CN103803521B - A kind of method utilizing hydro-thermal and fumigation technology to prepare the zirconium phosphate layer column material of sulfonic acid funtionalized - Google Patents
A kind of method utilizing hydro-thermal and fumigation technology to prepare the zirconium phosphate layer column material of sulfonic acid funtionalized Download PDFInfo
- Publication number
- CN103803521B CN103803521B CN201410069265.7A CN201410069265A CN103803521B CN 103803521 B CN103803521 B CN 103803521B CN 201410069265 A CN201410069265 A CN 201410069265A CN 103803521 B CN103803521 B CN 103803521B
- Authority
- CN
- China
- Prior art keywords
- zirconium phosphate
- sulfonic acid
- pillared
- column material
- phosphate layer
- 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.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention belongs to technical field of material, particularly a kind of method utilizing hydro-thermal and fumigation technology to prepare the zirconium phosphate layer column material of sulfonic acid funtionalized.The bedded zirconium phosphate supportted in advance with cetylamine is starting raw material, introduce between zirconium phosphate laminate by solvation process by collaborative to silicon source and template, regulate the fast hydrolyzing polycondensation in silicon source between pH trigger layer, firmness and the stability of silicon rod structure between zirconium phosphate layer is increased again by hydrothermal method, organic amine and template is removed after filtration drying, last is oxygenant with hydrogen peroxide, utilize the technology of stifling oxidation, sulfydryl in reactant is oxidized, obtains the zirconium phosphate layer column material that the silicon oxide of sulfonic acid funtionalized is pillared.Not only the P-OH acidic site on zirconium phosphate laminate surface obtains good preservation, and after sulfonic acid funtionalized, Bronsted acidic site increases, and the orderly regularity of the veneer structure of zirconium phosphate have also been obtained good preservation.
Description
Technical field
The invention belongs to technical field of material, particularly a kind of method utilizing hydro-thermal and fumigation technology to prepare the zirconium phosphate layer column material of sulfonic acid funtionalized.
Background technology
In recent years, the intercalation research of lamellar compound reaches its maturity, and on this basis, the concept of " pillared " (pillared) is suggested.As a kind of special methods activated lamellar compound, it effectively can improve interlamellar spacing, the specific surface area isostructuralism energy of lamellar compound, improves the catalytic effect of material thus.
Patent CN101475192A discloses a kind of synthetic method of layer column mesoporous titanium silicon molecular sieve, the method has first synthesized JDF-L1 micro porous molecular sieve presoma, again by organic amine support its interlamellar spacing large, method finally by dagger introduces organosilicon at JDF-L1 interlayer, and high-temperature roasting obtains layer column mesoporous titanium silicon molecular sieve.This material has larger interlamellar spacing and obvious mesoporous performance.By pillared method, modification is carried out to lamellar compound, the advantage of pillared thing can be added on the basis keeping the original advantage of its presoma, two kinds of advantages can be acted synergistically.
Patent CN101003374A and patent CN101066765A discloses a kind of synthetic method of composite material of organic-inorganic bentonite, the method is using wilkinite as material of main part, carry out inorganic modified with the hydroxy aluminum aqueous solution to wilkinite, the aluminium pillared bentonite containing reactive hydroxyl is obtained after roasting, then with the Silanization reaction of silylating reagent and aluminium pillared bentonite surfaces externally and internally hydroxyl by the silylation grafting containing organic group on aluminium pillared bentonite, final must Organic-inorganic composite bentonite composite material.But the matrix material prepared by the method, carrying out in katalysis process, the silylation of grafting easily comes off.(the Journal of Catalysis such as Qihua Yang, 2004,228:265-272) (chemistry is circulated a notice of with Zhang Cui etc., 2006,7:529-531) carry out graft reaction by hydroxyl that is organic group is direct and bulk material surface, prepared organic group decorative material, poor stability, repeating utilization factor is low.Utilize pillared method, can the material (as amine ester, estersil etc.) containing organic group is inserted between laminate, prepare the stratified composite that the more excellent organic group of structure properties is modified.
