CN107010611A - The preparation method of Mesoporous zirconium phosphate - Google Patents
The preparation method of Mesoporous zirconium phosphate Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of Mesoporous zirconium phosphate, the zirconium phosphate material specific surface area that mainly solves prior art synthesis is low, the less problem in aperture.The present invention uses hydrothermal synthesis method, using cetyl trimethylammonium bromide and APES mixed solution as template, zirconium source and phosphorus source are introduced into system respectively, pass through hydrothermal crystallizing, filtration washing, drying and roasting processing again, a kind of Mesoporous zirconium phosphate material is prepared, its θ of XRD diffracting spectrums 2 preferably resolves above-mentioned technical problem in 2.2 ± 0.4 technical schemes for having characteristic peak.The inventive method is easy to operate, favorable reproducibility, and the basic zirconium phosphate mesoporous order degree prepared is high, specific surface area is big, heat endurance is high, resistance to acids and bases good, available for being catalyzed, the industrial circle such as adsorbing separation.
Description
Technical field
The present invention relates to a kind of preparation method of Mesoporous zirconium phosphate.
Background technology
Zirconium phosphate compound is the nearlyer novel and multifunctional stratified material of a class grown up, is ground in the sour material of layered solid
Study carefully most materials.Basic zirconium phosphate has solid acid catalysis function in itself, and using inner layer space as reactor, because of reactant
Or product shape is different, them are caused to pass in and out the dynamic process of interlayer difference, so as to occur in catalytic reaction process shape-selective
Selectivity.Because basic zirconium phosphate has good chemistry, heat endurance and a mechanical strength, and it can provide and sizable compare table
Area, has broad application prospects so being gathered around in terms of catalysis.The catalytic performance of basic zirconium phosphate is not only in that the acidity of itself,
The prior composite for being to obtain after other object insertions.On the one hand, make basic zirconium phosphate acidity that there is adjustable denaturation, change
It has been apt to the geometrical property and shape selectivity of pore passage structure；On the other hand, basic zirconium phosphate can introduce all kinds of different by various means
Active material, to prepare the catalyst or catalyst carrier of different purposes, makes it have composite catalyzing performance, therefore to this kind of
The research of composite will have very vast potential for future development.Application of the currently reported basic zirconium phosphate in catalysis has alcohol to take off
The reactions such as water, esterification, condensation, oxidation, addition, carbonylation hydrogenation, polymerization, substitution.
Being presently used for the main method of synthesising mesoporous basic zirconium phosphate has circumfluence method, direct precipitation method, hydrothermal synthesis method, template to close
Into method etc..
CN103228574A discloses a kind of plate-like type basic zirconium phosphate, wherein, including P-OH groups among structure, and
There is peak crystallization in the case where 2 θ values are 11.6 ± 2 degree during X-ray diffraction analysis, and in 2 θ values less than 11.6 ± 2 degree
In the case of do not observe peak crystallization.The plate-like type basic zirconium phosphate manufactured due to the invention is with plate-like type structure and nanoscale size to quilt
Uniformly disperseed inside overlay film and with good surface gloss and barrier property, and due to surface P-OH bases and
It with good corrosion resistance, and can not only be scattered in the aqueous solution, can also disperse among organic solvent etc..
CN101058411 discloses a kind of preparation method of spherical zirconium phosphate material.Specifically related to a kind of particle size exists
Adjustable spherical basic zirconium phosphate and preparation method thereof between 10 to 100 Μ M.Circumfluence method answer print bedded zirconium phosphate is used first
Former powder, then by the method for organic amine delamination, carries out delamination processing by bedded zirconium phosphate powder sample, obtains individual layer basic zirconium phosphate
Colloid, is finally molded using rotary spray dryer, and spherical basic zirconium phosphate sample is made.This method process conditions are unique,
Simple to operate, synthesis condition is gentle.Shaping zirconium phosphate material can be used as catalyst, catalyst carrier, adsorbent, ion
Exchanger etc. is used.
