JPS60239313A - Crystalline zirconium phosphate and its manufacture - Google Patents

Abstract

PURPOSE:To obtain crystalline zirconium phosphate having a novel structure and producing a significant effect peculiar to a cation exchanger by bringing a specified liq. mixture contg. a zirconium compound, a carboxylic acid compound and a phosphoric acid compound into a reaction. CONSTITUTION:Crystalline zirconium phosphate represented by the formula (where R is NH4 and/or amine cation, 0<=n<=1, and 0<=m<=2) is obtd. by bringing a liq. mixture into a reaction. The liq. mixture contains a zirconium compound, a carboxylic acid compound and a phosphoric acid compound by amounts in the region defined by straight lines connecting points A (28, 3, 69), B (63, 6, 31), C (44, 43, 13) and D (1, 97, 2) in the triangular component diagram showing the amounts (mol%) of the compounds (expressed in terms of Zr, C2O4 and PO4, respectively) and further contains an ammonium compound and/or an amine compound by 0.2-100mol (expressed in terms of ammonium ions and amine cations, respectively) per 1mol Zr.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to crystalline zirconium phosphate having a novel structure and unique physical properties based thereon, and a method for producing the same.

The crystalline zirconium phosphate of the present invention can be used as a porous adsorbent,
It is useful as an iosci exchanger, a fixing agent for toxic metals and high-level radioactive waste, a catalyst, a super sioconductor and its manufacturing raw material, a gas separation agent, a ceramic material, etc.

Prior Art Crystalline zirconium phosphate is a known compound comprising:
Various manufacturing methods have also been proposed. Focusing on its unique physical properties, we developed heat resistance.

In addition to being a high-exchangeability sulfur exchanger with excellent chemical resistance, oxidation-reduction resistance, and radiation resistance, its application as an intercalation compound, catalyst, etc. is also being widely studied.

However, the known crystalline zirconium phosphate has room for improvement in various practical properties, and its production method is not suitable for industrialization due to operational risks and other reasons.

Structure of the Invention In view of the above-mentioned problems of the prior art, the present inventor has conducted various experiments and researches, and as a result, has developed a simple method for producing crystalline zirconium phosphate with a new structure, which was impossible to synthesize using the prior art. It could be manufactured by the method. That is, the present invention provides the following crystalline zirconium phosphate and its manufacturing method.

(1) (1) General formula HnR1-nZr2(PO4)3・mH2O(I) [However, R represents MH4 or amiccation, 0≦n≦1
, 0≦m≦2], (II) As an oxide by analytical calculation, the formula 4ZrO2.
Crystalline zirconium phosphate, characterized in that it is represented by 3P2O5(II).

(2) A mixed liquid containing (I) a zirconium compound, a carposis acid compound, and a phosphoric acid compound, and at least one of an ammonium compound and an amine compound, comprising (II) a zirconium compound (as Zr), a carboxylic acid compound (C2O4 ) and phosphate compounds (PO4
In the molar ratio triangular component diagram shown in Figure 1, the proportions of
The mixture has a composition within a region surrounded by a straight line connecting each point of C (44, 43, 13) and D (1, 97.2), and has an ammonium content of 0.2 to 100 mol per 1 mol of Zr. General formula HnR1-nZr2(PO4)3·mH2O(I) characterized by reacting a mixture containing a compound (as acymonium iodine) and/or an amine compound (as amiccation) at (III) pH 10 or less [However, R represents NH4 or amine cation, and 0≦n≦1
, 0≦m≦2] A method for producing crystalline zirconium phosphate.

Examples of the zirconium compound used in the method of the present invention include compounds that are water-soluble or become water-soluble with acid, such as zirconium halides such as zirconium oxychloride, hydroxyzirconium chloride, zirconium tetrachloride, and zirconium bromide, zirconium sulfate, and bases. Zirconium salts of mineral acids such as zirconium sulfate and zirconium nitrate, zirconium salts of organic acids such as zirconyl acetate and zirconyl formate, ammonium zirconium carbonate, sodium zirconium sulfate, asimonium zirconium acetate, sodium zirconium oxalate, ammonium zirconium citrate, etc. Examples include zirconium complex salts.

Among these compounds, zirconium oxychloride, zirconium sulfate, etc. are more preferred.

Examples of the carboxylic acid compound include aliphatic polycarboxylic acids having two or more -COOH groups that are water-soluble or become water-soluble with acid, and salts thereof. Specifically, oxalic acid,
Aliphatic dibasic acids and their salts such as sodium oxalate, sodium hydrogen oxalate, asimonium oxalate, ammonium hydrogen oxalate, lithium oxalate, maleic acid, malonic acid, succinic acid and their salts; quesitic acid, citric acid Examples include aliphatic oxyacids such as ammonium acid, tartaric acid, and malic acid, and salts thereof. Among these, oxalic acid and its sodium and ammonium salts are more preferred.

Examples of the phosphoric acid compound include compounds that are water-soluble or water-soluble due to acid. Specifically, at least one of the alkali metal salts and ammonium salts of orthophosphoric acid such as phosphoric acid, monobasic sodium phosphate, diammonium diphosphate, and tribasic sodium phosphate; metallisic acid, pyrrolisic acid, etc.
Examples include alkali metal salts and ammonium salts of condensed phosphoric acid having P-O-P bonds. Among these, ammonium salts of phosphoric acid and orthophosphoric acid are more preferred.

Examples of ammonium compounds and amine compounds include compounds that are water-soluble or become water-soluble with acid. Examples of ammonium compounds include inorganic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium hydrogen carbonate; and organic ammonium compounds such as tetrapropylammonium hydroxide and tetraethylammonium hydroxide. When at least one of the above-mentioned zirconium compound, carposi acid compound, and phosphoric acid compound is an asimonium-containing compound, these can be simultaneously used as an ammonium ion source. Amine compounds include monoethanolamine, diethanolamine, triethanolamine, di(
Examples include N-butyl)amine, triethylamine, tripropylamide, pyridine, and N,N-dimethylethanolamine. Among these, ammonium phosphate, aqueous asimonia, ammonium chloride, and asimonium oxalate are more preferred.

The method of the present invention is carried out, for example, as follows. First, a carposi acid compound aqueous solution is added to a zirconium compound aqueous solution, or a phosphoric acid compound or its aqueous solution is added to a mixed solution obtained by adding a zirconium compound aqueous solution to a carposi acid compound aqueous solution.

