CA1042179A - Production of zirconium carbonate - Google Patents
Production of zirconium carbonateInfo
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- CA1042179A CA1042179A CA222,315A CA222315A CA1042179A CA 1042179 A CA1042179 A CA 1042179A CA 222315 A CA222315 A CA 222315A CA 1042179 A CA1042179 A CA 1042179A
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- Prior art keywords
- carbonate
- zirconium
- solution
- basic
- salt
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Pure, reactive basic zirconium carbonate which is stable and soluble in organic acids for commercial usage in the manufacture of zirconium chemicals is produced by reaction of a soluble zirconium salt in acid solution in the presence of sulfate ion with an aqueous solution of an alkali metal or ammonium carbonate or bicarbonate; the reactive basic zirconium carbonate is produced in a single stage process via a polymeric zirconium sulphate intermediate; in particular the process avoids formation of the zirconium carbonate as a gelatinous mass which is difficult to filter.
Pure, reactive basic zirconium carbonate which is stable and soluble in organic acids for commercial usage in the manufacture of zirconium chemicals is produced by reaction of a soluble zirconium salt in acid solution in the presence of sulfate ion with an aqueous solution of an alkali metal or ammonium carbonate or bicarbonate; the reactive basic zirconium carbonate is produced in a single stage process via a polymeric zirconium sulphate intermediate; in particular the process avoids formation of the zirconium carbonate as a gelatinous mass which is difficult to filter.
Description
1~34'~17~3 The present invention relates to a process for manu-facturing basic zirconium carbonate from zirconium salts, especially such salts as produced on the decomposition of naturally occurring zirconium ores.
Basic zirconium carbonate is known to be prepared by different techniques relying upon the reaction of a solution of an ammonium or alkali metal carbonate with acid solutions of zirconyl chloride or solid basic zirconium sulfate. A known method for preparing basic zirconium carbonate consists of reacting an acid solution of zirconyl chloride with an aqueous solution of ammonium carbonate whereby a gelatinous precipitate of the basic carbonate is formed. This process, however, suffers from several disadvantages due to the nature of the precipitate and the final product. The precipitate is very difficult to filter and consequently difficult to free from soluble impurities.
Although useful for other purposes, these forms of zirconium carbonate are not suitable for use as intermediates for the pro-duction of zirconium chemicals as they have low zirconia contents.
Further, an essential property of basic zirconium carbonate for commercial usage is that it should be completely soluble on treatment with an organic acid. The products of the process, as described above, do not retain this property for long periods.
The production of basic zirconium carbonates from basic zirconium sulfate iq usually by processes which entail at least two stages, namely 1) precipitating the basic zirconium ~ulfate by reacting an aqueous soluble sulfate at an elevated temperature with a solution of a zirconium salt and 2) reacting the solid basic sulfate with an ammonlum carbonate solution to form the required basic carbonate. m e carbonates of this pro-CeSs are usually more stable and reactive than those of the for-mer process and have high zirconia contents.
Basic zirconium carbonate is known to be prepared by different techniques relying upon the reaction of a solution of an ammonium or alkali metal carbonate with acid solutions of zirconyl chloride or solid basic zirconium sulfate. A known method for preparing basic zirconium carbonate consists of reacting an acid solution of zirconyl chloride with an aqueous solution of ammonium carbonate whereby a gelatinous precipitate of the basic carbonate is formed. This process, however, suffers from several disadvantages due to the nature of the precipitate and the final product. The precipitate is very difficult to filter and consequently difficult to free from soluble impurities.
Although useful for other purposes, these forms of zirconium carbonate are not suitable for use as intermediates for the pro-duction of zirconium chemicals as they have low zirconia contents.
Further, an essential property of basic zirconium carbonate for commercial usage is that it should be completely soluble on treatment with an organic acid. The products of the process, as described above, do not retain this property for long periods.