Alpha zirconium phosphate (α-Zr (HPO
4)
2h
2o, α-ZrP) veneer structure stablize, the high (6.67mmolg of theoretical exchange capacity
-1), be the desirable presoma of prepared layer column material.Layered mesoporous zirconium phosphate isomery material has the advantages such as unique two-dimensional channel, large specific surface sum surface acid sites be controlled, has shown huge using value.(the Journal of Molecular CatalysisA:Chemical such as Ke Liu, 2013,380:84-89) report with CTAB-ZrP is parent material, take cetylamine as template, silicone grease and organosilane are the method that the Mesoporous zirconium phosphate pillared material of methyl, ethyl, propyl group and phenyl functionalization is prepared in silicon source, and this material is used for alkylated reaction and esterification.Experiment shows: material prepared by the method has meso-hole structure, and the modification of organic group increases the hydrophobicity of zirconium phosphate material, and the available acidic site of zirconium phosphate in reaction process is increased, but the total acidic of this material does not have and significantly increases.
Li Ying (Shanghai: Fudan University, 2009) a kind of novel layer post zirconium phosphate preparation method is reported, the method is in hydrolytic process, rely on the effect of template to make estersil form pore passage structure between zirconium phosphate layer, and by the method for estersil cocondensation, active centre being incorporated between laminate, preparation has the layer post zirconium phosphate material of the Phenylsulfonic acid functionalization of meso-hole structure.The active sites of this material can design and expose, the diffusion being conducive to reactant molecule with contact, in the reaction of Resorcinol and the trimethyl carbinol, there is good catalytic effect.But layer post zirconium phosphate material prepared by the method, in sulfonation process, the regularity of its laminate is destroyed, thus have influence on the P-OH acidic site on laminate surface, in addition, interlayer silicon-dioxide delaminated structure becomes weak under the corrosion of strong acid, and firmness degree is impaired, and its structure in catalytic process is easily caved in.Therefore, find and can keep zirconium phosphate layer plate regularity and the method increasing its acidity has researching value.
Summary of the invention
Technical problem to be solved by this invention is: in prior art, and in the process of prepared layer post zirconium phosphate material, zirconium phosphate layer plate regularity and acidity are easily affected.
For solving this technical problem, the technical solution used in the present invention is:
The invention provides a kind of method utilizing hydro-thermal and fumigation technology to prepare the zirconium phosphate layer column material of sulfonic acid funtionalized,
The bedded zirconium phosphate supportted in advance with cetylamine is starting raw material, introduce between zirconium phosphate laminate by solvation process by collaborative to silicon source and template, regulate the fast hydrolyzing polycondensation in silicon source between pH trigger layer, firmness and the stability of silicon rod structure between zirconium phosphate layer is increased again by hydrothermal method, organic amine and template is removed after filtration drying, last is oxygenant with hydrogen peroxide, utilize the technology of stifling oxidation, sulfydryl in reactant is oxidized, obtains the zirconium phosphate layer column material that the silicon oxide of sulfonic acid funtionalized is pillared.
Concrete steps are:
With tetraethoxy and mercaptopropyl trimethoxysilane for silicon source, silicon source and template are made into the pillared liquid of microemulsion, the zirconium phosphate supportted in advance by cetylamine is distributed in above-mentioned pillared liquid and reacts 2h, then pH=10 is regulated to cause the cohydrolysis polycondensation in the mixing silicon source between zirconium phosphate layer, reaction times is 2h, form the silicon polymers crosslinking structure of the ordered arrangement containing mercapto propyl group, i.e. interlayer silicon rod structure; Transfer in water heating kettle, hydro-thermal reaction 12h at 150 DEG C, after filtration drying, removal organic amine and template obtain the pillared zirconium phosphate material that mercapto propyl group is modified; Finally, at 80 DEG C, be that oxidation sulfydryl fumigated by oxygenant with hydrogen peroxide, the reaction times is 8 ~ 48h, the pillared zirconium phosphate material of obtained sulfonic acid funtionalized.
In aforesaid operations, the mol ratio of mercaptopropyl trimethoxysilane and tetraethoxy is 0.5:1 ~ 2:1;
Template is quaternary ammonium salt, as dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride or cetalkonium chloride;
The preparation method of above-mentioned " zirconium phosphate that cetylamine supports in advance " is: by dispersed for the α-ZrP powder of 0.06g to 300mL concentration be 0.4mmol.L
-1cetylamine alcohol aqueous dispersions (volume ratio of alcohol to water is 1:1) in, wherein solid-to-liquid ratio is 1:5g/L, cetylamine: the mol ratio of alpha zirconium phosphate is 0.6:1, water-bath 50 DEG C of lower magnetic forces stir 24 hours, after filtration drying, obtain stratiform organic phosphoric acid zirconium, i.e. " zirconium phosphate that cetylamine supports in advance "
The mol ratio of the zirconium phosphate that template quaternary ammonium salt and cetylamine support in advance is 0.2:1,
The mol ratio of the zirconium phosphate that silicon source and cetylamine support in advance is 3:1,
The solid-to-liquid ratio of the zirconium phosphate that cetylamine supports in advance and pillared liquid is 100:3g/L,
In aforesaid operations, 36%(Solute mass fraction is used in the operation of " remove organic amine and template ") hydrochloric acid and the mixing solutions (volume ratio that 36% hydrochloric acid soln and ethanol mix is 1.5:200) of ethanol reflux 24h, filtration drying,
In the technology of stifling oxidation, carry out (sample dispersion being laid on non-woven fabrics in airtight closed PTFE vessel, again the non-woven fabrics that sample is housed is fixed on three-legged support, to prop up is placed at the bottom of tank again, sample and liquid level keep certain distance, distance between sample and liquid level equals 1-1.5 times of the hydrogen peroxide solution degree of depth in sealed can, thus reaches a unsettled effect), adopt Solute mass fraction to be the hydrogen peroxide of 30%.Device for fumigation simple diagram as shown in Figure 4.
