WO2009103250A2

WO2009103250A2 - Titanium dioxide catalyst structure for processes up to 1000 °c and the manufacturing thereof

Info

Publication number: WO2009103250A2
Application number: PCT/CZ2009/000020
Authority: WO
Inventors: Jan PROCHÁZKA JR.; Jan PROCHÁZKA SR.
Original assignee: Advanced Materials JTJ sro
Current assignee: Advanced Materials JTJ sro
Priority date: 2008-02-21
Filing date: 2009-02-19
Publication date: 2009-08-27
Anticipated expiration: 2010-08-21
Also published as: WO2009103250A4; WO2009103250A3; CZ200895A3; ES2819023T3; CN101952014A; EP2247369A2; US8435915B2; CZ301315B6; PL2247369T3; HK1148979A1; CN101952014B; SI2247369T1; EP2247369B1; US20100322832A1

Abstract

The TiO₂ catalyst structure consisting of TiO₂ nano-particles in the anatase crystal form, doped with 0.05 - 5 wt% phosphorus on the TiO₂ basis, organized in the circular planar aggregates with the specific surface area ranging from 40 to 120 m²/g, suitable for catalytic processes at the temperature up to 800°C, and the TiO₂ catalyst structure of with the morphology of the aggregated compact particles, with the specific surface area from 20 to 40m²/g, suitable for the catalytic processes at the temperature up to 1000°C. Active substances selected from the group consisting of silver, copper, gold, platinum metals, nickel, molybdenum and metal oxides except for alkaline metals oxides can be applied onto the surface of both types of the structure.

Description

Titanium dioxide catalyst structure for processes up to 1000 ⁰C and the manufacturing thereof.

Technical field

The invention relates to the planar TiO₂ catalyst structure suitable for the catalytic processes at the temperature up to 1000⁰C.

Background of the Invention

More efficient novel catalyst structures and catalyst support structures for heterogeneous catalysis are more and more meaningful considering the growing energy cost. The composition of the active substance is essential for the efficiency of catalyst structure, but its surface area and accessibility of the surface are also important. It is not easy to secure these two properties. Except for the final macro-shape, which is created for instance by peptization, it is the inner structure, its porosity and the geometrical configuration of particles that have an impact on the surface accessibility.

The choice of the proper catalyst support structure often plays a crucial role especially in the case where the creation of a chemical bond between the carrier and the catalyst is necessary. For example this is the case of the system of SiO₂ or TiO₂ (supporting structure) and MoO₃ (catalyst).

The synthesis problems and the thermal resistance of the catalyst structure are often important factors limiting its usability. The preparation or application of a catalyst often requires relatively high temperatures at which the structure can sinter, densify, lose the specific surface area, moreover an undesirable chemical reaction between the catalyst support structure and the catalyst can occur.

The TiO₂ nanoparticles in the hydrated or anatase form are especially sensitive to the thermal cycles exceeding 300⁰C. Despite the attractiveness of the TiO₂ anatase catalyst structures, their preparation using the sulfate process, i.e. hydrolysis of TiOSO₄ creating the titanium hydrate of the composition approximately Ti(OH)₄, which is consecutively calcined, has serious drawbacks, such as the poor heat resistance accompanied by the fast loss of the specific surface area during the heat exposure and finally the crystal phase transformation into rutile. Materials prepared by the sulfate process often show a high content of residual hydrate and sulfur, which don^'t disappear even at temperatures exceeding 450⁰C.

Summary of invention

The TiO₂ catalyst structure for the catalytic processes at the temperature up to 800⁰C eliminates the mentioned disadvantages. It consists of TiO₂ nanoparticles in the anatase crystal form, doped with phosphorus in the range of 0.05 - 5 wt % P on the TiO₂ basis. The nanoparticles are organized into the planar circular aggregates, which specific surface area varies from 40 to 120 m²/g.

The TiO₂ catalyst structure preferably consists of TiO₂ nanoparticles in the anatase crystal form, doped with 0.55 - 5 weight % of phosphorus on the TiO₂ basis.

The TiO₂ catalyst structure for the catalytic processes at the temperature up to 1000⁰C consists Of TiO₂ nanoparticles in the crystalline form of anatase, doped with 0.05 - 5 wt % of phosphorus on the TiO₂ basis, with the morphology of aggregated compact particles with the specific surface area 20

- 40 m²/g.