The production of basic zirconium carbonates from basic zirconium sulfate iq usually by processes which entail at least two stages, namely 1) precipitating the basic zirconium ~ulfate by reacting an aqueous soluble sulfate at an elevated temperature with a solution of a zirconium salt and 2) reacting the solid basic sulfate with an ammonlum carbonate solution to form the required basic carbonate. m e carbonates of this pro-CeSs are usually more stable and reactive than those of the for-mer process and have high zirconia contents.
- 2 --.................... ~ . ~ . , .
- ~4'~179 When, for example, sodium carbonate solution is mixed with a solution of acid zirconium sulfate, a gelatinous pre-cipitate of zirconium carbonate is produced. This material is not suitable for commercial use as it is difficult to free from entrained impurities and its reactivity to an organic acid declines rapidly on storage and is lost on drying.
Accordingly, an object of the present invention is to provide a single stage process for the manufacture of basic zirconium carbonate from water-soluble zirconium salts to pro-duce an easily filterable, stable, reactive product having azirconia content high enough for the product to be employed as a useful intermediate in the manufacture of other zirconium chemicals.
The present process comprises reacting a water-soluble zirconium salt in acid solution in the presence of the sulfate . . .
ion with an aqueous solution of an alkali metal or ammonium carbonate or bicarbonate.
According to one embodiment of the present invention, an acidified zirconyl chloride solution, produced, for example, ~ -from the decomposition of zircon sand or baddeleyite, is mixed with an aqueous soluble sulfate solution. The solution mixture is then passed into a reactor at a measured rate of flow while a solution of an aqueous soluble carbonate or bicarbonate is introduced from another source. The flows are stirred counter-currently for a set period while basic zirconium carbonate pre-cipitates. The precipitate i9 then filtered or centrifuged and washed by conventional methods to give as the final product a paste of basic zirconium carbonate.
In another embodiment of the present invention, the starting material is acid zirconium sulfate, an intermediate formed in the upgrading of zirconium ores. An aqueous solution .. . . . .
1~4;~17~
of this material is fed into a reacting vessel while an aqueous solution of a soluble carbonate or bicarbonate is introduced from another source. This mixture is stirred countercurrently while basic zirconium carbonate precipitates. The precipitate is then filtered and washed to produce the final product.
In a further embodiment of the present invention, the flow rates of the incoming solutions are controlled in order that basic zirconium carbonate may be manufactured on a continu-ous basis by incorporating an overflow system into the reactor whereby the zirconium carbonate product is collected.
It has been proposed that basic zirconium carbonate is, in fact, a carbonated trioxodizirconium hydroxide. This is based on a covalent Zr203 unit in which an oxygen atom links two zirconyl groups, while a six-membered ring is formed by the two zirconium atoms being coordinately linked to a common carbon dioxide molecule as follows:
HO-ozr-o-zro-oH
o = C = o The material is not composed of carbonate ions and zirconyl ions possessing electrovalent stability, but it is thought that it i8 stable only when a carbon dioxide molecule is linked at both ends to a Zr203 unit.
The structures of the basic sulfate and other zir-conium salts in solution differ in a fundamental way, that allows the former to be converted quantitatively to the stable carbonate by stirring with a carbonate solution while the latter are con-verted to a mixture of stable carbonate and weakly carbonated basic structures. This is because the basic sulfate already possesses the OZr-O-ZrO units found in the carbonate. ;~
It has now been found that a transient intermediate, probably similar in structure to the basic zirconium sulfate , ' - ' " ' ' ' ' ~ ~'' ' " '~'. ' .
1¢~4'~179 (possessing OZr-O-zro units), can be prepared in situ in a reactor which can then react with carbonate ions in solution to form the stable forms of basic zirconium carbonate. The forma-tion of the polymeric species is induced by monitoring the rates of entry of the carbonate and zirconium solutions into the reactor and the technique of mixing the solutions in the reactor.
On slowly raising the pH of an acidified sulfate sol-ution of zirconium, the polymeric species of zirconium sulfate are formed as a precipitate. These transient intermediates will -react with carbonate ions in solution to precipitate basic zirconium carbonate.