After adding the phosphoric acid compound to the zirconium compound aqueous solution,
When an aqueous solution of a carposis acid compound is added, amorphous zirconium phosphate is likely to be produced, resulting in a product with a low degree of crystallinity. The ammonium compound and/or amine compound may be added at any time during the preparation of the mixed solution,
No difference in effectiveness was observed due to differences in the timing of addition. When mixing each raw material, it is desirable to stir.
In particular, when adding a phosphoric acid compound, stirring is performed so that the phosphoric acid concentration does not remain partially high. In the mixed solution, zirconium compound (as Zr), carposi acid compound (as C2O4) and phosphoric acid compound (PO4
In the molar ratio triangular component diagram shown in Figure 1, the proportions of
It falls within the area surrounded by the straight line connecting each point of C (44, 43, 13) and D (1, 97, 2), and the amount of asimonium compound and/or amine compound is 0.
Each raw material is mixed so that the amount is about 2 to 100 moles. If the composition ratio of each raw material in the reaction mixture is outside the above range, the crystallization rate is slow, the yield is low, amorphous products are mixed, unreacted raw materials remain, or undesired results may occur. One or more problems such as becoming crystalline including crystalline forms occur. The mixed liquid in which each raw material is uniformly dissolved or dispersed may be in the form of a transparent solution or a slurry containing undissolved excess raw materials. The concentration of the reaction mixture is preferably such that Zr is 0.01 to 25%, more preferably 0.1 to 10%. A dilute solution containing less than 0.01% Zr is economically disadvantageous, whereas when the Zr content exceeds 25%, carposisate, ricinate, etc. will precipitate as crystals, resulting in a loss of product crystals. It becomes difficult to filter and wash the quality zirconium ricinate with water. The reaction mixture as described above is subjected to the reaction at a pH of 10 or less, preferably at a pH of 0.5 to 7. The pH of the reaction solution is 7~
10, crystalline zirconium ricinate with a high water content tends to be produced, and further, when the pH exceeds 10,
There is a tendency to produce crystalline zirconium ricinate with low crystallinity. As a pH adjusting agent for the reaction mixture, mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid; ammonium hydroxide, asimonium hydrogen carbonate, sodium hydroxide, potassium hydroxide,
Examples include asimonium such as sodium carbonate, and alkali metal hydroxides and carbonates. The reaction temperature (in the present invention, the reaction of each raw material component and the crystallization reaction of crystalline zirconium ricinate by aging are collectively referred to as reaction):
The temperature is preferably 50°C or higher. If the reaction temperature is less than 50°C, it will take a long time to crystallize the desired product, which is economically disadvantageous.

The upper limit of the reaction temperature is not particularly limited, but is approximately 200° C. from the economic point of view. The reaction time depends on the type of raw materials (
That is, the reactivity of the raw materials), the blending ratio of the raw materials, the concentration, temperature and pH of the reaction mixture, the desired degree of crystallinity of the reaction product, etc. may vary widely, but it is usually about 30 minutes to 20 days.

Produced crystalline zirconium ricinate HnP1-nZr2
(PO4)3.mH2O [where n, R, and m are the same as above] is separated from the liquid phase by known means such as filtration, decantation, centrifugation, etc., washed, and then dehydrated by conventional methods. Dry and further heat to 1080℃ if necessary
Heat treated below. Drying methods include heat drying,
The adsorbed water can be removed by air drying or by using a desiccant such as phosphorus pentoxide, calcium chloride, or silica gel. Heat treatment 1
When carried out at temperatures above 080°C, the desired crystal form is deformed and converted into zirconium pyrophosphate (ZrP2O7) and the like.

Incidentally, since the crystalline zirconium phosphate obtained by the present invention has ion exchange ability, it may take a form containing cations dissolved in the liquid mixture during or after the reaction. When crystalline zirconium ricinate is precipitated from the reaction mixture, two or more alkali ions,
In particular, when ammonium iodine and sodium iodine coexist, ammonium ions have a greater affinity, so unless the concentration of sodium is extremely high, ammonium ions are selectively exchanged, and ultimately sodium Crystalline zirconium ricinate is produced. The ammonium-exchanged zirconium phosphate produced is very stable in liquid. That is, while general ammonium-type cation exchangers become H-type due to a substitution reaction between ammonium ions and hydrogen ions when they come into contact with highly concentrated mineral acids, the ammonium-type zirconium phosphate of the present invention It is reversible and is not altered by concentrated mineral acids.

Although the mechanism of formation of crystalline zirconium ricinate in the method of the present invention is not clear, it is presumed as follows. That is,
First, a zirconium compound and a carboxylic acid compound react in a liquid to form a zirconium-carboxylic acid complex salt. Next, by adding a ricinic acid compound to the liquid,
The complex salt gradually decomposes, and the zirconium compound and ricinic acid sulfate react, and at the same time, the asimonium sulfuric acid or amine cation is exchanged, so that crystalline zirconium ricinic acid oxide homogeneously crystallizes and grows in a relatively low pH range. It seems to be.

The novel crystalline zirconium phosphate obtained by the method of the present invention will be explained in detail below.

In addition, in the X-ray powder diffraction data shown below, I is
It is the strength, and d is the lattice spacing. For X-ray diffraction, an X-ray diffraction device [Kigerflex RAD-2A, manufactured by Rigaku Denki Co., Ltd.] was used, and the irradiation source during measurement was 45 KV and 2
A copper target X-ray tube operated at 5 mA scanned the compacted powder at 2° (2θ)/min, CuKα irradiation and a Taraphite monochromator [λ(CuKa1) = 1.5
4056 Å). d is 2θ (where θ is
The diffraction pattern was obtained from the position of the diffraction peak, expressed as Black's angle, as observed on the chart. Also, I is
It was measured from the height of the diffraction peak after subtracting backclausside.

Specific examples of the novel crystalline zirconium phosphate obtained by the method of the present invention will be described in detail below.

(a) For example, the crystalline zirconium phosphate of the present invention synthesized directly from a reaction mixture containing ammonium ions has an extremely low water content and contains 4ZrO2.3P2O as an oxide.
It has a chemical composition of 5, contains NH4 iodine in the pores in its skeleton structure, and is represented by the general formula NH4Zr2(PO4)3. This crystalline zirconium phosphate exhibits a unique powder diffraction pattern including d shown in Table 1.

