CN1176045C - Metal zirconium phosphate in organic material, and its synthesis method and use - Google Patents

Metal zirconium phosphate in organic material, and its synthesis method and use Download PDF

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CN1176045C
CN1176045C CNB021269254A CN02126925A CN1176045C CN 1176045 C CN1176045 C CN 1176045C CN B021269254 A CNB021269254 A CN B021269254A CN 02126925 A CN02126925 A CN 02126925A CN 1176045 C CN1176045 C CN 1176045C
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inorganic materials
zirconium
metal
zirconium phosphate
zro
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CN1470476A (en
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孙振刚
刘中民
许磊
杨越
王锦航
桑石云
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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-12), the anhydrous chemical constituent of which can be presented as mR (Me<a>Zr<b>P<c>Fd) O2, wherein R is a mixture of one or a plurality of kinds of ethylene diamine which is a template agent, triethanolmine and tetraethyl ammonium hydroxide, m is the mole number of the R in each mole of (Me<a>Zr<b>P<c>Fd) O2, 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 0.80, b=0.10 to 0.95, c=0.10 to 0.90 and d=0.01 to 0.40, and meet the requirement of a+b+c+d=1. The Me is one of trivalent metal chromium, aluminium, gallium, indium, titanium, lanthanum, cerium, yttrium, ferrum and bismuth. The material of the present invention can be used for the technical fields of ion exchange, adsorption, catalysis, other inorganic functional materials, etc.