The invention will now be described with reference to the accompanying drawings, in which:-FIGURE 1 is a schematic illustration of a reactionvessel, and FIGURE 2 is another schematic illustration of a continuous reactor.
In the process of the present invention, an~alkali metal or ammonium carbonate or bicarbonate is used both to raise the pH of the solution and to provide the carbonate ions for subsequent formation of basic zirconium carbonate. However, it is essential that the inflowing zirconium solution is not diluted by a solution rich in carbonate ions or the gelatinous form of zirconium carbonate will precipitate. As shown in Fig. 1, the positions of inlets for zirconium and carbonate sol-utions are arranged in order that the pH of the zirconium sol-ution is raised slowly for the transient intermediate to form.
The stirring action in the reactor i8 therefore necessarily countercurrent.
To ensure sufficient dilution of the zirconium solution ~ S~
... , . . .. . . . , .-. . . . ~ . ~ ;: . ;
~, : - . :
.
1C~4~17~3 be~ore carbonate formation, it is advantageous to incorporate a suitable screen into the reactor to separate the two solutions.
However, if the rates of the incoming solutions are carefully controlled, this design feature will not always be necessary.
Variables to be considered in the production of sub-stantially pure, reactive basic zirconium carbonate according -to the process of the present invention include:
1. Reagent ratio 2. Solution strength
- ~4'~179 When, for example, sodium carbonate solution is mixed with a solution of acid zirconium sulfate, a gelatinous pre-cipitate of zirconium carbonate is produced. This material is not suitable for commercial use as it is difficult to free from entrained impurities and its reactivity to an organic acid declines rapidly on storage and is lost on drying.
Accordingly, an object of the present invention is to provide a single stage process for the manufacture of basic zirconium carbonate from water-soluble zirconium salts to pro-duce an easily filterable, stable, reactive product having azirconia content high enough for the product to be employed as a useful intermediate in the manufacture of other zirconium chemicals.
The present process comprises reacting a water-soluble zirconium salt in acid solution in the presence of the sulfate . . .
ion with an aqueous solution of an alkali metal or ammonium carbonate or bicarbonate.
According to one embodiment of the present invention, an acidified zirconyl chloride solution, produced, for example, ~ -from the decomposition of zircon sand or baddeleyite, is mixed with an aqueous soluble sulfate solution. The solution mixture is then passed into a reactor at a measured rate of flow while a solution of an aqueous soluble carbonate or bicarbonate is introduced from another source. The flows are stirred counter-currently for a set period while basic zirconium carbonate pre-cipitates. The precipitate i9 then filtered or centrifuged and washed by conventional methods to give as the final product a paste of basic zirconium carbonate.
In another embodiment of the present invention, the starting material is acid zirconium sulfate, an intermediate formed in the upgrading of zirconium ores. An aqueous solution .. . . . .
1~4;~17~
of this material is fed into a reacting vessel while an aqueous solution of a soluble carbonate or bicarbonate is introduced from another source. This mixture is stirred countercurrently while basic zirconium carbonate precipitates. The precipitate is then filtered and washed to produce the final product.
In a further embodiment of the present invention, the flow rates of the incoming solutions are controlled in order that basic zirconium carbonate may be manufactured on a continu-ous basis by incorporating an overflow system into the reactor whereby the zirconium carbonate product is collected.
It has been proposed that basic zirconium carbonate is, in fact, a carbonated trioxodizirconium hydroxide. This is based on a covalent Zr203 unit in which an oxygen atom links two zirconyl groups, while a six-membered ring is formed by the two zirconium atoms being coordinately linked to a common carbon dioxide molecule as follows:
HO-ozr-o-zro-oH
o = C = o The material is not composed of carbonate ions and zirconyl ions possessing electrovalent stability, but it is thought that it i8 stable only when a carbon dioxide molecule is linked at both ends to a Zr203 unit.
