CN1204086C - Metal zirconium phosphate, and its preparing method and use - Google Patents
Metal zirconium phosphate, and its preparing method and use Download PDFInfo
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Abstract
The present invention relates to a trivalent metal zirconium phosphate inorganic material (MeZrPO-15) whose anhydrous chemical constituent can be presented as mR (Me<a>Zr<b>PcFd) O2, wherein R is a mixture of one or a plurality of kinds of template agent 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-diaminobutane and 1, 6-hexamethylene diamine existing the trivalent metal zirconium phosphate inorganic material, m is a mole number of (Me<a>Zr<b>PcFd) O2 of each mole, Me, Zr, P and F are the metal, the zirconium, the phosphorus and the fluorine of the trivalent metal zirconium phosphate inorganic material, a, b, c and d are respectively the mole fractions of the Me, the Zr, the P and the F, wherein the a, the b, the c and the d have the ranges of a=0.05 to 0.85, b=0.10 to 0.90, c=0.10 to 0.94 and d=0.00 to 0.40, and meet the requirement of a+b+c+d=1. The Me is one of trivalent metal aluminium, ferrum, chromium, cerium, lanthanum, yttrium, titanium, scandium, gallium, indium, anadium and bismuth. The inorganic material of the present invention can be used for the technical fields of ion exchange, adsorption, catalysis, other inorganic functional materials, etc.
Description
Technical field
The present invention relates to a kind of inorganic materials MeZrPO-15 of trivalent metal zirconium phosphate, wherein MeZrPO-15 be this inorganic materials along number.
The invention still further relates to the preparation method of above-mentioned materials.
The invention still further relates to the application of above-mentioned materials.
Background technology
Reported first such as A.Clearfield in 1964 Zirconium phosphate crystal synthetic, tentatively determined this crystalline The Nomenclature Composition and Structure of Complexes, think that it has laminate structure and is defined as α-type, chemical formula is α-Zr (HPO
4)
2H
2O (is abbreviated as that α-ZrP), its laminate structure was confirmed by the structural analysis of monocrystalline X-ray diffraction afterwards.Nineteen sixty-eight A.Clearfield etc. has reported crystalline phase and the diverse bedded zirconium phosphate crystal of α type again, and is defined as γ-type, and its chemical constitution is γ-Zr (PO
4) (H
2PO
4) 2H
2O (is abbreviated as γ-ZrP).Zirconium phosphate receives numerous investigators' concern as inorganic materials owing to performances such as having catalysis, absorption and ion-exchange and is used widely.
1996, the people such as E.Kemnitz of Germany utilized hydrofluoric acid to make mineralizer, are that template synthesizes micropore the Zirconium phosphate crystal [(enH with three-dimensional framework structure first by the hydro-thermal synthetic technology with the organic amine
2)
0.5] [Zr
2(PO
4)
2(HPO
4) F] H
2O (called after ZrPO-1), and by the monocrystalline X-ray diffraction its structure is furtherd investigate.After this people such as E.Kemnitz utilizes different organic amine template to synthesize the similar fluorinated phosphate zirconium inorganic materials with three-dimensional framework structure of a series of The Nomenclature Composition and Structure of Complexes again, and represents with general formula ZrPOF-n.The weak point of this material is that moiety is more single, and thermostability is relatively poor; When adding the heat extraction template, collapse phenomenon appears in skeleton.By document Investigation as can be known, utilize organic amine to make template other atoms metal is incorporated in the zirconium phosphate skeleton, make it to become inorganic materials and yet there are no document and patent report with a plurality of chain carriers.The synthetic trivalent metal zirconium phosphate inorganic materials MeZrPO-15 of institute of the present invention has very high thermostability.
Summary of the invention
The object of the present invention is to provide a kind of trivalent metal zirconium phosphate.
Another purpose of the present invention is to provide the preparation method of above-mentioned trivalent metal zirconium phosphate.
Another object of the present invention is to provide the purposes of above-mentioned trivalent metal zirconium phosphate in ion-exchange, absorption, catalysis and other inorganic functional material fields.
