JPH06256020A - Method of preparing crystal antimonic acid - Google Patents

Abstract

PURPOSE: To improve the quality as a supporting type by precipitating an antimonic acid slurry by hydrolyzing antimony pentachloride and heating the obtained precipitated mixture at a reflux temp. for a prescribed time.

CONSTITUTION: An anion exchange resin and a granular ion exchange supporting body material selected from between alumina and silica-alumina and immersed with antimony pentachloride (V) to obtain an immersed material (a). Then, the (a) component is dried in an inert atmosphere to obtain the immersed material dried matter (b). Then, ammonium hydroxide is added slowly under the agitation of the (b) component to precipitate antimonic acid and to obtain the precipitated mixture (c). Then, water is added to the (c) component, after heating the obtained mixture at a reflux temp. for about 24 hr, the granular material is separated from the liq. to produce the supporting type crystalline antimonic acid.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an improved process for producing crystalline antimonic acid and a process for producing supported antimonic acid.

[0002]

BACKGROUND OF THE INVENTION There is a continuing need and interest in obtaining extremely high purity specialty chemicals and metals. The demand for low sodium lithium metal for battery applications requires low sodium lithium chloride feedstock for the electrolytic cells used to produce lithium metal. The sodium content in lithium metal from lithium chloride is about 50 ppm on a lithium metal basis. Although this is a low sodium concentration, battery metal users prefer sodium with very little or no sodium. High concentration lithium bra Even by, it is difficult to achieve by conventional separation techniques.

At present, antimonic acid (Sb ₂ O ₅ 4H
Only ₂ O) shows an affinity for sodium in the ion exchange method. Antimonic acid is manufactured by Mitsuo
Discussed in several patents by Abe and co-workers. These are Japanese Examined Patent Publications 45-22418, 48-
30,000, and 52-6949. Other published meaningful papers are the Journal of
Japan Chemistry, Vol: 87
1, 1174-1179 (1966) -which discusses the cationic nature of antimonic acid-Medium and the Bu
lletin of the Chemical Soc
Yety of Japan, Volume 41, 333-342
(1968) -which presents the production and properties of antimonic acid-.

As described by Abe et al., The production of crystalline antimonic acid is carried out by hydrolysis of antimony pentachloride to give amorphous antimonic acid, and then 0.1-6 mol / mol of amorphous antimonic acid. One liter is acidified with hydrochloric acid, nitric acid or sulfuric acid and the crystals are then cured or aged, isolated, washed and dried above room temperature and below 70 ° C. This is described in Japanese Patent Publication No. 45-22418, lines 24-35.

Japanese Examined Patent Publication No. 48-30000, Example 1 describes the application of crystalline antimonic acid to the removal of sodium from lithium chloride in acidic medium (lines 39-45). Initial amounts of sodium and potassium impurities were not mentioned. Published paper [Bulletin of the
Chemical Society of Japan
n, 41, 333-342 (1968)],
M. Abe states that crystallization of amorphous antimonic acid is facilitated by increasing the temperature during aging within the range of 0-80 or by increasing the concentration of strong mineral acid. X-ray powder data are shown; lattice constant is 10.38 A and space group is Fd3m. The selectivity order is Li ⁺ <K ⁺ <Cs ⁺ for alkali metals.
<Rb ⁺ <Na ⁺ , for alkaline earth metals Mg ² <
Ba ²⁺ <Sr ²⁺ <Ca ²⁺ .

The Journal of Japan
Nese Chemistry, Vol. 87: 11, 117
4-1179 (1966), in Section 3.3 of the article, M. Abbe states, "If antimonic acid is placed in a solution of sodium hydroxide, potassium hydroxide, or lithium hydroxide, sodium, potassium, or lithium ions will be adsorbed; and In general, antimonates have low solubility [sodium antimonate 0.0
3 ^12.6 , potassium antimonate 2.8 ²⁰ and lithium antimonate (unknown)], it may be possible to produce these substances by using a highly concentrated solution. We thought. " The basic solution is based on the concept that M. Abe performed all tests at pH = 3-4.