Beneficial effect of the present invention is:
The zirconium phosphate layer column material prepared by hydrothermal method, is possessed firmly interlayer silicon rod structure and good hydrothermally stable performance, layer pole structure can be avoided to occur caving in follow-up stifling oxidation;
With fumigation technology by sulfhydryl oxidase that material is with for sulfonic method, in the closed environment of certain temperature, the oxygen that the decomposing hydrogen dioxide solution being 30% by Solute mass fraction produces and steam, fully contact with layer post zirconium phosphate material, realize the oxidation to sulfydryl, avoid layer post zirconium phosphate material and hydrogen peroxide direct reaction, cause material structure to be destroyed;
With fumigation technology by sulfhydryl oxidase that material is with for sulfonic group, the quantity showed increased of its Bronsted acidic site of the material prepared after oxidation, acidity obviously strengthens, and acidity is close to super acids level;
In a word, method of the present invention is adopted to prepare the zirconium phosphate layer column material of sulfonic acid funtionalized, not only the P-OH acidic site on zirconium phosphate laminate surface obtains good preservation, and Bronsted acidic site increases after sulfonic acid funtionalized, the orderly regularity of the veneer structure of zirconium phosphate have also been obtained good preservation.
Accompanying drawing explanation
Accompanying drawing 1 is the XRD figure spectrum of the pillared zirconium phosphate layer column material of sulfonic acid funtionalized prepared by the embodiment of the present invention one.
Accompanying drawing 2 is the SEM figure of the pillared zirconium phosphate material of mercapto propyl group modification prepared by the embodiment of the present invention one.
Accompanying drawing 3 is the SEM figure of the pillared zirconium phosphate material of sulfonic acid funtionalized prepared by the embodiment of the present invention one.
Accompanying drawing 4 is in the present invention, the simple diagram of device for fumigation.
Embodiment
With in each lower embodiment, the preparation method of " zirconium phosphate that cetylamine supports in advance " that relate to is: by dispersed for the α-ZrP powder of 0.06g to 300mL concentration be 0.4mmol.L
-1cetylamine alcohol aqueous dispersions (volume ratio of alcohol to water is 1:1) in, wherein solid-to-liquid ratio is 1:5g/L, cetylamine: the mol ratio of alpha zirconium phosphate is 0.6:1, water-bath 50 DEG C of lower magnetic forces stir 24 hours, after filtration drying, obtain stratiform organic phosphoric acid zirconium, i.e. " zirconium phosphate that cetylamine supports in advance ".
Embodiment one:
In the 500mL beaker of drying, being made into mixing silicon source with 0.72mL tetraethoxy and 0.16mL mercaptopropyl trimethoxysilane, is 0.1mol.L with 3.20mL concentration
-1the dodecyl benzyl dimethyl ammonium chloride aqueous solution be made into the pillared liquid of microemulsion, cetylamine being supportted in advance zirconium phosphate is dispersed in pillared liquid, wherein the mol ratio of dodecyl benzyl dimethyl ammonium chloride and organic phosphoric acid zirconium is 0.2:1, the mol ratio of total silicon source and organic phosphoric acid zirconium is 3:1, the mol ratio of mercaptopropyl trimethoxysilane and tetraethoxy is 0.5:1, the solid-to-liquid ratio that cetylamine supports zirconium phosphate and microemulsion is in advance 100:3g/L, room temperature lower magnetic force stirs after 2h with 25%(Solute mass fraction) ammonia soln regulate the pH to 10 of above-mentioned solution, room temperature lower magnetic force stirs 2h,
Be transferred in water heating kettle, solid phase is filtered to isolate after hydro-thermal 12h at 150 DEG C, and fully wash with dehydrated alcohol and deionized water, drying overnight at 60 DEG C, gained solid with 36% hydrochloric acid and ethanolic soln (volume ratio is 1.5:200) reflux 24h at 70 DEG C, after filtration drying the pillared zirconium phosphate material (SEM figure as accompanying drawing 2) modified of mercapto propyl group;
Finally, at 80 DEG C, in airtight closed PTFE vessel, with 30%(Solute mass fraction) hydrogen peroxide be oxygenant, adopt stifling oxidation technology, sulfydryl be oxidized, take out dry after oxidation 8h, the pillared zirconium phosphate material (SEM figure is as accompanying drawing 3) of obtained sulfonic acid funtionalized.
