Zirconia supports for heterogeneous catalysts

Abstract

The present specification describes a zirconia support comprising > = 95 wt% ZrO2 wherein: the support has a crushing strength of 20 N to 140 N; the support has a total pore volume of from 0.10 mL / g to 0.40 mL / g when measured by N2 physical adsorption; the carrier has an acidic site density of 15 LNH3 / m < 2 > to 30 LNH3 / m < 2 >; and the carrier has an alkaline site density of from 0.006 wt% / m2 to 0.015 wt% / m2 as measured by the MBOH test. Also described is a method for producing a zirconia support starting from zirconia or zirconia hydroxide as a starting material.

Description

[0001] Invention Field This invention relates to the preparation of zirconia support, methods for manufacturing zirconia support, and supported catalysts made therefrom.

[0002] background Zirconia is a material with good stability and moderate acidity, making it an interesting catalyst carrier. Zirconia can be used to produce shaped articles, such as spheres, granules, or cylinders. Zirconia shaped articles formed by extrusion typically have low crushing strength, and several methods have been described to improve this strength.

[0003] WO2004 / 065002A1 (Shell) describes a process for preparing calcined zirconia extrusions, the process comprising the steps of: preparing a formable dough containing granular zirconia having a total solids content of 50% to 85% by weight; extruding the formable dough to form a zirconia extrusion; and drying and calcining the zirconia extrusion. A particular zirconia contains no more than 15% by weight of zirconia that is not monoclinic zirconia.

[0004] WO2010 / 101636A2 (Sud-Chemie Inc) describes the incorporation of a polybasic acid / accelerator material selected from polybasic acids, comprising the group consisting of polybasic acids in the form of oxides or acids of chromium, molybdenum, or tungsten. Typical molar ratios of zirconium to accelerator are between 2:1 and 20:1.

[0005] WO2015 / 167978A1 (Clariant) describes a material comprising 50 wt% to 99 wt% zirconium oxide and 1 wt% to 50 wt% of a metal oxide (metal-based) selected from nickel oxide, copper oxide, cobalt oxide, iron oxide, and zinc oxide. The presence of the metal oxide is believed to stabilize the zirconium oxide, preventing it from undergoing an undesirable phase transition from a tetragonal or amorphous phase to a less desirable monoclinic phase.

[0006] US5269990A describes shaped zirconia particles prepared by mixing zirconia powder and an aqueous or acidic aqueous solution of colloidal zirconia to obtain a formable mixture containing 4 wt% to 40 wt% water, shaping the mixture, and heating the shaped particles at a temperature above about 90°C.

[0007] US2002 / 0123424A1 and US20023 / 130117A1 describe a process for preparing a zirconium oxide catalyst by mixing zirconium hydroxide with a variety of additives to prepare a paste, then shaping the particles, drying them, and calcining the particles at a temperature of at least 400°C.

[0008] US2011 / 0301021A1 describes a polybasic acid-promoted zirconium oxide catalyst or catalyst support, which can be prepared by combining a zirconium compound with a polybasic acid / promoter material, said polybasic acid / promoter material may be Cr, Mo or W, phosphoric acid, sulfuric acid and polyorganic acid.

[0009] Zirconia supports are already commercially used in hydrodeoxygenation (HDO) catalysts, as described in US9314778B2 (Virent, Inc.) and the references cited therein. The HDO reaction is part of Virent Inc.'s BioForming technology for converting biomass into fuel. TM The key reaction in the technology. To further promote the adoption of this technology, a zirconia support is needed, which is simple and inexpensive to manufacture and ideally improves the performance of HDO catalysts containing Pd, Mo and Sn on a zirconia support.

[0010] The inventors seek to provide an alternative zirconia support that (i) is simple and inexpensive to manufacture; and (ii) performs well when used as a support for an HDO catalyst. Invention Overview The inventors' initial experiments sought to produce zirconia profiles with crush strength comparable to or better than commercially available zirconia supports. The profiles were also converted into hydrodeoxygenation (HDO) catalysts by impregnation with palladium, tin, and molybdenum salts, as will be described more fully in the examples. Crushing strength could be improved by increasing the calcination temperature, but it was found that increasing the calcination temperature ultimately negatively impacted the performance of the support in the HDO reaction due to variations in the concentrations of acidic and basic sites. Ultimately, it was found that careful control of the concentrations of acidic and basic sites within a certain range was necessary to achieve good performance in the HDO reaction. The concentrations of acidic and basic sites are influenced by several factors, including: the selection of raw materials; the additives used in the process; and the calcination conditions.

