JPS60103008A - Manufacture of crystalline zirconium phosphate - Google Patents

Abstract

PURPOSE:To manufacture the titled compound having a large grain size and a high degree of crystallinity under safe and mild conditions by reacting a zirconium compound with a carboxylic acid compound and a phosphoric acid compound in an aqueous medium in specified ratios. CONSTITUTION:To an aqueous soln. of a zirconium compound (a) such as zirconium oxychloride are successively added an aqueous soln. of a carboxylic acid compound (b) such as oxalic acid and a phosphoric acid compound (c) such as phosphoric acid under stirring, and they are mixed to prepare a mixed liq. contg. said three components by amounts (wt%) in the obliquely lined region defined by straight lines connecting points A, B, C, D in the triangular composition diagram. It is preferable that the concn. of Zr in the mixed liq. is adjusted to about 0.01-25wt%. The pH of the mixed liq. is adjusted to <=10 to cause a reaction at about 5-160 deg.C, and the reaction is allowed to proceed for about 20 days - 5sec. The resulting crystalline zirconium phosphate is dispersed, washed, and dried. The dried compound may be heat treated at <= about 850 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to mu'+ l'll'+ 71 phosphate di/L/
, , I-ram manufacturing method θ.

Crystalline zirconium phosphate has extreme heat resistance, chemical resistance, and dσ
(Adultification 19. A sharp spoon in the dramatic radiation rib property, etc., and a unique stroke + kAJ needle for cations (C is known as a large il exchanger. In history, the structure is Crystal r [phosphorus 1112 zirconium has the right interlayer distance] absorption > 1Q 41''4 and is used as an ion exchange type layered material for in-calation, catalysts, etc. 'fJ is seen telescopically, and Yuzu's minute yJ・ω
(Research and development is 1j muwa JL.

However, the problems of the known method for producing crystalline zirconium phosphate Q1.4i11 have been completely overcome. For example, chestnut 7 field etc. (A, 01 ear field &
J., A., 5tynes, J., Inorg.
, Ohem,'.

26.117.1964) was proposed by α-Zr (
In the method for producing JiPO4)2 (hereinafter referred to as α-2rP), amorphous zirconium phosphate "fI: lO 7 or more" is obtained by mixing and reacting an aqueous solution containing a zirconium compound such as zirconium chloride and phosphoric acid. It is crystallized by refluxing it upright for several days in a high-altitude phosphoric acid bath.

This method has (a) major practical problems as it requires the use of strong acid and reflux for a long period of time at high temperatures; and (b) the resulting filth is fine particles. Post-treatments such as filtration and water washing are difficult, and (iii) even as final products, they have low crystallinity and are fine particles, so handling is difficult. Alberti et al.
T&J, Tornacca, J.

Inorg, Nucl, Ohem, 80, 81
7, 1968). After adding all the hydrofluoric acid to the zirconium compound to create the complex k)ettk, phosphoric acid was added and the mixture obtained was 1. By heating and cotton-making, fluorine is scattered, and the complex is rapidly decomposed to obtain α-2rPt. However, this method is also impractical due to the release of harmful fluorine, difficulty in controlling heating conditions, corrosion of manufacturing equipment, low crystallinity as a product, and difficulty in handling fine particles. It's hard to believe that there is a way to do it. Furthermore, the improvement power of the method of Clearfield et al. and the method of Alberti et al.
It costs ¥tn, but with this V improvement method, it is 1♂ in one county!
I k'ft point is the reformation process, but what about the construction process? New difficulties have also arisen, such as the complexity of tz-ZrP.
There is room for a major change in the history of M production. crystalline phosphorus i
'+'r: ! / As ruconium, in addition to α-2rP, r-Zr(Ill'04-2-21120(i-Z
rP), I/-Zr(IJPO4)2・8J12U(θ
-Z rP ) 9β-21-(1(PO4)2,
a-Also El, ε-Zr(1,tPO4)2'! If the form of fi is not As 'Bl 6 tL tail, QJ and Daisako 414 are complicated, and the simple one with crystal ratio 1 is ff# r:>rt.

