation
Method.Using this method prepare catalyst, overcome the conventional homogeneous such as concentrated sulfuric acid catalyst cannot recycle, etching apparatus
The shortcomings of, while it is excessively high and active inadequate to overcome existing mesoporous silica gel load sulfonic acid catalyst preparation process complexity, cost
Height especially recycles the bad disadvantage of performance.In the esterification reaction process of catalysis carboxylic acid and alcohol, which presents
Very high activity and excellent repeat performance.
The technology used in the present invention is as follows：A kind of preparation method of mesoporous silica gel surface bond alkyl sulfonic acid catalyst,
It is as follows：
The first step, by 3- chloropropyls alkoxy silane, absolute ethyl alcohol, water and acid according to molar ratio be 1:5~20:1~50:
0~10 ratio wiring solution-forming impregnates mesoporous silica gel with this solution, is carried out using equi-volume impregnating or using excessive infusion process
Dipping is removed excessive liquid after dipping is abundant when using excessive infusion process；
Mesoporous silica gel after dipping that the first step obtains is dried second step according to known methods, removes volatilization
Property liquid component；
Third walks, and the mesoporous silica gel sample after dipping and drying that second step obtains is put into containing Na2SO3With
NaHSO3Mixed aqueous solution in, add absolute ethyl alcohol, reacted 0.5~10 hour at 80~180 DEG C, be then down to room temperature；
Third is walked the liquid in mixture obtained by the reaction and removed, solid product is put into strong acid aqueous solution by the 4th step
In be acidified in room temperature, at 0.5 hour or more, removing strong acid was then washed with deionized in the time, until wash water pH value
Stop when more than 6；
Solid sample of 4th step after washed is dried and removed moisture, obtains mesoporous silica gel surface bond by the 5th step
Alkyl sulfonic acid catalyst.
The present invention also has following technical characteristic：
1,3- chloropropyls alkoxy silane as described above is three ethoxy of 3- r-chloropropyl trimethoxyl silanes or 3- chloropropyls
Base silane.
2, the acid described in the first step as above is hydrochloric acid, sulfuric acid, nitric acid, formic acid or acetic acid.
3, the acid described in the first step as above or be acid aqueous solution, wherein 3- chloropropyls alkoxy silane, absolute ethyl alcohol,
The ratio for the amount of substance that the aqueous solution of water and acid is added is the amount ratio of the substance of the aqueous acid medium of acid, and acid is water-soluble
The gauge of the substance of water contained in liquid enters in the amount of the substance of the water of addition；
4, mesoporous silica gel as described above, including average pore size is in 2 nanometers or more of various amorphous silica gels and nanometer
Structural material MCM-41 or SBA-15 molecular sieve；
5, contain Na described in third step as above2SO3And NaHSO3Mixed aqueous solution, Na contained therein2SO3With
NaHSO3Total mole number be 1~10 times of the 3- chloropropyl alkoxy silanes being impregnated on mesoporous silica gel, Na2SO3And NaHSO3
Molar ratio be 0:1~1:0, gross mass percentage concentration is 5%~25%.
6, the addition of absolute ethyl alcohol contains Na for described in third step as above2SO3And NaHSO3Mixed aqueous solution body
Long-pending 0~1 times；
7, the strong acid aqueous solution described in the 4th step as above is hydrochloric acid, sulfuric acid or aqueous solution of nitric acid, a concentration of 0.5N~
5N, H contained therein+Molal quantity be 2~10 times of molal quantity of the 3- chloropropyl alkoxy silanes being impregnated on mesoporous silica gel.
8, a kind of mesoporous silica gel surface bond alkyl sulfonic acid catalyst prepared using preparation method as described above.
The principle of the present invention is as follows：
In above-mentioned preparation method, the purpose of the first step is that chloropropyl alkoxy silane is made to evenly spread to Silica Surface,
It is hydrolyzed into following structure simultaneously：
The purpose of second step is to make the hydroxyl and Silica Surface hydroxyl reaction bonding of above compound, and contracting between each other
Compound key realizes firm load.