As can be seen from accompanying drawing 2, accompanying drawing 3, the pillared zirconium phosphate material that mercapto propyl group is modified has more regular laminate structure. after oversulfonate, maintain the structure of stratiform.
Embodiment two:
In the 500mL beaker of drying, being made into mixing silicon source with 0.36mL tetraethoxy and 0.62mL mercaptopropyl trimethoxysilane, is 0.1mol.L with 3.20mL concentration
-1the dodecyl benzyl dimethyl ammonium chloride aqueous solution be made into the pillared liquid of microemulsion, cetylamine being supportted in advance zirconium phosphate is dispersed in pillared liquid, wherein the mol ratio of dodecyl benzyl dimethyl ammonium chloride and organic phosphoric acid zirconium is 0.2:1, the mol ratio of total silicon source and organic phosphoric acid zirconium is 3:1, the mol ratio of mercaptopropyl trimethoxysilane and tetraethoxy is 2:1, the solid-to-liquid ratio that cetylamine supports zirconium phosphate and microemulsion is in advance 100:3g/L
All the other operations are identical with embodiment 1.
Embodiment three:
In the 500mL beaker of drying, being made into mixing silicon source with 0.72mL tetraethoxy and 0.16mL mercaptopropyl trimethoxysilane, is 0.1mol.L with 3.20mL concentration
-1myristyl benzyl dimethyl aqueous ammonium chloride solution be made into the pillared liquid of microemulsion, cetylamine being supportted in advance zirconium phosphate is dispersed in pillared liquid, wherein the mol ratio of myristyl benzyl dimethyl ammonium chloride and organic phosphoric acid zirconium is 0.2:1, the mol ratio of total silicon source and organic phosphoric acid zirconium is 3:1, the mol ratio of mercaptopropyl trimethoxysilane and tetraethoxy is 0.5:1, the solid-to-liquid ratio that cetylamine supports zirconium phosphate and microemulsion is in advance 100:3g/L, room temperature lower magnetic force stirs after 2h with 25%(Solute mass fraction) ammonia soln regulate the pH to 10 of above-mentioned solution, room temperature lower magnetic force stirs 2h,
Be transferred in water heating kettle, solid phase is filtered to isolate after hydro-thermal 12h at 150 DEG C, and fully wash with dehydrated alcohol and deionized water, drying overnight at 60 DEG C, gained solid with 36% hydrochloric acid and ethanolic soln (volume ratio is 1.5:200) reflux 24h at 70 DEG C, after filtration drying mercapto propyl group modify pillared zirconium phosphate material;
Finally, at 80 DEG C, in airtight closed PTFE vessel, with 30%(Solute mass fraction) hydrogen peroxide be oxygenant, adopt stifling oxidation technology, sulfydryl be oxidized, take out dry after oxidation 28h, the pillared zirconium phosphate material of obtained sulfonic acid funtionalized.