The inventor has proposed that the general A Zr(ilPO4)2'nf
As a result of many years of research into the production method of crystalline phosphorus-based zirconium, which can be easily destroyed by i2Q, a mixed solution was prepared by adding a carboxylic acid compound solution and a phosphoric acid compound solution to the zirconium compound solution. , when reacting under specific conditions with the ratio of each compound in the mixed solution kept within a specific range, crystalline zirconium phosphate with large particles and high crystallinity is reacted under mild conditions. It has been found that there is no danger and that it can be easily obtained using simple manufacturing equipment. That is, the present invention provides all of the following methods.

(υ It is a mixed liquid in which a phosphoric acid compound is added to a liquid containing a zirconium compound and a carboxylic acid compound, and
The proportions of SiIV conium compound (as zr), carboxylic acid compound (as 0204), and phosphoric acid compound (1) as 0°) are shown in the composition diagram shown in Fig. 1.
A (2,95,8), B (85,55,10), G! (
8B, 10.57) and 1) (2, 8, 95> mixed precepts in the area t' surrounded by the old line connecting each point gold, song) p
Crystalline zirconium phosphate with the general formula Zr(HPO4)2 ・n) 120' [however, n=0 to 8], which is characterized by an intense reaction to Hematsutake mushrooms at less than flO Production method.

Examples of the zirconium compound used in the method of the present invention include compounds that are water-soluble or become 0.1' soluble in water with acid; Zirconium salts of mineral acids such as zirconium sulfate, basic zirconium sulfate, zirconium nitrate, zirconium salts of organic acids such as zirconyl acetate, zirconyl nitrate, ammonium zirconium carbonate, sodium zirconium sulfate, ammonium zirconium acetate, oxalic acid Examples include zirconium complex salts such as sodium zirconium and ammonium zirconium citrate. Among these compounds, oxS
More preferred are zirconium/quaternide, zirconium sulfate, and the like.

Examples of the carboxylic acid compound include aliphatic polycarboxylic acids having two or more 10001i that are water-soluble or become water-soluble with acid, and salts thereof. Specifically, salts such as oxalic acid, sodium oxalate, sodium oxalate hydrate, potassium oxalate, rubidium oxalate, cesium oxalate, ammonium oxalate, maleic acid, malonic acid, succinic rXk, and 0: iCre. Examples include aliphatic dibasic acids and their salts; citric acid, tartaric acid, malic acid, and other aliphatic oxyacids and their salts. Among these, oxalic acid and its alkali metal and ammonium salts are more preferred.

Examples of phosphoric acid compounds include compounds that are soluble in water depending on the amount of water. Specifically, phosphoric acid, sodium dibasic phosphate, dibasic sodium phosphate, dibasic sodium phosphate, etc. and ammonium salts of orthophosphoric acid; metaphosphoric acid, birophosphoric acid, etc. Alkali metal and ammonium salts of condensed phosphoric acid having a P-0-P bond are included in Example 7. Among these, phosphoric acid and O/L/1. Alkali metal salts of phosphoric acid are more preferred.

The method of the present invention is carried out, for example, as follows. First, an aqueous carboxylic acid compound is added to an aqueous solution of a zirconium compound, or an aqueous phosphoric acid compound or its aqueous solution is added to an aqueous solution of a zirconium compound to an aqueous carbonate compound γα.

