CN1202990C - Zirconium phosphate crystal, and its preparing method and use - Google Patents

Zirconium phosphate crystal, and its preparing method and use Download PDF

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CN1202990C
CN1202990C CN 02126927 CN02126927A CN1202990C CN 1202990 C CN1202990 C CN 1202990C CN 02126927 CN02126927 CN 02126927 CN 02126927 A CN02126927 A CN 02126927A CN 1202990 C CN1202990 C CN 1202990C
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zirconium
zirconium phosphate
phosphate crystal
crystal
zro
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CN1470456A (en
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孙振刚
刘中民
杨越
许磊
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 zirconium phosphate crystal (ZrPO4-n), the anhydrous chemical constituent of which can be presented as mR (ZraPbFc)O2, wherein R is a mixture of one or a plurality of kinds of template agent ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 1, 4-butanediamine, 1, 6-hexanediamine, 1, 4-cyclohexanediamine, dipropylamine and tripropylamine existing in the zirconium phosphate crystal (ZrPO4-n), m is the mole number of the R in per mole of (ZraPbFc)O2, Zr, P and F are zirconium, phosphorus and fluorine of the zirconium phosphate crystal (ZrPO4-n) and a, b and c are respectively the mole fractions of the Zr, the P and the F. The a, the b and the c have the ranges that ais 0.10 to 0.80, b is 0.10 to 0.90 and c is 0.00 to 0.40, and meet the following requirement of a+b+c=1. The crystal 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 Zirconium phosphate crystal and preparation method and application
Technical field
The present invention relates to a kind of Zirconium phosphate crystal ZrPO 4-n.
The invention still further relates to above-mentioned crystalline preparation method.
The invention still further relates to above-mentioned crystalline uses.
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 monocrystalline X-ray diffraction result 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).Receive numerous investigators' concern owing to performances such as having catalysis, absorption and ion-exchange and be used widely as the zirconium phosphate of inorganic materials.
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 several different organic amine template to synthesize the similar fluorinated phosphate zirconium crystal with three-dimensional framework structure of a series of The Nomenclature Composition and Structure of Complexes again, and represents with general formula ZrPOF-n.But the research work of this up to now micropore Zirconium phosphate crystal with three-dimensional framework structure also seldom, and the quantity of crystalline compounds is also very limited, and the research of application facet still belongs to blank.In addition, the weak point of this material is that thermostability is relatively poor; When adding the heat extraction template, collapse phenomenon appears in skeleton.
Summary of the invention
The object of the present invention is to provide a kind of Zirconium phosphate crystal ZrPO 4-n.
Another purpose of the present invention is to provide above-mentioned crystalline preparation method.
Another object of the present invention is to provide of the application of above-mentioned crystal as ion-exchanger, catalyzer and sorbent material.
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, synthesize Zirconium phosphate crystal.
Zirconium phosphate crystal ZrPO provided by the invention 4-n, its anhydrous chemical constitution can be expressed as: mR (Zr aP bF c) O 2, wherein R is the template quadrol, 1 that is present in this crystal, 2-propylene diamine, 1, and 3-propylene diamine, 1,4-butanediamine, 1,6-hexanediamine, 1, the mixture of one or more in 4-cyclohexanediamine, di-n-propylamine and the Tri-n-Propylamine, m are every mole of (Zr aP bF c) O 2The mole number of middle R; A, b, c are respectively the molar fraction of Zr, P, F, and its scope is a=0.10～0.80, b=0.10～0.90, and c=0.00～0.40, and satisfy a+b+c=1.
The principal character peak of X-ray diffraction in crystals of the present invention is shown shown in the 1-table 8 as described later.
Zirconium phosphate crystal ZrPO provided by the invention 4-n, its preparation process is as follows:
(1) in proportion zirconium source material, phosphorus source material, 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 the former powder of Zirconium phosphate crystal 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; Mineralizer is a kind of in Neutral ammonium fluoride or the hydrofluoric acid.
In the above-mentioned preparation process, each used raw material by oxide mol ratio is:
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.
The roasting in 300～400 ℃ of following air of the former powder of Zirconium phosphate crystal is no less than 3 hours, promptly gets Zirconium phosphate crystal, sorbent material or catalyzer can be used as ion-exchanger, sorbent material and heterogeneous reaction catalyzer.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1 ZrPO 4-5
With 3.22g zirconium oxychloride (ZrOCl 28H 2O, 10mmol), 1.80g quadrol (3mmol), 0.56g Neutral ammonium fluoride (15mmol), 4.03g ortho-phosphoric acid (contains H 3PO 485%, 35mmol) and 18g (1mol) deionized water 1: 3: 1.5 in molar ratio: 3.5: 100 mixed, stir about 2 hours until becoming homogeneous phase.Will the said mixture material move in the 23ml stainless steel synthesis reactor and seal, crystallization is 7 days under 180～195 ℃ and autogenous pressure, and the solid matter with deionized water washing is to neutral, and 100 ℃ of following air dryings 24 hours, product was ZrPO 4-5 crystal, the result is as shown in table 1 for its X-ray diffraction analysis.