Embodiment four:
In the 500mL beaker of drying, being made into mixing silicon source with 0.36mL tetraethoxy and 0.62mL mercaptopropyl trimethoxysilane, is 0.1mol.L with 3.20mL concentration
-1the cetalkonium chloride aqueous solution be made into the pillared liquid of microemulsion, cetylamine being supportted in advance zirconium phosphate is dispersed in pillared liquid, wherein the mol ratio of cetalkonium chloride and organic phosphoric acid zirconium is 0.2:1, the mol ratio of total silicon source and organic phosphoric acid zirconium is 3:1, the mol ratio of mercaptopropyl trimethoxysilane and tetraethoxy is 2:1, the solid-to-liquid ratio that cetylamine supports zirconium phosphate and microemulsion is in advance 100:3g/L, regulate the pH to 10 of above-mentioned solution after room temperature lower magnetic force stirs 2h with the ammonia soln of 25%, room temperature lower magnetic force stirs 2h;
Be transferred in water heating kettle, solid phase is filtered to isolate after hydro-thermal 12h at 150 DEG C, and fully wash with dehydrated alcohol and deionized water, drying overnight at 60 DEG C, gained solid with 36% hydrochloric acid and ethanolic soln (volume ratio is 1.5:200) reflux 24h at 70 DEG C, after filtration drying mercapto propyl group modify pillared zirconium phosphate material;
Finally, at 80 DEG C, in airtight closed PTFE vessel, with 30%(Solute mass fraction) hydrogen peroxide be oxygenant, adopt stifling oxidation technology, sulfydryl be oxidized, take out dry after oxidation 48h, the pillared zirconium phosphate material of obtained sulfonic acid funtionalized.
Comparative example 1:
Compared with embodiment 1, in comparative example 1, eliminate " hydro-thermal reaction " this operation; And when the pillared zirconium phosphate material modified mercapto propyl group is oxidized, do not adopt fumigation technology, but the pillared zirconium phosphate material that mercapto propyl group is modified and hydrogen peroxide direct reaction, all the other operation stepss are identical with embodiment 1, and concrete operations are as follows:
In the 500mL beaker of drying, being made into mixing silicon source with 0.72mL tetraethoxy and 0.16mL mercaptopropyl trimethoxysilane, is 0.1mol.L with 3.20mL concentration
-1the dodecyl benzyl dimethyl ammonium chloride aqueous solution be made into the pillared liquid of microemulsion, cetylamine being supportted in advance zirconium phosphate is dispersed in pillared liquid, wherein the mol ratio of dodecyl benzyl dimethyl ammonium chloride and organic phosphoric acid zirconium is 0.2:1, the mol ratio of total silicon source and organic phosphoric acid zirconium is 3:1, the mol ratio of mercaptopropyl trimethoxysilane and tetraethoxy is 0.5:1, the solid-to-liquid ratio that cetylamine supports zirconium phosphate and microemulsion is in advance 100:3g/L, room temperature lower magnetic force stirs after 2h with 25%(Solute mass fraction) ammonia soln regulate the pH to 10 of above-mentioned solution, room temperature lower magnetic force stirs 2h,
Filter to isolate solid phase, fully wash with dehydrated alcohol and deionized water, drying overnight at 60 DEG C, gained solid with 36% hydrochloric acid and ethanolic soln (volume ratio is 1.5:200) reflux 24h at 70 DEG C, after filtration drying mercapto propyl group modify pillared zirconium phosphate material;
The pillared zirconium phosphate material modified by mercapto propyl group obtained above is in round-bottomed flask, with 100mL ethanol for solvent, add the 30%(Solute mass fraction of 10mL) hydrogen peroxide be oxygenant, stirring reaction 8 hours at 80 DEG C, rear taking-up is dry, the pillared zirconium phosphate material of obtained sulfonic acid funtionalized.
Comparative example 2:
Compared with embodiment 1, in comparative example 1, eliminate " hydro-thermal reaction " this operation, all the other operation stepss are identical with embodiment 1, and concrete operations are as follows:
Compared with embodiment 1, in comparative example 1, eliminate " hydro-thermal reaction " this operation; And when the pillared zirconium phosphate material modified mercapto propyl group is oxidized, do not adopt fumigation technology, but the pillared zirconium phosphate material that mercapto propyl group is modified and hydrogen peroxide direct reaction, all the other operation stepss are identical with embodiment 1, and concrete operations are as follows:
In the 500mL beaker of drying, being made into mixing silicon source with 0.72mL tetraethoxy and 0.16mL mercaptopropyl trimethoxysilane, is 0.1mol.L with 3.20mL concentration
-1the dodecyl benzyl dimethyl ammonium chloride aqueous solution be made into the pillared liquid of microemulsion, cetylamine being supportted in advance zirconium phosphate is dispersed in pillared liquid, wherein the mol ratio of dodecyl benzyl dimethyl ammonium chloride and organic phosphoric acid zirconium is 0.2:1, the mol ratio of total silicon source and organic phosphoric acid zirconium is 3:1, the mol ratio of mercaptopropyl trimethoxysilane and tetraethoxy is 0.5:1, the solid-to-liquid ratio that cetylamine supports zirconium phosphate and microemulsion is in advance 100:3g/L, room temperature lower magnetic force stirs after 2h with 25%(Solute mass fraction) ammonia soln regulate the pH to 10 of above-mentioned solution, room temperature lower magnetic force stirs 2h,
Filter to isolate solid phase, fully wash with dehydrated alcohol and deionized water, drying overnight at 60 DEG C, gained solid with 36% hydrochloric acid and ethanolic soln (volume ratio is 1.5:200) reflux 24h at 70 DEG C, after filtration drying mercapto propyl group modify pillared zirconium phosphate material;
Finally, at 80 DEG C, in airtight closed PTFE vessel, with 30%(Solute mass fraction) hydrogen peroxide be oxygenant, adopt stifling oxidation technology, sulfydryl be oxidized, take out dry after oxidation 8h, the pillared zirconium phosphate material of obtained sulfonic acid funtionalized.