For achieving the above object, the present invention utilizes the low-temperature hydrothermal synthetic technology, is template with the organic amine, with fluorochemical (HF or NH
4F) make mineralizer,, introduced new chain carrier thus by in the synthetic mixture material, adding trivalent metal ion, synthesize the zirconium phosphate inorganic materials that contains trivalent metal.Owing in the skeleton of zirconium phosphate, introduce other metal heteroatom, thereby make newly-generated inorganic materials MeZrPO-15 have performances such as unique catalysis, absorption and ion-exchange.
Metal zirconium phosphate provided by the present invention, its anhydrous chemical constitution can be expressed as: mR (Me
aZr
bP
cF
d) O
2, wherein R is the template that is present in the inorganic materials, m is every mole of (Me
aZr
bP
cF
d) O
2The mole number of middle R; Me, Zr, P, F are metal, zirconium, phosphorus and the fluorine in the inorganic materials, and a, b, c, d are respectively the molar fraction of Me, Zr, P, F, and its scope is a=0.05~0.85, b=0.10~0.90, c=0.10~0.94, d=0.00~0.40, and satisfy a+b+c+d=1.Me is a kind of in trivalent metal aluminium, iron, chromium, cerium, lanthanum, yttrium, titanium, scandium, gallium, indium, vanadium and the bismuth.
Shown in the principal character peak following table of the X-ray diffraction of inorganic materials of the present invention, the data in the table are stronger peak values in above-mentioned each material diffraction peak:
No | 2θ | d() | 100×I/I o |
1 | 14.810~15.080 | 5.9767~5.8703 | By force |
2 | 19.200~19.520 | 4.6189~4.5439 | By force |
3 | 21.080~21.420 | 4.2110~4.1450 | A little less than |
4 | 25.910~26.320 | 3.4359~3.3833 | A little less than |
5 | 27.340~27.780 | 3.2594~3.2088 | By force |
6 | 28.710~29.160 | 3.1069~3.0600 | A little less than |
7 | 31.310~31.770 | 2.8546~2.8143 | A little less than |
8 | 32.510~33.000 | 2.7519~2.7121 | By force |
9 | 47.510~48.270 | 1.9122~1.8838 | A little less than |
Metal zirconium phosphate preparation process provided by the invention is as follows:
(1) in proportion zirconium source material, phosphorus source material, metal-salt, mineralizer, template and water are under agitation mixed, get initial gel mixture;
(2) the initial gel mixture material is moved in the band teflon-lined stainless steel synthesis reactor and seal, place baking oven, 160~200 ℃ of following crystallization 2~10 days;
(3) solid crystallized product is separated with mother liquor, to neutral, behind 90~110 ℃ of following air dryings, obtain trivalent metal and replace the former powder of zirconium phosphate inorganic materials with the deionized water washing;
In above-mentioned preparation process, used zirconium source is a kind of in zirconium nitrate, zirconium oxychloride or the tetrabutyl zirconate; The phosphorus source is a kind of in the oxide compound of 85% phosphoric acid, phosphoric acid salt or phosphorus; Metal-salt is nitrate, muriate or the acetate of metals such as aluminium, iron, chromium, cerium, lanthanum, yttrium, titanium, scandium, gallium, indium, vanadium and bismuth; Mineralizer is a kind of in Neutral ammonium fluoride or the hydrofluoric acid; Template is 1,2-propylene diamine, 1,3-propylene diamine, 1,4-butanediamine and 1, the mixture of one or more in the 6-hexanediamine.
In the above-mentioned preparation process, each used raw material by oxide mol ratio is:
Me
2O
3/ZrO
2=0.05~3.0;
P
2O
5/ZrO
2=0.50~5.0;
NH
4F/ZrO
2=0.20~8.0;
H
2O/ZrO
2=50~400;
R/ZrO
2=0.05~5.0; R is a template.
