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Zirconium hydroxide. RU patent 2434810.

IPC classes for russian patent Zirconium hydroxide. RU patent 2434810. (RU 2434810):

C01G25/02 - Oxides

B01J21/06 - Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof

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Catalyst contains porous carrier, buffer layer, interphase layer, and catalytically active layer on the surface wherein carrier has average pore size from 1 to 1000 μm and is selected from foam, felt, and combination thereof. Buffer layer is located between carrier and interphase layer and the latter between catalytically active layer and buffer layer. Catalyst preparation process comprises precipitation of buffer layer from vapor phase onto porous carrier and precipitation of interphase layer onto buffer layer. Catalytic processes involving the catalyst and relevant apparatus are also described.

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry and can be used in catalytic processes. Amorphous zirconium hydroxide has surface area of at least 300 m²/g, total pore volume of at least 0.70 cm³/g and average pore size from 5 nm to 15 nm. First, an aqueous solution containing sulphate anions and a zirconium salt with the ratio ZrC₂:SO₃ ranging from 1:0.40 to 1:0.52 are obtained. The solution is then cooled to temperature lower than 25°C. Alkali is then added to precipitate amorphous zirconium hydroxide which is then filtered and washed with water or alkali to remove residual sulphate and chloride. The washed residue undergoes thermal treatment at excess pressure of not less than 3 bars and dried.

EFFECT: obtained zirconium hydroxide is characterised by large surface area, large pore volume and wide pore size distribution.

26 cl, 2 tbl, 2 dwg

The present invention presents an improved amorphous zirconium hydroxide and a method thereof. The zirconium hydroxide may be alloyed or unalloyed. The term "zirconium hydroxide is used in this application is to combine different terms, known qualified and applied for this type of compounds, such as water, zirconium oxide and hydrated zirconium dioxide. The zirconium hydroxide in the present invention is particularly well suited for carrying out catalytic processes.

In international application no PCT/GB 2004/001840, international publication no WO 2004/096713 A1, disclosed a method of producing oxides of zirconium and mixed oxides of zirconium. The method involves the precipitation of zirconium hydroxide from an aqueous solution of zirconium salt in the reaction with the alkali in the presence of a controlled amount of sulfate anions at a temperature not exceeding 50°C. the Hydroxide is then calcined education practically free of sulfate of zirconium oxide.

In the published patent applications Japan No. 11-292538 and No. 2000-247641 describes the production of zirconium hydroxide from alkaline zirconium sulfate by adding a base to the suspension of sulfate. At the same time, the processes described in these patents do not generate hydroxide, circa the Oia, with increased porosity, pore size and surface area characteristic of zirconium hydroxide in the present invention.

It has been unexpectedly discovered that by modifying the reaction conditions used to obtain the precursors of zirconium hydroxide in the above international patent application can be obtained zirconium hydroxide with improved properties. In particular, the zirconium hydroxide in the present invention is amorphous and has a higher surface area (typically 380-420 m²/g), a large total pore volume (usually 0,78-1,18 cm³/g) and a wide distribution of pore size.

When firing such valuable characteristics of this material, as the total pore volume and the pore size is not reduced to the extent that is typical of previously produced varieties of zirconium hydroxide. After calcination at 450°C for 2 hours total pore volume is generally 0,42-0,61 cm³/g with an average pore size 15-22 nm, and after annealing at 650°C for 2 hours total pore volume is generally 0,26-0,42 cm³/g with an average pore size of the order 25-34 nm.

In addition, the distribution of particle size such that from this material it is possible to form extrudates.

The method of obtaining material, performance is undertaken in the present invention, includes obtaining an aqueous solution containing sulfate anions and salt of zirconium. Preferably, the sulfate anions were added in the form of sulfuric acid. The ratio of ZrO₂:SO₃should be 1:0,40-1:0,52, preferably 1:0,45. Salt of zirconium in the preferred embodiment, is oxalicacid.

This solution is cooled to a temperature below 25°C and add alkali to precipitate amorphous zirconium hydroxide. Preferably, the temperature of the solution did not exceed 10°C, more preferably, the temperature was less than 2°C and most preferably -2°C. In a preferred embodiment, the alkali is cooled in a refrigerator to a temperature below 25°C, and the preferred alkali is sodium hydroxide.

In the preferred embodiment, the method 10% sodium hydroxide added during 2 hours until, until the pH reaches a value of not less than 6, and then add warmed to room temperature 28% sodium hydroxide until then, until the pH reaches a value of not less than 11. Preferably, 10% sodium hydroxide was added over 2 hours until, until the pH reaches a value of 8. Preferably 28% sodium hydroxide was added until, until the pH reaches a value of 13.

