CN108654687A - A kind of mesoporous silica gel load alkyl sulfonic acid catalyst and preparation method thereof - Google Patents
A kind of mesoporous silica gel load alkyl sulfonic acid catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN108654687A CN108654687A CN201810412810.6A CN201810412810A CN108654687A CN 108654687 A CN108654687 A CN 108654687A CN 201810412810 A CN201810412810 A CN 201810412810A CN 108654687 A CN108654687 A CN 108654687A
- Authority
- CN
- China
- Prior art keywords
- silica gel
- mesoporous silica
- sulfonic acid
- preparation
- acid catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- 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
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- 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
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Abstract
The present invention relates to a kind of alkyl sulfonic acid catalyst and preparation method thereof of mesoporous silica gel load.Method is as follows：It after the aqueous solution of certain density alkali metal sulfite is mixed with ethyl alcohol, is heated to certain temperature and stirs, be then slowly added into the ethanol solution of 3 chloropropyl alkoxy silanes, react certain time.Then reaction mixture is filtered, concentrates filtrate, impregnate mesoporous silica gel with the filtrate after concentration.Silica gel after dipping obtains the catalyst of the present invention after drying, isolation air heat-activated, strong acid acidification, washing, drying.The method for preparing catalyst is simple, at low cost.During catalytic esterification, which presents higher activity and excellent repeat performance, and 6 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 alkyl sulfonic acid catalyst of mesoporous silica gel load
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 patent literatures such as CN103611569A and CN103623863A.Influence factor pole in its preparation process
It is more, cause to be difficult to control its final duct and surface texture, so not having high activity and stability as expected still, especially
It is 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：
By the so-called rear means such as grafting or direct synthesis technique, by silane coupling agent (the 3- mercaptopropyi trimethoxies with sulfydryl
Base silane etc.) be bonded with carrier, then again by sulfhydryl oxidase be sulfonic group.Carrier is with mesoporous silica zeolite (also referred to as mesoporous
Silica gel) based on such as MCM-41 and SBA-15.Above-mentioned catalyst is typical solid proton acid catalyst, can be effectively catalyzed
The reactions such as esterification, represent a developing direction of solid acid catalyst.But it, which is prepared, generally requires complicated hydrothermal synthesis mistake
Journey, and need to have the mercaptan compound of strong odor to participate in；The oxidation of sulfydryl is often incomplete, causes Surface acidity relatively low,
Catalyst activity is difficult to improve again；The recycling performance of catalyst is undesirable.
In conclusion mesoporous silica gel loads alkyl sulfonic acid catalyst, although years of researches are have passed through, but still there is
Various problems hinder its industrialized process.
Invention content
The present invention is based on the above shortcoming, a kind of mesoporous silica gel load sulfonic acid catalyst and preparation method thereof is provided.Profit
With this method prepare catalyst, overcome the conventional homogeneous such as concentrated sulfuric acid catalyst cannot recycle, etching apparatus the shortcomings of,
It is excessively high and active not high enough that existing mesoporous silica gel load sulfonic acid catalyst preparation process complexity, cost are overcome simultaneously, especially
It is to recycle the bad disadvantage of performance.In the esterification reaction process of catalysis carboxylic acid and alcohol, which presents very high
Active and excellent repeat performance.
The technology used in the present invention is as follows：A kind of preparation method of mesoporous silica gel load alkyl sulfonic acid catalyst, step
It is as follows：
Step 1, the alkali metal sulfite aqueous solution that production quality percentage concentration is 5%~20%, adds anhydrous second
Then alcohol is heated and is sufficiently stirred, when system temperature rises to 70~180 DEG C, maintain temperature constant, and starts to be added thereto
The ethanol solution of 3- chloropropyl alkoxy silanes is reacted, and feed time is at least 2 hours, is added constant at this again after feed liquid
At a temperature of be stirred to react at least 2 hours；
Step 2, the mixture obtained after step 1 is reacted are cooled to room temperature filtering, concentrate the filtrate to original volume
0.2~1 times, then with the mesoporous silica gel of the well-dried mistake of filtrate incipient impregnation after concentration；
Step 3, the silica dehydrator after the dipping that step 2 is obtained remove volatile liquid composition；
Step 4, the silica gel after the drying that step 3 is obtained dry 1 at 120 DEG C~300 DEG C in the absence of air conditions
~20 hours；
Silica gel sample after drying that step 4 obtains is put into strong acid aqueous solution and is acidified in room temperature by step 5,
At 0.5 hour or more, removing strong acid was then washed with deionized in time, until the pH value of wash water stops when being more than 6；
Step 6, the solid sample after step 5 is washed dry and remove moisture, obtain mesoporous silica gel surface bond alkane
Base sulfonic acid catalyst.