[0007] Another paper [Journal of In
organic and Nuclear Chemi
story, 43: 10, 2537-2542 (198)
1)]. Abe is 0.1M of each metal nitrate
Solution (pH = 3-4) of about 1. until the difference in metal ion concentration between the effluent and the feed is negligible.
At a flow rate of 5 ml / hour, H ⁺ form crystalline antimonic acid (C
-Called SbA) was continuously charged at the top of the column "to define his working range of solution pH for crystalline antimonic acid. Other published papers and patents by Abe show no pH value and are "acidic".
It is described as a solution. For example, Japanese Patent Publication 48-30000
In Example 1 of Abe, a solution of lithium chloride containing sodium and potassium impurities was prepared and 8 parts concentrated hydrochloric acid was added to 200 parts of this solution in 400 parts of water before use.
This solution is certainly in the relatively low acidic pH range.

The Journal of Inor
ganic and Nuclear Chemist
ry, 30 vol, 639-649 (1968) by the medium Betsuru and Huys, production of polyantimonic acid can be prepared by dissolving the _K 2 _H 2 _Sb 2 _{O 7} in water boiling, HCl / _NH 4 Cl This is done by adding the mixture to form a gale and then allowing it to stand overnight and then filter. The product is dried at 50 ° C. The selectivity order is Cs ⁺ <Rb ⁺ <NH for alkali metals.
₄ ⁺ <K ⁺ <Na ⁺ , and for alkaline earth metals Mg ²⁺ <Ca ²⁺ <Sr ²⁺ <Ba ²⁺ . The X-ray pattern of polyantimonic acid is similar to that reported by Abe, but with d-spacing (spacin).
g) is shifted slightly downwards.

It is named hydrated antimony pentoxide,
Another production method of antimonic acid is Radioanalyt
ical Chemistry, Volume 1, 169-178
(1968) Naka F. Gilard Day and E.I. Written by Sabioni. This sample was also prepared by hydrolysis of SbCl ₅ with water; however, the product was 2
It was dried at 70 ° C. for 5 hours. It showed excellent separation of radio-sodium from the neutron activated material.

[0010]

DISCLOSURE OF THE INVENTION In the present invention, the production of crystalline antimonic acid involves the hydrolysis of antimony pentachloride with water followed by at least 105 hours at about 105 ° C. without further acidification (but preferably up to 76 hours). Achieved by continuous reflux. Longer reflux periods of up to 7 days may be used and are useful in increasing the crystallinity of antimonic acid. X-ray diffraction studies show reflections corresponding to the formula Sb ₂ O ₅ 4H ₂ O. This pattern shows reflections with a pattern resembling one or the other of these Abe materials when compared to those obtained both before and after being heat treated by Abe for his antimonic acid at 100 ° C. This indicates that the present refluxing process for crystalline antimonic acid is new and has not been previously described.

In another aspect of the invention, crystalline antimonic acid is synthesized on and / or within an ion exchange support material selected from anion exchange resins, alumina, silica-aluminas and zeolites. . This method
Immersion of the support material with antimony (V) ions, then precipitation of antimonic acid on and / or on the surface of the support by addition of ammonia, then crystallinity of antimonic acid and adhesion of antimonic acid to the support. Reflux for at least 24 hours in order to increase the particle size, which results in relatively large size ion-exchanger particles, which is more useful in the column.

Support materials useful in making supported crystalline antimonic acid are Dowex ™ MSA-1,
Anion exchange resins (either chloride or hydroxide form) such as Dowex ™ MWA-1, Amberlite ™ IRA-900, etc .; gamma-aluminum oxide (γ
-Al ₂ O ₃₎ pellets or spheres and silicon oxide - encompasses aluminum oxide _(SiO 2 _-Al 2 _{O 3)} pellets or spheres, but are not limited to.