After adding the phosphoric acid compound to the zirconium compound aqueous solution,
When adding an aqueous solution of a carboxylic acid compound, amorphous negative zirconium phosphate tends to form, resulting in a product with a low degree of crystallinity. When mixing each raw material, it is difficult to stir, and especially during the gap where the phosphoric acid compound is added, a state where the phosphoric acid level is partially oriented is caused by stirring in a continuous manner. Do the following. Tejasilconium compound in mixture (as zr)
, carboxylic acid compound (as c2o4) and phosphoric acid compound (as PO4) in the weight ratio triangular component diagram shown in FIG.
,10), 0(8B, 10.57) and D(2,8,9
5) Each raw material is mixed so that it falls within the area surrounded by the straight line connecting each point. 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, the degree of crystallinity is low, amorphous products are mixed, or unreacted raw materials are present. Nine points - or two or more occur between remaining, mixed crystalline materials containing two or more types of crystalline alloys, etc. The form of the mixed liquid in which each raw material is uniformly dissolved or reduced to 1+l' may be in the form of a clear solution or a slurry containing undissolved excess IJ+. The degree a of the reaction tJd mixture is zr 0.01
The concentration is preferably 0.1 to 10%, more preferably 0.1 to 10%. If the zr is 0.01 inch, it will be disadvantageous for the rice to grow properly, and if the -10,000 zr is above 25% gold, it will cause the rice to be washed with water, phosphates, etc. precipitates as crystals, making it difficult to perform d3 filtration and water washing of the crystalline zirconium phosphate product. The reaction mixture as described above is subjected to the reaction at a plil of less than 0. pH of reaction solution
When is more than 10, crystalline zirconium phosphate with low crystallinity is produced! There is a strong tendency to In the method of the present invention, the synthesis control of the N+'i product is controlled by adjusting the pH of the reaction mixture.
``It is [su + i [ζ° (irini]). The crystal form is the polar type of the raw material (IIJJ, the ion yuzu in the reaction mixture)
, raw material blending ratio, reaction crystallization temperature, and pH of the reaction mixture
Generally, σ-ZrP, θ-2r
P etc. are easily generated in the low p1-I vessel area, and J1u is always pff
It is preferable to use a reaction product in the juvenile range of 4 or less. f
- In the case of Z rP, pH (7) j UW comparison 11-
It can be produced in the range of pn 0.5 to lO(7)Flu. pH of the reaction mixture; As a tl-regulator,
Mineral acids such as salt 1k, sulfur 12, nitric acid; hydroxides and carbonates of alkali metals such as sodium hydroxide, water 121 hicpotassium, and sodium carbonate; ammonia water, etc. are exemplified.

Reaction temperature (in the present invention, the crystallization of crystalline phosphorus zircoium by the reaction and aging of each raw material component is collectively referred to as ``tannoji''): d, 5'C or higher. It is preferable that the reaction polarity is less than 5'''C, which is economically disadvantageous because the crystallization length of the desired product is -1 and the crystallization length of the desired product is less than 6. 'j,'?
There is no K limit t″L, but from the economic point of view ID: 16
The temperature is about 0°C. The reaction time depends on the raw materials;
A melon of shi? +'i+Y degree and pl (, anti-throat life 1) χ
Monotodokoroe's mustache product +v':'1e(-1 greater than vt
c change j(、rug、total 5 seconds to 20 ti h'、
For example, σ-Z1-P has a faster crystallization rate than γ-2rP, and rough crystals precipitate after cooling the phosphoric acid compound. Get started.

The produced crystalline zirconium phosphate Z r (JLP O
4) 2・nl120 (where n=0 to 8) is separated from t(N4.+ by n1 washing a )san
After that, it is dehydrated and dried for 2 liters using the Hatake method, and further heat-treated at 850° C. or less if necessary. The drying method includes heat drying, removal of %f water using a desiccant such as phosphorus pentoxide, calcium chloride, or silica gel, and it is also possible to completely remove crystal water using a desiccant. It is. Heat treatment above 850'C i7u'+lj
When using zr(JIPO4)2 ・n112
Crystal permanent in zirconium 1.1. ' 4h iQ water is released and transformed into viroline 1 and zirconium (ZrP2O7). Sieve, according to the present invention, IL crystalline zirconium phosphate 14, strong 'S: ion father 4 + i4 ability is cured, mixing 1μ, Ji Qi during reaction in, late ARI existing cation after reaction In such cases, in a hasty step after the reaction process, the entire product is expressed as 1, (bii: 1 table 1
By letting it go, including all the cations in one valley ν, IE, the essence JJl! It is now possible to obtain crushed crystalline zirconium phosphate.

Although the mechanism of formation of crystalline zirconium phosphate 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 the entire phosphorus V compound to the vaginal fluid,
It is thought that the complex salt gradually decomposes, zirconium ions and phosphate ions react, and crystalline zirconium phosphate crystallizes and grows.

The crystalline phosphorous zirconium obtained by the method of the present invention increases or decreases its water of crystallization depending on various environmental conditions. For example, under the conditions of 1(t)Zr(HPO4)
2 ・8I (20 is stable under conditions of a temperature of 8°C and a humidity of 95%, but when it is left in a room with a temperature of 82"C and a humidity of 40%, crystal water f: Ij'H:, zr (JIPO4)2・)12
0, and this Zr()lPO4)2-H2Oe is stable under the conditions of further heat treatment at 400°C and humidity of 40%, but when this is heat-treated at 200°C, water of crystallization is released and Zr()lPO4) 2 and iru. As above < gr(1
(PO4)2 ・H2O and Z r (I4P04)
2 ・2) (Two types of Zr obtained by heat treating 20 respectively)
()lPO4)2 have the same composition, but while the former does not change even when exposed indoors, the latter absorbs all the moisture in the air by releasing IPe indoors, and 5J
'J-wise changes to Zr(HPO4)z ・2H20.