The roasting in 400~550 ℃ of following air of the former powder of trivalent metal zirconium phosphate is no less than 5 hours, promptly gets the porous inorganic material of trivalent metal zirconium phosphate.Can be used on ion-exchange, absorption, catalysis and other inorganic functional material fields.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1 FeZrPO-15
With 4.04g iron nitrate (Fe (NO
3)
39H
2O, 10mmol), 9.66g zirconium oxychloride (ZrOCl
28H
2O, 30mmol), 5.29g 1,4-butanediamine (60mmol), 1.11g Neutral ammonium fluoride (30mmol), 6.90g ortho-phosphoric acid (contains H
3PO
485%, 60mmol) and 54g (3mol) deionized water 1: 3: 6 in molar ratio: 3: 6: 300 mixed, stir about 2 hours until becoming homogeneous phase.To seal in the said mixture material immigration 100ml stainless steel synthesis reactor, crystallization was 8 days under 190 ℃ and autogenous pressure, and the solid matter with deionized water washing is to neutral, 100 ℃ of following air dryings 24 hours, product is the FeZrPO-15 inorganic materials, and the result is as shown in table 1 for its XRD analysis:
Table 1
No | 2θ | d() | 100×I/I o |
1 | 15.040 | 5.8858 | 87 |
2 | 19.500 | 4.5485 | 97 |
3 | 21.390 | 4.1507 | 38 |
4 | 26.300 | 3.3859 | 36 |
5 | 27.750 | 3.2122 | 100 |
6 | 29.150 | 3.0610 | 40 |
7 | 31.710 | 2.8195 | 20 |
8 | 32.980 | 2.7137 | 84 |
9 | 43.660 | 2.0715 | 21 |
10 | 44.620 | 2.0291 | 17 |
11 | 46.470 | 1.9525 | 17 |
12 | 48.270 | 1.8838 | 33 |
13 | 49.120 | 1.8532 | 18 |
Embodiment 2 AlZrPO-15
In embodiment 1, with 4.04g iron nitrate (Fe (NO
3)
39H
2O 10mmol) changes 3.75g aluminum nitrate (Al (NO into
3)
39H
2O, 10mmol), all the other components and crystallization condition are constant, and product is the AlZrPO-15 inorganic materials, and the result is as shown in table 2 for its XRD analysis.Compare with the XRD spectra of FeZrPO-15, the position of diffraction peak and peak type are very close, show that AlZrPO-15 and FeZrPO-15 have similar skeleton structure.
Table 2
No | 2θ | d() | 100×I/I o |
1 | 15.020 | 5.8936 | 92 |
2 | 19.470 | 4.5555 | 100 |
3 | 21.360 | 4.1565 | 37 |
4 | 26.290 | 3.3871 | 35 |
5 | 27.740 | 3.2133 | 96 |
6 | 29.100 | 3.0661 | 39 |
7 | 31.700 | 2.8203 | 19 |
8 | 32.960 | 2.7153 | 73 |
9 | 36.390 | 2.4669 | 13 |
10 | 43.630 | 2.0728 | 17 |
11 | 44.640 | 2.0282 | 16 |
12 | 48.250 | 1.8846 | 36 |
13 | 49.120 | 1.8532 | 16 |
Embodiment 3 CeZrPO-15
In embodiment 1, with 4.04g iron nitrate (Fe (NO
3)
39H
2O 10mmol) changes 4.34g cerous nitrate (Ce (NO into
3)
36H
2O, 10mmol), all the other components and crystallization condition are constant, and product is the CeZrPO-15 inorganic materials, and the result is as shown in table 3 for its XRD analysis.Compare with the XRD spectra of FeZrPO-15, the position of diffraction peak and peak type are very close, show that CeZrPO-15 and FeZrPO-15 have similar skeleton structure.
Table 3
No | 2θ | d() | 100×I/I o |
1 | 15.020 | 5.8936 | 79 |
2 | 19.440 | 4.5624 | 100 |
3 | 21.310 | 4.1661 | 40 |
4 | 26.200 | 3.3986 | 33 |
5 | 27.640 | 3.2247 | 82 |
6 | 29.010 | 3.0754 | 50 |
7 | 31.550 | 2.8334 | 21 |
8 | 32.830 | 2.7258 | 67 |
9 | 43.430 | 2.0819 | 17 |
10 | 45.260 | 2.0019 | 17 |
11 | 46.220 | 1.9625 | 25 |
12 | 48.010 | 1.8934 | 35 |
13 | 48.870 | 1.8621 | 22 |
Embodiment 4 CrZrPO-15
In embodiment 1, with 4.04g iron nitrate (Fe (NO
3)
39H
2O 10mmol) changes 2.65g chromium acetate (Cr (OAc) into
32H
2O, 10mmol), all the other components and crystallization condition are constant, and product is the CrZrPO-15 inorganic materials, and the result is as shown in table 4 for its XRD analysis.Compare with the XRD spectra of FeZrPO-15, the position of diffraction peak and peak type are very close, show that CrZrPO-15 and FeZrPO-15 have similar skeleton structure.