The structures of the basic sulfate and other zir-conium salts in solution differ in a fundamental way, that allows the former to be converted quantitatively to the stable carbonate by stirring with a carbonate solution while the latter are con-verted to a mixture of stable carbonate and weakly carbonated basic structures. This is because the basic sulfate already possesses the OZr-O-ZrO units found in the carbonate. ;~
It has now been found that a transient intermediate, probably similar in structure to the basic zirconium sulfate , ' - ' " ' ' ' ' ~ ~'' ' " '~'. ' .
1¢~4'~179 (possessing OZr-O-zro units), can be prepared in situ in a reactor which can then react with carbonate ions in solution to form the stable forms of basic zirconium carbonate. The forma-tion of the polymeric species is induced by monitoring the rates of entry of the carbonate and zirconium solutions into the reactor and the technique of mixing the solutions in the reactor.
On slowly raising the pH of an acidified sulfate sol-ution of zirconium, the polymeric species of zirconium sulfate are formed as a precipitate. These transient intermediates will -react with carbonate ions in solution to precipitate basic zirconium carbonate.
The invention will now be described with reference to the accompanying drawings, in which:-FIGURE 1 is a schematic illustration of a reactionvessel, and FIGURE 2 is another schematic illustration of a continuous reactor.
In the process of the present invention, an~alkali metal or ammonium carbonate or bicarbonate is used both to raise the pH of the solution and to provide the carbonate ions for subsequent formation of basic zirconium carbonate. However, it is essential that the inflowing zirconium solution is not diluted by a solution rich in carbonate ions or the gelatinous form of zirconium carbonate will precipitate. As shown in Fig. 1, the positions of inlets for zirconium and carbonate sol-utions are arranged in order that the pH of the zirconium sol-ution is raised slowly for the transient intermediate to form.
The stirring action in the reactor i8 therefore necessarily countercurrent.
To ensure sufficient dilution of the zirconium solution ~ S~
... , . . .. . . . , .-. . . . ~ . ~ ;: . ;
~, : - . :
.
1C~4~17~3 be~ore carbonate formation, it is advantageous to incorporate a suitable screen into the reactor to separate the two solutions.
However, if the rates of the incoming solutions are carefully controlled, this design feature will not always be necessary.
Variables to be considered in the production of sub-stantially pure, reactive basic zirconium carbonate according -to the process of the present invention include:
1. Reagent ratio 2. Solution strength
3. Residence time in reactor
4. Reaction temperature
5. Alkaline reagent employed The reagent ratio is defined as the quantity of alkaline reagent used, expressed as a percentage of the theoretical required to react with the sulfate groups of the inflowing zirconium sulfate solution. When acid zirconium sulfate is the starting solution, this will be according to the following equation. -2[H2ZrO(S04)2 3H20] + 4M2C03 2 3 (OH)2 CO2 7H20 + 4M2So4 + 3C2 The symbol M representing an alkali metal or ammonium ion.
Levels between 85% and ll~/o of the theoretical value have been found to be satisfactory for producing substantially pure basic zirconium carbonate. ~he preferred levels are between 95% and 105%. At levels between 60~o and 75% of the theoretical carbonate requirement, the intermediate polymeric sulfate material precipitates with minimal further reaction to produce the basic carbonate.
This polymeric material is easy to filter and wash free from impurities and on calcining forms high purity zirconia.
The Zr:SO4 ratio of the polymeric intermediate decreases from 2:1 to 5:3 on decreasing the ratio of percentage carbonate input.
Levels between 85% and ll~/o of the theoretical value have been found to be satisfactory for producing substantially pure basic zirconium carbonate. ~he preferred levels are between 95% and 105%. At levels between 60~o and 75% of the theoretical carbonate requirement, the intermediate polymeric sulfate material precipitates with minimal further reaction to produce the basic carbonate.
This polymeric material is easy to filter and wash free from impurities and on calcining forms high purity zirconia.
The Zr:SO4 ratio of the polymeric intermediate decreases from 2:1 to 5:3 on decreasing the ratio of percentage carbonate input.