The support material is soaked with an amount of antimony (V) pentachloride. The mixture is generally dried at room temperature (although higher temperatures can be used) with an inert gas, preferably argon gas. Concentrated ammonium hydroxide is added to this mixture to promote the precipitation of antimonic acid on the surface of the support material and throughout. Water is added with stirring and the mixture is refluxed for at least 24 hours or aged for at least 10 days.
Aging at room temperature, under high temperature or at reflux,
Increases the crystallinity of antimonic acid and its adhesion to substrates. 24 hours at reflux yields a useful product,
A reflux of about 3 days is preferred. The mixture is filtered to separate the solution from the solid supported antimonic acid product. The particulate product is then dried; conveniently the product can be air dried at external temperature, oven dried or by any technique convenient and compatible with the operator.

[0014]

The following example further illustrates this aspect of the invention. I. Synthesis of antimonic acid A. Comparative Example-Antimonic Acid Product I Distilled water 69 m in a 5 liter 3 neck flask equipped with stirrer, thermocouple, water condenser, and argon back bubbler.
I was prepared. Under stirring, at room temperature, 67 ml (156.5 g) of antimony pentachloride were slowly added (dropwise) to this reactor. The reaction was extremely vigorous and exothermic. No external cooling was added. A white precipitate formed, but about 1/3 of the antimony pentachloride charge was added and then redissolved. After the addition of antimony pentachloride was complete, sufficient distilled water was added until the reactor volume was 4600 ml. About 300 ml of distilled water was added to form a viscous white precipitate. The slurry was heated to 40 ° C. and kept at this temperature for 12 days with very slow stirring.
The slurry was transferred into a 5 liter separatory funnel where the precipitate was allowed to settle overnight. The precipitate was then separated from the mother liquor by centrifugation (filtration was attempted, but the precipitate was peptized and passed through filter paper). The mother liquor weighed 4918 g. The precipitate was washed several times with cold water; however, as the number of washes increased, the ability to centrifuge the slurry substantially diminished. The precipitate was air dried at room temperature for several days. The deposit, antimony pentoxide, weighs 100 g,
The recovery yield was 96.6%.

B. Inventive Example-Antimonic Acid Product II Distilled water 69 in a 5 liter 3-neck flask equipped with stirrer, thermocouple, water condenser, and argon back bubbler.
I charged ml. The flask was then placed in an ice water bath. With stirring, 69 ml of antimony pentachloride (161.
2 g) was added slowly (drop by drop). A white precipitate formed after the addition of 2 ml but redissolved as the addition of antimony pentachloride was continued. The reaction was vigorous and exothermic but was controlled by an ice water bath.
After the addition of antimony pentachloride was complete, additional distilled water was added until the volume of the flask was 4600 ml (about 300 ml of distilled water was added to form a viscous white precipitate). The slurry is refluxed and heated under slow stirring to produce 76.
Hold for 5 hours. The slurry was cooled to room temperature and transferred to a 5 liter separatory funnel where the precipitate was allowed to settle for 13 days. The precipitate was separated from the mother liquor by centrifugation. The mother liquor weighed 4463 g. The precipitate was washed once with cold distilled water and then air dried at room temperature for several days.
The precipitate, antimony pentoxide, weighs 100 g,
The recovery yield was 3.8%.

C. Inventive Example-Supported Antimonic Acid Product III Amberlite ™ IRA-900C OH ^- Anion Exchange Resin 50 g Antimony Pentachloride (V) About 50 m
1 was added. The mixture was dried by sending argon. Concentrated ammonium hydroxide (250
ml) was added slowly. After stirring for 4 days, about 850 ml of distilled water was added, and the solution was refluxed for 3 days (105-105).
110 ° C.) and then air dried. The product weighs about 85
It was g.