Table 4
No | 2θ | d() | 100×I/I o |
1 | 15.020 | 5.8936 | 80 |
2 | 19.440 | 4.5624 | 100 |
3 | 21.330 | 4.1622 | 35 |
4 | 26.220 | 3.3960 | 32 |
5 | 27.660 | 3.2224 | 84 |
6 | 29.050 | 3.0713 | 40 |
7 | 31.640 | 2.8255 | 20 |
8 | 32.860 | 2.7234 | 76 |
9 | 36.310 | 2.4721 | 13 |
10 | 43.480 | 2.0796 | 16 |
11 | 46.310 | 1.9589 | 14 |
12 | 48.040 | 1.8923 | 32 |
13 | 48.940 | 1.8596 | 16 |
Embodiment 5 LaZrPO-15
In embodiment 1, with 4.04g iron nitrate (Fe (NO
3)
39H
2O 10mmol) changes 4.32g lanthanum nitrate (La (NO into
3)
36H
2O, 10mmol), all the other components and crystallization condition are constant, and product is the LaZrPO-15 inorganic materials, and the result is as shown in table 5 for its XRD analysis.Compare with the XRD spectra of FeZrPO-15, the position of diffraction peak and peak type are very close, show that LaZrPO-15 and FeZrPO-15 have similar skeleton structure.
Table 5
No | 2θ | d() | 100×I/I o |
1 | 15.030 | 5.8897 | 100 |
2 | 19.450 | 4.5601 | 96 |
3 | 21.330 | 4.1622 | 37 |
4 | 26.210 | 3.3973 | 38 |
5 | 27.650 | 3.2235 | 74 |
6 | 29.030 | 3.0734 | 38 |
7 | 31.640 | 2.8255 | 20 |
8 | 32.850 | 2.7242 | 78 |
9 | 36.310 | 2.4721 | 15 |
10 | 43.030 | 2.1003 | 17 |
11 | 46.230 | 1.9621 | 19 |
12 | 48.000 | 1.8938 | 37 |
13 | 48.440 | 1.8776 | 15 |
Embodiment 6 YZrPO-15
In embodiment 1, with 4.04g iron nitrate (Fe (NO
3)
39H
2O 10mmol) changes 1.92g Yttrium trinitrate (Y (NO into
3)
36H
2O, 5mmol), all the other components and crystallization condition are constant, and product is the YZrPO-15 inorganic materials, and the result is as shown in table 6 for its XRD analysis.Compare with the XRD spectra of FeZrPO-15, the position of diffraction peak and peak type are very close, show that YZrPO-15 and FeZrPO-15 have similar skeleton structure.
Table 6
No | 2θ | d() | 100×I/I o |
1 | 14.810 | 5.9767 | 89 |
2 | 19.200 | 4.6189 | 100 |
3 | 21.080 | 4.2110 | 35 |
4 | 25.910 | 3.4359 | 30 |
5 | 27.350 | 3.2582 | 98 |
6 | 28.710 | 3.1069 | 37 |
7 | 31.310 | 2.8546 | 18 |
8 | 32.510 | 2.7519 | 78 |
9 | 36.240 | 2.4767 | 10 |
10 | 43.020 | 2.1008 | 18 |
11 | 46.170 | 1.9645 | 14 |
12 | 47.910 | 1.8972 | 31 |
13 | 48.440 | 1.8776 | 16 |
Embodiment 7 TiZrPO-15
In embodiment 1, with 4.04g iron nitrate (Fe (NO
3)
39H
2O 10mmol) changes the 7.23g titanium trichloride aqueous solution into and (contains 16% TiCl
3, 7.5mmol), all the other components and crystallization condition are constant, and product is the TiZrPO-15 inorganic materials, and the result is as shown in table 7 for its XRD analysis.Compare with the XRD spectra of FeZrPO-15, the position of diffraction peak and peak type are very close, show that TiZrPO-15 and FeZrPO-15 have similar skeleton structure.