After that saiden the th of zirconium hydroxide is filtered and washed with water or alkali, to remove the remnants of sulfates and chlorides. Then the wet residue is preferably resuspended in the water and bring the pH to a value of from 4 to 9 nitric acid, preferably 30% nitric acid, and the suspension is filtered and washed with water or acid to remove residual sodium. Most preferably, the washing and re-suspension held deionized water. In addition, in the preferred embodiment of the method, the pH is brought to 8.

The obtained wet residue is treated under hydrothermal pressure less than 3 bar I.D. and dried. The resulting zirconium hydroxide contains almost no impurities of sodium, chloride and sulfate. The preferred conditions of the hydrothermal treatment is 1 bar I.D. for 5 hours.

This method optionally includes the step of grinding after step hydrothermal treatment, which is carried out, for example, so that the product has dimensions suitable for extrusion. The grinding may be performed either prior to drying of the product or after it.

After drying, the amorphous zirconium hydroxide in the present invention, can be ignited. The preferred conditions of annealing temperature from 450°C to 900°C for a period of from 1 to 24 hours, more preferably at a temperature from 450°C to 750°C.

The method presented in n is stationary invention, allows obtaining amorphous zirconium hydroxide having a surface area of at least 300 m²/g, total pore volume, at least 0,70 cm³/g and an average pore size of from 5 nm to 15 nm.

Moreover, can be synthesized such amorphous hydroxides, which have a surface area of at least 80 m²/g, total pore volume, at least 0,35 cm³/g and an average pore size of from 10 nm to 30 nm after calcination at 450°C for 2 hours.

Furthermore, the method presented in this invention, allows to obtain amorphous hydroxides of zirconium, which, after annealing at 650°C for 2 hours and have a surface area of at least 30 m²/g, total pore volume of at least 0.20 cm³/g and an average pore size in the range from 20 nm to 40 nm.

You can also receive amorphous hydroxides of zirconium, which, after annealing at 700°C for 2 hours and have a surface area of at least 20 m²/g, total pore volume of at least 0.15 cm³/g and an average pore size in the range from 25 nm to 60 nm.

The zirconium hydroxide in the present invention, may be alloyed oxide, alkaline earth metal, oxide of rare earth metal oxide of the transition metal of the first series, silicon dioxide, aluminum oxide, tin oxide is whether the lead oxide or a mixture of these compounds. Preferred alloying additive is silicon dioxide, preferably in quantities of from 0.1 wt.% up to 10 wt.%.

Hereinafter the present invention will be illustrated using the following examples.

Example 1 (JH 15/04) Comparative

85,41 g of 98 wt.% an aqueous solution of sulfuric acid, 277,04 g deionized water and 970,87 g oxalicacid zirconium (20,6% wt. ZiO₂) were mixed and cooled to 10°C. thus was obtained a solution with a ratio of ZrO₂:SO₃at the level of 0.53. 10 wt.% aqueous sodium hydroxide solution, which was cooled in the refrigerator, add drops until, until the pH reached a value of 8. Brought to room temperature 28 wt.% an aqueous solution of sodium hydroxide was then added until, until the pH reached a value of 13.

The obtained precipitated zirconium hydroxide was then filtered and washed with deionized water to remove residual sulfate and chloride ions. Then wet the rest resuspendable in deionized water and brought the pH to 8 by the addition of 30 wt.% an aqueous solution of nitric acid. Thus obtained suspension was filtered and washed with deionised water to remove residual sodium. Then wet the residue was treated hydrothermally at 1 bar I.D. for 5 hours and then dried.

Example 2 (JH 13/04 was investigated) Comparative

G 98 wt.% an aqueous solution of sulfuric acid, 277.04 g deionized water and 970.87 g oxalicacid zirconium (20.6 wt.% ZrO₂) were mixed and cooled to 2°C. thus was obtained a solution with a ratio of ZrO₂:SO₃at the level of 0.53. 10 wt.% aqueous sodium hydroxide solution, which was cooled in the refrigerator, add drops until, until the pH reached a value of 8. Brought to room temperature 28 wt.%) an aqueous solution of sodium hydroxide was then added until, until the pH reached a value of 13.

The resulting precipitated zirconium hydroxide was filtered and washed with deionized water to remove residual sulfate and chloride ions. Then wet the rest resuspendable in deionized water and brought the pH to 8 by the addition of 30 wt.% an aqueous solution of nitric acid. Thus obtained suspension was filtered and washed with deionised water to remove residual sodium. Then wet the residue was treated hydrothermally at 1 bar I.D. for 5 hours and then dried.