Table 1
No 2θ d() 100×I/I o
1 7.290 12.1165 100
2 9.160 9.6467 30
3 14.680 6.0294 38
4 15.280 5.7939 5
5 19.210 4.6165 7
6 21.740 4.0847 13
7 22.150 4.0100 28
8 23.260 3.8211 27
9 25.990 3.4255 11
10 27.050 3.2937 9
11 27.660 3.2224 10
12 29.680 3.0075 10
13 30.920 2.8897 4
14 33.260 2.6915 6
15 45.240 2.0027 7
Embodiment 2 ZrPO 4-8
With 3.22g zirconium oxychloride (ZrOCl 28H 2O, 10mmol), 0.60g quadrol (10mmol), 0.37g Neutral ammonium fluoride (10mmol), 4.60g ortho-phosphoric acid (contains H 3PO 485%, 40mmol) and 18g (1mol) deionized water 1: 1: 1 in molar ratio: 4: 100 mixed, stir about 2 hours until becoming homogeneous phase.Will the said mixture material move in the 23ml stainless steel synthesis reactor and seal, crystallization is 3 days under 180～195 ℃ and autogenous pressure, and the solid matter with deionized water washing is to neutral, and 100 ℃ of following air dryings 24 hours, product was ZrPO 4-8 crystal, the result is as shown in table 2 for its XRD analysis.
Table 2
No 2θ d() 100×I/I o
1 7.310 12.0834 100
2 10.880 8.1252 36
3 13.760 6.4304 18
4 17.300 5.1217 37
5 19.850 4.4691 36
6 21.910 4.0534 10
7 22.170 4.0064 11
8 22.470 3.9536 11
9 24.830 3.5829 43
10 26.790 3.3250 23
11 27.830 3.2031 12
12 29.740 3.0016 20
13 30.900 2.8915 28
14 36.840 2.4378 16
15 42.290 2.1353 8
16 43.610 2.0737 9
17 44.780 2.0222 10
18 45.260 2.0019 9
Embodiment 3 ZrPO 4-12
With 3.22g zirconium oxychloride (ZrOCl 28H 2O, 10mmol), 0.60g quadrol (10mmol), 0.37g Neutral ammonium fluoride (10mmol), 4.60g ortho-phosphoric acid (contains H 3PO 485%, 40mmol) and 18g (1mol) deionized water 1: 1: 1 in molar ratio: 4.5: 100 mixed, stir about 2 hours until becoming homogeneous phase.Will the said mixture material move in the 23ml stainless steel synthesis reactor and seal, crystallization is 2 days under 190 ℃ and autogenous pressure, and the solid matter with deionized water washing is to neutral, and 100 ℃ of following air dryings 24 hours, product was ZrPO 4-12 crystal, the result is as shown in table 3 for its XRD analysis.
Table 3
No 2θ d() 100×I/I o
1 7.330 12.0504 55
2 13.840 6.3934 28
3 15.050 5.8820 100
4 17.320 5.1158 33
5 19.450 4.5601 26
6 19.890 4.4602 28
7 21.330 4.1622 16
8 22.190 4.0028 10
9 22.530 3.9432 11
10 23.260 3.8211 9
11 24.850 3.5801 32
12 26.210 3.3937 24
13 26.830 3.3202 24
14 27.660 3.2224 31
15 27.910 3.1941 22
16 29.030 3.0734 10
17 29.770 2.9986 12
18 30.200 2.9569 8
19 30.930 2.8888 20
20 31.630 2.8264 8
21 32.860 2.7234 34
22 36.300 2.4728 9
23 36.900 2.4339 15
24 42.380 2.1310 11
25 43.470 2.0801 10
26 45.300 2.0002 9
27 46.230 1.9621 15
28 48.010 1.8934 15
Embodiment 4 ZrPO 4-18
With 3.22g zirconium oxychloride (ZrOCl 28H 2O, 10mmol), 1.16g 1,6-hexanediamine (10mmol), (40%, 20mmol), 2.30g ortho-phosphoric acid (contains H to 1.00g hydrofluoric acid 3PO 485%, 20mmol) and 9g (0.5mol) deionized water 1: 1: 2 in molar ratio: 2: 50 mixed, stir about 2 hours until becoming homogeneous phase.Will the said mixture material move in the 23ml stainless steel synthesis reactor and seal, crystallization is 12 days under 180 ℃ and autogenous pressure, and the solid matter with deionized water washing is to neutral, and 100 ℃ of following air dryings 24 hours, product was ZrPO 4-18 crystal, the result is as shown in table 4 for its XRD analysis.