Table 7
No | 2θ | d() | 100×I/I o |
1 | 15.030 | 5.8897 | 62 |
2 | 19.480 | 4.5532 | 100 |
3 | 21.340 | 4.1603 | 34 |
4 | 26.250 | 3.3922 | 33 |
5 | 27.690 | 3.2190 | 91 |
6 | 29.070 | 3.0692 | 47 |
7 | 31.660 | 2.8238 | 21 |
8 | 32.900 | 2.7201 | 83 |
9 | 36.240 | 2.4767 | 15 |
10 | 43.500 | 2.0787 | 20 |
11 | 46.270 | 1.9605 | 21 |
12 | 48.050 | 1.8920 | 45 |
13 | 48.690 | 1.8686 | 20 |
Embodiment 8 ScZrPO-15
In embodiment 1, with 4.04g iron nitrate (Fe (NO
3)
39H
2O 10mmol) changes 2.85g Scium trinitrate (Sc (NO into
3)
33H
2O, 10mmol), all the other components and crystallization condition are constant, and product is the ScZrPO-15 inorganic materials, and the result is as shown in table 8 for its XRD analysis.Compare with the XRD spectra of FeZrPO-15, the position of diffraction peak and peak type are very close, show that ScZrPO-15 and FeZrPO-15 have similar skeleton structure.
Table 8
No | 2θ | d() | 100×I/I o |
1 | 15.000 | 5.9014 | 83 |
2 | 19.420 | 4.5671 | 100 |
3 | 21.310 | 4.1661 | 40 |
4 | 26.200 | 3.3986 | 35 |
5 | 27.640 | 3.2247 | 87 |
6 | 29.000 | 3.0765 | 43 |
7 | 31.600 | 2.8290 | 21 |
8 | 32.840 | 2.7250 | 74 |
9 | 36.330 | 2.4708 | 14 |
10 | 43.430 | 2.0819 | 18 |
11 | 44.430 | 2.0373 | 16 |
12 | 46.220 | 1.9625 | 16 |
13 | 48.040 | 1.8923 | 31 |
Embodiment 9 GaZrPO-15
In embodiment 1, with 4.04g iron nitrate (Fe (NO
3)
39H
2O 10mmol) changes 4.00g gallium nitrate (Ga (NO into
3)
38H
2O, 10mmol), all the other components and crystallization condition are constant, and product is the GaZrPO-15 inorganic materials, and the result is as shown in table 9 for its XRD analysis.Compare with the XRD spectra of FeZrPO-15, the position of diffraction peak and peak type are very close, show that GaZrPO-15 and FeZrPO-15 have similar skeleton structure.
Table 9
No | 2θ | d() | 100×I/I o |
1 | 14.830 | 5.9687 | 80 |
2 | 19.220 | 4.6142 | 100 |
3 | 21.080 | 4.2110 | 33 |
4 | 25.920 | 3.4346 | 31 |
5 | 27.340 | 3.2594 | 85 |
6 | 28.730 | 3.1048 | 33 |
7 | 31.310 | 2.8546 | 18 |
8 | 32.510 | 2.7519 | 68 |
9 | 36.330 | 2.4708 | 12 |
10 | 43.030 | 2.1003 | 17 |
11 | 45.740 | 1.9820 | 14 |
12 | 47.510 | 1.9122 | 27 |
13 | 48.270 | 1.8838 | 11 |
Embodiment 10 InZrPO-15
In embodiment 1, with 4.04g iron nitrate (Fe (NO
3)
39H
2O 10mmol) changes 3.55g indium nitrate (In (NO into
3)
33H
2O, 10mmol), all the other components and crystallization condition are constant, and product is the InZrPO-15 inorganic materials, and the result is as shown in table 10 for its XRD analysis.Compare with the XRD spectra of FeZrPO-15, the position of diffraction peak and peak type are very close, show that InZrPO-15 and FeZrPO-15 have similar skeleton structure.