The purpose of third step is acted on using the nucleophilic displacement of fluorine of inferior sulfate radical group, by surface propyl chloride thaumatropy at table
Face propyl sulfonic acid sodium salt structure.
The purpose of 4th step and the 5th step is that the propyl sulfonic acid sodium salt structure for making Silica Surface be bonded is changed into propyl sulfonic acid
Structure, as shown below：
Advantages of the present invention and advantageous effect：It is catalyzed using mesoporous silica gel surface bond alkyl sulfonic acid provided by the present invention
Catalyst prepared by the preparation method of agent will not cause to corrode to equipment；Between the active group and carrier of catalyst with
Chemical bond is combined, and very securely, is not lost in during the reaction；Since mesoporous silica gel carrier used has larger hole
Diameter, diffusional resistance is smaller in reaction process, so molecular dimension wider range of reactant applicatory；The preparation side of catalyst
Method is fairly simple, at low cost.During being catalyzed the esterification of carboxylic acid and alcohol, mesoporous silica gel surface provided by the present invention
It is bonded the catalyst prepared by the preparation method of alkyl sulfonic acid catalyst and presents higher activity and excellent reuse
Performance.
Description of the drawings
Fig. 1 is catalyst carrier (amorphous mesoporous silica gel) used in the embodiment of the present invention 1 and thus carrier is prepared into
The solid sulfoacid catalyst arrived29Si MAS NMR spectras.
Fig. 2 is catalyst prepared in the embodiment of the present invention 11H→13C CP/MAS NMR spectras.
Specific implementation mode
Using specific embodiment below, the present invention will be further described, but is not intended to limit protection scope of the present invention.
Embodiment 1
(1) in molar ratio 1:8.6:22:1.7 ratio weighs 3- r-chloropropyl trimethoxyl silanes 4.0g, anhydrous second respectively
Alcohol 8.0g, deionized water 8.0g and glacial acetic acid 2.0g, are sufficiently mixed rear wiring solution-forming, with this solution dipping 10.0g through fully dry
Dry amorphous silica gel particle, 20~40 mesh, specific surface area 298m2/ g, average pore size 16.5nm, dip time are 24 hours.
Above-mentioned dipping process is incipient impregnation process, and silica gel all adsorbs maceration extract；
(2) silica gel after the dipping for obtaining (1) step dries 2 hours at 100 DEG C, is then loaded into the stainless steel of 100ml
In reaction kettle, while Na is added2SO3And NaHSO3Mixed aqueous solution 50ml, Na2SO3And NaHSO3Molar ratio be 1:1, always
Mass percentage concentration is 19%, absolute ethyl alcohol 12.5ml.Reaction kettle is heated to 170 DEG C, is stopped after maintaining 4 hours, so
After be down to room temperature；
(3) reaction kettle of (2) step is opened, through solid matter is obtained by filtration.Above-mentioned solid matter is added to 100ml's
It in the aqueous hydrochloric acid solution of 2N, stirs, stops after carrying out 2 hours at room temperature simultaneously.Then hydrochloric acid solution is removed by filtration,
With the abundant washed solid of deionized water, to the pH value of wash water up to until 6~7；
(4) solid matter for obtaining (3) step is 2 hours dry at 120 DEG C, obtains mesoporous silica gel surface bond alkyl sulphur
Acid catalyst.
In attached drawing 129It is shown on Si MAS NMR spectras：Most of silicone hydroxyl on mesoporous silica gel carrier surface and 3- chlorine
Condensation reaction has occurred in the silicone hydroxyl generated after propyl trimethoxy silicane hydrolysis, forms the organic silicon species in surface, wherein silicon
Atom is mainly combined with three Si-O-Si keys with Silica Surface.