Comparative example 3:
Compared with embodiment 1, in comparative example 1, when the pillared zirconium phosphate material modified mercapto propyl group is oxidized, do not adopt fumigation technology, but the pillared zirconium phosphate material that mercapto propyl group is modified and hydrogen peroxide direct reaction, all the other operation stepss are identical with embodiment 1, and concrete operations are as follows:
In the 500mL beaker of drying, being made into mixing silicon source with 0.72mL tetraethoxy and 0.16mL mercaptopropyl trimethoxysilane, is 0.1mol.L with 3.20mL concentration
-1the dodecyl benzyl dimethyl ammonium chloride aqueous solution be made into the pillared liquid of microemulsion, cetylamine being supportted in advance zirconium phosphate is dispersed in pillared liquid, wherein the mol ratio of dodecyl benzyl dimethyl ammonium chloride and organic phosphoric acid zirconium is 0.2:1, the mol ratio of total silicon source and organic phosphoric acid zirconium is 3:1, the mol ratio of mercaptopropyl trimethoxysilane and tetraethoxy is 0.5:1, the solid-to-liquid ratio that cetylamine supports zirconium phosphate and microemulsion is in advance 100:3g/L, room temperature lower magnetic force stirs after 2h with 25%(Solute mass fraction) ammonia soln regulate the pH to 10 of above-mentioned solution, room temperature lower magnetic force stirs 2h,
Be transferred in water heating kettle, solid phase is filtered to isolate after hydro-thermal 12h at 150 DEG C, and fully wash with dehydrated alcohol and deionized water, drying overnight at 60 DEG C, gained solid with 36% hydrochloric acid and ethanolic soln (volume ratio is 1.5:200) reflux 24h at 70 DEG C, after filtration drying mercapto propyl group modify pillared zirconium phosphate material;
The pillared zirconium phosphate material modified by mercapto propyl group obtained above is in round-bottomed flask, add the 30%(Solute mass fraction of 10mL) hydrogen peroxide be oxygenant, stirring reaction 8 hours at 80 DEG C, rear taking-up is dry, the pillared zirconium phosphate material of obtained sulfonic acid funtionalized.
The analysis of product catalyst performance:
Adopt embodiment 1-4, and " the pillared zirconium phosphate material of sulfonic acid funtionalized " in comparative example 1-3, as solid catalyst, the alkylated reaction of catalysis Resorcinol and the trimethyl carbinol, concrete operations are as follows:
Experiment 1:
The alkylated reaction of Resorcinol and the trimethyl carbinol carries out interior being lined with in the stainless steel autoclave of tetrafluoroethylene, uses magnetic agitation and controls temperature of reaction by oil bath. reaction conditions: Resorcinol 5g, trimethyl carbinol 10g, solvent xylene 20g, catalyzer 2g, reaction times 4h, temperature 150 DEG C
Product uses gas chromatographic analysis: SE-30 capillary chromatographic column (30m × 0.25mm x0.3 μm), column temperature 180 DEG C, vaporizer temperature 220 DEG C, detector temperature 250 DEG C.