Table 10
No | 2θ | d() | 100×I/I o |
1 | 14.860 | 5.9567 | 79 |
2 | 19.260 | 4.6047 | 100 |
3 | 21.110 | 4.2051 | 34 |
4 | 25.960 | 3.4294 | 34 |
5 | 27.390 | 3.2535 | 93 |
6 | 28.760 | 3.1016 | 34 |
7 | 31.340 | 2.8519 | 18 |
8 | 32.540 | 2.7494 | 80 |
9 | 36.500 | 2.4597 | 12 |
10 | 43.050 | 2.0994 | 16 |
11 | 44.920 | 2.0162 | 14 |
12 | 45.820 | 1.9787 | 15 |
13 | 47.610 | 1.9084 | 29 |
Embodiment 11 VZrPO-15
In embodiment 1, with 4.04g iron nitrate (Fe (NO
3)
39H
2O 10mmol) changes 1.57g vanadium trichloride (VCl into
3, 10mmol), all the other components and crystallization condition are constant, and product is the VZrPO-15 inorganic materials, and the result is as shown in table 11 for its XRD analysis.Compare with the XRD spectra of FeZrPO-15, the position of diffraction peak and peak type are very close, show that VZrPO-15 and FeZrPO-15 have similar skeleton structure.
Table 11
No | 2θ | d() | 100×I/I o |
1 | 14.960 | 5.9171 | 68 |
2 | 19.360 | 4.5811 | 100 |
3 | 21.240 | 4.1797 | 34 |
4 | 26.090 | 3.4126 | 38 |
5 | 27.530 | 3.2373 | 94 |
6 | 28.890 | 3.0879 | 38 |
7 | 31.500 | 2.8378 | 19 |
8 | 32.720 | 2.7347 | 80 |
9 | 40.400 | 2.2308 | 14 |
10 | 43.270 | 2.0892 | 21 |
11 | 45.100 | 2.0086 | 16 |
12 | 46.050 | 1.9694 | 17 |
13 | 47.780 | 1.9020 | 33 |
Embodiment 12 BiZrPO-15
In embodiment 1, with 4.04g iron nitrate (Fe (NO
3)
39H
2O 10mmol) changes 4.85g Bismuth trinitrate (Bi (NO into
3)
35H
2O, 10mmol), all the other components and crystallization condition are constant, and product is the BiZrPO-15 inorganic materials, and the result is as shown in table 12 for its XRD analysis.Compare with the XRD spectra of FeZrPO-15, the position of diffraction peak and peak type are very close, show that BiZrPO-15 and FeZrPO-15 have similar skeleton structure.
Table 12
No | 2θ | d() | 100×I/I o |
1 | 15.080 | 5.8703 | 100 |
2 | 19.520 | 4.5439 | 50 |
3 | 21.420 | 4.1450 | 21 |
4 | 26.320 | 3.3833 | 23 |
5 | 27.780 | 3.2088 | 58 |
6 | 29.160 | 3.0600 | 22 |
7 | 31.770 | 2.8143 | 8 |
8 | 33.000 | 2.7121 | 51 |
9 | 36.500 | 2.4597 | 8 |
10 | 43.660 | 2.0715 | 11 |
11 | 44.620 | 2.0291 | 7 |
12 | 46.460 | 1.9529 | 11 |
13 | 48.260 | 1.8842 | 21 |
Embodiment 13
With the roasting 4 hours in 500 ℃ of following air of resulting sample among the embodiment 1.Take by weighing the sample of 1.5 grams after the roastings, join in the nickel nitrate solution of 100 milliliters of 1M.80 ℃ of down exchanges 12 hours, exchange repeatedly 4 times, resulting sample after filtration, the deionized water washing and in 100 ℃ dry down, promptly get the sample Ni-FeZrPO-15 inorganic materials after nickel exchanges.