The method of the present invention achieves the following remarkable effects.

(1) Since strong acids and harmful gas-generating materials are not used, it is safe and easy to manufacture.

tN) # The manufacturing process is simple and the operating conditions are not harsh.

++n+ Since the size of the reaction product is large, ν111 is recovered from the liquid phase and water 61. is easy to swallow.

aV+ Reaction product purity +04 and crystallinity.

IV) By adjusting reaction conditions and/or heat treatment conditions, etc., different crystals of crystalline quince can be obtained.

EXAMPLES The present invention will be explained in more detail with reference to Examples below. 11. The present invention can also be carried out at °C by methods other than these Examples, and is limited only to the Examples. It's not something you can do.

Various measurements in the following examples were performed as follows.

(1) X-ray diffraction analysis is performed using X-ray diffraction equipment I'e (Science 1
Measurements were made from two X-glue powder diffraction patterns obtained using a Geigerflex box AD-2A (manufactured by Kiriki Co., Ltd.) at 0uKllZ with 20 degrees ranging from 5 degrees to 75 degrees.

(2) Regarding ZrO2, the product was melt-decomposed using sodium carbonate, extracted with water, and then the insoluble matter was separated by dj. In order to complete the decomposition, the insoluble matter was repeatedly melted and fractionated with sodium carbonate and extracted with water. The final remaining insoluble matter was melted and decomposed with potassium biromate, then extracted with water, converted into a mandelic acid salt, and further incinerated and ignited to form ZrO2 fc.

(3) For P 205, after performing the same melting and water extraction with sodium carbonate as above, ammonium molybdophosphate was precipitated from the extract, and a total excess of normal thorium hydroxide solution was added to the extract. , and quantified using a normal nitric acid solution.

<4) n2oNitsiC is a thermal analysis device (Rigaku Denki (ceramic, differential thermal thermobalance 811!II"t'IJ-1)'1
'A high-temperature type) is used.
0 m, 17. Measured at an ascending IM speed of 10'C/min, the above X +hl+! Il, Jl and H2° were measured in conjunction with chemical analysis.

Example 1 Zirconium oxychloride crystal (ZrO(J2・8f12
0199.0% test m) 11.6p was dissolved in ion-exchanged water to make a liquid volume of 74I. Oxalic acid crystal (H2O204
・2112. O1 reagent grade) 24.0 pf! : Hot water 23
The oxalic acid solution was then added to the pregelatinized zirconium solution under conditions to obtain a mixture of K Hjl, K'J oxalic acid (l(31' 048
5. O%s reagent special grade) 18.2I and water 106.
A total of 11 phosphoric acid solutions consisting of Jll were added and mixed with stirring. The 116-n reacted rJd compound was placed in a heat-resistant plastic container with a small hole in the inner lid to completely prevent excessive moisture evaporation, and was heated under natural pressure in a thermostatic chamber at 96°C.
After holding for 0 hours, the clear supernatant liquid gold was removed. Residual anastomosis within the vessel 1)'l 1i11. After suction PJ using 'lz, wash repeatedly with approximately 500 ml of ion-exchanged water until no oxalate ions are detected (ILfx).
6+1: I did. The dried product 10.6.9 obtained by drying the cake-like solid reaction product at 80° C. for 8 hours to obtain 4rk c)t” is a smooth white powder.

According to chemical and thermal analysis, the product is ZrO241
,0%, P2O546,8% and H2O12,2% gold alloy, expressed as molar ratio of oxides, i, ozro2.
The product composition was 1.0P205/2.0f120.

The results of analyzing the obtained product powder by X-ray diffraction are shown in FIG. This diffraction pattern was determined by Arland et al.
gen A4bertSSO]I, Acta Oh
em, 5cand, 2B (4).

1446, 1969), the product is tz Zr(fiPo4)2+
It shows H2o terror.