After testing, in the product generated after reaction, except object product 2-Tert. Butyl Hydroquinone (TBHQ), also has by product 2,5-di-tert-butyl hydroquinone (DTBHQ), 2,5-di-t-butyl benzoquinone (DTBBQ) and tert.-butylbenzene phenolic ether (TBPE) they are the transformation efficiency (in Resorcinol) of catalyzed reaction in table 1, and generate in product, the mass percentage of object product and various by product:
Table 1
Data as can be seen from upper table, " the pillared zirconium phosphate material of sulfonic acid funtionalized " prepared by the present invention, as solid catalyst, during the alkylated reaction of catalysis Resorcinol and the trimethyl carbinol, not only can ensure high yield, and good to the selectivity of target product;
Experiment 2:
Experiment 1 reaction terminate after, by catalyzer centrifuging out, with absolute ethanol washing (20mL × 3), after 60 DEG C of dryings, for reacting next time, concrete operations are identical with experiment 1, and (alkylated reaction of Resorcinol and the trimethyl carbinol carries out interior being lined with in the stainless steel autoclave of tetrafluoroethylene, use magnetic agitation and control temperature of reaction by oil bath. reaction conditions: Resorcinol 5g, trimethyl carbinol 10g, solvent xylene 20g, catalyzer 2g, reaction times 4h, temperature 150 DEG C), so circulate, experimental data is as shown in table 2:
Table 2(is for the catalyzer of embodiment 1)
Data as can be seen from upper table, " the pillared zirconium phosphate material of sulfonic acid funtionalized " prepared by the present invention, as solid catalyst, during the alkylated reaction of catalysis Resorcinol and the trimethyl carbinol, Repeatability is good.
Table 3(is for the catalyzer of comparative example 2)
Table 4(is for the catalyzer of comparative example 3)
Claims (7)
1. the preparation method of the zirconium phosphate layer column material of a sulfonic acid funtionalized, it is characterized in that: described method is, the bedded zirconium phosphate supportted in advance with cetylamine is starting raw material, introduce between zirconium phosphate laminate by solvation process by collaborative to silicon source and template, regulate the fast hydrolyzing polycondensation in silicon source between pH trigger layer, firmness and the stability of silicon rod structure between zirconium phosphate layer is increased again by hydrothermal method, organic amine and template is removed after filtration drying, last is oxygenant with hydrogen peroxide, utilize the technology of stifling oxidation, sulfydryl in reactant is oxidized, obtain the zirconium phosphate layer column material that the silicon oxide of sulfonic acid funtionalized is pillared,
The concrete steps of described method are,
With tetraethoxy and mercaptopropyl trimethoxysilane for silicon source, silicon source and template are made into the pillared liquid of microemulsion, the zirconium phosphate supportted in advance by cetylamine is distributed in above-mentioned pillared liquid and reacts 2h, then pH=10 is regulated to cause the cohydrolysis polycondensation in the mixing silicon source between zirconium phosphate layer, reaction times is 2h, form the silicon polymers crosslinking structure of the ordered arrangement containing mercapto propyl group, i.e. interlayer silicon rod structure; Transfer in water heating kettle, hydro-thermal reaction 12h at 150 DEG C, after filtration drying, removal organic amine and template obtain the pillared zirconium phosphate material that mercapto propyl group is modified; Finally, at 80 DEG C, be that oxidation sulfydryl fumigated by oxygenant with hydrogen peroxide, the reaction times is 8 ~ 48h, obtains the zirconium phosphate layer column material that the silicon oxide of sulfonic acid funtionalized is pillared.
2. the preparation method of the zirconium phosphate layer column material of sulfonic acid funtionalized as claimed in claim 1, it is characterized in that: in silicon source, the mol ratio of mercaptopropyl trimethoxysilane and tetraethoxy is 0.5:1 ~ 2:1.
3. the preparation method of the zirconium phosphate layer column material of sulfonic acid funtionalized as claimed in claim 1, is characterized in that: described template is dodecyl benzyl dimethyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride or cetalkonium chloride.
4. the preparation method of the zirconium phosphate layer column material of sulfonic acid funtionalized as claimed in claim 1, is characterized in that: the mol ratio of the zirconium phosphate that template and cetylamine support in advance is 0.2:1.
5. the preparation method of the zirconium phosphate layer column material of sulfonic acid funtionalized as claimed in claim 1, is characterized in that: the mol ratio of the zirconium phosphate that silicon source and cetylamine support in advance is 3:1.
6. the preparation method of the zirconium phosphate layer column material of sulfonic acid funtionalized as claimed in claim 1, is characterized in that: the solid-to-liquid ratio of the zirconium phosphate that cetylamine supports in advance and pillared liquid is 100:3g/L.