The present invention also has following feature：
1, alkali metal sulfite as described above is sodium sulfite, potassium sulfite or seven hydration sodium sulfites.
2, the addition of absolute ethyl alcohol is the 0~1 of alkali metal sulfite aqueous solution volume used in step 1 as above
Times.
3,3- chloropropyls alkoxy silane as described above is three ethoxy of 3- r-chloropropyl trimethoxyl silanes or 3- chloropropyls
Base silane.
4, the ethanol solution of 3- chloropropyls alkoxy silane as described above, wherein 3- chloropropyls alkoxy silane and ethyl alcohol
Molar ratio be 1:0~1:20.
5, the molal quantity of the 3- chloropropyl alkoxy silanes described in step 1 as above is alkali metal sulfite used
0.6~1.1 times of molal quantity.
6, the side of the ethanol solution that 3- chloropropyl alkoxy silanes are added into reaction system described in step 1 as above
Formula is：It is at the uniform velocity added dropwise or is added in batches, complete soln adds within 48 hours.
7, mesoporous silica gel as described above is various amorphous silica gels, nanostructure material of the average pore size at 2 nanometers or more
Expect MCM-41 or SBA-15 molecular sieves.
8, the strong acid aqueous solution described in step 5 as above is hydrochloric acid, sulfuric acid or aqueous solution of nitric acid, a concentration of 0.5N~5N,
H contained by strong acid aqueous solution described in step 5+Molal quantity be 3- chloropropyls alkoxy silane used in step 1 mole
Several 2~10 times.
9, alkyl sulfonic acid catalyst is loaded using a kind of mesoporous silica gel prepared by preparation method as described above.
The principle of the present invention is as follows：
In the preparation method of above-mentioned mesoporous Silica Surface load alkyl sulfonic acid catalyst, the purpose of the first step is to utilize sulfurous
The nucleophilic displacement of fluorine of acid group acts on, and so that the chlorine atom on chloropropyl alkoxy silane is converted into sulfonate sodium structure, while in solution
The presence of water can make alkoxy be hydrolyzed to silicone hydroxyl, generate the compound such as lower structure：
The purpose of second step and third step is the surface for making above compound evenly spread to mesoporous silica gel.
The purpose of 4th step is that hydroxyl in above compound is made fully to react bonding with Silica Surface hydroxyl, and mutually
Between be condensed bonding, realize firm load.
The purpose of 5th step and the 6th step is that the propyl sulfonic acid sodium salt structure for making Silica Surface be bonded is changed into propyl sulfonic acid
Structure, as follows：
Advantages of the present invention and advantageous effect：Alkyl sulfonic acid catalyst is loaded using mesoporous silica gel provided by the present invention
Catalyst prepared by preparation method will not cause to corrode to equipment；With chemistry between the active group and carrier of catalyst
Key is combined, and very securely, is not lost in during the reaction；Since mesoporous silica gel carrier used has larger aperture, instead
Diffusional resistance is smaller during answering, so molecular dimension wider range of reactant applicatory；The preparation method ratio of catalyst
It is relatively simple, it is at low cost.During being catalyzed the esterification of carboxylic acid and alcohol, loaded using mesoporous silica gel provided by the present invention
Catalyst prepared by the preparation method of alkyl sulfonic acid catalyst presents higher activity and excellent repeat 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 later infrared spectrum of the infrared spectrum and the Catalyst Adsorption pyridine of the solid sulfoacid catalyst arrived.
Fig. 2 is catalyst carrier (SBA-15 molecular sieves) used in the embodiment of the present invention 6 and thus carrier is prepared
Solid sulfoacid catalyst infrared spectrum.