Table 1 d (Å) 100×I/Io 6.48-6.32 10-80 4.76-4.61 22-98 4.43-4.32 34-135 3.86-3.81 100 3.21-3.18 22-98 2.98-2.92 20-140 2.88-2.81 0-35 2.59-2.56 3-40 2.54-2.50 5-60 2.14-2.12 2-35 2.04-2.02 1-30 1.99-1.97 1-30 1.92-1.90 5-50 1.85-1.82 2-50 1.79-1.78 0-25 1.67-1.65 0-30 1.65-1.64 2-45 1.59-1.57 2-40 1.53-1.52 0-30 1.49-1.48 0-30 1.33-1.32 0-25 General formula Hn crystallized from the reaction mixture by the method of the present invention
R1-nZr2(PO4)3・mH2O(n, R and m
The X-ray powder diffraction data of crystalline zirconium phosphate (same as above) has a figure that falls within the general figure shown by the numerical values shown in Table 2.

Table 2 d (Å) 100×I/Io 6.48-6.32 10-80 4.76-4.61 22-98 4.43-4.32 34-135 3.86-3.81 100 3.21-3.18 22-98 2.98-2.92 20-140 2.54-2.50 5-60 2.14-2.12 2-35 1.92-1.90 5-50 1.85-1.82 2-50 (b) About 400 to 108
Heat treatment at 0°C converts NH4 ions in the skeleton structure into NH
3. It is released as a gas such as N2, and the general formula HZr2(P
It transforms into crystalline zirconium ricinate, denoted by O4)3.

As an oxide, this material is 4ZrO2.3P2.
d represented by the chemical composition O5 and shown in Table 3
It exhibits a unique powder diffraction pattern containing .

Table 3 d (Å) 100×I/Io Low temperature type High temperature type 6.41-6.30 7-68 4.66-4.50 100 26-100 4.46-
4.38 55-100 1003.86-3.78
55-128 3.20-3.14 24-82 2.93-2.84 25-83 2.57-2.53 7-60 2.22-2.19 0-22 2.13-2.10 0-25 1.99-1.97 3-40 1.92-1.90 2-30 1.81-1.77 1-30 1.68-1.66 5-45 1.53-1.52 0-20 1.48-1.47 0-25 1.34-1.33 0-15 General formula HnR crystallized from the reaction mixture by the method of the present invention
The X-ray powder diffraction data of crystalline zirconium phosphate HZr2(PO4)3 obtained by heat-treating 1-nZr2(PO4)3·mH2O (n, R and m are the same as above) at 400 to 1080°C are shown in Table 4. It has a figure that falls within the general figure indicated by the numerical value shown.

As is clear from Table 4, d is constant regardless of the heat treatment temperature, but the diffraction peaks are divided into two types of patterns at about 650 to 750°C.

In the table, the figures at 650-1080℃ are high-temperature type,
The figure at 400 to 750°C was distinguished from the low-temperature type (the same applies to Table 3).

Table 4 d (Å) 100×I/Io Low temperature type High temperature type 6.41-6.30 7-68 4.66-4.50 100 26-100 4.46-
4.38 55-100 1003.86-3.78
55-128 3.20-3.14 24-82 2.93-2.84 27-83 2.57-2.53 7-60 1.99-1.97 3-40 1.68-1.66 5-45 Crystalline zirconium phosphate HZr2(PO4)3 obtained by heat treatment at 400 to 1080°C has hygroscopicity, but its rate of moisture absorption is relatively low, and 1
It retains moisture absorption ability even after a week. Further, when the crystalline zirconium phosphate is stored in a water-permeable polyethylene bag, it still retains its moisture absorption ability even after one month. Conversely, even if the crystalline zirconium phosphate is poured into water, water absorption may not be completely completed within several minutes.

(c) The water absorbed as described above enters as crystal water into the pores of the essential skeleton having the chemical composition of 4ZrO2.3P2O5 when expressed as an oxide. The amount of crystallization water varies depending on the heat treatment temperature and heat treatment time.
The low-temperature type has a higher water absorption rate than the high-temperature type.

The crystalline zirconium phosphate obtained from crystal water has the general formula HZ
It is represented by r2(PO4)3·mH2O [m is the same as above] and has a unique powder diffraction pattern including d shown in Table 5.

Table 5 d (Å) 100×I/Io 6.49-6.33 7-58 4.73-4.60 45-90 4.44-4.35 50-110 3.86-3.80 100 3.23-3.17 30-85 2.95-2.90 25-128 2.88-2.83 0-25 2.60-2.56 2-44 2.55-2.52 5-45 2.14-2.11 2-27 2.12-2.00 0-26 1.99-1.98 2-35 1.92-1.90 5-45 1.83-1.81 3-44 1.72-1.70 0-15 1.68-1.66 0-29 1.66-1.65 3-40 1.58-1.56 2-30 1.49-1.47 0-15 1.33-1.32 0-15 1.27-1.26 0-15 1.17-1.16 0-15 1.11-1.10 0-15 The above HZr2(PO4)3・mH2O When hydrous crystalline zirconium phosphate is heat-treated at, for example, 150 to 250°C, a dehydration reaction results in HZr2 (
Reversibly crystallizes to PO4)3.

General formula HnR crystallized from the reaction mixture by the method of the present invention
Crystalline zirconium phosphate 1-nZr2(PO4)3・mH2O is heat-treated at about 400 to 1080°C to change the crystal to HZr2(PO4)3, and then water is absorbed to obtain the general formula HZr2(PO4)3・mH2O The X-ray powder diffraction data of the hydrated crystalline zirconium phosphate has a shape that falls within the general shape shown by the numerical values shown in Table 6.

Table 6 d (Å) 100×I/Io 6.49-6.33 7-58 4.73-4.60 45-90 4.44-4.35 50-110 3.86-3.80 100 3.23-3.17 30-85 2.95-2.90 25-128 2.55-2.52 5-45 1.92-1.90 5-45 1.83-1.81 3-44 1.66-1.65 3-40 The novel crystalline zirconium phosphate crystal according to the present invention has a skeletal structure with a chemical composition of 4ZrO2:3P2O5 expressed in molar ratio of oxides, and has microscopic structures within the crystal. It is assumed that it has pores.

That is, the known Zr(HPO4)3 has a chemical composition as an oxide of ZrO2:P2O5=1:1 (molar ratio).
・While the crystalline zirconium phosphate represented by nH2O has a two-dimensional layered structure, the crystalline zirconium phosphate of the present invention has a three-dimensional network structure.
Ammonium ions, hydrogen ions, and H with small molecular diameter
It is presumed to have a zeolite-like tocinel structure in which 2O molecules are partially contained within the pores of the network structure. The X-ray diffraction patterns of the various crystalline zirconium phosphates included in the present invention are similar, depending on the iodine and molecules present in the pores, especially 4.6 to 4.3 A, 2. 9~
At 2.8 Å and from 2.6 to 2.5 Å, a graphical change indicated by d is seen.