Example 2 Hydroxyzirconium chloride solution (zrooklcl)
W: itk, zro, 85.0%) 11.5
g, Shul Shun (I1210204 ・21J, 20
) '18.0! q Gold heat water 3oo; Hc solution PW
The solution obtained in the above step was added (VJ) while stirring. After heating this mixed melt swamp to 65°C, phosphorous ammonium (N, ti
4n2po498.0%”) Water-soluble w containing 9.8 gi
87 x 2°I was added with stirring, and then 6N aqueous ammonia was added until the pk reached 12.0. Obtained reaction mixture f: Placed in a plastic container similar to that used in Example 1 and kept under natural pressure in a 7L1'96°C IJL greenhouse for 24 hours, after which the solid reaction product and mother liquor were taken out into a glass container. , and n were added with concentrated hydrochloric acid 82.0.9, and stirred for 30 minutes. The solid product was suctioned and filtered using R paper, washed with hot water until no chlorine ions were detected, and then separated into solid and liquid. By drying the obtained cake in a constant temperature and humidity chamber at a temperature of 80°C and a humidity of 40%, 10.2g of a smooth white powder was obtained. According to chemical analysis and thermal analysis, the product was zr0289.
．． 0%, P2. Article os44.1 and l12016.9%
1. expressed as a molar ratio of oxides. OOZrO2
・0,98 P2O5・2゜96dan20 composition was shown.

Figure 3 shows the results of 11 grains analyzed by total product powder X-ray diffraction. This diffraction pattern II1, Yamanaka et al. (J, Inorg, NucCOhem, 41(1),
45.1979), it is necessary that the product is γ-Zr(flPo4)2 ・2'
Being klzO is k 7F.

Example 3 Pure water 840I and oxalic acid (H20204/21120)
Basic di-A carbonate/
:Z = fy A hair 7. (Zr0240.
0%) 15.0. After adding F and stirring to mix uniformly, concentrated hydrochloric acid (12N) aO, Og was added, and stirring was continued until all the liquid was mixed.

Water 224I and phosphoric acid (85.0% 113P) were added to the mixed solution.
o4) 45.6! ! After adding all the phosphoric acid solution and mixing, put it in a glass container and boil it further! The glass container was placed in a 1liL water path and kept heated for 6 hours. The solid 4-component was filtered using suction paper, washed with pure water, and then the solid-liquid fraction was filtered.

Next, the obtained product was placed in an all-porcelain crucible and heat-treated in an electric JJ for 44 o'C-Cs to obtain 18.6 g of rough white gold.

The powdered chemical composition is ZrO248.0%, P2O550.4
% and 1i206.6%Ihami, expressed as molar ratio of oxide 1.00 ZrO2・1.02P205-1.05
The composition of H2O is 2J comb (.

X-ray IL of the product! The results of analysis using the IJ++ method are shown in FIG. This diffraction pattern was developed by Chernorukov et al.
Inorga-nic Chemistry, 22,1
119.1977) and the diffraction pattern of the raw J-shaped specimen reported above, and the 41-paraboloid is α-Zr (fiPO4).
2.

Example 4 6+, branched silconi/l/[Zr(0,)1)2(02
-11i 111x solution of 03(J2)2) (zr0□
13.0%) 48.1 & ammonium oxalate [
(NIl14)2c2o4. a2o, c+ 9.5%]
700 y of an aqueous solution containing 9.5 g of gold was added to Shandong while stirring.

Next, 650 ml of water was added to the mixture. j9 and phosphoric dihydrogen ammonium (N) 14L (2PO4, 98,0%) 2(i
, 0 & was added with stirring, and 3N ammonia water was added while stirring to adjust the mixture to 1° and 4°. The entire fire was kept in a plastic container similar to that used in Example 1 at 85°C under natural pressure in a thermostatic chamber for 2 days. After separation by a suction core using the II!11 reaction product,
After repeated washing, the resulting cake was placed in a crucible and heat-treated at about 205° C. for 8 hours.

According to chemical analysis and heating, the resulting smooth white powder product (12.8 g) had a
%, P2O54! J, 8% and Jl (containing 206,9% Teoli, oxidation? ab in % Iv ratio, 1.00
zro,.

The composition of -1,00P2O5-1,119n, o is shown.

The result of analyzing the product powder using the X+Ig+: times (J? method) is shown in Figure 2155.
hem, fllO.