Product IV This manufacture is similar to that described in Manufacture III. To 80 ml of antimony (V) pentachloride was added very slowly about 20 ml of concentrated NH ₄ OH. About 15 g of Amberlite ™ IRA-900C (OH ⁻ form) was added and a viscous slurry was obtained. Additional ammonia (200 ml) and water (150 ml) were added to the slurry to reduce the viscosity. Other resin 30g and ammonia 40
After adding 0 ml, the mixture was stirred with heating at 80 ° C. for 2 hours. The mixture is dried in air and 950 ml of water
Was re-slurried with, refluxed (105 ° C.) for 2 days and filtered. The air dried material was 195 g.

Product V Antimony pentachloride (100 ml) was added to 50 g of γ-alumina spheres having a surface area of 220 m ² / g. Argon was pumped over the slurry overnight. About 500 ml concentrated ammonia and 900 ml water were added and the mixture was refluxed for 3 days. The exchanger was dried in an oven at 110 ° C. and had a dry weight of 195 g.

About 150 ml of antimony pentachloride (V) was added to 55 g of product VI SiO ₂ -Al ₂ O ₃ . The mixture was stirred at room temperature for 2 days. Ammonia (36%, 250m
1), then 750 ml of water were added very slowly. The solution was refluxed for 1.5 hours and filtered. The solid was dried in an oven at 110 ° C. for 24 hours. The product obtained weighed 255 g.

Product VII 97 ml of distilled water were charged into a 5 liter 3-neck flask equipped with stirrer and water condenser. The flask was then placed in an ice water cooling bath. Under extremely slow stirring, 71 ml (165.9 g) of antimony (V) pentachloride was slowly added (dropwise) to the flask. A white precipitate formed after the addition of 1-2 ml but redissolved as the addition of antimony pentachloride (V) continued. The hydrolyzed antimony pentachloride (V) was viscous and was light yellow in color. next,
90 ml of Dowex ™ MWA-1 was added to the hydrolyzed antimony pentachloride (V), which was aged for 3 days at room temperature under an argon sparge to blow out generated HCl and excess water. After this aging period, additional distilled water was added until the flask volume was 4600 ml. After adding 300 ml of H ₂ O, a white precipitate formed. The slurry was then aged for several months and post-filtered. 110 in the oven
Dry at 24 ° C. for 24 hours. The dry weight was 127 g.

II. X-Ray Powder Diffraction X-ray powder diffraction patterns were obtained for Product I, Product II, Product VII and polyantimonic acid. M. A list of X-ray powder data from Abe (1), Bets and Whistle (2), and Product I, Product II, Product VII (supported antimonic acid), and Atomagic polyantimonic acid is shown in Table 1. Product I is prepared according to a modification of the method described by Abe and Ito, which has a
Included 12 days aging at 0 ° C. but without previous acidification, while Product II was made crystalline by refluxing for 3 days. A comparison of the X-ray pattern of Product I and that produced by Abe and Ito shows an exact match of d-spacing. However, Product I has smaller peak intensities and smaller crystallinity indices than the Abé sample which exactly corresponds to the X-ray data in the ASTM X-ray diffraction pattern file. Product II is similar to product I, but has higher crystallinity as indicated by the increased peak height. However, product II is about 105 ° C
At reflux for at least 3 days. Thus, the increased crystallinity of antimonic acid is not only due to aging for a minimum of 7 days, but also to at least 3
It can be concluded that this can also be achieved by refluxing for a day. A comparison of the X-ray data of Product II and Abe shows the same reflection; however, it is more similar to Abe's crystalline antimonic acid (Japanese Patent 52-6949, 1979) heat treated at 100 ° C. The polyantimonic acid obtained from Atomagic Chemicals does not show the same X-ray pattern as the polyantimonic acid reported by Betzl and Huis. The peak is slightly shifted to a lower d-spacing compared to the crystalline antimonic acids of Abe and Ito and Product I and Product II. The pattern is similar to that of product II except for the inversions in the peak intensities of the 311 and 222 peaks. In product II, the 222 peak is a stronger peak, whereas in the atomagic polyantimonic acid, the 311 peak is a stronger peak. The X-ray pattern of product VII, Dowex MWA-1 supported antimonic acid, showed only four peaks, of which 222 was stronger. Antimonic acid samples from Product I, Product II, supported antimonic acid, and polyantimonic acid were evaluated in a wide range of test series such as pH, time, temperature. Results are reported as follows:

III. pH Variation Initial tests were performed on dilute LiCl brine (1.4 wt%) to determine the best possible working pH range. An analysis of the test brine (listed as initial LiCl), as well as the test results, is presented in Table 2. From this data, a pH working range of 11-12 resulted in optimal sodium removal. Thus, the next test is high pH.
There therefore enhance the exchange of ^{H +} and Na ^+, pH = 11~1
It was done in 2. A decrease in pH was observed after the exchange, as evident at the initial pH of 2.8 and 8.6; the final pH values were 2.0 (No. 2) and 2.4 (No. 4), respectively. ) And H ⁺ due to Na ⁺ incorporation
Release of Presence of more OH ⁻ (Example No. 4)
Favors the removal of H ⁺ from within the ion exchange agent body, which provides ion exchange sites for more Na ⁺ , thus increasing Na ⁺ removal (˜99%). An increase in distribution coefficient, Kd, was also observed with increasing pH. This is the formula:

[0023]

[Equation 1]

Is obtained by using The data reported here have been obtained using ICP (Inductively Coupled Plasma Spectroscopy). As reported by Abe, antimonic acid also has a high affinity for Ca, and a low affinity for K, as shown in this and later studies.

IV Alkaline Fluctuation The ratio of antimonic acid and the amount of lithium hydroxide added to raise the pH to 11-12 was adjusted to 100% LiOH H ₂ O per 100 ml of 26 wt.
Vary from 0.05 to 2.0 g. The results are shown in Table 3. Addition of 0.05 g LiOH H ₂ O per 100 ml resulted in an increase in sodium uptake of 12% to 4
Up to 1% (see Examples 7 and 8) and from 70% to 85% (see Examples 15 and 16) were observed. A ratio of 10 for antimonic acid: lithium hydroxide-water was the minimum required to increase sodium uptake. Soluble antimony was not significantly changed by the addition of lithium hydroxide-water; ie initial antimony value 3.2.
ppm (Example 7) and 3.8 ppm (Example 15), and the final antimony value is 2.0 to 4.3 ppm (Examples 8 to 1).
4) and 2.6-6.6 ppm (Examples 16-18). A decrease in calcium from 5 ppm to <0.1 ppm was also observed, corresponding to about 98% calcium removal. A very small amount of potassium was exchanged.

V Contact time and temperature fluctuations A. 1.4 wt% LiCl 1.4 wt% LiCl at room temperature (pH = 11-1
The effect of contact time on 2) was evaluated. The results (Table 4) show that Na ⁺ with increasing contact time up to 24 hours.
Shows increased uptake. The crystalline antimonic acids of Product I and Product II show about 99% Na ⁺ after a contact time of 24 hours.
Have removal.

B. 26 wt% LiCl 26 wt% LiCl (pH 11-12) 1,
5, and 24 hours contact time at room temperature and 70-73
Studied at ° C. These results will be reported later.

1. Room temperature, 1 hour Results for 1 hour contact time at room temperature show that Product I and Product II C-SbA and polyantimonic acid have the same sodium uptake (Table 5). An increase in sodium uptake was also observed with increasing amount of exchange agent. Soluble antimony increased slightly; about 1.2-2.6 ppm after initial exchange from ~ 1 ppm
Until. The expected increase in soluble Sb was also noted for each increase in the amount of antimonic acid used. Calcium dropped from 6-7 ppm in brine to <0.1 ppm. No potassium uptake was observed. Three exchange agents, crystalline antimonic acid (Product I and Product I
I), as well as polyantimonic acid, all showed very similar behavior in their ability to remove Na from LiCl brine.