Effects of the Invention (1) The crystalline zirconium phosphate of the present invention exhibits unique and excellent effects as a cation exchanger. Namely, known organic ion exchangers and zirconium phosphate (e.g. Zr
(HPO4)2・nH2O), zeolite, and other inorganic ion exchangers may thermally decompose or change into a structure unsuitable for use as an exchanger (for example, the exchange group (decomposition, crystal change, etc.) or a significant decrease in the amount of exchange, so its use is mainly limited to use as an ion exchanger in solution. In contrast, the crystalline zirconium phosphate of the present invention exhibits excellent ion exchange ability not only in solution but also in dry and high temperature conditions.

(2) The ion exchange action of the crystalline zirconium phosphate of the present invention is irreversible, and in this respect it is significantly different from known ion exchangers. That is, the cations fixed by ion exchange within the micropores of the skeleton structure of the zirconium phosphate of the present invention are extremely stable under various environmental conditions. For example, Na iodine is easily fixed to the zirconium phosphate of the present invention by wet or dry methods to form crystalline zirconium phosphate, NaZr2(PO4)3. Its crystals and composition do not change even when heated at a high temperature of 1000°C or higher, and it is also immersed in concentrated hydrochloric acid and aqua regia for a long time, or exposed to NaHSO4 (or NaHSO4).
Heating with Cl) at 900° C. does not cause any change. Therefore, it is possible to develop Na iodine conductors, which have been considered difficult, as well as metal ions other than Na (Ka iodine, Li
iodine, Cu iodine, etc.) and nonmetallic ions (H ion,
It has become easier to manufacture conductors for NH4 ions, etc.

(3) As mentioned above, since the ion-exchanged metal is extremely stable, the zirconium phosphate of the present invention can be used as a harmful metal immobilization material that does not elute under various environmental conditions, such as
It is also useful as a material for immobilizing high-level radioactive element Cs.

(4) Since the zirconium phosphate of the present invention has a zeolite-like tocinel structure, it exhibits extremely excellent effects as a microporous material for catalysts, gas separation agents, ceramic materials, and the like.

EXAMPLES The present invention will be explained in more detail with reference to Examples below. Note that the present invention can be implemented by methods other than those described in the Examples, and is not limited to the Examples.

Various measurements in the following examples were performed as follows.

(1) Regarding ZrO2, the reaction product was melted and decomposed using sodium carbonate, extracted with water, and insoluble matter was filtered out. In order to complete the decomposition, the insoluble matter was repeatedly decomposed with sodium carbonate. , extracted with water. The final remaining insoluble material was melted and decomposed with potassium pyrosulfate, extracted with water, converted into a maciderate salt, and further incinerated and ignited to form ZrO2.

(2) Regarding P2O5, after performing melt decomposition with sodium carbonate and water extraction in the same manner as in (1) above,
Molybutridate was precipitated from the extract, an excess amount of a normal sodium hydroxide solution was added thereto, and the mixture was titrated with a normal nitric acid solution for quantitative determination.

(3) NH4+ and amino acid concentration were measured using differential thermal analysis and IR analysis, and were combined with the aforementioned X-ray diffraction analysis and chemical analysis.

(4) H2O was obtained by further reducing the weight of Asimonium and Amici based on the weight loss when the sample was heated at 1000°C.

Example 1 Zirconium oxychloride crystal (ZrOCl2.8H2O
After dissolving 32.7 g of the reagent in water to make a liquid volume of 200 g, 300 g of an aqueous solution containing 17.9 g of oxalic acid crystals (H2C2O4.2H2O reagent) was added thereto with stirring. Then, acymonium hydrogen ricinate (NH4H) was added to the mixture.
2PO4 98.0%) 100% aqueous solution containing 12.5g
g was added and mixed with stirring. The composition of the thus obtained mixture was as follows: 1.0Zr:1.1PO4:1.4C2O4. 3N aqueous asimonia was added to this mixture while stirring to adjust the pH of the mixture to 4.5. The reaction mixture thus obtained was placed in a heat-resistant plastic container with a small hole in the inner lid to prevent excessive water evaporation, and after being kept under natural pressure in a thermostatic chamber at 96°C for 5 days, the solid reaction inside the container was The product was suction filtered, washed repeatedly with water until no oxalate ions were detected, and then solid-liquid separated. The cake-like solid reaction product is
16.7 g of dried material obtained by processing at 50° C. for 16 hours was a white powder. As a result of composition analysis of the dried product, the product contained ZrO251.2%, P2O544.0%, H2O
It contains 1.2% and 3.6% of NH4, and expressed in terms of molar ratio of oxides: 1.9NH4.4.0ZrO2.3.
Show the product composition of 0P2O5.0.6H2O.

The results of analyzing the dry product thus obtained by X-ray diffraction are shown in Table 7. This X-ray diffraction pattern had essentially the same X-ray diffraction pattern as the main phase in Table 2 and contained no crystalline impurities. This product is crystalline zirconium ricinate NH4Zr2 (PO
4) It was determined to be 3.

Table 7 d(Å) 100×I/Io d(Å) 100×I/
Io6, 40 37 1.64 18 4.72 51 1.63 1 4.35 66 1, 61 2 3.83 89 1.60 2 3.20 57 1.58 17 2.96 100 1.57 14 2. 83 34 1.52 12 2.57 11 1.49 8 2.51 29 1.48 6 2.45 2 1.46 4 2.36 2 1.45 5 2.31 3 1.41 4 2.29 5 1.39 3 2.20 1 1.36 3 2.17 4 1.34 4 2.13 15 1.33 3 2.10 2 1.32 7 2.07 2 1.27 2 2.06 2 1, 26 4 2.04 12 1.231 1 2.02 1 1.227 2 1.97 13 1.22 4 1.91 31 1.21 2 1.86 3 1.20 3 1.84 31 1.16 5 1.79 4 1.14 2 1.72 4 1.13 1 1.69 3 1.10 2 1.66 10 Example 2 Zirconium sulfate solution (Zr containing 28.0% ZrO2
OSO4 solution) 44.6g ammonium oxalate crystals [(NH4)2C2O4・H2O99.5%) 30.5
An oxalic acid solution prepared by dissolving 1.0 g of oxalic acid in 420 g of water was added with stirring. Next, this was added to sodium phosphate (NaH2PO
4.2H2O98.0%) and 150 g of an aqueous solution containing 20.0 g of ammonium chloride were mixed under stirring. The composition of the mixture was as follows: 1.0Zr:1.4PO4:0.7C2O4. The mixture thus obtained is
The pH was adjusted to 2.8 with 0% NaOH to obtain a reaction mixture. The mixture thus obtained was placed in a plastic container similar to that used in Example 1 and kept in a constant temperature room at 96°C under natural pressure for 2 days, and then the product was filtered by suction using filter paper. After separation and repeated washing, the resulting cake was air-dried indoors for 1 day to obtain 21.7 g of white powder. As a result of the composition analysis of the dried product, the product contained 50.2% of ZrO2, 543.6% of P2O, and H2O2.
．． 7% and NH43.5%, expressed as oxide molar ratio 1.9NH4.0ZrO2.3.0P2
The product composition of O5.1.5H2O was shown. As a result of Na analysis in the product, it was found that it did not contain Na. Na
The analysis was performed by dissolving the reaction product powder using the necessary minimum amount of hydrogen fluoride, and measuring by the standard addition method using an atomic absorption spectrophotometer. The results of analyzing the product by X-ray diffraction are shown in Table 8.