[0012] In a first aspect, the present invention relates to a zirconium oxide support comprising ≥ 95 wt% ZrO2, wherein: The carrier has a crushing strength of 20 N to 140 N; When measured by N2 physisorption, the support has a total pore volume of 0.10 mL / g to 0.40 mL / g; The carrier has 15 µL NH3 / m 2 Up to 30 µL NH3 / m 2 The density of acidic sites; and The carrier has a concentration of 0.006 wt% / m as measured by the MBOH test. 2 Up to 0.015 wt% / m 2 The density of basic sites.

[0013] According to the first aspect, the zirconia support has a good balance between crushing strength and performance in the HDO reaction.

[0014] In a second aspect, the present invention relates to a method for manufacturing a zirconia support, the method comprising the following steps: (i) Combining raw materials selected from ZrO2 or Zr(OH)4 with lubricants; (ii) The product of step (i) is mixed with an additive selected from acids, bases or zirconium salts and the mixture is extruded to form a molded article; or the product of step (i) is compressed into a tablet to form a molded article. (iii) Drying the shaped article; and (iv) Calcining into a shape.

[0015] The zirconium oxide support is preferably as defined in the first aspect.

[0016] Attached Figure Description Figure 1 The relationship between basic sites / BET surface area and activity is shown.

[0017] Figure 2 The relationship between acidic site / BET surface area and activity is shown.

[0018] Figure 3 This shows how to measure the average diameter of a trilobe; the trilobe shown has an average diameter of 1.4 mm.

[0019] Detailed Explanation Any subheadings are included for convenience only and should not be construed as limiting the content of this disclosure in any way.

[0020] carrier The support comprises ≥ 95 wt% ZrO2 based on the total weight of the support. The amount of metal oxides other than ZrO2 is ≤ 5 wt% (support comprises ≥ 95 wt% ZrO2), preferably ≤ 4 wt% (support comprises ≥ 96 wt% ZrO2), ≤ 3 wt% (support comprises ≥ 97 wt% ZrO2), ≤ 2 wt% (support comprises ≥ 98 wt% ZrO2), or ≤ 1 wt% (support comprises ≥ 99 wt% ZrO2).

[0021] When measured using the procedures reported in the examples, the carrier has a total pore volume of 0.10 mL / g to 0.40 mL / g. A typical total pore volume is 0.12 mL / g to 0.30 mL / g.

[0022] The carrier has a concentration of 0.006 wt% / m³ as measured by the MBOH test reported in the examples. 2 Up to 0.015 wt% / m 2 Preferably 0.0075 wt% / m 2 Up to 0.014 wt% / m 2 More preferably 0.010 wt% / m 2 Up to 0.014 wt% / m 2 More preferably 0.010 wt% / m 2 Up to 0.013 wt% / m 2 The density of basic sites. When impregnated with Pd, Mo, and Sn, supports with basic site densities within these ranges exhibit optimal performance as HDO catalysts, such as... Figure 1 As shown in the image.

[0023] When measured using the procedure reported in the examples, the carrier has 15 µL. NH3 / m 2 Up to 30 µL NH3 / m 2 Preferably 19µL NH3 / m 2 Up to 28 µL NH3 / m 2 The density of acidic sites. When impregnated with Pd, Mo, and Sn, supports with acidic site densities within these ranges exhibit optimal performance as HDO catalysts, such as... Figure 2 As shown in the image.

[0024] When measured using the procedures reported in the examples, the carrier has a crushing strength of 20 N to 140 N. Typical crushing strengths are 20 N to 80 N, such as 20 N to 60 N.

[0025] In one embodiment, the support is a tungstate catalyst comprising ≥ 95 wt% ZrO2 and ≤ 5 wt% WO3. These supports can be used to prepare HDO catalysts, as described in US9314778B2.

[0026] In one embodiment, the support is substantially free of tungsten (W), for example containing ≤ 0.1 wt% W, such as ≤ 0.05 wt% W.