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) 7.5g anhydrous sodium sulfites are weighed, 42.5g water is added, is made into the solution of mass percentage concentration 15%, is put into peace
In the 250ml three-neck flasks for having filled spherical condensation tube and thermometer, and 10ml absolute ethyl alcohols are added.With oil bath heating three-neck flask
Temperature to reaction mixture reaches 80 DEG C and keeps, and starts the second that 34.5g 3- r-chloropropyl trimethoxyl silanes are added dropwise thereto
Alcoholic solution, wherein 3- r-chloropropyl trimethoxyl silanes:Ethyl alcohol molar ratio=1:The quality of 8.3,3- r-chloropropyl trimethoxyl silanes
For 11.8g, molal quantity is identical as the molal quantity of anhydrous sodium sulfite used.To be at the uniform velocity added dropwise, added within 10 hours,
It is maintained at 80 DEG C to continue to stop after being stirred to react 2.5 hours, three-neck flask is taken out to cooling from oil bath；
(2) reaction mixture that (1) step obtains is cooled to room temperature, is filtered, remove a small amount of solid matter (1.0g
Left and right).Filtrate total volume is 93ml or so.Filtrate heating is concentrated to 50ml, then incipient impregnation 25g is fully dried
Amorphous silica gel particle, 20~40 mesh, specific surface area 298m2/ g, average pore size 16.5nm, dip time are 24 hours；
(3) silica gel after impregnating (2) step dries 3 hours in 120 DEG C of baking oven；
(4) solid matter that (3) step obtains is put into tube furnace, in the N of 240 DEG C of flowing2It is dried 4 hours in atmosphere；
(5) it in the aqueous hydrochloric acid solution for the 2N that the solid matter that (4) step obtains is added to 250ml, stirs simultaneously, in room temperature
Lower progress stops after 2 hours.Then hydrochloric acid solution is removed by filtration, with the abundant washed solid of deionized water, until washing
The pH value of water is up to until 6~7；
(6) solid matter for obtaining (5) step is 2 hours dry at 120 DEG C, obtains mesoporous silica gel load alkyl sulfonic acid and urges
Agent.
Attached drawing 1 is shown：There is the unexistent characteristic absorption peak of pure silicon glue on the infrared spectrum of silica gel load sulfonic acid catalyst,
The vibration for corresponding respectively to sulfonic group and propyl group shows there is propyl sulfonic acid structure on catalyst surface；Silica gel load sulphur
Infrared spectrum after acid catalyst Adsorption of Pyridine further confirms sulfonic presence on catalyst surface.
Embodiment 2
(1) 2.5g anhydrous potassium sulfites are weighed, 47.5g water is added, is made into the solution of mass percentage concentration 5%, is put into peace
In the 250ml three-neck flasks for having filled spherical condensation tube and thermometer, and 50ml absolute ethyl alcohols are added.With oil bath heating three-neck flask
Temperature to reaction mixture reaches 70 DEG C and keeps, and starts that 20.2g 3- chloropropyl triethoxy silicon is added in batches thereto
The ethanol solution of alkane, wherein 3- chloropropyl triethoxysilanes:Ethyl alcohol molar ratio=1:20,3- chloropropyl triethoxysilanes
Quality is 4.18g, and molal quantity is 1.1 times of anhydrous potassium sulfite molal quantity.1ml solution is added every time, adds one within every 20 minutes
It is secondary, 70 DEG C are maintained after adding and continues to stop after being stirred to react 2 hours, and three-neck flask is taken out to cooling from oil bath；
(2) reaction mixture that (1) step obtains is cooled to room temperature, is filtered, remove a small amount of solid matter (0.5g
Left and right).Filtrate total volume is 116ml or so.Filtrate heating is concentrated to 0.2 times, i.e. 23ml of original volume, then in equal volume
Impregnate 11.5g amorphous silica gel particles fully dried, 20~40 mesh, specific surface area 298m2/ g, average pore size 16.5nm,
Dip time is 24 hours；
(3) silica gel after impregnating (2) step dries 3 hours in 120 DEG C of baking oven；
(4) solid matter that (3) step obtains is put into tube furnace, in the N of 300 DEG C of flowing2It is dried 1 hour in atmosphere；
(5) it in the aqueous sulfuric acid for the 0.5N that the solid matter that (4) step obtains is added to 69.5ml, stirs simultaneously,
Stop after carrying out 0.6 hour at room temperature.Then sulfuric acid solution is removed by filtration, solids is fully washed with deionized water
Matter, to the pH value of wash water up to until 6~7；
(6) solid matter for obtaining (5) step is 2 hours dry at 120 DEG C, obtains mesoporous silica gel load alkyl sulfonic acid and urges
Agent.
Embodiment 3
It is identical as the preparation method in embodiment 1, it is a difference in that amorphous silicon fully dry used in (2) step
Glue particle is 30g, 20~40 mesh, specific surface area 353m2/ g, average pore size 5.6nm.
Embodiment 4
It is identical as the preparation method in embodiment 1, it is a difference in that amorphous silicon fully dry used in (2) step
Glue particle is 28g, 20~40 mesh, specific surface area 326m2/ g, average pore size 11.8nm.