Example 3 (JH 11/04)

80,58 g of 98 wt.% an aqueous solution of sulfuric acid, 281,88 g deionized water and 970,87 g oxalicacid zirconium (20,6% wt. ZrO₂) were mixed and cooled to 2°C. thus was obtained a solution with a ratio of ZrO₂:SO₃at the level of 0.50. 10 wt.% aqueous sodium hydroxide solution, which was cooled in the refrigerator, EXT is ulali drops until until the pH reached a value of 8. Brought to room temperature 28 wt.% an aqueous solution of sodium hydroxide was then added until, until the pH reached a value of 13.

Then wet the residue was treated hydrothermally at 1 bar I.D. for 5 hours and then dried.

Example 4 (JH 17/04)

75,75 g of 98 wt.% an aqueous solution of sulfuric acid, 231,95 g deionized water and 1025,64 g oxalicacid zirconium (19,5% wt. ZrO₂) were mixed and cooled to 2°C. thus was obtained a solution with a ratio of ZrO₂:SO₃at the level of 0.47. 10 wt.% aqueous sodium hydroxide solution, which was cooled in the refrigerator, add drops until, until the solution reached pH 8. Brought to room temperature 28 wt.% an aqueous solution of sodium hydroxide was then added until, until the pH reached a value of pH 13.

The resulting precipitated zirconium hydroxide was filtered promyvali deionized water to remove residual sulfate and chloride ions. Then wet the rest resuspendable in deionized water and brought the pH to 8 by the addition of 30 wt.% an aqueous solution of nitric acid. Thus obtained suspension was filtered and washed with deionised water to remove residual sodium. Then wet the residue was treated hydrothermally at 1 bar I.D. for 5 hours and then dried.

Example 5 (JH 18/04)

80,58 g of 98 wt.% an aqueous solution of sulfuric acid / 227,11 g deionized water and 1025,64 g oxalicacid zirconium (19,5% wt. ZrO₂) were mixed and cooled to 6°C. thus was obtained a solution with a ratio of ZrO₂:SO₃at the level of 0.50. 10 wt.% aqueous sodium hydroxide solution, which was cooled in the refrigerator, add drops until, until the pH reached a value of 8. Brought to room temperature 28 wt.% an aqueous solution of sodium hydroxide was then added until, until the pH reached a value of 13.

Received after this precipitated zirconium hydroxide was filtered and washed with deionized water to remove residual sulfate and chloride ions. Then wet the rest resuspendable in deionized water and brought the pH to 8 by the addition of 30 wt.% an aqueous solution of nitric acid. Received after this suspension was filtered and washed with deionised water to remove residual sodium. Then wet the residue was treated hydrothermally at 1 bar I.D. for 5 hours and then dried.

Example 6 (JH 23/04)

72,52 g of 98 wt.% an aqueous solution of sulfuric acid, 245,58 g deionized water and 1015,23 g oxalicacid zirconium (19,7% wt. ZrO₂) were mixed and cooled to -2°C. thus was obtained a solution with a ratio of ZrO₂:SO₃at the level of 0.45. 10 wt.% aqueous sodium hydroxide solution, which was cooled in the refrigerator, add drops until, until the pH reached a value of 8. Brought to room temperature 28 wt.% an aqueous solution of sodium hydroxide was then added until, until the pH reached a value of 13.

Example 7 (JH 46/04)

67,69 g of 98 wt.% an aqueous solution of sulfuric acid, 250,42 g deionized water and 1015,23 g oxalicacid zirconium (19,7% wt. ZrO₂) were mixed and cooled to -2°C. thus was obtained a solution with a ratio of ZrO_{2 :SO₃at the level of 0.42. 10 wt.% aqueous sodium hydroxide solution, which was cooled in the refrigerator, add drops until, until the pH reached a value of 8. Brought to room temperature 28 wt.% an aqueous solution of sodium hydroxide was then added until, until the pH reached a value of pH 13.}

Example 8 (JH 47/04)

64,46 g of 98 wt.% an aqueous solution of sulfuric acid, 253,64 g deionized water and 1015,23 g oxalicacid zirconium (19,7% wt. ZrO₂) were mixed and cooled to -2°C.

It was a solution with a ratio of ZrO₂:SO₃at the level of 0.40. 10 wt.% aqueous sodium hydroxide solution, which was cooled in the refrigerator, add drops until, until the pH reached a value of 8. Brought to room temperature 28 wt.% an aqueous solution of sodium hydroxide to relax the do then as long until the solution pH reached a value of 13.