Table 4
No 2θ d() 100×I/I o
1 11.540 7.6619 100
2 11.700 7.5575 86
3 19.700 4.5028 3
4 21.910 4.0534 2
5 23.460 3.7889 3
6 24.890 3.5744 15
7 25.160 3.5366 14
8 27.680 3.2201 2
9 28.950 3.0817 2
10 33.790 2.6505 6
11 34.070 2.6294 5
12 35.560 2.5225 4
13 37.280 2.4100 6
14 41.040 2.1975 2
15 44.450 2.0365 2
16 44.760 2.0231 2
17 48.400 1.8791 6
18 51.200 1.7827 2
19 51.720 1.7660 2
Embodiment 5 ZrPO 4-24
With 3.22g zirconium oxychloride (ZrOCl 28H 2O, 10mmol), the positive dipropyl amine of 1.02g (10mmol), (40%, 30mmol), 4.60g ortho-phosphoric acid (contains H to 1.5g hydrofluoric acid 3PO 485%, 40mmol) and 14.4g (0.8mol) deionized water 1: 1: 3 in molar ratio: 4: 80 mixed, stir about 2 hours until becoming homogeneous phase.Will the said mixture material move in the 23ml stainless steel synthesis reactor and seal, crystallization is 7 days under 190 ℃ and autogenous pressure, and the solid matter with deionized water washing is to neutral, and 100 ℃ of following air dryings 24 hours, product was ZrPO 4-24 crystal, the result is as shown in table 5 for its XRD analysis.
Table 5
No 2θ d() 100×I/I o
1 11.620 7.6094 100
2 23.540 3.7762 3
3 24.990 3.5603 14
4 33.860 2.6452 5
5 35.660 2.5157 4
6 37.370 2.4044 6
7 48.520 1.8747 7
8 60.140 1.5373 3
9 61.300 1.5110 3
Embodiment 6 ZrPO 4-28
With 12.88g zirconium oxychloride (ZrOCl 28H 2O, 40mmol), 2.96g 1,2-propylene diamine (40mmol), 2.96g Neutral ammonium fluoride (80mmol), 20.7g ortho-phosphoric acid (contains H 3PO 485%, 180mmol) and 36g (2mol) deionized water 1: 1: 2 in molar ratio: 4.5: 50 mixed, stir about 2 hours until becoming homogeneous phase.Will the said mixture material move in the 100ml stainless steel synthesis reactor and seal, crystallization is 7 days under 190 ℃ and autogenous pressure, and the solid matter with deionized water washing is to neutral, and 100 ℃ of following air dryings 24 hours, product was ZrPO 4-28 crystal, the result is as shown in table 6 for its XRD analysis.
Table 6
No 2θ d() 100×I/I o
1 13.770 6.4257 11
2 14.970 5.9132 75
3 19.390 4.5741 100
4 21.270 4.1738 33
5 23.200 3.8308 12
6 26.150 3.4049 26
7 27.590 3.2304 75
8 28.970 3.0796 36
9 31.560 2.8325 15
10 32.780 2.7298 72
11 36.240 2.4767 10
12 43.400 2.0833 13
13 44.330 2.0417 12
14 46.150 1.9653 14
15 47.940 1.8960 31
16 48.830 1.8635 13
Embodiment 7 ZrPO 4-34
With 12.88g zirconium oxychloride (ZrOCl 28H 2O, 40mmol), 2.40g quadrol (40mmol), 1.48g Neutral ammonium fluoride (40mmol), 20.7g ortho-phosphoric acid (contains H 3PO 485%, 180mmol) and 72g (4mol) deionized water 1: 1: 1 in molar ratio: 4.5: 100 mixed, stir about 2 hours until becoming homogeneous phase.Will the said mixture material move into sealing (filling degree is 70%) in the 100ml stainless steel synthesis reactor, crystallization is 7 days under 190 ℃ and autogenous pressure, and the solid matter with deionized water washing is to neutral, and 100 ℃ of following air dryings 24 hours, product was ZrPO 4-34 crystal, the result is as shown in table 7 for its XRD analysis.