Catalyst in attached drawing 21H→13In C CP/MAS NMR spectras, positioned at 54.1ppm, 18.5ppm and 11.9ppm
Spectral peak corresponds respectively to three carbon atoms contained in the propyl sulfonic acid group of surface.
Embodiment 2
The present embodiment is identical as the preparation method in embodiment 1, is a difference in that amorphous silica gel used in the first step
For 20~40 mesh, specific surface area 353m2/ g, average pore size 5.6nm.
Embodiment 3
The present embodiment is identical as the preparation method in embodiment 1, is a difference in that amorphous silica gel used in the first step
For 20~40 mesh, specific surface area 326m2/ g, average pore size 11.8nm.
Embodiment 4
(1) in molar ratio 1:8.6:22:1.7 ratio weighs 3- r-chloropropyl trimethoxyl silanes 4.0g, anhydrous second respectively
Alcohol 8.0g, deionized water 8.0g and glacial acetic acid 2.0g, are sufficiently mixed rear wiring solution-forming, well-dried with this solution dipping 4.0g
Nano structural material MCM-41 molecular sieve powders, specific surface area 917m2/ g, average pore size 2.9nm, dipping while, are filled
The stirring divided, mixing time are 5 hours.Above-mentioned dipping process is excessive dipping process.It after stirring stops, being filtered, removes
Excessive maceration extract (for the 1/3 of original solution), solid matter is statically placed in air 48 hours；
(2) the MCM-41 molecular sieves after the dipping for obtaining (1) step dry 2 hours at 100 DEG C, are then loaded into 50ml's
In stainless steel cauldron, while Na is added2SO3And NaHSO3Mixed aqueous solution 30ml, Na2SO3And NaHSO3Molar ratio be
1:1, gross mass percentage concentration is 19%, absolute ethyl alcohol 7.5ml.Reaction kettle is heated to 170 DEG C, is stopped after maintaining 4 hours
Only, then it is down to room temperature；
(3) reaction kettle of (2) step is opened, through solid matter is obtained by filtration.Above-mentioned solid matter is added to 27ml's
It in the aqueous solution of nitric acid of 5N, stirs, stops after carrying out 2 hours at room temperature simultaneously.Then salpeter solution is removed by filtration,
With the abundant washed solid of deionized water, to the pH value of wash water up to until 6~7；
(4) solid matter for obtaining (3) step is 4 hours dry at 120 DEG C, obtains MCM-41 molecular sieve surfaces bonding alkane
Base sulfonic acid catalyst.
Embodiment 5
The present embodiment is identical as the preparation method in embodiment 4, is a difference in that nanostructure used in the first step
Material MCM-41 molecular sieve powders are replaced with SBA-15 molecular sieve powders, specific surface area 787m2/ g, average pore size 6.5nm.Finally
Obtain SBA-15 molecular sieve surfaces bonding alkyl sulfonic acid catalyst.
Embodiment 6
(1) in molar ratio 1:20:50:0 ratio weighs 3- r-chloropropyl trimethoxyl silanes 4.0g, absolute ethyl alcohol respectively
18.5g and deionized water 18.1g, is sufficiently mixed rear wiring solution-forming, impregnates 22.5g amorphous silicons fully dried with this solution
Glue particle, 20~40 mesh, specific surface area 298m2/ g, average pore size 16.5nm, dip time are 24 hours.Above-mentioned dipping process
For incipient impregnation process, silica gel all adsorbs maceration extract；
(2) silica gel after the dipping for obtaining (1) step dries 2 hours at 100 DEG C, is then loaded into the stainless steel of 100ml
In reaction kettle, while Na is added2SO3And NaHSO3Mixed aqueous solution 46ml, Na2SO3And NaHSO3Molar ratio be 1:1, always
Mass percentage concentration is 5%, absolute ethyl alcohol 12ml.Reaction kettle is heated to 180 DEG C, is stopped after maintaining 0.5 hour, then
It is down to room temperature；
(3) reaction kettle of (2) step is opened, through solid matter is obtained by filtration.Above-mentioned solid matter is added to 81ml's
It in the aqueous sulfuric acid of 0.5N, stirs, stops after carrying out 2 hours at room temperature simultaneously.Then sulfuric acid solution is filtered out by crossing
It goes, with the abundant washed solid of deionized water, to the pH value of wash water up to until 6~7；
(4) solid matter for obtaining (3) step is 2 hours dry at 120 DEG C, obtains mesoporous silica gel surface bond alkyl sulphur
Acid catalyst.