Example 9 (PH 02/41) Comparative

102,56 g 77 wt.% an aqueous solution of sulfuric acid, 259,90 g deionized water and 970,87 g oxalicacid zirconium (20,6% wt. ZrO₂) were mixed and cooled to 1.5°C. thus was obtained a solution with a ratio of ZrO₂:SO₃at the level of 0.50. 10 wt.% aqueous sodium hydroxide solution, which was cooled in the refrigerator, added drops up until the pH of the solution reached a value of 8. Brought to room temperature 28 wt.% an aqueous solution of sodium hydroxide was then added to until the solution pH reached a value of 13.

The resulting precipitated zirconium hydroxide was filtered and washed with deionized water to remove residual sulfate and chloride ions. Then wet the rest resuspendable the deionized water and brought the pH to 8 by the addition of 30 wt.% an aqueous solution of nitric acid. Thus obtained suspension was filtered and washed with deionised water to remove residual sodium. Then wet the residue was subjected to hydrothermal treatment under pressure 3 bar I.D. for 5 hours and then dried.

This comparative example shows that the use of high-pressure stage hydrothermal treatment affects the surface area, total pore volume, pore size and phase characteristics of the material.

The magnitude of the surface area (SA), total pore volume (TPV) and pore size (PS) for Examples 1 to 9 shown in table 1 (xln=crystalline).

It was found that the hydrothermal processing of zirconium hydroxide improves his size surface area, total porosity and pore size. Additional Examples presented below are carried out to study the optimal conditions of the hydrothermal treatment.

Example 10 (JH 74b/05) Comparative

217,57 g of 98 wt.% an aqueous solution of sulfuric acid, 705,51 g deionized water and 3076,92 g oxalicacid zirconium (19,5% wt. ZrO₂) were mixed and cooled to -2°C. thus was obtained a solution with a ratio of ZrO₂:SO₃at the level of 0.45. 10 wt.% aqueous sodium hydroxide solution, which was cooled in the refrigerator, add drops until p is ka solution pH reached a value of 8. Brought to room temperature 28 wt.% an aqueous solution of sodium hydroxide was then added to until the solution pH reached a value of 13.

The resulting precipitated zirconium hydroxide was filtered and washed with deionized water to remove residual sulfate and chloride ions. Then wet the rest resuspendable in deionized water and brought the pH to 8 by the addition of 30 wt.% an aqueous solution of nitric acid. Thus obtained suspension was filtered and washed with deionised water to remove residual sodium. Then one third of the raw sludge was treated hydrothermally at 5 bar I.D. for 5 hours and then dried.

Example 11 (JH s/05) Comparative

One third of the raw sludge obtained in example 10 (JH 74b/04) was treated hydrothermally at 8,5 bar I.D. for 5 hours and then dried.

Example 12 (JH 05g/04) Comparative

6153,4 g 77 wt.% an aqueous solution of sulfuric acid, 15594,18 g deionized water and 58252,43 g oxalicacid zirconium (20,6% wt. ZrO₂) were mixed and cooled to +2°C. thus was obtained a solution with a ratio of ZrO₂:SO₃at the level of 0.50. 10 wt.% aqueous sodium hydroxide solution, which was cooled in the refrigerator, added drops up until the pH of the solution reached a value of 8. Brought to room temperature 28 wt.% water is a solution of sodium hydroxide was then added until until the solution pH reached a value of 13.

The resulting precipitated zirconium hydroxide was filtered and washed with deionized water to remove residual sulfate and chloride ions. Then wet the rest resuspendable in deionized water and brought the pH to 8 by the addition of 30 wt.% an aqueous solution of nitric acid. Thus obtained suspension was filtered and washed with deionised water to remove residual sodium. Then the sample weight 1307,2 g (equivalent to 200 g of ZrO₂) was dried without carrying out hydrothermal treatment.

Example 13 (JH 05k/04)

1307,2 g of raw sludge obtained in example 12 (JH 05g/04), was treated hydrothermally at 1 bar I.D. for 9 hours and then dried.

The magnitude of the surface area (SA), total porosity (TPV) and pore size (PS) for examples 10 through 14, are presented in table 2, along with the values of example 6, is included for comparison.

Figure 1 shows curves of x-ray diffraction obtained for example 11 (top), 10 (middle) and example 6 (bottom). Curves for examples 11 and 10 show that these samples have a slightly crystalline structure, while found in example 6 no curve on the x-ray diffraction distinct peaks, especially in the area of 20-40 °2 Theta, shows that this about ASEC is amorphous.