This diffraction pattern had the same X-ray diffraction pattern as the main phase in Table 2, and was the same type of NH4Zr(PO4)3 as in Example 1. Furthermore, the results of TG-DTA analysis measurements on the air-dried product showed slight and gradual changes in dehydration up to 400°C. In addition, the results of X-ray diffraction analysis of the product heat-treated at 400°C for 3 hours showed that it contained no impurities.
The X-ray diffraction pattern was essentially the same as in the table. Furthermore, at 400 to 600°C, the weight decreased while giving off an asimonia odor, and crystal changes occurred.

Table 8 d(Å) 100×I/Io d(Å) 100×I/
Io6.42 23 1.84 33 4.72 49 1.79 5 4.35 88 1.66 10 3.84 100 1.64 18 3.20 51 1.58 21 2.96 82 1.57 8 2. 83 6 1.52 8 2.57 11 1.49 7 2.51 34 1.45 4 2, 18 4 1.41 4 2.13 12 1.32 6 2.04 15 1.26 3 1.97 11 1.92 21 d: Main diffraction peaks up to 1.20 Å were described.

Example 3 Zirconyl nitrate [ZrO(NO3)2.2H2O crystal 9
Add water to 16.4g of 9.0%) to dissolve and reduce the liquid volume to 75g.
g. Add this to diammonium citrate [(NH
4) Add 300 g of an aqueous solution containing 15.3 g of 2HC6H5O (799.0%), and then add 300 g of an aqueous solution containing 15.3 g of ricinic acid (H3PO485.0%).
0% solution) 12.9 g and ammonium nitrate (NH4NO
3 reagent) 60g of aqueous solution obtained by mixing and preparing 10.0g of
were mixed under stirring. The composition of this mixture is 1.0ZrO
The raw material blending ratio (molar ratio) was 2:1.8PO4:1.7C2O4. Further, this mixture was adjusted to pH 3.5 with 3N aqueous ammonia to obtain a reaction mixture. The reaction mixture thus obtained was placed in a glass flask equipped with a stirrer and a reflux device, and refluxed for 3 days while stirring using a machine heater. The solid product was suction filtered using filter paper, washed repeatedly with hot water, and then solid-liquid separated. The resulting cake was dried in a constant temperature and humidity chamber at 32° C. and 40% for 40 hours to obtain 15.2 g of white powder. As a result of compositional analysis of the dried product, the product showed values of ZrO244.1%, P2O541.2%, and H2O plus NH4414.7%. The results of measuring the product by X-ray diffraction are shown in Table 9. In this diffraction pattern the dried product contains crystalline impurities and has the same X-ray powder diffraction pattern as the NH4Zr2(PO4)3 product of Example 1 and is essentially the same as the main phase in Table 2. It had an X-ray diffraction pattern. The crystalline impurities are gasimer-type zirconium phosphate containing asimonium, that is, asimonium-exchanged zirconium phosphate [general formula γ] consisting of 2 moles of PO4 per 1 mole of Zr.
-HnNH42-nZr(PO4)2・mH2O (0≦
n≦2]). In Table 9, the (γ) mark indicates the diffraction peak of the crystalline impurity, and the (M) mark indicates the overlapping diffraction peak of the crystalline impurity and NH4Zr2(PO4)3.

Table 9 d(Å) 100×I/Io d(Å) 100×I/
Io6.42 35 2.13 19 5.72 97γ 2.05 35 5.02 4γ 2.04 20 4.72 49 1.97 12 4.59 35γ 1.91 22 4.35 68 1.85 29 4. 10 90γ 1.82 15γ 3.83 93 1.76 18γ 3.65 65γ 1.74 12γ 3.31 65γ 1.69 7M 3.20 79 1.66 17M 2.96 100 1.64 17 2.91 36γ 1.58 18 2.81 17M 1.57 21M 2.69 6γ 1.52 13 2.65 26γ 1.49 7 2.58 18M 1.46 4 2.51 28 1.45 8 2.45 17γ 1. 40 13M 2.43 11γ 2.32 8M 2.17 22γ γ: γ- for main diffraction peaks up to d=1.40 Å
HnNH42-nZr(PO4)2・mH2O impurity M
: Diffraction peaks with three overlaps of γ and NH4Zr2 (PO4) Example 4 After dissolving 22.6 g of zirconium oxychloride crystal (ZrCl2.8H2O reagent) in water to make a liquid volume of 150 g, oxalic acid crystal (H2C2O4. 2H2O reagent)
200 g of an aqueous solution containing 8.1 g was added with stirring, and to this mixture was added 150 g of a ricic acid solution containing 7.4 g of ricic acid (H3PO485.4%) and 25.0 g of NH4Cl to form a mixed solution. Raw material blending ratio (molar ratio) of this mixture
is 1.0ZrO2・0.9P2O5・0.9C2O4
It was. This was purified using 20% NaOH solution.
H was adjusted to 2.0. This reaction mixture was placed in the same plastic container as in Example 1 and kept under natural pressure in a thermostatic chamber at 96° C. for 2 days, and then the solid reaction product was repeatedly filtered and washed with water to separate solid and liquid.

The product obtained after dehydration was a product with a high moisture content, and its amount was 62.1 g. Further, when the above cake was heat treated in a dryer at 105°C for 24 hours, a dry white mass of 14
Obtained 0g. The results of analyzing the product by X-ray diffraction are shown in Table 10. This diffraction pattern shows that the dried product contains impurities with poor crystallinity and the N of Example 1.
It had the same X-ray powder diffraction pattern as the H4Zr2(PO4)3 product and essentially the same X-ray diffraction pattern as the main phase in Table 2.