CN101602512 discloses a kind of Zirconium phosphate crystal material and preparation method, belongs to inorganic chemistry synthesis field.Specifically
For be related to the technical scheme of Zirconium phosphate crystal material prepared by structure directing agent of quinoline and preparation method a kind of.Its feature
It is, is a kind of nitrogenous heterocyclic organic amine quinoline molecule to be incorporated into the synthesis of Zirconium phosphate crystal material, it is to avoid tradition
Organic short chain amine or organic diamine, use the basic zirconium phosphate that hydrothermal synthesis method prepared using quinoline molecule as structure directing agent brilliant
Body material, the advantage of the invention is to use nitrogenous heterocyclic quinoline molecule as structure directing agent, by changing synthesis condition,
The Zirconium phosphate crystal material with stratiform or chain structure feature is prepared.
CN102992293A discloses a kind of rod-shaped zirconium phosphate and preparation method thereof.A diameter of the 0.4 of the rod-shaped zirconium phosphate~
1.0um, draw ratio is 5~20, and its preparation method is specific as follows：A certain amount of eight water oxygen is sequentially added into deionized water
After zirconium chloride, ethanedioic acid, phosphoric acid and ethylenediamine, stirring reaction, rod-shaped zirconium phosphate is obtained after suction filtration, washing, drying；Its
In, eight water oxygen zirconium chlorides, ethanedioic acid, phosphoric acid, the mol ratio of ethylenediamine are 1: a: 1: b, middle a correspondences ethanedioic acid mole
Ratio, is worth for 3~5；B correspondence ethylenediamine molar ratios, are worth for 3~5, a, b are integer or non-integer.The preparation side
Method technique is simple, prepared rod-shaped zirconium phosphate size uniform, can be applied to the fields such as catalysis, ion exchange, particularly can
It is used as carrier.
CN103011118A discloses a kind of using the method that package technique prepares zirconium phosphate layer column material is oriented to, and belongs to material
Preparing technical field.This method is first carried out using bedded zirconium phosphate as raw material with the long-chain such as cetylamine organic amine to bedded zirconium phosphate
It is organically-modified, after by the long-chain such as dodecyl benzyl dimethyl ammonium chloride quaternary ammonium salts between the zirconium phosphate layer organised, and
Silester is cooperateed with long chain quaternary by introducing by solvation process.It is isometric using dodecyl benzyl dimethyl ammonium chloride
The micella of chain quaternary ammonium salt formation is as template, and the silicon polymers for forming ordered arrangement between zirconium phosphate layer by being oriented to package technique is handed over
It is coupled structure, removes organic amine and quaternary ammonium salt finally by roasting, obtain the pillared zirconium phosphate layer column material of silica.
The content of the invention
One of technical problems to be solved by the invention be prior art synthesis zirconium phosphate material specific surface area is low, aperture is smaller
The problem of there is provided a kind of new Mesoporous zirconium phosphate material.The material has the advantages that meso-hole structure, specific surface area are big；This hair
The two of bright technical problem to be solved are to provide the preparation method with solving one of technical problem corresponding Mesoporous zirconium phosphate.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of Mesoporous zirconium phosphate, its XRD
The θ of diffracting spectrum 2 has characteristic peak 2.2 ± 0.4, and specific surface area is 250~450m2/ g, pore volume are 0.3~0.6cm3It is/g, flat
Equal aperture is 2.5~4.5nm.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：The preparation method of Mesoporous zirconium phosphate, bag
Include following steps：
1. by template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and go from
Sub- water mixes to clarification, is designated as solution A；
2. zirconium source and phosphorus source are dissolved in wiring solution-forming B and C in deionized water respectively；
3. solution B is slowly added dropwise in solution A, after stirring 0.5~2 hour, solution C is slowly added dropwise, continue to stir
Aging is calculated in molar ratio as after 1~24 hour：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：0.25~4：0.15~
0.5：0.03~0.08：500~800 mixed solution D；
4. mixed solution D is fitted into crystallizing kettle, in 12~100h of crystallization at 70~150 DEG C, the good product cooling of crystallization
After take out, through filtering, washing, dry, under 350~650 DEG C of air atmospheres be calcined 0.5~24h after, be made mesoporous phosphorus
Sour zirconium.
In above-mentioned technical proposal, described zirconium source in basic zirconium chloride, zirconyl nitrate, zirconium nitrate or zirconium carbonate at least one
Kind.