2249.1968), the diffraction pattern of the product reported by
(kIPO4)2.

Example 5, txy4 conversion: r = uA (zrocg 2
・8M20.

99.0%) 21.1.7 Totally dissolved in pure water, liquid jti
After 100y, sea L t rY&! Dihydrate (1120204-2) 120) 44-0. 11'ft of aqueous Mk a o o containing @'i was added to obtain a clear mixed solution. Potassium dihydrogen phosphate (KH2P) is added to the transparent door mixture.
O4) Aqueous solution containing 41.4.9 8601! After adding the gold powder under stirring, the pB of the mixture was brought to 1.5 by adding 20% potassium hydroxide. The obtained reaction mixture is
: Added to the same glass stick as used in Example 1.
After incubating for 24 hours under natural conditions at 96°C in a thermostatic chamber, the supernatant was extracted, the crystallized product was transferred to a glass container, and the glass was poured with 700 rtl of pure water. In addition, after dispersing the crystallized gold, sedimentation was performed, and the supernatant liquid was removed again. IN 4k 400 m to the remaining slurry
Add A' and continue to stir for 80 molecules with a magnetic star. After that, filter the solid material ([-[-] through filtration with silver nitrate, and remove salt ions with silver nitrate.
The solution was washed with pure water until it disappeared, and 111 of the liquid was poured out.

The obtained n/c cake was kept in a constant temperature and humidity chamber at a temperature of 10°C and a humidity of 9.
After leaving for 8 days under conditions of 2-95%, a white product 2B, 0.9 containing some water was obtained.

The product contains Zr0g 27.81%, p2o5a i
-it s and Jl (including 2041, 18'%,
Expressed as molar ratio of oxides: 1.00 ZrO2,-1,
The composition was 00P2O5-10,4fi20.

The results of analyzing the processed material using the X-ray radiation method are shown in FIG. This diffraction pattern was described by Clearfield et al. (J. Inorg-Nucg, Ohem, 85
, 1099.

In the x & 1 diffraction pattern reported by (1978), the diffraction peak is α-Zr (JH'04) 2-8820, which is 9.76χ in the interplane depression d = IO, 4^.
(7) 6 diffraction patterns with the same ~(.

Almsgiving l16 implemented? J 5 'T' Mj rough 1.7cθ-Zr(
nPO4)z ・8f1207 powder product k lu
Warm 111f M ”tri K in n 1'kxlL 8
By leaving it at 2'C-7m degree 40% for 2 days,
A smooth white powder was obtained.

The obtained t' white dry powder was determined to be α-Zr by X-win diffraction.
(HPO4) 3 ・fi20 T# is confirmed tL
fc.

Example 7 Put 19.4 g of basic silium sulfate solution (Zr0804 solution containing 8.0% Zr022) into a Ga'7X container.
Add to this 300 I of water and 28.6 l of oxalic acid (H202
04・2H20) 28.6 After adding the aqueous solution consisting of @・6N1i2SO4250fi fr: Added.

Then, due to the refined mixture obtained, pure water 184I and phosphorous-removed sodium (Nali2PO4j 2)-120,98,0
%) 46. Add the 17 to 1 liter solution under stirring,
llj combined liquid ff 10 minutes after the end of side addition r:'PIi,
Make sure to aspirate the liquid and aspirate it with warm water until no sulfur ions are detected. After obtaining a cake, remove the cake at 10s'C.
By drying, white powder 1B, 8jjτ was obtained.

The product contains 0241.1% zro, 547.8% P2O and 112011,696 gold, expressed in molar ratio of oxides 1.00 zro2·t, o OP2O5"1.9
The results of analysis of the product powder powder by the rapid diffraction method are as shown in Figure 7, and the product has a composition of The daily diffraction pattern (Fig. 2 No. 11 (〉) was gold-bore. Therefore, the product obtained without invention was α-Zr (HPO
4) 2.H20T: One thing is clear.