Embodiment 5
(1) it weighs 15.0g seven and is hydrated sodium sulfite, 35.0g water is added, is made into the solution of mass percentage concentration 15%, puts
In the 100ml three-neck flasks for entering to be mounted with spherical condensation tube and thermometer.With oil bath heating three-neck flask to reaction mixture
Temperature reaches 100 DEG C and keeps, and starts that 3- r-chloropropyl trimethoxyl silanes 11.8g is added dropwise thereto.To be at the uniform velocity added dropwise, at 4
It is added in hour, is maintained at 100 DEG C and continues to stop after being stirred to react 3 hours, three-neck flask is taken out to cooling from oil bath；
(2) reaction mixture that (1) step obtains is cooled to room temperature, is filtered, remove a small amount of solid matter (1.5g
Left and right).Filtrate total volume is 60ml or so.Filtrate does not have to concentration, direct incipient impregnation 20g nanostructures fully dried
Material MCM-41 molecular sieve powders, specific surface area 917m2/ g, average pore size 2.9nm, dip time are 48 hours；
(3) the MCM-41 molecular sieve powders after impregnating (2) step are dried 5 hours in 120 DEG C of baking oven；
(4) solid matter that (3) step obtains is put into tube furnace, in the N of 200 DEG C of flowing2It is dried 10 hours in atmosphere；
(5) it in the aqueous solution of nitric acid for the 5N that the solid matter that (4) step obtains is added to 119ml, stirs simultaneously, in room temperature
Lower progress stops after 2 hours.Then salpeter solution is removed by filtration, with the abundant washed solid of deionized water, until washing
The pH value of water is up to until 6~7；
(6) solid matter for obtaining (5) step is 5 hours dry at 120 DEG C, obtains the molecular sieve carried alkyl sulphurs of MCM-41
Acid catalyst.
Embodiment 6
(1) 10.0g anhydrous sodium sulfites are weighed, 40.0g water is added, is made into the solution of mass percentage concentration 20%, is put into
It is mounted in the 250ml three-neck flasks of spherical condensation tube and thermometer, and 10ml absolute ethyl alcohols is added.It is burnt with three neck of oil bath heating
The temperature of bottle to reaction mixture reaches 110 DEG C and keeps, and starts that 70.5g 3- r-chloropropyl trimethoxyl silanes are added dropwise thereto
Ethanol solution, wherein 3- r-chloropropyl trimethoxyl silanes:Ethyl alcohol molar ratio=1:The matter of 15,3- r-chloropropyl trimethoxyl silanes
Amount is 15.7g, and molal quantity is equal with the molal quantity of anhydrous sodium sulfite.To be at the uniform velocity added dropwise, added within 48 hours, then
It maintains 110 DEG C to continue to stop after being stirred to react 2 hours, three-neck flask is taken out to cooling from oil bath；
(2) reaction mixture that (1) step obtains is cooled to room temperature, is filtered, remove a small amount of solid matter (1.8g
Left and right).Filtrate total volume is 129ml or so.Filtrate heating is concentrated to 40ml, then incipient impregnation 13g is well-dried
SBA-15 molecular sieve powders, specific surface area 787m2/ g, average pore size 6.5nm, dip time are 48 hours；
(3) the SBA-15 molecular sieve powders after impregnating (2) step are dried 5 hours in 120 DEG C of baking oven；
(4) solid matter that (3) step obtains is put into tube furnace, in the N of 240 DEG C of flowing2It is dried 6 hours in atmosphere；
(5) it in the aqueous hydrochloric acid solution for the 2N that the solid matter that (4) step obtains is added to 200ml, stirs simultaneously, in room temperature
Lower progress stops after 10 hours.Then hydrochloric acid solution is removed by filtration, with the abundant washed solid of deionized water, until washing
The pH value of water is up to until 6~7；
(6) solid matter for obtaining (5) step is 6 hours dry at 120 DEG C, obtains the molecular sieve carried alkyl sulphurs of SBA-15
Acid catalyst.
Attached drawing 2 is shown：SBA-15 is loaded on the infrared spectrum of sulfonic acid catalyst, and there is the unexistent features of pure SBA-15 to inhale
Peak is received, the vibration of sulfonic group and propyl group is corresponded respectively to, shows that there is propyl sulfonic acid structure on catalyst surface.