Description

Metal zirconium phosphate in organic material and synthetic method and application
Technical field
The present invention relates to a class trivalent metal zirconium phosphate inorganic materials MeZrPO-12, wherein MeZrPO-12 be this inorganic materials along number.
The invention still further relates to the synthetic method of above-mentioned materials.
The invention still further relates to above-mentioned materials and can be used on ion-exchange, absorption, catalysis and other inorganic functional material fields.
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 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 is subjected to numerous investigators' extensive concern owing to performances such as having catalysis, absorption and ion-exchange as inorganic materials.
1996, the people such as E.Kemnitz of Germany utilized hydrofluoric acid to make mineralizer, are that template synthesizes the Zirconium phosphate crystal [(enH with the zeolite structured feature of class first by the hydro-thermal synthesizing mean with the organic amine 2) 0.5] [Zr 2(PO 4) 2(HPO 4) F] H 2O (called after ZrPO-1) furthers investigate its structure by the monocrystalline X-ray diffraction.Studies show that this crystalline compounds has the skeleton structure of class zeolite, and show some character of molecular sieve.After this, people such as E.Kemnitz utilize dissimilar organic amine template to synthesize the fluorinated phosphate zirconium crystalline compounds with three-dimensional framework structure that a series of The Nomenclature Composition and Structure of Complexes all are similar to ZrPO-1 again, and represent 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 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.
Summary of the invention
The object of the present invention is to provide a kind of trivalent metal to replace the zirconium phosphate inorganic materials.
Another object of the present invention is to provide the synthetic method of above-mentioned inorganic materials.
Another purpose of the present invention is to provide above-mentioned inorganic materials to can be used on ion-exchange, absorption, catalysis and other inorganic functional material fields.
For achieving the above object, trivalent metal provided by the invention replaces the zirconium phosphate inorganic materials, and its anhydrous chemical constitution is: 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=0.05-0.80, b=0.10-0.95, c=0.10-0.90, d=0.01-0.40, and satisfy a+b+c+d=1; Me is trivalent metal chromium, aluminium, gallium, indium, titanium, lanthanum, cerium, yttrium, iron or bismuth.
The X-ray diffraction principal character peak of inorganic materials of the present invention is as shown in the table, and the data in the table are stronger peak values in above-mentioned each material diffraction peak:
No 2θ D() 100×I/I o
1 7.300-7.450 12.0999-11.8566 Very strong
2 13.750-13.920 6.4350-6.3568 A little less than
3 15.070-17.440 5.8742-5.0809 By force
4 19.370-20.010 4.5788-4.4337 By force
5 24.810-24.980 3.5857-3.5617 By force
6 26.100-27.100 3.4114-3.2877 A little less than
7 28.910-30.960 3.0858-2.8860 By force
8 30.320-32.920 2.9455-2.7185 By force
9 36.830-37.010 2.4384-2.4270 A little less than
Its process of trivalent metal zirconium phosphate inorganic materials preparation method provided by the invention is as follows: utilizing 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 the inorganic materials of generation have performances such as unique catalysis, absorption and ion-exchange.
Specifically, its preparation method is: in proportion zirconium source material, phosphorus source material, metal-salt, mineralizer, template and water are under agitation mixed, get initial gel mixture;
The initial gel mixture material is moved in the band teflon-lined stainless steel synthesis reactor seals, place baking oven, at 160-200 ℃ of following crystallization 2-10 days;
Solid crystallized product is separated with mother liquor, be washed till neutrality, behind 80-140 ℃ of following air drying, obtain the former powder of trivalent metal zirconium phosphate inorganic materials with deionized water;
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 chromium, aluminium, gallium, indium, titanium, lanthanum, cerium, yttrium, iron and bismuth; Mineralizer is a kind of in Neutral ammonium fluoride or the hydrofluoric acid; Template is one or more the mixture in quadrol, trolamine and the tetraethyl ammonium hydroxide.
In above-mentioned preparation process, each used raw material by the mol ratio of oxide compound is:
Me 2O 3/ZrO 2＝0.05-3.0；
P 2O 5/ZrO 2＝0.50-5.0；
NH 4F/ZrO 2＝0.50-5.0；
H 2O/ZrO 2＝50-400；
R/ZrO 2=0.10-5.0, R are template.
With the former powder of synthetic metal zirconium phosphate inorganic materials of the present invention in 400-550 ℃ of following air roasting 3-7 hour, the inorganic materials that obtains 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 CrZrPO-12
With 3.96g chromium acetate (Cr (OAc) 32H 2O, 15mmol), 9.66g zirconium oxychloride (ZrOCl 28H 2O, 30mmol), 3.60g quadrol (60mmol), 1.11g Neutral ammonium fluoride (30mmol), 6.90g ortho-phosphoric acid (contains H 3PO 485%, 60mmol) and 54g (3mol) deionized water 1: 2: 4 in molar ratio: 2: 4: 200 mixed, stir about 2 hours until becoming the homogeneous phase gel.To seal in the said mixture material immigration 100ml stainless steel synthesis reactor, crystallization was 7 days under 180 ℃ and autogenous pressure, and the solid matter with deionized water washing is to neutral, 100 ℃ of following air dryings 24 hours, product is the CrZrPO-12 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 7.320 12.0669 100