In above-mentioned technical proposal, described phosphorus source is selected from least one of phosphoric acid, ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
In above-mentioned technical proposal, 3. whipping temp is 30~90 DEG C to described step.
In above-mentioned technical proposal, described ageing time is 3~12 hours.
In above-mentioned technical proposal, described crystallization temperature is 80~140 DEG C.
In above-mentioned technical proposal, described crystallization time is 24~72 hours.
In above-mentioned technical proposal, described sintering temperature is 400~550 DEG C.
In above-mentioned technical proposal, described roasting time is 3~6 hours.
The Mesoporous zirconium phosphate prepared by above-mentioned technical proposal, available for being catalyzed, the industrial circle such as adsorbing separation.
Using technical solution of the present invention, prepared and added in Mesoporous zirconium phosphate, preparation process again by the method for hydrothermal crystallizing
Shuttering agent CTAB and OP-10, CTAB category cationic, OP-10 category are non-ionic, in two types template
Under synergistic effect, zirconium source and phosphorus source are assembled into the zirconium phosphate material containing mesoporous distribution, improve the ratio surface of the material
Product.In addition, OP-10 introducing can effectively reduce CTAB consumption so that production cost is reduced, and reduces pollutant
Discharge.Prepare in this way and in turn simplify synthesis technique, product it is reproducible, these are all beneficial to industrial
Produce in enormous quantities, achieve preferable technique effect.
Brief description of the drawings
The typical collection of illustrative plates of low angle X-ray diffraction of Mesoporous zirconium phosphate materials of the Fig. 1 to prepare.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 100g deionized waters are mixed
In, after 60 DEG C are stirred 1 hour, phosphoric acid (85w%) 69g is slowly added dropwise, continues stirring aging and is massaged for 12 hours
You are calculated as ratio：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0.2：0.04：800 mixed solution；Will mixing
Solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, takes out, through filtering, washing, dries after the good product cooling of crystallization,
It is calcined under 500 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 2】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 100g deionized waters are mixed
In, in after 60 DEG C of stirrings 1 hour, be slowly added dropwise phosphoric acid (85w%) 86.3g, continue to stir aging obtain within 12 hours by
Molar ratio computing is：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2.5：0.2：0.04：800 mixed solution；Will
Mixed solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, is taken out after the good product cooling of crystallization, through filtering, washing,
Dry, be calcined under 500 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 3】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 100g deionized waters are mixed
In, in after 60 DEG C of stirrings 1 hour, be slowly added dropwise phosphoric acid (85w%) 34.5g, continue to stir aging obtain within 12 hours by
Molar ratio computing is：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：1：0.2：0.04：800 mixed solution；Will be mixed
Conjunction solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, takes out, through filtering, washing, does after the good product cooling of crystallization
It is dry, it is calcined under 500 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 4】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution is slowly added into after 96.7g basic zirconium chlorides and 300g deionized waters are mixed
In A, after 60 DEG C are stirred 1 hour, the solution of the ammonium dihydrogen phosphate containing 69g is slowly added dropwise, continues to stir aging 12 hours
It is calculated in molar ratio as：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0.2：0.04：800 mixed solution；
Mixed solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, taken out after the good product cooling of crystallization, through filtering, washing,
Dry, be calcined under 500 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 5】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution is slowly added into after 96.7g basic zirconium chlorides and 300g deionized waters are mixed
In A, after 60 DEG C are stirred 1 hour, the solution of the ammonium dihydrogen phosphate containing 103.5g is slowly added dropwise, continues stirring aging 12 small
When be calculated in molar ratio as：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：3：0.2：0.04：800 mixing is molten
Liquid；Mixed solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, taken out after the good product cooling of crystallization, through filtering,
Wash, dry, be calcined under 500 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 6】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 100g deionized waters are mixed
In, in after 60 DEG C of stirrings 1 hour, be slowly added dropwise phosphoric acid (85w%) 69g, continue to stir aging obtain within 6 hours by mole
Than being calculated as：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0.2：0.04：800 mixed solution；It will mix molten
Liquid is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, takes out, through filtering, washing, dries after the good product cooling of crystallization,
It is calcined under 500 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 7】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 100g deionized waters are mixed
In, after 60 DEG C are stirred 1 hour, phosphoric acid (85w%) 69g is slowly added dropwise, continues stirring aging and is massaged for 12 hours
You are calculated as ratio：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0.2：0.04：800 mixed solution；Will mixing
Solution is fitted into crystallizing kettle, in 100 DEG C of crystallization 48h, takes out, through filtering, washing, dries after the good product cooling of crystallization,
It is calcined under 500 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 8】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 100g deionized waters are mixed
In, after 60 DEG C are stirred 1 hour, phosphoric acid (85w%) 69g is slowly added dropwise, continues stirring aging and is massaged for 12 hours
You are calculated as ratio：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0.2：0.04：800 mixed solution；Will mixing
Solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 72h, takes out, through filtering, washing, dries after the good product cooling of crystallization,
It is calcined under 500 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 9】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 100g deionized waters are mixed
In, after 60 DEG C are stirred 1 hour, phosphoric acid (85w%) 69g is slowly added dropwise, continues stirring aging and is massaged for 12 hours
You are calculated as ratio：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0.2：0.04：800 mixed solution；Will mixing
Solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, takes out, through filtering, washing, dries after the good product cooling of crystallization,
It is calcined under 450 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 10】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 100g deionized waters are mixed
In, after 60 DEG C are stirred 1 hour, phosphoric acid (85w%) 69g is slowly added dropwise, continues stirring aging and is massaged for 12 hours
You are calculated as ratio：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0.2：0.04：800 mixed solution；Will mixing
Solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, takes out, through filtering, washing, dries after the good product cooling of crystallization,
It is calcined under 500 DEG C of air atmospheres after 4h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 11】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 100g deionized waters are mixed
In, after 80 DEG C are stirred 1 hour, phosphoric acid (85w%) 69g is slowly added dropwise, continues stirring aging and is massaged for 12 hours
You are calculated as ratio：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0.2：0.04：800 mixed solution；Will mixing
Solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, takes out, through filtering, washing, dries after the good product cooling of crystallization,
It is calcined under 500 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 12】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution is slowly added into after 69.4g zirconyl nitrates and 100g deionized waters are mixed
In A, in after 60 DEG C of stirrings 1 hour, be slowly added dropwise phosphoric acid (85w%) 69g, continue to stir aging obtain within 12 hours by
Molar ratio computing is：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0.2：0.04：800 mixed solution；Will be mixed
Conjunction solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, takes out, through filtering, washing, does after the good product cooling of crystallization
It is dry, it is calcined under 500 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 13】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 100g deionized waters are mixed
In, after 60 DEG C are stirred 1 hour, phosphoric acid (85w%) 69g is slowly added dropwise, continues stirring aging and is massaged for 12 hours
You are calculated as ratio：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0.4：0.08：800 mixed solution；Will mixing
Solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, takes out, through filtering, washing, dries after the good product cooling of crystallization,
It is calcined under 500 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 14】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 100g deionized waters are mixed
In, after 60 DEG C are stirred 1 hour, phosphoric acid (85w%) 69g is slowly added dropwise, continues stirring aging and is massaged for 12 hours
You are calculated as ratio：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0.3：0.04：800 mixed solution；Will mixing
Solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, takes out, through filtering, washing, dries after the good product cooling of crystallization,
It is calcined under 500 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 15】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 100g deionized waters are mixed
In, after 60 DEG C are stirred 1 hour, phosphoric acid (85w%) 69g is slowly added dropwise, continues stirring aging and is massaged for 12 hours
You are calculated as ratio：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0.2：0.06：800 mixed solution；Will mixing
Solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, takes out, through filtering, washing, dries after the good product cooling of crystallization,
It is calcined under 500 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Embodiment 16】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 62.5g deionized waters are mixed
In, after 60 DEG C are stirred 1 hour, phosphoric acid (85w%) 69g is slowly added dropwise, continues stirring aging and is massaged for 12 hours
You are calculated as ratio：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0.2：0.04：500 mixed solution；Will mixing
Solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, takes out, through filtering, washing, dries after the good product cooling of crystallization,
It is calcined under 500 DEG C of air atmospheres after 6h, Mesoporous zirconium phosphate is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Comparative example 1】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 62.5g deionized waters are mixed
In, after 60 DEG C are stirred 1 hour, phosphoric acid (85w%) 69g is slowly added dropwise, continues stirring aging and is massaged for 12 hours
You are calculated as ratio：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0.2：0：800 mixed solution；It will mix molten
Liquid is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, takes out, through filtering, washing, dries after the good product cooling of crystallization,
It is calcined under 500 DEG C of air atmospheres after 6h, basic zirconium phosphate A is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
【Comparative example 2】
By template cetyl trimethylammonium bromide (CTAB) and APES (OP-10) and deionized water
Clarification is mixed to, solution A is designated as；Solution A is slowly added into after 41.4g zirconium carbonates and 62.5g deionized waters are mixed
In, after 60 DEG C are stirred 1 hour, phosphoric acid (85w%) 69g is slowly added dropwise, continues stirring aging and is massaged for 12 hours
You are calculated as ratio：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：2：0：0.04：800 mixed solution；Will mixing
Solution is fitted into crystallizing kettle, in 120 DEG C of crystallization 48h, takes out, through filtering, washing, dries after the good product cooling of crystallization,
It is calcined under 500 DEG C of air atmospheres after 6h, basic zirconium phosphate B is made.