- 6 -- ~., .. .. . . ::
- - . - - , . . .
~, :. - . . , . :- : - , . .. . . .
, .
1¢~4'~17~
The flow rates of the respective solutions into the reactor are usually equal, the adjustments of the reagent ratio being made externally.
The strengths of the feed solutions are dependent as an upper limit on the solubility of the salts in solution after carbonate formation to avoid possible coprecipitation. However, in practice, more dilute solutions are used to ensure complete conversion of the incoming zirconium solution to the polymeric intermediate before reaction with the carbonate ions.
The residence time is defined as the average time spent by the reactants in the reaction vessel for the production of basic zirconium carbonate. The reaction of the inflowing zirconium salt to form the transient sulfate intermediate and subsequently the carbonating reaction both proceed rapidly and it has been found that residence times as low as ten minutes can be employed. The preferred residence times of the reactants using the process of the invention are between about 30 minutes and 2 hours.
Using the present process, basic zirconium carbonate can be manufactured at temperatures up to approaching the boiling points of the solutions. However, it is preferred to manufacture the materials at ambient temperature.
As stated in the foregoing, any aqueous soluble car-bonate or bicarbonate is suitable as an alkaline reagent. Sodium carbonate is usually selected on economic grounds the exception being when sodium contamination of the product is undesirable.
Other suitable reagents include potassium carbonate, ammonium carbonate and the corresponding bicarbonates.
The invention can be further illustrated by the following examples.
- - . - - , . . .
~, :. - . . , . :- : - , . .. . . .
, .
1¢~4'~17~
The flow rates of the respective solutions into the reactor are usually equal, the adjustments of the reagent ratio being made externally.
The strengths of the feed solutions are dependent as an upper limit on the solubility of the salts in solution after carbonate formation to avoid possible coprecipitation. However, in practice, more dilute solutions are used to ensure complete conversion of the incoming zirconium solution to the polymeric intermediate before reaction with the carbonate ions.
The residence time is defined as the average time spent by the reactants in the reaction vessel for the production of basic zirconium carbonate. The reaction of the inflowing zirconium salt to form the transient sulfate intermediate and subsequently the carbonating reaction both proceed rapidly and it has been found that residence times as low as ten minutes can be employed. The preferred residence times of the reactants using the process of the invention are between about 30 minutes and 2 hours.
Using the present process, basic zirconium carbonate can be manufactured at temperatures up to approaching the boiling points of the solutions. However, it is preferred to manufacture the materials at ambient temperature.
As stated in the foregoing, any aqueous soluble car-bonate or bicarbonate is suitable as an alkaline reagent. Sodium carbonate is usually selected on economic grounds the exception being when sodium contamination of the product is undesirable.
Other suitable reagents include potassium carbonate, ammonium carbonate and the corresponding bicarbonates.
The invention can be further illustrated by the following examples.
- 7 -, , , . :, . :
- . . .
'- ~ - :' - - :' ~, : . - . : ~- .
- -1'1~4'~179 EXAMPLE I
A 300 ml. reaction vessel as shown in Fig. 1 was charged with 100 ml. of water. A solution of acid zirconium sulfate was prepared containing 15 per cent ZrO2 W/V. Sodium carbonate solution containing a reagent ratio equivalent to 101 per cent of the theoretical value was prepared in a separate vessel. The two solutions were pumped into the reaction vessel at ambient temperature at a rate of 150 ml. per hour using a positive displacement metering pump. The solutions were stirred at a rate of approximately 500 rpm until the reaction vessel was full. The resultant product was vacuum filtered and washed with water.
The paste product contained 34.5% ZrO2, 0.5% SO4, -0.2% Na and 5.3% CO2.
The procedures employed were similar to that of Example 1 with the variations indicated in the following table.