The catalyst structure of TiO₂ for the catalytic processes at the temperature up to 1000⁰C preferably consists of TiO₂ nanoparticles in the anatase crystal form, doped with 0.55 - 5 wt % of phosphorus on the TiO₂ basis. The use of the TiO₂ catalyst structure is convenient for many catalytic processes, where according to the invention, the active substances selected from the group consisting of silver, copper, gold, platinum metals, nickel, molybdenum and metal oxides with the exception of alkaline metal oxides are deposited on the surface of the TiO₂ structure.

According to the invention, the manufacturing method of the catalyst structure for processes at the temperature up to 800⁰C is based on the addition of phosphorus compound in the amount of 0.05 - 5 wt % of phosphorus on the TiO₂ basis to the titanum hydrate paste, prepared by the hydrolysis of titanum oxysulphate. The intermediate product is dried and consequently calcined at the temperature 350 - 900⁰C, preferably at 450 - 800⁰C for the period of time from 1 to 24 hours. The obtained catalyst structure is in the form of powder.

According to the invention, the manufacturing method of the catalyst structure for processes at the temperature up to 1000°C is based on the addition of phosphorus compound in the amount of 0.05 - 5 wt % of phosphorus on the TiO₂ basis to the titanum hydrate paste, prepared by the hydrolysis of titanum oxysulphate. The intermediate product is dried and consequently calcined at the temperature 500 - 1000°C, preferably at 450 - 800⁰C for the period of time from 1 to 24 hours. The obtained catalyst structure is in the form of powder.

The phosphorus compound is selected from the group of substances consisting of phosphoric acid and water-soluble phosphates.

It is convenient to apply the active substances onto the powder of this TiO₂ catalyst structure. It is possible to process the obtained powder of the catalyst structures, possibly with the active substances, into the shape required for catalysis by pressing, granulation, peptization, flaking, micronizing or by another common technique.

The catalyst structures consisting of the circular, planar aggregates of TiO₂ nanoparticles in the anatase form, with the specific surface 40 - 120 m²/g can be used for the long - term applications at the temperature up to 800⁰C.

The catalyst structures consisting of the aggregates of compact TiO₂ nanoparticles in the anatase form, with the specific surface 20 - 40 m²/g can be used for the short - term applications at the temperature up to 1000⁰C.

The catalyst structures can be conveniently used for the catalytic destruction of nitrogen oxides NO_x from the diesel aggregates and exhaust gasses. They can also be used for the photocatalytic applications or as a catalyst support structure for the active substances selected from the group consisting of silver, copper, gold, platinum metals, nickel, molybdenum and metal oxides with the exception of alkaline metals oxides.

The catalyst structures are in the crystal phase of anatase. The anatase nanoparticles are organized in roughly circular planar formations. The circular planar formations consist of individual nanoparticles which size varies typically from 5 to 25 nanometers. The average radius size of planar circular unit, on which the nanoparticles are organized, is usually 30 - 50 nanometers and its thickness varies from 5 to 25 nanometers (it corresponds to the size of the individual anatase nanoparticles). Some of the units are interconnected forming larger units with the size up to 100 nanometers. Thanks to its morphology, the mentioned planar nano-anatase structure possess very high specific surface area, high porosity, excellent accessibility of the surface and significantly higher thermal stability than the undoped TiO₂. The organization of nanoparticles aggregated into the planar circular structure was surprisingly discovered when a small amount of phosphorus was added as a dopant to the paste of titanum hydrate which was consequently calcined. Whereas the undoped material simply fuses into large aggregates creating a mixture of nanoparticles with a low specific surface area, broad particle size distribution and without any signs of an organization into a planar circular substructure, the doped material is organized in the circular planar units after the calcination at the same temperature.

Moreover the addition of phosphorus evidently stabilizes the crystalline phase of anatase and shifts its thermal transformation into the rutile up to higher temperatures.

It was experimentally proven that this structure forms during the thermal processing of phosphorus doped titanum hydrate Ti(OH)₄ at the temperatures above 350⁰C. The titanium hydrate is made from the titanium oxysulphate TiOSO₄ precursor. The specific surface area of the titanium hydrate paste which is the input material for the reaction typically varies from 200 to 350 m²/g.

The exact reason is not known; however, using of the titanium hydrate prepared differently, for instance by the hydrolysis of titanium oxychloride, in combination with the phosphorus doping, doesn't produce the morphology of aggregates organized in the planar circles.