Embodiment 7
(1) 7.5g anhydrous sodium sulfites are weighed, 42.5g water is added, is made into the solution of mass percentage concentration 15%, is put into
In the stainless steel autoclave of 250ml, and 10ml absolute ethyl alcohols are added.With the temperature of oil bath heating reaction kettle to reaction mixture
Degree reaches 140 DEG C and keeps, and then starts that 31.8g 3- r-chloropropyl trimethoxyls are added dropwise into reaction kettle using High pressure feeding pump
The ethanol solution of silane, wherein 3- r-chloropropyl trimethoxyl silanes:Ethyl alcohol molar ratio=1:15,3- r-chloropropyl trimethoxyl silanes
Quality be 7.1g, be 0.6 times of anhydrous sodium sulfite molal quantity.To be at the uniform velocity added dropwise, adds within 10 hours, then maintain
Stop after continuing to be stirred to react 2.5 hours at 140 DEG C, reaction kettle is taken out to cooling from oil bath；
(2) reaction mixture that (1) step obtains is cooled to room temperature, is filtered, remove a small amount of solid matter (0.5g
Left and right).Filtrate total volume is 95ml or so.Filtrate heating is concentrated to 50ml, then incipient impregnation 25g is fully dried
Amorphous silica gel particle, 20~40 mesh, specific surface area 298m2/ g, average pore size 16.5nm, dip time are 24 hours；
(3) silica gel after impregnating (2) step dries 3 hours in 120 DEG C of baking oven；
(4) solid matter that (3) step obtains is put into tube furnace, in the N of 120 DEG C of flowing2It is dried 20 hours in atmosphere；
(5) it in the aqueous hydrochloric acid solution for the 2N that the solid matter that (4) step obtains is added to 250ml, stirs simultaneously, in room temperature
Lower progress stops after 2 hours.Then hydrochloric acid solution is removed by filtration, with the abundant washed solid of deionized water, until washing
The pH value of water is up to until 6~7；
(6) solid matter for obtaining (5) step is 2 hours dry at 120 DEG C, obtains mesoporous silica gel load alkyl sulfonic acid and urges
Agent.
Embodiment 8
(1) 7.5g anhydrous sodium sulfites are weighed, 42.5g water is added, is made into the solution of mass percentage concentration 15%, is put into
In the stainless steel autoclave of 250ml, and 10ml absolute ethyl alcohols are added.With the temperature of oil bath heating reaction kettle to reaction mixture
Degree reaches 160 DEG C and keeps, and then starts that 31.3g 3- r-chloropropyl trimethoxyls are added dropwise into reaction kettle using High pressure feeding pump
The ethanol solution of silane, wherein 3- r-chloropropyl trimethoxyl silanes:Ethyl alcohol molar ratio=1:10,3- r-chloropropyl trimethoxyl silanes
Quality be 9.45g, be 0.8 times of anhydrous sodium sulfite molal quantity.To be at the uniform velocity added dropwise, adds within 6 hours, then maintain
Stop after continuing to be stirred to react 2 hours at 160 DEG C, reaction kettle is taken out to cooling from oil bath；
(2) reaction mixture that (1) step obtains is cooled to room temperature, is filtered, remove a small amount of solid matter (0.3g
Left and right).Filtrate total volume is 90ml or so.Filtrate heating is concentrated to 50ml, then incipient impregnation 25g is fully dried
Amorphous silica gel particle, 20~40 mesh, specific surface area 298m2/ g, average pore size 16.5nm, dip time are 24 hours；
(3) silica gel after impregnating (2) step dries 3 hours in 120 DEG C of baking oven；
(4) solid matter that (3) step obtains is put into tube furnace, in the N of 150 DEG C of flowing2It is dried 15 hours in atmosphere；
(5), (6) step is identical as (5) in embodiment 1, (6) step.
Embodiment 9
(1) 7.5g anhydrous sodium sulfites are weighed, 42.5g water is added, is made into the solution of mass percentage concentration 15%, is put into
In the stainless steel autoclave of 250ml, and 10ml absolute ethyl alcohols are added.With the temperature of oil bath heating reaction kettle to reaction mixture
Degree reaches 180 DEG C and keeps, and then starts that 25.5g 3- r-chloropropyl trimethoxyls are added dropwise into reaction kettle using High pressure feeding pump
The ethanol solution of silane, wherein 3- r-chloropropyl trimethoxyl silanes:Ethyl alcohol molar ratio=1:5,3- r-chloropropyl trimethoxyl silanes
Quality be 11.8g, it is identical as the molal quantity of anhydrous sodium sulfite.To be at the uniform velocity added dropwise, adds within 2 hours, then maintain
Stop after continuing to be stirred to react 2 hours at 180 DEG C, reaction kettle is taken out to cooling from oil bath；
(2) reaction mixture that (1) step obtains is cooled to room temperature, is filtered, remove a small amount of solid matter (0.2g
Left and right).Filtrate total volume is 85ml or so.Filtrate heating is concentrated to 50ml, then incipient impregnation 25g is fully dried
20~40 mesh of amorphous silica gel particle, specific surface area 298m2/ g, average pore size 16.5nm, dip time are 24 hours；
(3) silica gel after impregnating (2) step dries 3 hours in 120 DEG C of baking oven；
(4) solid matter that (3) step obtains is put into tube furnace, in the N of 180 DEG C of flowing2It is dried 10 hours in atmosphere；
(5), (6) step is identical as (5) in embodiment 1, (6) step.