2 13.890 6.3705 17
3 15.070 5.8742 55
4 19.450 4.5601 43
5 24.850 3.5801 52
6 26.910 3.3105 24
7 29.080 3.0682 31
8 32.920 2.7185 36
9 36.830 2.4384 25
Embodiment 2 AlZrPO-12
5.63g aluminum nitrate (Al (NO 3) 39H 2O, 15mmol), all the other components and crystallization condition are with embodiment 1, and product is the AlZrPO-12 inorganic materials, and the result is as shown in table 2 for its XRD analysis.
Table 2
No 2θ d() 100×I/I o
1 7.390 11.9527 100
2 13.840 6.3934 24
3 17.370 5.1012 31
4 19.910 4.4558 53
5 24.890 3.5744 61
6 27.100 3.2877 26
7 29.790 2.9967 47
8 30.990 2.8833 30
9 36.900 2.4339 23
Embodiment 3 GaZrPO-12
6.00g gallium nitrate (Ga (NO 3) 38H 2O, 15mmol), all the other components and crystallization condition are with embodiment 1, and product is the GaZrPO-12 inorganic materials, and the result is as shown in table 3 for its XRD analysis.
Table 3
No 2θ d() 100×I/I o
1 7.360 12.0014 88
2 13.850 6.3888 29
3 17.340 5.1100 60
4 19.920 4.4536 100
5 24.870 3.5772 84
6 26.850 3.3177 27
7 27.920 3.1930 41
8 30.960 2.8860 48
9 36.900 2.4339 33
Embodiment 4 InZrPO-12
5.32g indium nitrate (In (NO 3) 33H 2O, 15mmol), all the other components and crystallization condition are with embodiment 1, and product is the InZrPO-12 inorganic materials, and the result is as shown in table 4 for its XRD analysis.
Table 4
No 2θ d() 100×I/I o
1 7.430 11.8885 100
2 13.890 6.3705 37
3 17.410 5.0896 56
4 19.970 4.4425 86
5 24.940 3.5673 73
6 26.900 3.3117 31
7 29.820 2.9937 47
8 31.010 2.8815 45
9 36.960 2.4301 30
Embodiment 5 TiZrPO-12
14.46g titanium trichloride aqueous solution (contains 16% TiCl 3, 15mmol), all the other components and crystallization condition are with embodiment 1, and product is the TiZrPO-12 inorganic materials, and the result is as shown in table 5 for its XRD analysis.
Table 5
No 2θ d() 100×I/I o
1 7.300 12.0999 100
2 13.830 6.3980 25
3 17.300 5.1217 33
4 19.860 4.4669 46
5 24.820 3.5843 53
6 26.790 3.3250 17
7 30.320 2.9455 35
8 30.910 2.8906 28
9 36.960 2.4301 20
Embodiment 6 LaZrPO-12
3.25g lanthanum nitrate (La (NO 3) 36H 2O, 7.5mmol), all the other components and crystallization condition are with embodiment 1, and product is the LaZrPO-12 inorganic materials, and the result is as shown in table 6 for its XRD analysis.
Table 6
No 2θ d() 100×I/I o
1 7.450 11.8566 100
2 13.920 6.3568 12
3 17.440 5.0809 27
4 20.010 4.4337 28
5 24.980 3.5617 37
6 26.930 3.3081 16
7 29.870 2.9888 29
8 31.060 2.8770 24
9 37.010 2.4270 14
Embodiment 7 CeZrPO-12
2.17g cerous nitrate (Ce (NO 3) 36H 2O, 5mmol), all the other components and crystallization condition are with embodiment 1, and product is the CeZrPO-12 inorganic materials, and the result is as shown in table 7 for its XRD analysis.
Table 7
No 2θ d() 100×I/I o
1 7.300 12.0999 100
2 13.750 6.4350 15
3 17.280 5.1276 32
4 19.850 4.4691 28
5 24.810 3.5857 37
6 26.770 3.3275 19
7 29.720 3.0036 26
8 30.880 2.8933 26
9 36.830 2.4384 16
Embodiment 8 YZrPO-12
5.75g Yttrium trinitrate (Y (NO 3) 36H 2O, 15mmol), all the other components and crystallization condition are with embodiment 1, and product is the YZrPO-12 inorganic materials, and the result is as shown in table 8 for its XRD analysis.
Table 8
No 2θ d() 100×I/I o
1 7.380 11.9689 100
2 13.790 6.4164 25
3 17.360 5.1041 35
4 19.930 4.4514 33
5 24.890 3.5744 57
6 26.100 3.4114 23
7 28.910 3.0858 30
8 31.500 2.8378 39
9 36.870 2.4358 22
Embodiment 9 FeZrPO-12
6.06g iron nitrate (Fe (NO 3) 39H 2O, 15mmol), all the other components and crystallization condition are with embodiment 1, and product is the FeZrPO-12 inorganic materials, and the result is as shown in table 9 for its XRD analysis.
Table 9
No 2θ d() 100×I/I o
1 7.300 12.0999 100
2 13.760 6.4304 16
3 17.280 5.1276 43
4 19.490 4.5508 75
5 24.810 3.5857 53
6 26.310 3.3846 30
7 29.200 3.0559 33
8 31.060 2.8770 70
9 36.830 2.4384 25
Embodiment 10 BiZrPO-12
7.28g Bismuth trinitrate (Bi (NO 3) 35H 2O, 15mmol), all the other components and crystallization condition are with embodiment 1, and product is the BiZrPO-12 inorganic materials, and the result is as shown in table 10 for its XRD analysis.
Table 10
No 2θ d() 100×I/I o
1 7.360 12.0014 100
2 13.850 6.3888 19
3 17.340 5.1100 40
4 19.920 4.4536 34
5 24.870 3.5772 54
6 26.850 3.3177 27
7 29.720 3.0036 30
8 30.960 2.8860 38
9 36.900 2.4339 23
Embodiment 11
With the roasting 4 hours in 450 ℃ 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 Cupric Chloride 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 Cu-CrZrPO-12 inorganic materials after copper exchanges.
Embodiment 12
With the roasting 4 hours in 450 ℃ of following air of resulting sample among the embodiment 1-10.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-12 inorganic materials after the roasting has water-absorbent, and the adsorptive value to water under its room temperature is as shown in table 11.
The water-absorbent of MeZrPO-12 inorganic materials (%) after table 11 roasting
Me- Cr- Al- Ga- In- Ti- La- Ce- Y- Fe- Bi-
Water regain 20.5 20.3 19.7 19.5 18.2 17.9 19.4 17.8 18.4 19.8