Obtained Mesoporous zirconium phosphate is N as stated above2Absorption test, pore structure parameter is shown in Table 1.
Table 1
Table 1 continues
Claims (10)
1. a kind of Mesoporous zirconium phosphate, it is characterised in that the θ of XRD diffracting spectrums 2 has characteristic peak 2.2 ± 0.4.
2. Mesoporous zirconium phosphate according to claim 1, it is characterised in that specific surface area is 250~450m2/ g, pore volume
For 0.3~0.6cm3/ g, average pore size are 2.5~4.5nm.
3. the preparation method of the Mesoporous zirconium phosphate described in claim 1 or 2, comprises the following steps：
1. template cetyl trimethylammonium bromide CTAB, APES OP-10 and deionized water are mixed
Conjunction is stirred to clarify, and is designated as solution A；
2. zirconium source and phosphorus source are dissolved in wiring solution-forming B and C in deionized water respectively；
3. solution B is slowly added dropwise in solution A, after stirring 0.5~2 hour, solution C is slowly added dropwise, continue to stir
Aging is calculated in molar ratio as after 1~24 hour：Zr4+：PO4 3-：CTAB：OP-10：H2O=1：0.25~4：0.15~
0.5：0.03~0.08：500~800 mixed solution D；
4. mixed solution D is fitted into crystallizing kettle, in 12~100h of crystallization at 70~150 DEG C, the good product cooling of crystallization
After take out, through filtering, washing, dry, under 350~650 DEG C of air atmospheres be calcined 0.5~24h after, be made mesoporous phosphorus
Sour zirconium.
4. the preparation method of Mesoporous zirconium phosphate according to claim 3, it is characterised in that described zirconium source is selected from chlorine oxygen
Change at least one of zirconium, zirconyl nitrate, zirconium nitrate or zirconium carbonate.
5. the preparation method of Mesoporous zirconium phosphate according to claim 3, it is characterised in that described phosphorus source be selected from phosphoric acid,
At least one of ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
6. the preparation method of Mesoporous zirconium phosphate according to claim 3, it is characterised in that 3. described step stirs temperature
Spend for 30~90 DEG C.
7. the preparation method of Mesoporous zirconium phosphate according to claim 3, it is characterised in that described ageing time is 3~
12 hours.
8. the preparation method of Mesoporous zirconium phosphate according to claim 3, it is characterised in that described crystallization temperature is 80~
140℃。
9. the preparation method of Mesoporous zirconium phosphate according to claim 3, it is characterised in that described crystallization time is 24~
72 hours.
10. the preparation method of Mesoporous zirconium phosphate according to claim 2, it is characterised in that described sintering temperature is
400~550 DEG C, roasting time is 3~6 hours.
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| CN112479171B (en) * | 2020-11-24 | 2022-11-15 | 南京师范大学 | Metal phosphate, preparation method thereof and application thereof in catalytic esterification reaction |
| CN114316747A (en) * | 2022-01-13 | 2022-04-12 | 区雪娣 | Fireproof coating material and preparation method thereof |
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