Embodiment 7
The present embodiment is identical as the preparation method in embodiment 1, is a difference in that and is added without nothing in the reaction of second step
Water-ethanol.
Embodiment 8
The present embodiment is identical as the preparation method in embodiment 7, is a difference in that Na used in second step2SO3With
NaHSO3Molar ratio be：0:1.
Embodiment 9
The present embodiment is identical as the preparation method in embodiment 7, is a difference in that Na used in second step2SO3With
NaHSO3Molar ratio be：1:2.
Embodiment 10
The present embodiment is identical as the preparation method in embodiment 7, is a difference in that Na used in second step2SO3With
NaHSO3Molar ratio be：2:1.
Embodiment 11
The present embodiment is identical as the preparation method in embodiment 7, is a difference in that Na used in second step2SO3With
NaHSO3Molar ratio be：1:0.
Embodiment 12
(1) in molar ratio 1:5:1:10 ratio weighs 3- chloropropyl triethoxysilanes 4.85g, absolute ethyl alcohol respectively
4.63g, deionized water 0.36g and formic acid 9.3g, are sufficiently mixed rear wiring solution-forming, fully dried with this solution dipping 9.3g
Amorphous silica gel particle, 20~40 mesh, specific surface area 298m2/ g, average pore size 16.5nm, dip time are 24 hours.It is above-mentioned
Dipping process is incipient impregnation process, and silica gel all adsorbs maceration extract；
(2) silica gel after the dipping for obtaining (1) step dries 2 hours at 120 DEG C, and the stainless steel for being then loaded into 50ml is anti-
It answers in kettle, while Na is added2SO3And NaHSO3Mixed aqueous solution 20ml, Na2SO3And NaHSO3Molar ratio be 1:1, total matter
It is 25% to measure percentage concentration, absolute ethyl alcohol 20ml.Reaction kettle is heated to 80 DEG C, stops after maintaining 10 hours, then drops
To room temperature；
(3), (4) step is identical as (3) in embodiment 1, (4) step.
Embodiment 13
The present embodiment is identical as the preparation method in embodiment 1, is a difference in that in the first step that weighing deionized water is
5.9g, glacial acetic acid are replaced with mass concentration by 37% concentrated hydrochloric acid 3.3g.
Embodiment 14
The present embodiment is identical as the preparation method in embodiment 1, is a difference in that the deionized water weighed in the first step is
8.0g, glacial acetic acid are replaced with mass concentration by 98.3% concentrated sulfuric acid 1.6g.
Embodiment 15
The present embodiment is identical as the preparation method in embodiment 1, is a difference in that the deionized water weighed in the first step is
7.0g, glacial acetic acid are replaced with mass concentration by 68% concentrated nitric acid 3.1g.
Embodiment 16
Catalyst prepared in above-described embodiment 1-7 and embodiment 12 is used for catalytic esterification.Reaction condition is：
0.2g catalyst and stirring magneton are added in the stainless steel autoclave of 50ml, and the mixed solution of carboxylic acid and alcohol is then added
20g is as reactant.Oil bath heating device is put into after reaction kettle is closed, magnetic stirring apparatus is installed in bottom.Oil bath heating is opened,
It is raised to the reaction temperature of setting in 20 minutes, opens stirring immediately and is reacted, and start timing.The reaction of setting to be achieved
After time, reaction kettle is taken out from oil bath immediately, cold water flush is used in combination to be rapidly decreased to room temperature.Then reaction kettle is opened, is filtered
Solid catalyst is removed, the acid base titration method Ca-5a-40 that product liquid is announced with American Oil Chemists Society is divided
Analysis.