2.73 ± 1 ° C., 1 hour Raising the temperature to 73 ° C. resulted in a slight increase in Na ⁺ uptake, but at the same time increased the amount of soluble antimony in the brine. Uptake of calcium and potassium was unchanged. The data are displayed in Table 6.

3. Room temperature, 5 hours Increasing contact time from 1 hour to 5 hours showed a slight increase in Na uptake for 1 g of exchange agent, but similar uptake for 2 g and 5 g exchange agent (Product I , Product II, and polyantimonic acid). The results are shown in Table 7. Soluble Sb values <1 in all tests
It was in the range of ~ 5. Removal of calcium

4.73 ± 1 ° C., 5 hours Increasing reaction temperature from 25 ° C. to 73 ° C. did not affect Na uptake of Product I, Product II, and polyantimonic acid. An increase in the amount of dissolved antimony for all exchange agents was observed when compared to that performed at room temperature after exchange. Is shown in Table 8.

5. Room temperature, 24 hours The ion exchange behavior of Product I, Product II as well as polyantimonic acid did not change at room temperature with increasing contact time from 5 hours to 24 hours. Calcium removal was>99%; K removal was zero or very low. The results are displayed in Table 9. 26% by weight
In the case of LiCl, the sodium removal vs. contact time at room temperature was calculated according to Examples 30-32, 48 for polyantimonic acid.
˜50 and 66 to 68. Equilibrium is reached around 24 hours.

VI Batch Test for Lithium Hydroxide Brine As can be seen from the data in Table 10, crystalline antimonic acid showed advantageous sodium removal from 9.52 wt% lithium hydroxide. About 99% of the sodium was removed from the use of an amount of 5 g of the exchange agent for a 200 ml sample of brine at room temperature and 24 hours contact time.
Calcium removal was 23%, some potassium was also replaced, and residual antimony was in the range of 3-27 ppm.

VII Illustrative Additions The present invention is further illustrated by the following examples selected from the table to guide in the use of exchangers.

Example 29. Na 166ppm, K 31
26 wt% lithium chloride brine with an initial concentration of ppm, Ca 6 ppm, and Sb <1 ppm (pH
= 11 to 12) of the solution was brought into contact with 5 g of crystalline antimonic acid. After stirring for 1 hour at room temperature, the solution was filtered. The filtrate is Na 1.2 ppm, K 30
ppm, Ca <0.1 ppm, and Sb 1.6 pp
was analyzed as m. This corresponds to> 99% Na removal and 98% Ca removal.

Example 31. Na 179 ppm, K 30
26 wt% lithium chloride brine with an initial concentration of ppm, Ca 7 ppm, and Sb 1 ppm (pH
= 11 to 12) solution of 200 ml and polyantimonic acid 5
g was contacted. The filtrate is Na 2.2 ppm, K 3
0ppm, Ca <0.1ppm, and Sb 1.7p
It was analyzed as pm. This corresponds to 99% Na removal and 99% Ca removal.

Example 47. Product II 5 g and 26% by weight
LiCl brine solution mixture (pH = 11-12)
Was prepared. The stirring time was 5 hours at room temperature. Initial concentration is Na 225ppm, K 31pp
m, Ca 11 ppm, and Sb <1 ppm. The final concentration after treatment with crystalline antimonic acid is N
a 3 ppm, K 27 ppm, Ca <1 ppm, and Sb 2 ppm.

Example 50. Polyantimonic acid 5g and 26
Wt% LiCl brine 200 ml solution mixture (p
H = 11-12) was prepared. The initial concentration is Na 16
6ppm, K31ppm, Ca 6ppm, and Sb
It was <1 ppm. After contact for 5 hours at room temperature,
The obtained filtrate is Na 1.1 ppm, K 31 pp
m, Ca <0.1 ppm, and Sb 1.8 ppm. This corresponds to 99% Na and Ca removal.