Embodiment 10
Catalyst prepared in above-described embodiment 1-9 is used for catalytic esterification.Reaction condition is：50ml not
Addition 0.2g catalyst and stirring magneton, are then added the mixed solution 20g of acetic acid and ethyl alcohol in rust steel autoclave, wherein
Ethyl alcohol:Acetic acid molar ratio=6:1, as reactant.Oil bath heating device is put into after reaction kettle is closed, bottom installation magnetic force stirs
Mix device.Oil bath heating is opened, 80 DEG C are raised in 20 minutes, stirring is opened immediately and is reacted, keeps temperature-resistant 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 is opened
Kettle is filtered to remove solid catalyst, the acid base titration method Ca-5a- that product liquid is announced with American Oil Chemists Society
40 are analyzed.
Reaction result is as shown in the table：
Table 1
The investigation of catalyst repeat performance：
Mesoporous silica gel area load sulfonic acid catalyst made from embodiment 1 is applied to the esterification of lauric acid and ethyl alcohol
In, reaction condition is：0.1g catalyst and stirring magneton are added in the stainless steel autoclave of 50ml, and bay is then added
The mixed solution 20g of acid and ethyl alcohol is as reactant, wherein ethyl alcohol：Lauric acid molar ratio=8：1.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, keep temperature-resistant and starts timing.After 2 hours, reaction kettle is taken out from oil bath immediately, cold water flush is used in combination
It is rapidly decreased to room temperature.Then reaction kettle is opened, solid catalyst is filtered to remove, by product liquid American Oil Chemists Society
The acid base titration method Ca-5a-40 of announcement is analyzed.The catalyst filtered out is directly used in next secondary response, reaction condition
It is identical as the last time.It is so repeated 6 times, investigates the variation of lauric acid conversion ratio.As a result it is listed in the table below：
Table 2
| Number of repetition | 0 | 1 | 2 | 3 | 4 | 5 | 6 |
| Lauric acid conversion ratio (%) | 92.4 | 91.7 | 91.6 | 91.5 | 91.8 | 92.0 | 91.7 |
Claims (10)
1. a kind of preparation method of mesoporous silica gel load alkyl sulfonic acid catalyst, which is characterized in that steps are as follows：
Step 1, the alkali metal sulfite aqueous solution that production quality percentage concentration is 5%~20%, adds absolute ethyl alcohol,
Then it heats and is sufficiently stirred, when system temperature rises to 70~180 DEG C, maintain temperature constant, and start that 3- is added thereto
The ethanol solution of chloropropyl alkoxy silane is reacted, and feed time is at least 2 hours, is added after feed liquid again in the constant temperature
It is stirred to react under degree at least 2 hours；
Step 2, the mixture obtained after step 1 is reacted are cooled to room temperature filtering, concentrate the filtrate to original volume 0.2~
1 times, then with the mesoporous silica gel of the well-dried mistake of filtrate incipient impregnation after concentration；
Step 3, the silica dehydrator after the dipping that step 2 is obtained remove volatile liquid composition；
Step 4, the silica gel after the drying that step 3 is obtained dry 1~20 at 120 DEG C~300 DEG C in the absence of air conditions
Hour；
Silica gel sample after drying that step 4 obtains is put into strong acid aqueous solution and is acidified in room temperature by step 5, the time
At 0.5 hour or more, removing strong acid is then washed with deionized, until the pH value of wash water stops when being more than 6；
Step 6, the solid sample after step 5 is washed dry and remove moisture, obtain mesoporous silica gel surface bond alkyl sulphur
Acid catalyst.
2. a kind of preparation method of mesoporous silica gel load alkyl sulfonic acid catalyst as described in claim 1, it is characterised in that：Institute
The alkali metal sulfite stated is sodium sulfite, potassium sulfite or seven hydration sodium sulfites.
3. a kind of preparation method of mesoporous silica gel load alkyl sulfonic acid catalyst as described in claim 1, it is characterised in that：Step
The addition of absolute ethyl alcohol is 0~1 times of alkali metal sulfite aqueous solution volume used in rapid one.