Claims (6)

1, a kind of trivalent metal zirconium phosphate inorganic materials, its anhydrous chemical constitution is: mR (Me aZr bP cF d) O 2, wherein:
R is a template, and this template is an organic amine;
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;
A, b, c, d are respectively the molar fraction of Me, Zr, P, F, and its scope is respectively a=0.05-0.80, b=0.10-0.95, and c=0.10-0.90, d=0.01-0.40, and satisfy a+b+c+d=1;
Me is trivalent metal chromium, aluminium, gallium, indium, titanium, lanthanum, cerium, yttrium, iron or bismuth.
2,, it is characterized in that angle 2 θ at the X-ray diffraction principal character peak of described inorganic materials are: 7.300-7.450,15.070-17.440,19.370-20.010,24.810-24.980,28.910-30.960 and 30.320-32.920 according to the described inorganic materials of claim 1.
According to the described inorganic materials of claim 1, it is characterized in that 3, described organic amine is one or more the mixture in quadrol, trolamine and the tetraethyl ammonium hydroxide.
4, a kind of method for preparing the described metal zirconium phosphate inorganic materials of claim 1 is characterized in that being 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 product with the deionized water washing behind 80-140 ℃ of 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＝0.50-5.0；
H 2O/ZrO 2＝50-400；
R/ZrO 2=0.10-5.0, wherein R is a template;
Used zirconium source is zirconium nitrate, zirconium oxychloride or tetrabutyl zirconate;
Used phosphorus source is the oxide compound of 85% phosphoric acid, phosphoric acid salt or phosphorus
Employed metal-salt is nitrate, muriate or the acetate of the trivalent metal of chromium, aluminium, gallium, indium, titanium, lanthanum, cerium, yttrium, iron and bismuth.
5, in accordance with the method for claim 3, it is characterized in that,, obtain the porous inorganic material through the former powder of zirconium phosphate inorganic materials of step C preparation in 400-550 ℃ of following air roasting 3-7 hour.
6, by the inorganic materials of claim 5 preparation purposes in ion-exchange, absorption, catalysis and other inorganic functional material fields.
CNB021269254A 2002-07-26 2002-07-26 Metal zirconium phosphate in organic material, and its synthesis method and use Expired - Fee Related CN1176045C (en)

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