Example 56. 2 g of 5 g of crystalline antimonic acid
6 wt% thylium chloride brine, 200 ml, pH =
11 to 12 were contacted at 73 ° C. for 5 hours. Initial concentration is Na 221ppm, K 36ppm, Ca 1
It was 2 ppm and Sb 4 ppm. The final concentrations obtained are: Na 5 ppm, K 31 ppm, Ca <1
ppm and Sb 27 ppm. This corresponds to 98% Na removal and 92% Ca removal.

Example 65. Product II 5 g and 26% by weight
LiCl brine 200 ml solution mixture (pH = 1
1-12) were prepared. Contact time is 24 at room temperature
It was time. Initial concentration is Na 179ppm, K
It was 30 ppm, Ca 7 ppm, and Sb 1 ppm. Final concentration: Na 1ppm, K 27pp
m, Ca <1 ppm, and Sb 10 ppm.

EXAMPLE 6 A solution of 68.26 wt% LiCl brine in 200 ml (pH = 11-12) was contacted with 5 g of polyantimonic acid for 24 hours at room temperature. Initial concentration is Na 179ppm, K 30ppm, Ca 7
ppm and Sb 1 ppm. The final concentration after replacement is Na 2ppm, K 27ppm, Ca <1p
It was pm and Sb 9ppm. This is equivalent to 99% Na and Ca removal with polyantimonic acid.

Example 72. 26 wt% LiCl brine containing 180 ppm Na (200 ml, pH = 1
1-12) was contacted with polyantimonic acid (2 g) for 24 hours at room temperature. The obtained filtrate is Sb 4pp
m and Na 1.1ppm, 99.4%
Corresponding to the removal of Na. The exchange agent was changed to 3 in 1N HCl.
_N-NH 4 Cl, then regenerated with 0.05 N-HCl. Reuse of this exchanger in fresh LiCl brine containing 117 ppm Na resulted in 98.2% Na.
Removal (2 ppm) and Sb 4 ppm. The exchanger was then regenerated again and contacted with LiCl, the resulting brine was 94.9% Na removed and Sb 2.3p.
pm was obtained. After the third regeneration, this exchange agent is again L
Contacted with iCl. The filtrate was 87.2% Na removed and Sb 2.5 ppm was obtained.

Example 73. An experiment similar to Example 72 was conducted. 26 wt% LiCl brine initially containing 240 ppm Na and 34 ppm Ca (200 ml,
pH = 11.2) was contacted with polyantimonic acid for 24 hours at room temperature. The obtained filtrate is Na 14 pp
It contained m, Ca 0.9 ppm, and Sb 18 ppm. Next, an exchange agent was added to 3N-NH in 1N-HC
Regenerated with ₄ OH and then 0.05 N HCl. The regenerant contained 217 ppm Na (96.0% Na regeneration) and 7.7 ppm Ca. Next, this exchange agent
Contact with another 200 ml sample of LiCl brine,
As a result, Na 4 ppm (98.3% Na removed), C
A filtrate containing a <1 ppm and Sb 4 ppm was obtained. Regeneration resulted in 97.1% Ca and 34.8% Na regeneration. A third recycle with LiCl resulted in 76.7% Na removal, 99.4% Ca removal,
And Sb 3.4 ppm were obtained. The regeneration was complete for Na and Ca. The fourth cycle using LiCl brine gave 85.4% Na removal, 100% Ca removal, and Sb 2.9 ppm.

Batch Test Example VIII for VIII Supported Antimonic Acids 74. A sample of 5 g of the exchange agent (Product III) supported on Amberlite ™ IRA-900C was
Wt% lithium chloride brine (pH = 11-12) 2
It was contacted with 00 ml at room temperature for 24 hours. Initial concentration is Na 166ppm, K 31ppm, Ca 6p
It was pm. Final concentration is Na 3ppm, K28p
pm and Ca <1 ppm.