Prod uct A~ ~alvsis Example zrO2 inPUt Residence Reagent ZrO SO Na CO2 _ solution time (hr) Ratio % 2 %4 % %
2 5 1 105 34.2 0.3 0.5 6.5 3 15 - 1/2 100 36.1 0.7 0.1 6.4 `
4 10 2 96 34.0 1.0 ~0.1 6.0 6 10 2 70 Z6.0 12.2 <0.1 5.8 ~. .
All of the products in Examples 1 - 6 were obtained in a paste form. The products may be further dried by air dry-ing or washing with a solvent mixture and air drying without loss of reactivity to organic acids.
A 300 ml. continuous reactor as shown in Fig. 2 was charged with 100 ml. of water. A solution of acid zirconium
- . . .
'- ~ - :' - - :' ~, : . - . : ~- .
- -1'1~4'~179 EXAMPLE I
A 300 ml. reaction vessel as shown in Fig. 1 was charged with 100 ml. of water. A solution of acid zirconium sulfate was prepared containing 15 per cent ZrO2 W/V. Sodium carbonate solution containing a reagent ratio equivalent to 101 per cent of the theoretical value was prepared in a separate vessel. The two solutions were pumped into the reaction vessel at ambient temperature at a rate of 150 ml. per hour using a positive displacement metering pump. The solutions were stirred at a rate of approximately 500 rpm until the reaction vessel was full. The resultant product was vacuum filtered and washed with water.
The paste product contained 34.5% ZrO2, 0.5% SO4, -0.2% Na and 5.3% CO2.
The procedures employed were similar to that of Example 1 with the variations indicated in the following table.
Prod uct A~ ~alvsis Example zrO2 inPUt Residence Reagent ZrO SO Na CO2 _ solution time (hr) Ratio % 2 %4 % %
2 5 1 105 34.2 0.3 0.5 6.5 3 15 - 1/2 100 36.1 0.7 0.1 6.4 `
4 10 2 96 34.0 1.0 ~0.1 6.0 6 10 2 70 Z6.0 12.2 <0.1 5.8 ~. .
All of the products in Examples 1 - 6 were obtained in a paste form. The products may be further dried by air dry-ing or washing with a solvent mixture and air drying without loss of reactivity to organic acids.
A 300 ml. continuous reactor as shown in Fig. 2 was charged with 100 ml. of water. A solution of acid zirconium
- 8 -- . - - . . . .
lU4'~179 sulfate was prepared containing 5 per cent ZrO2. Sodium car-bonate solution containing a reagent ratio equivalent to 104 per cent of the theoretical value was prepared in a separate vessel. The two solutions were pumped continuously into the reaction vessel at a rate of 150 ml. per hour. The solutions were stirred at a rate of approximately 500 rpm continuously.
The basic zirconium carbonate, in the form of a slurry, continuously overflowed from the product overflow outlet from which it is pumped or gravity fed to filters or a centrifuge to obtain the final paste product.
After filtration, the product showed an average analysis of 34.8% ZrO2; 0.5% S04; 0.2% Na and 5.8% C02.
Sodium sulfate solution was added to an acid solution of zirconyl chloride to give a ZrO2:S04 ratio of 4:3. The pro-cedure as described in Example 7, was employed to produce a product of basic zirconium carbonate.
The undesirable impurities, iron and heavy metals, usually found in zirconyl chloride solutions after the decompo-sition of zirconium ores, can be complexed before the productionof zirconium carbonate so that they will pass into the effluent.
Various changes and modifications of the invention can be made, and, to the extent that such variations incorporate the spirit of this invention, they are intended to be included within the scope of the appended claims.
: . .
.
.- , ....
' ~, . . .
,
lU4'~179 sulfate was prepared containing 5 per cent ZrO2. Sodium car-bonate solution containing a reagent ratio equivalent to 104 per cent of the theoretical value was prepared in a separate vessel. The two solutions were pumped continuously into the reaction vessel at a rate of 150 ml. per hour. The solutions were stirred at a rate of approximately 500 rpm continuously.
The basic zirconium carbonate, in the form of a slurry, continuously overflowed from the product overflow outlet from which it is pumped or gravity fed to filters or a centrifuge to obtain the final paste product.