Table 7
No 2θ d() 100×I/I o
1 13.820 6.4026 39
2 14.950 5.9211 100
3 19.400 4.5718 34
4 20.360 4.3583 8
5 21.290 4.1700 17
6 23.230 3.8259 47
7 26.170 3.4024 13
8 27.590 3.2304 19
9 27.900 3.1952 34
10 28.960 3.0806 8
11 30.170 2.9598 10
12 31.630 2.8264 11
13 32.810 2.7274 21
14 46.180 1.9641 10
15 47.950 1.8957 13
Embodiment 8 ZrPO 4-38
With 12.88g zirconium oxychloride (ZrOCl 28H 2O, 40mmol), 2.96g 1,2-propylene diamine (40mmol), 1.48g Neutral ammonium fluoride (40mmol), 18.4g ortho-phosphoric acid (contains H 3PO 485%, 160mmol) and 36g (2mol) deionized water 1: 1: 1 in molar ratio: 4: 50 mixed, stir about 2 hours until becoming homogeneous phase.Will the said mixture material move in the 100ml stainless steel synthesis reactor and seal, crystallization is 7 days under 190 ℃ and autogenous pressure, and the solid matter with deionized water washing is to neutral, and 100 ℃ of following air dryings 24 hours, product was ZrPO 4-38 crystal, the result is as shown in table 8 for its XRD analysis.
Table 8
No 2θ d() 100×I/I o
1 14.900 5.9408 74
2 19.310 4.5929 100
3 21.190 4.1894 33
4 26.070 3.4152 33
5 27.510 3.2396 90
6 28.880 3.0890 41
7 31.470 2.8404 19
8 32.700 2.7363 76
9 43.310 2.0874 14
10 44.260 2.0448 14
11 47.870 1.8986 37
12 48.740 1.8668 18
Embodiment 9
With the roasting 4 hours in 450 ℃ of following air of resulting sample among the embodiment 2.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-ZrPO after copper exchanges 4-8 inorganic materials.
Embodiment 10
With the roasting 4 hours in 450 ℃ of following air of resulting sample among the embodiment 1～8.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, the ZrPO after the roasting 4-n inorganic materials has water-absorbent, and the adsorptive value to water under its room temperature is as shown in table 9.
ZrPO after table 9 roasting 4The water-absorbent of-n inorganic materials (%)
-n -5 -8 -12 -18 -24 -28 -34 -38
Water regain 14.9 14.3 14.1 10.5 10.7 9.8 9.3 8.5

Claims (5)

1. a preparation method who prepares Zirconium phosphate crystal is characterized in that, is undertaken by following step:
(a) in proportion zirconium source material, phosphorus source material, 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 step a obtained moved in the synthesis reactor and seals, and places baking oven, 160～200 ℃ of following crystallization 2～10 days;
(c) solid crystallized product that step b is obtained separates with mother liquor, to neutral, promptly obtains Zirconium phosphate crystal with the deionized water washing behind 90～110 ℃ of following air dryings;
Synthetic each used raw material of this crystalline compounds by oxide mol ratio is:
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.
2, in accordance with the method for claim 1, it is characterized in that described phosphorus source is the oxide compound of 85% phosphoric acid, phosphoric acid salt or phosphorus.
3, in accordance with the method for claim 1, it is characterized in that described zirconium source is zirconium nitrate, zirconium oxychloride or tetrabutyl zirconate.
4, in accordance with the method for claim 1, it is characterized in that, through the roasting 3 hours in 300-400 ℃ of following air of the former powder of Zirconium phosphate crystal of step c preparation.
5, according to the application of the Zirconium phosphate crystal of claim 1 preparation at ion-exchange, absorption and catalytic field.
CN 02126927 2002-07-26 2002-07-26 Zirconium phosphate crystal, and its preparing method and use Expired - Fee Related CN1202990C (en)

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CN101602512B (en) * 2009-07-18 2011-01-19 太原理工大学 Zirconium phosphate crystal material and method for preparing same
CN103072965B (en) * 2013-01-28 2014-05-28 太原理工大学 Preparation method and application method of CuZr(PO4)2*4H2O material
CN104250002A (en) * 2014-10-08 2014-12-31 上海红桔实业有限公司 Preparation method of crystalline zirconium phosphate for purifying nuclear uranium ions
CN104743538B (en) * 2015-03-13 2017-01-18 东华大学 Microwave-assisted preparation method for spherical transition metal and zirconium diphosphonate in one step
CN107129851B (en) * 2017-04-20 2019-11-22 太原理工大学 One kind is with the pillared N of interlayer, N`-lupetazin basic zirconium phosphate lubricating grease and preparation method thereof
CN107188150A (en) * 2017-07-31 2017-09-22 绵竹耀隆化工有限公司 A kind of preparation method of Mesoporous zirconium phosphate
CN108910854A (en) * 2018-10-19 2018-11-30 绵竹耀隆化工有限公司 A kind of micron order sheet basic zirconium phosphate and preparation method thereof
CN110980680B (en) * 2019-12-31 2021-04-30 河北北方学院 Method for preparing rare earth phosphate based on hydrothermal synthesis method

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