Example 75. Amber Light ™ IRA
A sample of 5 g of the exchange agent (Product IV) supported on -900 C was stirred with 200 ml of 26 wt% lithium chloride brine initially containing Na 166 ppm, K 31 ppm, and Ca 6 ppm. 24 at room temperature
After a contact time of hours, the filtrate obtained is Na 6 pp.
m, K 29 ppm, Ca <1 ppm.

Example 76. A sample of 5 g of the exchange agent prepared according to Product IV was initially loaded with Na 166 ppm, K 3
26 wt% containing 1 ppm and Ca 6 ppm
Of 200 ml of lithium chloride brine. After 24 hours at room temperature, the filtrate is Na 2 ppm, K 2
It was analyzed as 9 ppm and Ca <1 ppm.

Example 77. About 5 g of the exchange agent prepared according to product VI was contacted with 200 ml of 26% by weight lithium chloride brine at pH = 11-12. Initial brine analysis was Na 166 ppm, K 31 ppm,
And Ca 6 ppm. The final filtrate is Na 4
ppm, K 29 ppm, and Ca <1 ppm.

Example 78. A sample of 5 g of the exchanger prepared according to product VII was contacted with 200 ml of 26% by weight lithium chloride brine at pH = 11-12 for 24 hours at room temperature. Analysis of the initial brine was Na 1
It showed 66 ppm, K 31 ppm, and Ca 6 ppm. Final concentration after treatment is Na 7 ppm, K 2
8 ppm and Ca <1 ppm.

Column Test Example IX for IX Supported Antimonic Acid-Product VII 79. Column containing antimonic acid (Product VII) supported on Dowex MWA-1 (29.2 ×
1.5 cm) was prepared. Lithium chloride containing 180 ppm of Na (28.9 wt% P = 1.179 g / m
1, pH = 11.3) was passed through the column at room temperature with a flow rate of 11 ml / min. A 200 ml sample was taken. 1
After 000 ml, Na was 4 ppm in brine.
The exchange agent is then treated with 3N NH ₄ Cl 2.6 in 1N HCl.
L was regenerated at a flow rate of 15 ml / min. 0.05N
After passing the HCl wash through the column, fresh 26% brine (pH = 11.1, Na = 174 ppm, flow rate = 8 ml / min) was sent again. Leakage occurred after sending 2.4 L of brine (Na = 3 ppm).

X Particle Size Analysis The particle size of the support material can range from about 6.3 mm (0.25 inches) to about 150 μm below. Non-supported antimonic acid is product I or product II.
The particle size can be largely larger than 212 μm (70 mesh) by one of the above methods. Thus,
A wide range of supported and unsupported ion exchange agents can be prepared by the method of the present invention.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

[Table 6]

[0057]

[Table 7]

[0058]

[Table 8]

[0059]

[Table 9]

[0060]

[Table 10]

[0061]

[Table 11]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Teresita Sea Fly Anther Cool Burg 28054 Gastonia Amite Avenue 2357 (72) Inventor Darish Wayne Burnett 28054 Gastonia Green View Live 1612

Claims (4)

[Claims] 1. A process for producing crystalline antimonic acid, characterized in that antimony pentachloride is hydrolyzed to precipitate an antimonic acid slurry, which is heated to a reflux temperature for at least 24 hours. 2. The method according to claim 1, wherein crystalline antimonic acid is produced by refluxing the slurry for 24 hours to 7 days. 3. A method for producing a supported antimonic acid characterized by the following steps: (a) a particulate ion-exchange support material selected from anion exchange resin, alumina and silica-alumina is used as antimony pentachloride (V). (B) dry the impregnated particulate support material in an inert atmosphere; (c) slowly add ammonium hydroxide to the dried impregnated particulate support material with stirring. To precipitate antimonic acid; (d) add water to the mixture and heat the mixture at reflux temperature for about 24 hours; (e) separate the particulate material from the liquid. 4. The method according to claim 2, wherein the crystalline antimonic acid is produced by refluxing the mixture at a reflux temperature for 24 hours to 7 days.