The impurity with poor crystallinity contained was a zirconium compound with a high water content and a characteristically very high diffraction peak at d=3.20 Å.

In Table 10, the (M) mark indicates the diffraction peak of the impurity, and the (M) mark indicates the overlapping diffraction peak of the impurity and NH4Zr2(PO4)3.

Table 10 d(Å) 100×I/Io d(Å) 100×I/
Io6.42 37 2.04 10 5.18 8Z 1.97 14 4.73 55 1.91 29 4.25 8Z 1.84 28 4.08 8Z 1.66 11 3.83 80 1.64 21 3. 26 78Z 1.58 14 3.20 67M 1.52 12 2.96 100 1.49 7 2.83 9 1.41 4 2.58 11 1.32 7 2.51 27 1.56 5 2.13 16 1.10 4 Main diffraction peak Z to d = 1.10 Å - Overlapping diffraction peaks of impurity M = Z and NH4Zr2(PO4)3 Example 5 375 g of water, 10.0 g of ammonium chloride and 2 oxalic acid After stirring and mixing 61.3 g of a solution with a ZrO2 concentration of 20.4% obtained by dissolving zirconium oxychloride in water to a solution consisting of 26.1 g of hydrate (H2C2O4.2H20), sodium ricinate (NaH2PO4・2H2
200 g of a solution containing 13.0 g of O) were mixed.

This mixture is 1.0ZrO2:0.9PO4:2.0
It was the raw material blending ratio (molar ratio) of C2O4. This mixture was adjusted to pH 3.8 with 3N ammonia water, placed in the same plastic container as in Example 1, and kept in a constant temperature room at 90° C. for 3 days. After the obtained reaction product was filtered and washed with water, the obtained dehydrated cake was heat-treated in an electric furnace at 580°C for 1 hour, and after cooling, it was poured into water and stirred for 30 minutes using a Maknetic stirrer. The mixture was dispersed in water and left in water for 2 days (during which time the sediment at the bottom of the beaker was dispersed using a stirrer for 30 minutes). The solid reactant thus obtained was filtered with suction and air-dried indoors for 2 days to form a white powder 14.
2g was obtained. As a result of analysis, the product is ZrO249,7
%, P2O 543.0% and H2O 7.3%, expressed as an oxide molar ratio of 4.0 ZrO2.3.
The product composition of 0P2O5.4.0H2O was shown. Furthermore, the results of analysis by X-ray diffraction are shown in Table 11. This diffraction pattern had essentially the same X-ray diffraction pattern as the main phase in Table 6 and contained no crystalline impurities. This product was converted into crystalline zirconium ricinate H
It was determined to be Zr2(PO4)3·mH2O (m=1.5).

Table 11 d(Å) 100×I/Io d(Å) 100×I/
Io6.40 31 1.72 5 4.68 64 1,67 11 4.39 78 1.66 21 3.83 100 1.57 15 3.19 63 1.55 7 2.93 97 1.53 11 2. 85 10 1.48 6 2.76 3 1.47 4 2.58 17 1.40 4 2.53 31 1.33 7 2.26 6 1.32 5 2, 19 5 1.26 6 2.13 12 1.22 6 2.06 7 1.16 4 2.01 11 1.104 5 1.98 14 1.095 4 1.92 26 1.87 4 1.83 26 1.79 5 TG- The results of DTA analysis showed that a slight and gradual dehydration reaction occurred up to about 150°C.

A crystal change accompanied by a rapid dehydration phenomenon still occurred between 150 and 250°C.

Example 6 In the same manner as in Example 5, a dehydrated cake precipitated from a reaction mixture containing raw material compounds of zirconium, oxalic acid, and ricic acid was heat-treated at 750° C. for 3 hours in an electric furnace. This product was placed in a breathable paper bag and left indoors for one month. The analysis result after leaving it was ZrO251.1
%, P2O544.1% and H2O4.8%, expressed as oxide molar ratio 4.0ZrO2・3.0P2O5・
The product composition was 2.6H2O. The X-ray diffraction pattern was as shown in Table 12. This figure is the 6th
It had essentially the same X-ray diffraction pattern as the main phase in the table and contained no crystalline impurities. This product is
Similar to Example 5, crystalline zirconium ricinate HZr2 (
PO4)3·mH2O (m=0.8).

Table 12 d(Å) 100×I/Io d(Å) 100×I/
Io6.41 19 1.92 21 4.67 23 1.83 25 4.38 93 1.79 4 3.83 100 1.67 10 3.19 47 1.65 21 2.94 72 1.57 14 2. 85 7 1.55 7 2.58 17 1.53 8 2.53 35 1.48 5 2.27 5 1.46 9 2.19 6 1.40 4 2.13 11 1.33 5 2.06 5 1.32 5 2.01 10 1.26 4 1.98 11 1.21 4 1.16 3 1.10 4 Example 7 Oxalic acid dihydrate crystal (H2C2O4.2H2O) 1
300 g of a solution containing 5.6 g and 30 g of ammonium chloride
g, a solution consisting of 35.7 g of zirconium sulfate solution (ZrO2 28.0% concentration) and 114.3 g of water was mixed with stirring, and then a solution containing 7.1 g of phosphoric acid (85%) 15
0g was mixed. This mixture is 1.0Zr:0.8P
The raw material blending (nil ratio) ratio was O4:1.5C2O4. The mixture thus obtained was placed in a plastic container similar to that used in Example 1 and kept in a thermostatic chamber at 96° C. for 2 days, and then the solid reaction product was filtered and washed with water to separate solid and liquid. The obtained dehydrated cake was heat treated in an electric furnace at 580° C. for 20 hours to obtain 9.1 g of white powder. As a result of analysis of this product, the product was ZrO2 52.6%,
Showing a composition of 545.5% P2O and 1.9% H2O,
Expressed in molar ratio of oxides: 4.0ZrO2・3.0P2
The composition of O5.1.0H2O is shown below.

In addition, the results of analysis by X-ray diffraction immediately after heat treatment showed that
As shown in Table 13. This diffraction pattern had essentially the same X-ray diffraction pattern as the main phase in the low temperature type in Table 5, and contained no crystalline impurities. This product was determined to be crystalline zirconium ricinate HZr2(PO4)3.

