CN1204086C - Metal zirconium phosphate, and its preparing method and use - Google Patents

Metal zirconium phosphate, and its preparing method and use Download PDF

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CN1204086C
CN1204086C CN 02126926 CN02126926A CN1204086C CN 1204086 C CN1204086 C CN 1204086C CN 02126926 CN02126926 CN 02126926 CN 02126926 A CN02126926 A CN 02126926A CN 1204086 C CN1204086 C CN 1204086C
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inorganic materials
zirconium phosphate
zirconium
trivalent metal
zro
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CN1470477A (en
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孙振刚
刘中民
杨越
许磊
王锦航
魏迎旭
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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

A kind of metal zirconium phosphate and preparation method and application
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.
CN 02126926 2002-07-26 2002-07-26 Metal zirconium phosphate, and its preparing method and use Expired - Fee Related CN1204086C (en)

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CN107115879B (en) * 2017-04-14 2019-10-15 复旦大学 The Phosphorus composite oxide catalysts of chromium-and preparation method thereof for glycerol synthesis propenyl
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