4. a kind of preparation method of mesoporous silica gel load alkyl sulfonic acid catalyst as described in claim 1, it is characterised in that：Institute
The 3- chloropropyl alkoxy silanes stated are 3- r-chloropropyl trimethoxyl silanes or 3- chloropropyl triethoxysilanes.
5. a kind of preparation method of mesoporous silica gel load alkyl sulfonic acid catalyst as described in claim 1, it is characterised in that：Institute
The ethanol solution for the 3- chloropropyl alkoxy silanes stated, the wherein molar ratio of 3- chloropropyls alkoxy silane and ethyl alcohol are 1:0~
1:20。
6. a kind of preparation method of mesoporous silica gel load alkyl sulfonic acid catalyst as described in claim 1, it is characterised in that：Step
The molal quantity of 3- chloropropyl alkoxy silanes described in rapid one be the molal quantity of alkali metal sulfite used 0.6~
1.1 again.
7. a kind of preparation method of mesoporous silica gel load alkyl sulfonic acid catalyst as described in claim 1, it is characterised in that：Step
Into reaction system, the mode of the ethanol solution of addition 3- chloropropyl alkoxy silanes is in rapid one：It is at the uniform velocity added dropwise or adds in batches
Enter, complete soln adds within 48 hours.
8. a kind of preparation method of mesoporous silica gel load alkyl sulfonic acid catalyst as described in claim 1, it is characterised in that：Institute
The mesoporous silica gel stated is various amorphous silica gels, nano structural material MCM-41 or SBA-15 of the average pore size at 2 nanometers or more
Molecular sieve.
9. a kind of preparation method of mesoporous silica gel load alkyl sulfonic acid catalyst as described in claim 1, it is characterised in that：Step
Strong acid aqueous solution described in rapid five is hydrochloric acid, sulfuric acid or aqueous solution of nitric acid, a concentration of 0.5N~5N, the strong acid described in step 5
H contained by aqueous solution+Molal quantity be 2~10 times of the molal quantity of 3- chloropropyls alkoxy silane used in step 1.
10. being urged using a kind of mesoporous silica gel load alkyl sulfonic acid prepared such as claim 1-9 any one of them preparation methods
Agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810412810.6A CN108654687A (en) | 2018-05-03 | 2018-05-03 | A kind of mesoporous silica gel load alkyl sulfonic acid catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810412810.6A CN108654687A (en) | 2018-05-03 | 2018-05-03 | A kind of mesoporous silica gel load alkyl sulfonic acid catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108654687A true CN108654687A (en) | 2018-10-16 |
Family
ID=63781766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810412810.6A Pending CN108654687A (en) | 2018-05-03 | 2018-05-03 | A kind of mesoporous silica gel load alkyl sulfonic acid catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108654687A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109879905A (en) * | 2019-02-18 | 2019-06-14 | 大连工业大学 | A kind of preparation method of naphthyl sulphonic acids base modified SBA-15 and in synthesis rich in the application in unsaturated fatty acid structure phosphatide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004083164A1 (en) * | 2003-03-19 | 2004-09-30 | Ube Industries, Ltd. | PROCESS FOR PRODUCING ω-CYANOALDEHYDE COMPOUND |
| CN1944443A (en) * | 2006-10-20 | 2007-04-11 | 山东大学 | Process for preparing silicon material containing sulfonic group |
| CN101570471A (en) * | 2008-04-29 | 2009-11-04 | 中国石油化工股份有限公司 | Method for synthesizing dichloropropanol by glycerine |
| CN102600896A (en) * | 2012-01-20 | 2012-07-25 | 山东华阳油业有限公司 | Solid catalyst of bonded type organic sulfonic acid and its preparation method |
| CN103990475A (en) * | 2014-05-30 | 2014-08-20 | 湖南利洁科技有限公司 | Composite solid acid catalyst as well as preparation method and application thereof |
| CN105521823A (en) * | 2016-01-07 | 2016-04-27 | 哈尔滨理工大学 | Mesoporous-silica-gel surface bonded alkylsulfonic acid catalyst and preparation and catalysis methods therefor |
-
2018
- 2018-05-03 CN CN201810412810.6A patent/CN108654687A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004083164A1 (en) * | 2003-03-19 | 2004-09-30 | Ube Industries, Ltd. | PROCESS FOR PRODUCING ω-CYANOALDEHYDE COMPOUND |
| CN1944443A (en) * | 2006-10-20 | 2007-04-11 | 山东大学 | Process for preparing silicon material containing sulfonic group |
| CN101570471A (en) * | 2008-04-29 | 2009-11-04 | 中国石油化工股份有限公司 | Method for synthesizing dichloropropanol by glycerine |