After filtration, the product showed an average analysis of 34.8% ZrO2; 0.5% S04; 0.2% Na and 5.8% C02.
Sodium sulfate solution was added to an acid solution of zirconyl chloride to give a ZrO2:S04 ratio of 4:3. The pro-cedure as described in Example 7, was employed to produce a product of basic zirconium carbonate.
The undesirable impurities, iron and heavy metals, usually found in zirconyl chloride solutions after the decompo-sition of zirconium ores, can be complexed before the productionof zirconium carbonate so that they will pass into the effluent.
Various changes and modifications of the invention can be made, and, to the extent that such variations incorporate the spirit of this invention, they are intended to be included within the scope of the appended claims.
: . .
.
.- , ....
' ~, . . .
,
Claims (10)
1. A process for producing reactive basic zirconium carbonate comprising (a) providing an aqueous acidified solution of a zirconium salt containing sufficient sulphate ion to form an intermediate polymeric zirconium sulphate upon the addition of an alkaline carbonate, (b) admixing the said aqueous solution of zirconium salt with an aqueous solution of an alkaline carbonate selected from the group consisting of alkali metal carbonate, ammonium carbonate, alkali metal bicarbonate and ammonium bi-carbonate, in an amount sufficient to provide between 85% and 110% of the theoretical amount of carbonate ion required to produce basic zirconium carbonate upon reaction with the zirconium salt, said admixing step being conducted under conditions such that the pH of the reaction mixture thus formed is slowly raised to form the intermediate polymeric zirconium sulphate before zirconium carbonate is precipitated, and the zirconium salt solution is not diluted by a solution rich in carbonate ions, (c) maintaining the reaction mixture for a time effective for the precipitation of the basic zirconium carbonate: and (d) separating the precipitated basic zirconium carbonate and washing the precipitate to yield the reactive form of basic zirconium carbonate.
2. The process according to claim 1, wherein said alkaline carbonate is sodium carbonate.
3. The process according to claim 1, in which said solution of zirconium salt is diluted prior to contact with said alkaline carbonate.
4. The process of claim 1, 2 or 3, in which said zirconium salt is zirconium chloride.
5. The process of claim 1, 2 or 3, in which said zirconium salt is zirconium sulfate.
6. The process according to claim 1, 2 or 3, in which about 95 to 105% of the theoretical quantity of said alkaline carbonate required to react with the sulfate ions is employed.
7. The process according to claim 1, 2 or 3, in which the reaction mixture in (c) is maintained for a residence time of from about 0.5 to 2 hours.
8. The process according to claim 1, 2 or 3, in which said reaction takes place at ambient temperature.
9. The process according to claim 1, 2 or 3, in which a dilute aqueous solution of acid zirconium sulfate and an aqueous solution of sodium carbonate are separately added under conditions of countercurrent stirring to a mixing vessel at ambient temperature.
10. A process for producing reactive basic zirconium carbonate, comprising:
(a) providing an aqueous acidified solution of a zirconium salt containing sufficient sulphate ion to form a polymeric zirconium sulphate intermediate upon the addition of an alkaline carbonate, (b) admixing the said aqueous solution of zirconium salt with a dilute aqueous solution of an alkaline carbonate selected from the group consisting of alkali metal carbonate, ammonium carbonate, alkali metal bicarbonate and ammonium bi-carbonate, in an amount sufficient to provide between 85% and 110% of the theoretical amount of carbonate ion required to produce basic zirconium carbonate upon reaction with the zirconium salt, said admixing step being conducted under conditions of countercurrent stirring such that the pH of the reaction mixture thus formed is slowly raised, to form the polymeric zirconium sulphate intermediate before zirconium carbonate is precipitated, and the zirconium salt solution is not diluted by a solution rich in carbonate ions;
(c) stirring reaction mixture for a period of at least 10 minutes to precipitate the basic zirconium carbonate; and (d) separating the precipitated basic zirconium carbonate and washing the precipitate to yield a reactive form of basic zirconium carbonate as the final product.