Table 13 d(Å) 100×I/Io d(Å) 100×I/
Io6.35 44 2.02 9 4.57 100 1.98 13 4.43 45 1.90 11 3.81 87 1.78 9 3.17 52 1.67 20 2.87 47 1.58 4 2. 57 32 1.54 5 2.55 32 1.52 4 2.28 3 1.48 7 2.21 4 1.40 3 2.11 4 1.34 4 Example 8 Hydroxy salt silconium solution (ZrO235.0 , ZrOOHCl solution) and 50 g of water were added to 15.7 g of ZrOOHCl solution).

Add sodium tartrate (Na2C4H4O6・2H2
400 g of an aqueous solution containing 26.3 g of O, 99.0%),
Next, 100 g of an aqueous solution containing 3.3 g of 85.0% ricic acid solution
g were added sequentially under stirring to prepare a reaction mixture. The raw material blending ratio (mol) of this mixture is 1.0Zr:0.
6PO4:2.5C2O4. Add tetraethylacimonium hydroxide [(C2H5)4NOH] to this mixed solution.
After adding 18.0 g of a 10% aqueous solution of , the pH was adjusted to 5.0 using a 20% caustic sorter.

This slurry mixture was refluxed in a flask for 7 days using the same equipment as in Example 3.

Next, the solid reaction product in the flask was suction filtered, washed repeatedly with water, and then separated into solid and liquid. The obtained dehydrated cake was air-dried indoors for 2 days to obtain 5.5 g of white powder. A portion of this air-dried product was taken and subjected to X-ray diffraction measurement, and the result showed the same shape as the product of Example 1. Separately, as a result of X-ray diffraction of a part of the air-dried product that was heat-treated in a high-temperature dryer at 250°C for 4 hours, the diffraction peak was different intensities (but the d value is the same, especially d = 2.96 Å and d =
(Change in intensity of 3.84 Å) A diffraction pattern identical to that of Example 2 was obtained. The remaining air-dried material was heat treated in an electric furnace at 775°C for 60 minutes. ■The results of the analysis of pottery indicate that ZrO2
52.9%, P2O545.6% and H2O1.5%, expressed as oxide molar ratio, 4.0Zr
The product composition was shown as O2.3.0P2O5.0.8H2O. (2) The X-ray diffraction pattern of the baked product is shown in Table 14. This diffraction pattern was essentially the same as the main phase in the high temperature type shown in Table 4, and contained no crystalline impurities.

Table 14 d(Å) 100×I/Io d(Å) 100×I/
Io6.38 18 1.91 19 4.59 64 1.80 11 4.41 100 1.69 25 3.82 92 1.59 3 3.17 51 1.56 7 2. 63 1.53 9 2.58 22 1.47 8 2.54 42 1.40 3 2.29 2 1.37 2 2.20 7 1.33 5 2.12 9 1.27 4 2.03 8 1 .22 3 1.99 14 1.16 2 1.10 3 This figure is essentially the same as Example 7 in terms of interplanar spacing, and the intensities of the diffraction peaks are d=4.6 and d=4.
．． 4, and those baked at high temperatures have d
=4.4 has a thicker peak intensity. (2) The calcination product was determined to be crystalline zirconium ricinate HZr2(PO4)3.

Example 9 Zirconium sulfate solution (Zr containing 28.0% ZrO2)
Oxalic acid dihydrate (H2
An oxalic acid solution in which 9.4 g of C2O4.2H20) was dissolved in 200 g of hot water was added with stirring. Next, ricic acid (85
After adding 200 g of an aqueous solution containing 16.5 g of %H3PO4), monoethanolamine (NH2CH2CH2OH
A mixture was prepared by sequentially adding 8.0 g of reagent). The composition of the mixture is 1.0Zr・1.4PO4・0.7C2O
The raw material blending ratio (molar ratio) was 4. The pH of the thus obtained mixture was adjusted to 5.0 with 20% NaOH,
This was used as a reaction mixture. The reaction mixture was placed in the same plastic container as used in Example 1, kept in a thermostatic chamber at 96° C. under natural pressure for 7 days, filtered by suction filtration, and washed with water. The resulting dehydrated cake was baked in an electric furnace at 750° C. for 16 hours, stored in a polyethylene bag for one day, and then subjected to each measurement. ■The analysis results of the sintered product are ZrO252,
7%, P2O 545.6% and H2O 1.7%, expressed in molar ratio of oxides, 4.0ZrO2.3.0P2O
The product composition was 5.0.9H2O. The X-ray diffraction pattern is as shown in Table 15. This diffraction pattern had essentially the same X-ray pattern as the main phase in Table 4. This figure was a crystalline zirconium phosphate HZr2(PO4)3 with an intermediate figure of HZr2(PO4)3 of the low-temperature type of Example 7 and the high-temperature type of Example 8, respectively.

Table 15 d(Å) 100×I/Io d(Å) 100×I/
Io6.36 47 2.03 6 4.57 85 1.98 14 4.40 100 1.91 13 3.81 98 1.80 9 3.17 62 1.66 17 2.88 48 1.58 2 2. 57 22 1.55 4 2.54 37 1.52 4 2.28 2 1.47 5 2.20 5 1.40 3 2.11 6 1.33 3 Example 10 Obtained by the same operation as Example 6 HZr2(PO4)3・
The powdered product of 0.8H2O was heat treated in a high temperature dryer at 250°C for 3 hours. The obtained heat-treated product is ZrO
251.7%, P2O544.7% and H2O3.6%
Contains 4.0Z, expressed as the molar ratio of oxides.
The generated composition of rO2・3.0P2O5・1.9H2O is shown.

Moreover, the X-ray diffraction pattern is as shown in Table 16.

This had essentially the same X-ray diffraction pattern as in Table 4 and was crystalline zirconium phosphate low temperature HZr2(PO4)3.

This means that HZr2(PO4)3・mH2O and HZr
2(PO4)3 changes reversibly due to moisture absorption and dehydration, and 2
HZr2(PO4) with the X-ray diffraction pattern shown in Table 4 at 50℃
) means changing to 3.