Embodiment 14
With the roasting 4 hours in 500 ℃ of following air of resulting sample among the embodiment 1~12.Accurately the quality of weighing sample is placed in the moisture eliminator that saturated aqueous common salt is housed, and places 12 hours under the room temperature.By taking by weighing the variation of sample front and back quality, obtain the suction numerical value of sample.Experiment shows that the MeZrPO-15 inorganic materials after the roasting has water-absorbent, and the adsorptive value to water under its room temperature is as shown in table 13.
The water-absorbent of MeZrPO-15 inorganic materials (%) after table 13 roasting
Me- | Fe- | Al- | Ce- | Cr- | La- | Y- | Ti- | Sc- | Ga- | In- | V- | Bi- |
Water regain | 15.2 | 13.4 | 16.3 | 14.1 | 13.8 | 13.3 | 15.9 | 13.6 | 14.7 | 15.3 | 14.3 | 13.8 |
Claims (7)
1, a kind of trivalent metal zirconium phosphate inorganic materials, its anhydrous chemical constitution can be expressed as: mR (Me
aZr
bP
cF
d) O
2, wherein R is a template, and this template is an organic amine, and m is every mole of (Me
aZr
bP
cF
d) O
2The mole number of middle R; Me, Zr, P, F are metal, zirconium, phosphorus and the fluorine in the inorganic materials, and a, b, c, d are respectively the molar fraction of Me, Zr, P, F, and its scope is a=0.05~0.85, b=0.10~0.90, c=0.10~0.94, d=0.00~0.40, and satisfy a+b+c+d=1; Me is a kind of in trivalent metal aluminium, iron, chromium, cerium, lanthanum, yttrium, titanium, scandium, gallium, indium, vanadium and the bismuth.
According to the described inorganic materials of claim 1, it is characterized in that 2, angle 2 θ at the principal character peak of the X-ray diffraction of described inorganic materials are: 14.810~15.080,19.200~19.520,27.340~27.780 and 32.510~33.000.
According to the described inorganic materials of claim 1, it is characterized in that 3, described organic amine is 1,2-propylene diamine, 1,3 propylene diamine, 1,4-butanediamine and 1, the mixture of one or more in the 6-hexanediamine.
4, a kind of method for preparing the described metal zirconium phosphate of claim 1 is characterized in that, is undertaken by following step:
A. in proportion zirconium source material, phosphorus source material, metal-salt, mineralizer, template and water are under agitation mixed, get initial gel mixture, wherein said mineralizer is Neutral ammonium fluoride or hydrofluoric acid;
B. the initial gel mixture material that steps A is obtained moves in the synthesis reactor and seals, and places baking oven, at 160-200 ℃ of following crystallization 2-10 days;
C. the solid crystallized product that step B is obtained separates with mother liquor, to neutral, obtains the former powder of zirconium phosphate that trivalent metal replaces with the deionized water washing behind 90-110 ℃ of following air drying;
Above-mentioned each used raw material by oxide mol ratio is:
Me
2O
3/ZrO
2=0.05-3.0;
P
2O
5/ZrO
2=0.50-5.0;
NH
4F/ZrO
2=0.20-8.0;
H
2O/ZrO
2=50-400;
R/ZrO
2=0.05-5.0, R are template;
Described metal-salt is nitrate, muriate or the acetate of trivalent metal aluminium, iron, chromium, cerium, lanthanum, yttrium, titanium, scandium, gallium, indium, vanadium and bismuth;
Described phosphorus source is the oxide compound of 85% phosphoric acid, phosphoric acid salt or phosphorus;
Described zirconium source is zirconium nitrate, zirconium oxychloride or tetrabutyl zirconate.
5, in accordance with the method for claim 4, it is characterized in that synthesis reactor described in the step B is for having teflon-lined stainless steel synthesis reactor.
6, in accordance with the method for claim 4, it is characterized in that,, obtain the porous inorganic material through the former powder of zirconium phosphate of step C preparation in 400-550 ℃ of following air roasting 3-7 hour.
7, by the inorganic materials of claim 6 preparation purposes in ion-exchange, absorption, catalysis and other inorganic functional material fields.
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