(a) providing an aqueous acidified solution of a zirconium salt containing sufficient sulphate ion to form a polymeric zirconium sulphate intermediate upon the addition of an alkaline carbonate, (b) admixing the said aqueous solution of zirconium salt with a dilute aqueous solution of an alkaline carbonate selected from the group consisting of alkali metal carbonate, ammonium carbonate, alkali metal bicarbonate and ammonium bi-carbonate, in an amount sufficient to provide between 85% and 110% of the theoretical amount of carbonate ion required to produce basic zirconium carbonate upon reaction with the zirconium salt, said admixing step being conducted under conditions of countercurrent stirring such that the pH of the reaction mixture thus formed is slowly raised, to form the polymeric zirconium sulphate intermediate before zirconium carbonate is precipitated, and the zirconium salt solution is not diluted by a solution rich in carbonate ions;
(c) stirring reaction mixture for a period of at least 10 minutes to precipitate the basic zirconium carbonate; and (d) separating the precipitated basic zirconium carbonate and washing the precipitate to yield a reactive form of basic zirconium carbonate as the final product.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB11840/74A GB1495267A (en) | 1974-03-18 | 1974-03-18 | Process for the production of basic zirconium carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1042179A true CA1042179A (en) | 1978-11-14 |
Family
ID=9993663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA222,315A Expired CA1042179A (en) | 1974-03-18 | 1975-03-17 | Production of zirconium carbonate |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS50127897A (en) |
| CA (1) | CA1042179A (en) |
| DE (1) | DE2510743A1 (en) |
| FR (1) | FR2264780B1 (en) |
| GB (1) | GB1495267A (en) |
| ZA (1) | ZA751656B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54155199A (en) * | 1978-03-20 | 1979-12-06 | Organon Teknika Bv | Sodium zirconium carbonate compound and its manufacture |
| US4256718A (en) * | 1978-03-20 | 1981-03-17 | Organon Teknika Corporation | Sodium zirconium carbonate compound and the method of its preparation |
| US4360507A (en) * | 1979-01-24 | 1982-11-23 | Organon Teknika Corporation | Sodium zirconium carbonate compound and the method of its preparation |
| DE3143921C2 (en) * | 1981-11-05 | 1984-06-28 | Dynamit Nobel Ag, 5210 Troisdorf | Process for the production of basic zirconium carbonate |
| NZ215774A (en) * | 1985-05-02 | 1988-08-30 | Ici Australia Ltd | Purification of zirconium compounds |
| KR880701275A (en) * | 1986-06-17 | 1988-07-26 | 알프레드 펄내트 | Hydrolyzed Zirconium-Containing Substances, Zirconium Oxides and Their Preparation Methods |
| US6627164B1 (en) * | 2000-11-28 | 2003-09-30 | Renal Solutions, Inc. | Sodium zirconium carbonate and zirconium basic carbonate and methods of making the same |
| CN115340126B (en) * | 2022-09-15 | 2024-04-12 | 包头稀土研究院 | Rare earth zirconate particles and preparation method thereof |
-
1974
- 1974-03-18 GB GB11840/74A patent/GB1495267A/en not_active Expired
-
1975
- 1975-03-12 DE DE19752510743 patent/DE2510743A1/en not_active Withdrawn
- 1975-03-17 FR FR7508229A patent/FR2264780B1/fr not_active Expired
- 1975-03-17 CA CA222,315A patent/CA1042179A/en not_active Expired
- 1975-03-18 ZA ZA00751656A patent/ZA751656B/en unknown
- 1975-03-18 JP JP50031916A patent/JPS50127897A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FR2264780B1 (en) | 1981-01-16 |
| DE2510743A1 (en) | 1975-09-25 |
| GB1495267A (en) | 1977-12-14 |
| JPS50127897A (en) | 1975-10-08 |
| ZA751656B (en) | 1976-03-31 |
| FR2264780A1 (en) | 1975-10-17 |
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