Presents as an illustration, figure 2 shows an example of a typical pattern obtained by x-ray diffraction of the amorphous sample of zirconium hydroxide obtained in the present invention method (bottom). The upper curve obtained by x-ray diffraction pattern of zirconium hydroxide with poorly pronounced crystalline structure; the arrows on it are marked and pronounced peaks, which begin to appear on the broad amorphous background.

1. Amorphous zirconium hydroxide having a surface area of at least 300 m²/g, total pore volume, at least 0,70 cm³/g and an average pore size in the range from 5 nm to 15 nm.

2. Amorphous zirconium hydroxide according to claim 1, which after calcination at 450°C for 2 h has a surface area of at least 80 m²/g, total pore volume, at least 0,35 cm³/g and an average pore size in the range from 10 nm to 30 nm.

3. Amorphous zirconium hydroxide according to claim 1, which, after annealing at 650°C for 2 h has a surface area of at least 30 m²/g, total pore volume, at least 0,20 cm³/g and an average pore size in the range from 20 nm to 40 nm.

4. Amorphous zirconium hydroxide according to claim 1, which, after annealing at 700°C for 2 h has a surface area of at least 20 m²/g, total pore volume, less than the least 0.15 cm³/g and an average pore size in the range from 25 nm to 60 nm.

5. Amorphous zirconium hydroxide according to claim 1, doped oxide, alkaline earth metal, oxide of rare earth metal oxide of the transition metal of the first series, silicon dioxide, aluminum oxide, tin oxide, or lead oxide, or a mixture of these compounds.

6. Amorphous zirconium hydroxide according to claim 5, doped with silicon dioxide in an amount of from 0.1 wt.% up to 10 wt.%.

7. The method of obtaining amorphous zirconium hydroxide, which includes the following steps:
(a) obtaining an aqueous solution containing sulfate anions and salt of zirconium, with a ratio of ZrO₂:SO₃1:0.40 to 1:0,52,
(b) cooling the solution to a temperature below 25°C,
(c) adding alkali to precipitate amorphous zirconium hydroxide,
(d) filtering and washing the precipitated zirconium hydroxide with water or alkali to remove residual sulfate and chloride,
(e) hydrothermal processing of zirconium hydroxide under pressure less than 3 bar I.D., and
(f) drying the hydroxide of zirconium.

8. The method according to claim 7, wherein the sulfate anions added in the form of sulphuric acid.

9. The method according to claim 7, in which the ratio of ZrO₂:SO₃is 1:0,45.

10. The method according to claim 7, in which the zirconium salt is zirconium oxychloride.

11. The method according to claim 7, in which the solution is cooled to totemperature less than 10°C.

12. The method according to claim 11, wherein the solution is cooled to a temperature less than 2°C.

13. The method according to item 12, wherein the solution is cooled to a temperature of -2°C.

14. The method according to claim 7, in which the alkali is cooled to a temperature less than 25°C.

15. The method according to claim 7, in which the alkali is a hydroxide of sodium.

16. The method according to item 15, in which 10% sodium hydroxide added for 2 h until, until the pH reaches a value of not less than 6, and then add brought to room temperature 28% sodium hydroxide until then, until the pH reaches a value of not less than 11.

17. The method according to clause 16, in which 10% sodium hydroxide added for 2 h until, until the pH reaches a value of 8.

18. The method according to item 16, which is brought to room temperature 28% sodium hydroxide added until, until the pH reaches a value of 13.

19. The method according to claim 7, in which step hydrothermal treatment is performed under a pressure of 1 bar overpressure (I.D.) for 5 hours

20. The method according to claim 7, which is optionally after step (d) and before step (e) includes the following steps:
(i) re-suspension of washed precipitate in water and bringing the pH to a value in the range from 4 to 9 nitric acid, and
(ii) filtering and washing the precipitate with water or acid to remove residual sodium.

21. The method according to claim 20, in cat the rum on the stage (i) pH adjusted to a value of 8.

22. The method according to claim 20, in which the washing and re-suspension is carried out using deionized water.

23. The method according to claim 7, in which amorphous zirconium hydroxide crushed.

24. The method of producing zirconium oxide, including the production of amorphous zirconium hydroxide by the method according to claim 7, which further includes the step of annealing the amorphous zirconium hydroxide after step (f).

25. The method according to paragraph 24, in which amorphous zirconium hydroxide calcined at a temperature of from 450°C to 900°C for 1 to 24 hours

26. The method according A.25, in which amorphous zirconium hydroxide calcined at a temperature of from 450°C to 750°C.