Table 17 d(Å) 100×I/Io d(Å) 100×I/
Io6.35 45 2.02 13 4.56 100 1.98 16 4.42 87 1.90 12 3.81 91 1.78 8 3.21 20 1.67 21 3.16 56 1.58 5 2. 87 46 1.54 5 2.65 5 1.52 4 2.57 34 1.47 6 2.55 34 1.40 3 2.28 3 1.34 5 2.21 5 2.11 6 Example 11 Implementation The same operations as in Example 1 were repeated, except that the raw material composition, reaction time, and product drying conditions in Example 1 were changed as described below. 15.0 g of triethanolamine solution ((CH2CH2OH)3N: reagent) was added to the mixed solution of each compound of zirconium, oxalic acid, and ricinic acid, and after adjustment, it was kept under natural pressure in a constant temperature room at 96 ° C. for 10 days. After that, the same operations as in Example 1 were carried out, and the cake obtained by filtering and washing with water was air-dried indoors for 3 days.
6 g of air-dried material was obtained. The results of analysis using X-ray diffraction method for a part of it showed the same figure as in Table 8 of Example 2,
It had essentially the same shape as the main phase in Table 2. Further, the air-dried product was calcined in an electric furnace at 950°C for 2 hours. ■
The results of X-ray diffraction measurements on the baked goods are shown in Table 18. In this figure, the high-temperature firing product contains crystalline impurities and has the same X-ray powder diffraction pattern as the crystalline zirconium ricinate, high-temperature type HZr2(PO4)3 product of Example 8. Ta. Furthermore, crystalline impurities are
This is a part of the crystalline zirconium ricinate of the present invention that has undergone crystal changes (mainly to form pyrophosphate) by high-temperature baking at 1080° C. or higher. In Table 18, the (P) mark indicates the impurity, and the (M) mark indicates the impurity and NH4Zr2(P
The overlapping diffraction peaks of O4)3 are shown, respectively.

Table 18 d(Å) 100×I/Io d(Å) 100×I/
Io6.37 22 2.04 8 5.17 29P 1.98 21 4.61 49 1.91 19 4.41 100 1.85 16P 4.15 100P 1.81 14 3.82 80 1.71 6 3. 72 22P 1.66 27 3.18 44 1.53 9 2.90 56M 1.47 12 2.66 31P 1.39 6 2.58 22 1.33 6 2.54 40 1.27 3 2.31 3 1.22 3 2.21 6 1.16 2 2.12 10 1.15 3 2.08 7P P: Impurity M: Diffraction peaks where P and HZr2(PO4)3 overlap Example 12 Same as Example 5 By this operation, crystalline zirconium ricinate HZr2(PO4)3.1.5H2O was obtained. The product thus obtained was dried at 164°C for 2 hours using a constant temperature dryer.
Heat treated for hours. The dried product obtained by this heat treatment contains Zr
O250.7%, P2O543.8% and H2O5.5
% analysis results are shown. In addition, the dried product was measured by X-ray diffraction,
The results for the main diffraction peaks are shown in Table 19. This diffraction pattern is from HZr2(PO4)3・mH2O to H
In the process of changing to Zr2(PO4)3, the shape was a mixture of two types of crystalline materials of the present invention. In Table 19 (H)
Mark, (O) mark and (OH) mark are HZr2(PO4)
3, HZr2(PO4)3・mH2O and HZr2(
The diffraction peaks of PO4)3 and HZr2(PO4)3·mH2O weights are shown, respectively. Furthermore, when this dried product is left indoors for several days, it absorbs moisture and the diffraction peak of HZr2(PO4)3 decreases to such an extent that it cannot be confirmed.
Most of the diffraction peaks were PO4)3.mH2O.

Table 19 d(Å) 100×I/Io d(Å) 100×I/
Io6.44 41OH 1.99 15OH4,66
60O 1.92 20OH4.62 35H 1.
83 15O 4,41 72H 1.79 4OH 3,84 100H 1.72 5O 3,20 67O 1.67 13OH3,18 15
H 1.66 13O 2,93 59O 1.57 9O 2,89 14OH 1.53 9O 2,59 23O 1.48 6OH 2,55 6H 1.40 3OH 2,54 24O 1.33 4OH 2,13 9O 1 .32 2O 2,06 6O 1.27 3O O:HZr2(PO4)3・mH2O(0<m<2)H
:HZr2(PO4)3 OH:O. and H Weight Example 13 Crystalline zirconium ricinate NH4Zr2(PO4)3 was obtained by the same operation as in Example 1. The product thus obtained was heat treated at 550° C. for 90 minutes using an electric furnace. The results of measuring the thus obtained baked goods by X-ray diffraction are shown in Table 20. This diffraction pattern is from NH4Zr2(PO4)3 to HZr2(PO4)
In the process of changing to 2, the crystalline material of the present invention had a mixed pattern. In Table 20, marks (a), (b) and (ab) indicate NH4Zr2(PO4)3, HZr2(
PO4)3 and NH4Zr2 (PO4)3 and HZr2
The diffraction peaks of the (PO4)3 weights are shown, respectively. HZ
After several hours, the r2(PO4)3 heat becomes crystalline zirconium ricinate HZr2(PO4)3・m containing crystal water.
It changed to H2O.

Table 20 d(Å) 100×I/Io d(Å) 100×I/
Io6.39 52ab 2.02 4b 4.68 45a 1.98 14ab4.63 53
b 1.91 32ab4.41 64ab 1.83
8a 3.83 100ab 1.80 8b3.19 64
ab 1.71 3a 2.94 42a 1.67 13ab2.91 32
b 1.65 7a 2.58 20a 1.57 6ab 2.54 17b 1.52 8ab 2.52 14a 1.47 5b 2.21 2b 1.40 3ab 2.13 9a 1.33 3ab 2.04 4a 1 .32 3a 1.26 2a a: NHZr2(PO4)3 b: HZr2(PO4)3 ab: Weight of (a) (b)

[Brief explanation of the drawing]

FIG. 1 is a triangular molar component diagram showing the blending ranges of a zirconium compound (as Zr), a carposis acid compound (as C2O4), and a ricinic acid compound (as PO4) in the present invention. (Above) Agent: Eiji Saegusa, patent attorney

Claims (2)

[Claims] (1) (I) General formula HnR1-nZr2(PO4)3・mH2O [However, R represents NH4 or amishikathioshi, 0≦n≦1, 0≦
m≦2], (II) As an oxide by analytical calculation, the formula 4ZrO2.
Crystalline zirconium ricinate, characterized in that it is represented by 3P2O5. (2) A mixed liquid containing (I) a zirconium compound, a carboxylic acid compound, and a ricinic acid compound, and at least one of an ammonium compound and an amine compound, comprising (II) a zirconium compound (as Zr), a carboxylic acid compound (C2O4 ) and ricinic acid compounds (PO4
In the molar ratio triangular component diagram shown in Figure 1, the proportions of
It has a mixture composition within the area surrounded by the straight line connecting each point of C (44, 43, 13) and D (1, 97, 2), and contains 0.2 to 100 moles of ammonium per 1 mole of Zr. The general formula HnR1-nZr2(PO4)3·mH2O [where R is , NH4 or amishikachioshi, 0≦n≦1, 0≦
m≦2] A method for producing crystalline zirconium ricinate.