Example 8 In 40p of water? +Il rIIrtdi)v co= A/
(Zr○(NO3)2-21120.99.0%)
11.1I4-Including M throw: tetrium (Na2(j 204, 99.5% >
After adding a solution containing 22.1 J/ and 1 + IS water 420 I, 50%') nlQ,'7 + trim(
Na, 1i2PO4-2k120) 49.017 was added to the mixture, and the pH was adjusted to 20%-011 due to Q mixing.
Gold 3, adjusted to 1, 0 thus obtained γ J1.・ Mix 'i;' flk 'C'JG IM bQ l ”c
Using InJ 4) rj v>gura, Lf7 riyogi LiC input If, 'f/u' at 92'G under natural pressure in the room 1° old%,': J'ir Shitsu, In the meantime, after charging the anti-moisture evaporation photovoltaic sleeve every 2 days,
7. I took it out and moved it to the remaining number of IJ galanubica,
Decantation and washing with water were performed once to remove the upper cooling sludge. 60 liters of concentrated hydrochloric acid was added to the obtained fL slurry, and after stirring with a magnetic stirrer for 1 hour, it was washed with water until no chloride ions were detected with silver nitrate, and then filtered with suction using Oki paper. . Obtained by solid-liquid separation
Place the dehydrated cake in a flat-bottomed porcelain evaporating dish and dry at temperature): 2
9 at 180° C. for 4 hours. Next, by leaving the dried product in the entire room for 4 days, white grains that are easily powdered are obtained. ! I like it again.

The white grains are zro, a, 8.8%, P2.05
44.7% and H2O 16.5%, expressed as oxide molar ratio 1.0OZr02-1, OOP2O
5.2. It had 901120 Bi deposits.

When the product of Example 2 was subjected to X-win diffraction, Example 2
The product of the same cycle -1t+' figure (Fig. 8),
It became clear that the product was γ-Zr(flPO4)2.2H20.

Example 9 Zirconium oxychloride, oxalic acid and phosphorus bχ total 21
Crystal r1 Silconinium k on phosphorus white ?v7'C0 7th'CNo, 1
．． -6eJ1, by the method of the present invention -C, No.
7 and 8 are in the comparison section.

In addition, the X-ray diffraction patterns of the reaction products No. 1 to 7 are as follows.

No, 1...2nd (k) No, 2...Same as Figure 2 N+3.8...Same as 21st XI) J (No,
4...8th C and 11th jj<No, 5...
...No. 2181 and IIIJ No. 6... No. 7 No. 7... No. 101 No. 1 The composition ratio of each raw material is outside the scope of the minor invention No. 7 The product has a low degree of crystallinity, as is clear from the X-ray diffraction pattern shown in No. 10-1. In addition, in No. 8, no crystalline tB zirconium phosphate was formed.

Example 1O Crystalline zirconium phosphate was obtained in the same manner as in Example 2, except that di-Ireconium hydroxyloxychloride, oxalic acid, and ammonium phosphate were used in the proportions shown in Table 2. The yield, crystal form, and degree of crystallinity of the product are also shown in Table 2.

The X-ray diffraction patterns of the products of the present invention obtained in Nos. 1 to 6 were substantially the same as the diffraction patterns of the products according to Example 2 (FIG. 8).

On the other hand, the product obtained using NO67, which is outside the scope of the present invention, was zirconium phosphate with a low crystal ratio, as shown in Figure 11. Moreover, PO4'le is Ma of the present invention.
', No. 8 outside the gate, crystalline zirconium phosphate was not produced.

[Brief explanation of the drawing]

FIG. 1 is a triangular component diagram of the M amount ratio showing the blending range of the zirconium compound (as zr), the carboxylic acid compound (as 0204), and the phosphoric acid compound (as PO4) in the present invention. Figures 2 to 9 show the X-ray diffraction patterns of zirconium coated with crystalline phosphorus obtained by the method of the present invention, and Figures 10 and 11 show the X-ray diffraction patterns of the product obtained by the method of the comparative example. X M+1 diffraction 181 is shown. (and above) 'J Agent Patent Attorney Eiji Saegusa 5゜2) 1L2'

Claims (1)

[Scope of Claims] (1) A mixed solution in which a phosphoric acid compound is added to a solution containing a zirconium compound and a carboxylic acid compound, (11) a zirconium compound (as Zr) and a carboxylic acid compound (as C204); and phosphoric acid compounds (po
In the n:t M ratio triangular component diagram shown in FIG.
0), C(8B, 10.57) and D(2,B,9
5) 1g of mixture within the area surrounded by a straight line connecting each point of
i, 1ii11 General formula Zr(fiPO4)2, n1120 [where n=
0 to 8] A method for producing crystalline zirconium phosphate.