The stages of the formation, existence and transformation of the circular planar morphology of the aggregates are schematically depicted in the Figure 1. Figure 2A shows a SEM photograph of the mentioned aggregates suggestive of little flat rings. Figure 2B captures the transformation of the circular planar aggregates into the compact nano-particles of anatase with the average individual particle size corresponding approximately to the original size of the radius of the circular planar structure. From the figures 2A and 2B it is obvious that the change of morphology is accompanied by a significant decrease of the specific surface area of the nano-anatase product. The temperature at which the planar circular structure transforms into the morphology of compact particles is specific for the particular content of phosphorus. The phosphorus concentration stabilizes the circular morphology at high temperatures, at which the undoped material completely sinters, loses the specific surface area or even changes the crystal phase.

To create the planar circular nano-anatase structure, it is convenient using the phosphorus level in the range from 0.05 to 5 wt % with the optimal phosphorus level from 0.1 to 1 wt % on the Tiθ₂ basis.

If the amount of phosphorus is zero, the particles spontaneously fuse together and a broad particle size distribution is created as early as the hydrate converts into the oxide. Without phosphorus the organized planar circular morphology is not created.

At the low content of phosphorus between 0.05 - 0.1 wt % on the TiO₂ basis, the planar circular structure of nano-anatase aggregates is stable approximately in the temperature range from 500 to 600⁰C.

Another increase of the phosphorus content to 1 to 5 wt % on the TiO₂ basis shifts the temperature of transformation of the circular planar structure higher to 650 to 800⁰C. If we increase the calcination temperature approximately by another 100 to 250⁰C higher, another change of morphology occurs due to the intensive fusion of particles into the large, hard-fused aggregates, similar to these in the undoped product. We will see a collapse of the specific surface area and creation of the broad particle size distribution. The typical product of this fusion is shown in the Figure 3. The hard-sintered particles of anatase are mostly outside the nanosize range. The specific surface of the fused products is typically below 20m²/g, most frequently from 5 to 15 m²/g. Despite its disadvantages it is this type of hard-sintered products, which is now used for the catalyst structures for variety of syntheses in the industry.

The manufacturing of the above mentioned products with the planar circular nano-anatase structure is based on the preparation of titanium hydrate Ti(OH)₄ paste via hydrolysis of titanium oxysulphate TiOSO₄, addition of a compound containing phosphorus, drying the doped paste and consequential calcination in the temperature range from 350⁰C to 900⁰C for the period of time from 1 to 24 hours. In the case of preparing the titanium oxysulphate from an ore already containing phosphorus, for example ilmenite, the amount of phosphorus is just brought to the required level with the appropriate quantity of the phosphorus compound.

The further increase of the calcination temperature by 100°C to 200°C produces the porous structures consisting of compact nano-particles of anatase, created by the fusion of the planar circular aggregates. These structures have an outstanding thermal stability and still possess relatively high specific surface area. Phosphoric acid or a phosphate, soluble in water, can be conveniently used for doping the titanium hydrate paste. The flow sheet diagram of manufacture is shown in the Figure 7.

Even though the morphology of planar circular aggregates with the significantly higher accessibility of the surface is optimal for use as a catalyst, the structure of compact nano-particles of anatase, created from the circular structure, is also usable. This concerns especially applications, where the catalyst is exposed to the long-term high temperatures up to 850⁰C and requires the ability to resist short-term temperatures as high as 1000⁰C without a significant loss of the specific surface area.

The specific surface area of the materials with the morphology of circular planar aggregates is usually well above 40m²/g. It typically ranges from 50 to 120m²/g (the specific surface area is determined from the adsorption isotherms of nitrogen at 77K and is referred to as BET). The important characteristic of this morphology is the high specific surface area and also good accessibility of the surface.

The materials with the structure of compact particles, created from the circular aggregates, usually have the specific surface area higher than 20m²/g, and frequently it varies from 25 to 35m²/g. These materials show a low content of sulfur, which is convenient for functioning as a catalyst structure. From the viewpoint of its use as a catalyst structure, this morphology has high enough and accessible surface (Figure 6). Fifty percent of the TiO₂ surface is typically lost in the connections between sintered particles contrary to the planar circular structure where the TiO2 open (accessible) surface is tens of percent higher.

Very high loss of the specific surface area is typical for the third phase of the fusion. It usually drops down under 15m²/g. Also the degree of sintered particles, where the ratio of the open Tiθ2 surface to the surface used by sintered connections between the particles drops down (Figure 3). The further heat treatment above this limit results in the Tiθ₂ crystal phase transformation from anatase into rutile.