7. the preparation method of the zirconium phosphate layer column material of sulfonic acid funtionalized as claimed in claim 1, is characterized in that: the operation of removing organic amine and template is, with the hydrochloric acid of Solute mass fraction 36% and the mixing solutions of ethanol, and backflow 24h, filtration drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410069265.7A CN103803521B (en) | 2014-02-27 | 2014-02-27 | A kind of method utilizing hydro-thermal and fumigation technology to prepare the zirconium phosphate layer column material of sulfonic acid funtionalized |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410069265.7A CN103803521B (en) | 2014-02-27 | 2014-02-27 | A kind of method utilizing hydro-thermal and fumigation technology to prepare the zirconium phosphate layer column material of sulfonic acid funtionalized |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103803521A CN103803521A (en) | 2014-05-21 |
| CN103803521B true CN103803521B (en) | 2015-08-12 |
Family
ID=50700973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410069265.7A Expired - Fee Related CN103803521B (en) | 2014-02-27 | 2014-02-27 | A kind of method utilizing hydro-thermal and fumigation technology to prepare the zirconium phosphate layer column material of sulfonic acid funtionalized |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103803521B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3211215B2 (en) * | 1991-07-12 | 2001-09-25 | 東亞合成株式会社 | Method for producing crystalline zirconium phosphate compound |
| JP5757605B2 (en) * | 2010-10-29 | 2015-07-29 | 国立大学法人九州大学 | Phosphate coating material, apatite coating material, and production method thereof |
| CN102443023B (en) * | 2011-01-24 | 2014-12-17 | 山东理工大学 | Preparation method of sulfonated cerium phenylphosphinate |
| CN103011118B (en) * | 2012-12-10 | 2014-08-13 | 常州大学 | Method for preparing zirconium phosphate layer column material by guide assembly technology |
| CN103236553B (en) * | 2013-04-10 | 2016-08-03 | 清华大学深圳研究生院 | A kind of cluster ion exchange membrane and preparation method thereof, flow battery |
-
2014
- 2014-02-27 CN CN201410069265.7A patent/CN103803521B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103803521A (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Current application of MOFs based heterogeneous catalysts in catalyzing transesterification/esterification for biodiesel production: A review | |
| Gouda et al. | Metal-organic framework as a heterogeneous catalyst for biodiesel production: A review | |
| CN103011118B (en) | Method for preparing zirconium phosphate layer column material by guide assembly technology | |
| CN103399064B (en) | A kind of graphene oxide/brucite/Nafion laminated film modified electrode and preparation method thereof | |
| CN110105580B (en) | Hierarchical pore zeolite imidazole ester framework material and preparation method thereof | |
| CN104525260B (en) | Polymeric solid acid catalyst for esterification reaction and preparation method thereof | |
| CN108097261A (en) | A kind of ferro manganese composite oxides catalyst of efficient stable and preparation method and application | |
| CN104162447B (en) | A kind of preparation method and application of solid catalyst | |
| CN102993221A (en) | Method for preparing nano-zeolite metal-organic framework compounds by microreactor | |
| Hasan et al. | Desilication of ZSM-5 zeolites for mesoporosity development using microwave irradiation | |
| CN105712367B (en) | A kind of core shell type micro-hole/composite mesoporous Titanium Sieve Molecular Sieve and preparation method thereof | |
| CN108996655A (en) | A kind of microwave-assisted Fe/Fe3The method of C@C quick catalysis degradation of organic waste water | |
| CN104326881A (en) | Preparation method of 3,5-dimethyl-4-chlorophenol | |
| CN105521825B (en) | Catalyst for preparing phenol by benzene oxidation and preparation method and application thereof | |
| CN102728402B (en) | Synthetic propylene carbonate catalyst, preparation method and application thereof | |
| CN102861609A (en) | Gradient composite molecular sieve membrane catalytic material and preparation method and application thereof | |
| CN103127957B (en) | Mesoporous PW/MoO3-TiO2-SiO2 catalyst and preparation method and application thereof | |
| CN106669841A (en) | Phosphotungstic acid- and sulfonic acid-functionalized organosilicon composite material with mesoporous structure and preparation method | |
| CN103803521B (en) | A kind of method utilizing hydro-thermal and fumigation technology to prepare the zirconium phosphate layer column material of sulfonic acid funtionalized | |
| CN104888766A (en) | Hydrogenation deoxidation catalyst and preparation method thereof | |
| CN106215969A (en) | A kind of cerium dopping solid super acid catalyst and preparation method thereof | |
| CN102600851A (en) | Preparation method of catalyst for synthesizing methanol by carbon dioxide hydrogenation | |
| CN103877952B (en) | Similar soft sweet type polysiloxane adsorption material as well as preparation and application of surface modified sponge | |
| Yang et al. | Preparation and application of ordered mesoporous carbon-based solid acid catalysts for transesterification and epoxidation | |
| Chen et al. | One-pot synthesis of hierarchically porous Co2O3–WO3/ZrO2 solid acid catalyst and its application in phenol alkylation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150812 Termination date: 20210227 |