Reaction condition and the results are shown in table below：
Table 1
4 catalyst prepared in embodiment 8-11 are used for the esterification of catalysis ethanol and acetic acid.Reaction condition is：
0.2g catalyst and stirring magneton are added in the stainless steel autoclave of 50ml, and ethyl alcohol is then added and the mixing of acetic acid is molten
Liquid, ethyl alcohol：Acetic acid molar ratio=6：1,20g as reactant.Oil bath heating device, bottom installation are put into after reaction kettle is closed
Magnetic stirring apparatus.Oil bath heating is opened, 80 DEG C are raised in 20 minutes, stirring is opened immediately and is reacted, and start timing.Instead
After answering 3 hours, reaction kettle is taken out from oil bath immediately, cold water flush is used in combination to be rapidly decreased to room temperature.Then reaction kettle is opened,
Be filtered to remove solid catalyst, the acid base titration method Ca-5a-40 that product liquid is announced with American Oil Chemists Society into
Row analysis.The results are shown in table below：
Table 2
3 catalyst prepared in embodiment 13-15 are used for the esterification of ethyl alcohol and acetic acid.Reaction condition is same as above.
The results are shown in table below：
Table 3
| Catalyst source | Embodiment 13 | Embodiment 14 | Embodiment 15 |
| Prepare type sour used in (1) step | Concentrated hydrochloric acid | The concentrated sulfuric acid | Concentrated nitric acid |
| The conversion ratio of acetic acid | 92.4% | 90.6% | 91.2% |
The investigation of catalyst repeat performance：
Mesoporous silica gel surface bond alkyl sulfonic acid catalyst made from embodiment 1 is applied to the esterification of lauric acid and ethyl alcohol
In reaction, reaction condition is：0.2g catalyst and stirring magneton are added in the stainless steel autoclave of 50ml, are then added
Lauric acid and ethyl alcohol, ethyl alcohol：Lauric acid molar ratio=8：1, mixed solution 20g is as reactant.It is put into after reaction kettle is closed
Magnetic stirring apparatus is installed in oil bath heating device, bottom.Oil bath heating is opened, 120 DEG C are raised in 20 minutes, opens stirring immediately
It is reacted, and starts timing.After 2 hours, reaction kettle is taken out from oil bath immediately, cold water flush is used in combination to be rapidly decreased to room
Temperature.Then reaction kettle is opened, solid catalyst is filtered to remove, the soda acid that product liquid is announced with American Oil Chemists Society
Titration method Ca-5a-40 is analyzed.The catalyst filtered out is directly used in next secondary response, reaction condition and last phase
Together.It is so repeated 7 times, investigates the variation of lauric acid conversion ratio.As a result it is listed in the table below：
Table 4
Claims (9)
1. a kind of preparation method of mesoporous silica gel surface bond alkyl sulfonic acid catalyst, which is characterized in that steps are as follows：
The first step, by 3- chloropropyls alkoxy silane, absolute ethyl alcohol, water and acid according to molar ratio be 1:5~20:1~50:0~
10 ratio wiring solution-forming impregnates mesoporous silica gel with this solution, is soaked using equi-volume impregnating or using excessive infusion process
Stain is removed excessive liquid after dipping is abundant when using excessive infusion process；
Mesoporous silica gel after dipping that the first step obtains is dried second step according to known methods, removes volatility liquid
Body ingredient；
Third walks, and the mesoporous silica gel sample after dipping and drying that second step obtains is put into containing Na2SO3And NaHSO3
Mixed aqueous solution in, add absolute ethyl alcohol, reacted 0.5~10 hour at 80~180 DEG C, be then down to room temperature；
Third is walked the liquid in mixture obtained by the reaction and removed, solid product is put into strong acid aqueous solution by the 4th step
Room temperature is acidified, and at 0.5 hour or more, removing strong acid was then washed with deionized in the time, until the pH value of wash water is more than 6
When stop；
Solid sample of 4th step after washed is dried and removed moisture, obtains mesoporous silica gel surface bond alkyl by the 5th step
Sulfonic acid catalyst.