The open morphology of these products is convenient for deposition of the active substances on the TiO₂ surface such as platinum and platinum metals, nickel, cobalt, silver, copper, gold and metal oxides except for alkaline metal oxides. For example, water solution of ions of these active substances can be used to prepare a suspension with the TiO₂ catalyst structure, which is further dried e.g. in a spray dryer and eventually calcined. Thanks to the open morphology and accessibility of the surface, a suspension of circular planar catalyst structure is convenient for the deposition of the active substances by variety of methods such as precipitation, complexing, gas phase vapor deposition, or thermal decomposition on the surface of the TiO₂ structure, and similar.

The products manufactured by the described method show a high photocatalytic activity. They can be conveniently used not only as a catalyst structure but also as a photocatalyst.

The described intermediate products can be directly used in the form of loose powder or they can be further processed into the desired form by micronization, pressing, granulation, milling or other processes typical for making catalysts.

Description of the drawings

Figure 1 shows schematically the process of formation of the TiO₂ nano- anatase circular planar aggregates from the titanium hydrate, an interval of their existence and alteration of their morphology into the compact particles during elevation of the calcination temperature. The diameter of the circle mark is 30 nm.

Figure 2 shows electron scanning microscope (SEM) micrographs on the same scale:

A) Nanoparticles TiO₂ - anatase organized in the circular planar aggregates, typically from 20 to 50 nm in size

B) The compact nanoparticles of TiO₂ - anatase created by heating the circular planar aggregates above 800⁰C. The typical size of the created compact particles typically varies from 20 to 50nm and correlates roughly to the diameter of the original planar aggregates before the fusion. Figure 3 shows a scanning electron microscope (SEM) photograph of the fused nano-anatase doped with phosphorus after the calcination at the temperature above 900⁰C.

Figure 4 shows a SEM photograph which depicts the circular planar structure of nano-anatase prepared according to example 1.

Figure 5 shows a SEM photograph which depicts the circular planar structure of nano - anatase prepared according to example 2.

Figure 6 shows a SEM photograph which depicts the structure of nano- anatase compact particles prepared according to example 3.

Figure 7 shows a flowchart of the production process of the nano-anatase circular planar structure and the following processing into the specific products.

Examples

The following examples illustrate but do not limit the presented invention.

Example 1 .

A concentrated solution of titanium oxysulphate TiOSO₄ was hydrolyzed by addition of hot water and by bubbling hot water vapor through the solution. Titanium hydrate of an approximate composition Ti(OH)₄ was obtained and separated from the sulphuric acid solution by sedimentation and filtration. The amount of 1 % phosphoric acid corresponding to 1 wt% of phosphorus in TiO₂ was added to the filtered titanium hydrate paste. The suspension was properly mixed and after that it was dried at the temperature 150⁰C. The dry intermediate product was further calcined at the temperature 600°C for 10 hours. The obtained product was a soft white powder with the specific surface area (BET) 77m²/g. The average particle size 9 nm was determined from the roentgen diffraction (XRD) and calculated using the Scherrer's equation. The particle size and the circular planar morphology of this product are noticeable from Figure 4. The sample shows high photocatalytic activity. If 1wt% AgNO₃ solution is applied to the Tiθ₂ surface, silver rapidly develops on it, showing one of the ways of applying the active substance for catalysis onto the Tiθ₂ structure. This structure is stable at the temperature up to 750⁰C.

Example 2.

An amount of 0.5% phosphoric acid corresponding to 0.5 wt% of phosphorus in Tiθ₂ was added to the titanium hydrate paste, created by the hydrolysis of TiOSO4. The suspension was properly mixed and after that it was dried at the temperature 15O⁰C. The dry intermediate product was further calcined at temperature 650⁰C for 10 hours. The obtained product is a soft white powder with specific surface area (BET) 50m²/g and 22nm particle size that was determined from roentgen diffraction and calculated using the Scherrer's equation. The product consists of relatively large nano-particles and possesses the circular morphology, which is noticeable in Figure 5.

Example 3.

The amount of 0.1% phosphoric acid corresponding to 0.1 wt% of phosphorus in TiO₂, was added to the titanium hydrate paste. The suspension was properly mixed and after that it was dried at the temperature 15O⁰C. The dry intermediate product was further calcined at 700°C for 10 hrs. The obtained product is a soft white powder with the specific surface area (BET) 30m²/g. The average particle size 30nm was determined from roentgen diffraction and calculated using the Scherrer's equation. The created material shows the morphology of compact particles, as it is noticeable in Figure 6. For comparison, materials doped with 1 to 5 wt % of phosphorus were calcinated in parallel. They still show the circular planar morphology of aggregates with the double specific surface area compared to the material described above.