| CN102600896A (en) * | 2012-01-20 | 2012-07-25 | 山东华阳油业有限公司 | Solid catalyst of bonded type organic sulfonic acid and its preparation method |
| CN103990475A (en) * | 2014-05-30 | 2014-08-20 | 湖南利洁科技有限公司 | Composite solid acid catalyst as well as preparation method and application thereof |
| CN105521823A (en) * | 2016-01-07 | 2016-04-27 | 哈尔滨理工大学 | Mesoporous-silica-gel surface bonded alkylsulfonic acid catalyst and preparation and catalysis methods therefor |
Non-Patent Citations (1)
| Title |
|---|
| 屈文: "含表面硅羟基材料的表面改性及其在环境中的应用", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109879905A (en) * | 2019-02-18 | 2019-06-14 | 大连工业大学 | A kind of preparation method of naphthyl sulphonic acids base modified SBA-15 and in synthesis rich in the application in unsaturated fatty acid structure phosphatide |
| CN109879905B (en) * | 2019-02-18 | 2021-07-06 | 大连工业大学 | Preparation method of naphthyl sulfonic group modified SBA-15 and application of naphthyl sulfonic group modified SBA-15 in synthesis of phospholipid rich in unsaturated fatty acid structure |
| CN109824719B (en) * | 2019-02-18 | 2021-07-06 | 大连工业大学 | Preparation method of phenylsulfonic-modified SBA-15 composite material and application of phenylsulfonic-modified SBA-15 composite material in synthesis of structured phospholipid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gholami et al. | Recent advances of biodiesel production using ionic liquids supported on nanoporous materials as catalysts: a review | |
| CN105772077B (en) | A kind of magnetism attapulgite loaded ionic-liquid catalyst and preparation method thereof | |
| CN108654687A (en) | A kind of mesoporous silica gel load alkyl sulfonic acid catalyst and preparation method thereof | |
| CN110540210B (en) | Low-energy-consumption large-pore-volume silica gel and production method thereof | |
| CN105521823A (en) | Mesoporous-silica-gel surface bonded alkylsulfonic acid catalyst and preparation and catalysis methods therefor | |
| CN108654688A (en) | A kind of mesoporous silica gel surface bond alkyl sulfonic acid catalyst and preparation method thereof | |
| CN106669841B (en) | A kind of organic silicon composite and preparation method based on phosphotungstic acid and sulfonic acid funtionalized with meso-hole structure | |
| CN107597186A (en) | A kind of short mesoporous solid alkali BG/Zr SBA 15 of the water resistance of catalytically synthesizing biological diesel oil preparation method | |
| CN112246283A (en) | Bismuth tungstate @ MIL-100(Fe) composite material and preparation method and application thereof | |
| CN102218347B (en) | Polyoxometalates-based organic-inorganic hybrid catalyst with core-shell structure and preparation method thereof | |
| CN104525261B (en) | Keggin structural homopoly-anion-cation built catalyst as well as preparation method and application thereof | |
| CN101708464A (en) | Cation resin matrix CdS-loaded composite material and preparation method thereof | |
| CN109233281A (en) | A kind of preparation method of alkalinity quaternary amine PS membrane | |
| CN103349998A (en) | Catalyst for one step conversion of cellulose into sorbitol | |
| CN112044454A (en) | Biodiesel magnetic solid base catalyst, preparation method and application | |
| CN103508845B (en) | A kind of method of cyclohexane oxidation | |
| CN109734722B (en) | Method for preparing isosorbide by dehydrating sorbitol | |
| CN114210367B (en) | Halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material, and preparation method and application thereof | |
| CN108435209A (en) | A kind of preparation method of hydrophobic highly acid Carbon Materials | |
| CN112978754B (en) | Preparation method and application of basic titanium silicalite TS-1 | |
| CN110090662B (en) | Preparation method and catalytic application of sulfonic group covalent modified vacancy polyacid composite material | |
| WO2009117862A1 (en) | Catalyst for gasoline desulfuration deodorization, its preparation method and utilization | |
| Ristiana et al. | Simple One-Pot Synthesis of Sulfonic-Acid-Functionalized Silica for Effective Catalytic Esterification of Levulinic Acid | |
| CN101941711B (en) | Preparation method of highly stable MSUY-41 molecular sieve | |
| CN101941712B (en) | Preparation method of mesopore molecular sieve containing beta zeolite secondary structural unit |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181016 |
|
| WD01 | Invention patent application deemed withdrawn after publication |