2. a kind of preparation method of mesoporous silica gel surface bond alkyl sulfonic acid catalyst as described in claim 1, feature exist
In：The 3- chloropropyl alkoxy silanes are 3- r-chloropropyl trimethoxyl silanes or 3- chloropropyl triethoxysilanes.
3. a kind of preparation method of mesoporous silica gel surface bond alkyl sulfonic acid catalyst as described in claim 1, feature exist
In：Acid described in the first step is hydrochloric acid, sulfuric acid, nitric acid, formic acid or acetic acid.
4. a kind of preparation method of mesoporous silica gel surface bond alkyl sulfonic acid catalyst as described in claim 1, feature exist
In：Acid described in the first step or the aqueous solution for acid, the wherein water of 3- chloropropyls alkoxy silane, absolute ethyl alcohol, water and acid
The ratio for the amount of substance that solution is added is the amount ratio of the substance of the aqueous acid medium of acid, and contained in the aqueous solution of acid
The gauge of the substance of water enters in the amount of the substance of the water of addition.
5. a kind of preparation method of mesoporous silica gel surface bond alkyl sulfonic acid catalyst as described in claim 1, feature exist
In：The mesoporous silica gel, including average pore size is in 2 nanometers or more of various amorphous silica gels and nano structural material
MCM-41 or SBA-15 molecular sieves.
6. a kind of preparation method of mesoporous silica gel surface bond alkyl sulfonic acid catalyst as described in claim 1, feature exist
In：Contain Na described in third step2SO3And NaHSO3Mixed aqueous solution, Na contained therein2SO3And NaHSO3It is total
Molal quantity is 1~10 times of the 3- chloropropyl alkoxy silanes being impregnated on mesoporous silica gel, Na2SO3And NaHSO3Molar ratio be
0:1~1:0, gross mass percentage concentration is 5%~25%.
7. a kind of preparation method of mesoporous silica gel surface bond alkyl sulfonic acid catalyst as described in claim 1, feature exist
In：The addition of absolute ethyl alcohol contains Na for described in third step2SO3And NaHSO30~1 times of mixed aqueous solution volume.
8. a kind of preparation method of mesoporous silica gel surface bond alkyl sulfonic acid catalyst as described in claim 1, feature exist
In：Strong acid aqueous solution described in 4th step is hydrochloric acid, sulfuric acid or aqueous solution of nitric acid, a concentration of 0.5N~5N, H contained therein+Molal quantity be 2~10 times of molal quantity of the 3- chloropropyl alkoxy silanes being impregnated on mesoporous silica gel.
9. using a kind of mesoporous silica gel surface bond alkyl sulfonic acid prepared such as claim 1-8 any one of them preparation methods
Catalyst.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN109824719A (en) * | 2019-02-18 | 2019-05-31 | 大连工业大学 | A kind of preparation method of phenylbenzimidazole sulfonic acid base modified SBA-15 composite material and its application in composite structure phosphatide |
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| CN113426481A (en) * | 2021-07-19 | 2021-09-24 | 昆明理工大学 | Catalyst for preparing alpha-tetralone by catalytic oxidation and preparation method and application thereof |
| CN113426481B (en) * | 2021-07-19 | 2023-10-10 | 昆明理工大学 | Catalyst for preparing alpha-tetralone by catalytic oxidation and preparation method and application thereof |
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