Industrial utilization

The catalyst structures described in this invention have significantly larger and more accessible surface, high thermal resistance, phase purity of anatase and show easier processing of the powder than the undoped TiO₂. These nano-structures are a good substitution of the materials which are industrially used today as the catalyst structures.There we can expect an improvement of the process effectiveness. The nano-anatase catalyst structures are suitable for applications which require a high thermal resistance. The thermal resistance of these structures significantly widens the use of TiO₂ in processes for degradation of nitrogen oxides NO_x from diesel aggregates and exhaust gasses. It is also convenient to use the structures created by this method for photocatalysis.

Claims

Patent claims

1. The Tiθ₂ catalyst structure for the catalytic processes at the temperature up to 800⁰C₁ consisting of TiO₂ nano-particles in the anatase crystal form, doped with 0.05 - 5 wt% phosphorus on the TiO₂ basis, organized into the circular planar aggregates with the specific surface area from 40 to 120 m²/g.

2. The TiO₂ catalyst structure according to the claim 1 , consisting of TiO₂ nanoparticles in the crystal form of anatase, doped with 0.55 - 5 % weight amount of phosphorus on the TiO₂ basis.

3. The TiO₂ catalyst structure for the catalytic processes at the temperature up to 1000⁰C, consisting of TiO₂ nano-particles in the anatase crystal form, doped with 0.05 - 5 wt% phosphorus on the TiO₂ basis, with the morphology of aggregated compact particles with the specific surface area from 20 to 40 m²/g.

4. The TiO₂ catalyst structure according to the claim 3, consisting of TiO₂ nanoparticles in the anatase crystal form, doped with 0.55 - 5 wt% phosphorus on the TiO₂ basis.

5. The catalyst structure of TiO₂ according to claims from 1 to 4 wherein the active substances selected from the group consisting of silver, copper, gold, platinum metals, nickel, molybdenum and metal oxides with the exception of alkaline metals oxides are applied onto the surface of the structure.

6. The method of manufacturing of the catalyst structure, described in the claims 1 and 2, wherein the phosphorus compound corresponding to 0.05 to 5 wt % of phosphorus on the TiO₂ basis is added to titanium hydrate paste, prepared by hydrolysis of titanium oxysulphate, the intermediate product is dried and subsequently calcined in the temperature range from 350 to 900⁰C for 1 to 24 hours, which produces the catalyst structure in the form of a powder.

7. The manufacturing method according to the claim 6, wherein the dried intermediate product is calcined in the temperature range from 450 to 800⁰C for 1 to 24 hours, which produces the catalyst structure in the form of a powder.

8. The method of manufacturing of the catalyst structure of claims 3 and 4 wherein the phosphorus compound corresponding to the 0.05 - 5 wt% of phosphorus on the TiC>2 basis is added to the titanium hydrate paste, prepared by the hydrolysis of titanium oxysulphate, the intermediate product is dried and subsequently calcined in the temperature range from 500 - 1000⁰C for 1 to 24 hours, which produces the catalyst structure in the form of a powder.

9. The method of manufacturing according to the claims 6 to 8 wherein the phosphorus compound is selected from the group consisting of phosphoric acid and water soluble phosphates.

10. The method of manufacturing the catalyst structure described in the claim 5 wherein according to the claims 6 to 9 the active substances are applied onto the surface of the Tiθ₂ catalyst structure.

11. The method of manufacturing according to the claims 6 to 10 wherein the obtained catalyst structure or the catalyst structure with the active substances in the form of a powder is further processed into the required shape by pressing, granulation, peptization, flaking, micronizing or by another common technique.

12. Use of the catalyst structure according to the claims 1 , 2 and 5 for the long-term applications at the temperatures up to 800⁰C.

13. Use of the catalyst structure according to claims 2, 3 and 5 for the short- term applications at the temperatures up to 1000⁰C.

14. Use of the catalyst structure according to the claims 1 to 4 for the catalytic decomposition of nitrogen oxides NO_x from diesel aggregates and exhausts gasses.

15. Use of the catalyst structure according to the claims 1 - 4 for the photocatalytic applications.

16. Use of the catalyst structure according to claims no. 1 - 4 as a catalyst support structure for active substances selected from the group consisting of silver, copper, gold, platinum metais, nickel, molybdenum and metal oxides except for alkaline metals oxides.