[0027] In one embodiment, the carrier has a spherical cross-section.

[0028] In a preferred embodiment, the carrier has a trilobal or tetralobal cross-section. Particularly preferred carriers have a trilobal cross-section with an average diameter of 1.0 mm to 4.0 mm, such as 1.0 mm to 2.0 mm.

[0029] Carrier manufacturing The inventors investigated the use of zirconium oxide (ZrO2) or Zr(OH)4 as a raw material in step (i). Regardless of the raw material used, a carrier with good radial crushing strength can be produced.

[0030] Any suitable lubricant can be used in step (i). Preferred lubricants include microcrystalline cellulose, hydroxymethyl cellulose, or metal stearates. Typically, the lubricant and ZrO2 or Zr(OH)4 are dried and blended in step (i).

[0031] Step (ii) involves forming an extrudate or tablet. In the case of extrusion, an additive is first added to the product mixture from step (i). The additive is typically provided as an aqueous solution. The additive acts as a binder for the ZrO2 or Zr(OH)4 raw materials. It is not intended to be bound by any theory that the additive can cause crosslinking (in the case of zirconium acetate or zirconium nitrate) or peptization (in the case of nitric acid or ammonium hydroxide).

[0032] In step (iv), the calcination temperature of the support affects its properties. As the calcination temperature increases, the number of acidic sites (in µL) increases. NH3 / g 载体 (Measurement), number of basic sites (in wt% / g) 载体 (Measured by volume) and surface area decrease. Although the number of acidic and basic sites decreases with increasing calcination temperature, if the surface area decreases at a faster rate than the decrease in the number of acidic and basic sites, the concentration of acidic and basic sites (expressed in µL) will decrease. NH3 / m 2 and wt% / m 2The measurement may increase. Besides acting as a binder for ZrO2 or Zr(OH)4 raw materials, additives can also be used to adjust the density of acidic and basic sites. The inventors have discovered that the choice of additives affects the acid / basic properties of the resulting zirconia support, which can affect the suitability of the support for the catalyst in question.

[0033] In some embodiments, the additive is ammonia or an acid, such as nitric acid. In both cases, a support with acceptable strength and good performance as an HDO catalyst can be produced. While adding ammonia or an acid as an additive produces a support with good strength and good to excellent performance as an HDO catalyst, the use of ammonia or an acid may be incompatible with the manufacturing equipment. Therefore, in some embodiments, zirconium salts are used. Preferred zirconium salts include zirconium nitrate, zirconium acetate, and ammonium zirconium carbonate. Surprisingly, the use of zirconium salts as additives results in a support with a higher strength than that achievable with ammonia or nitric acid. Therefore, the use of zirconium salts may be preferred when a high-strength zirconia support is required. The use of zirconium salts, especially zirconium acetate, is generally also more compatible with the manufacturing equipment than ammonia or an acid, and for this reason, zirconium salts may be preferred.

[0034] In the case of tableting, it is not necessary to add additives to the product of step (i) before tableting.

[0035] Step (ii) also involves forming a shaped article by extrusion (“extrudate”) or by tableting (“tablet”). In each case, the cross-section of the shaped article may be spherical (e.g., cylindrical) or shaped. Preferably, the shaped article has a trilobal or tetralobal cross-section, as this provides a catalyst with a high geometrical surface area beneficial to activity. Extrusion and tableting conditions will be well known to those skilled in the art.

[0036] Typically, the shaped article (“extrudate”) formed by extrusion will have an elongated shape. The cross-section of the extrudate can be spherical (i.e., cylindrical extrudate) or shaped. Multi-lobed shapes such as trefoil or tetralobes are preferred, especially trefoil shapes, because these shapes have a relatively high surface area and low pressure drop. Particularly suitable shapes are trefoil shapes with an average diameter of 1.0 mm to 4.0 mm, such as 1.0 mm to 2.0 mm. Figure 3 It shows how to measure the average diameter of a trefoil.

[0037] Step (iii) involves drying the molded article to remove excess water. The drying conditions will be readily determined by those skilled in the art.

[0038] Step (iv) involves calcining the product of step (iii). As previously explained, increasing the calcination temperature is associated with a reduction in the number and surface area of ​​acidic and basic sites. When the support is used as an HDO catalyst, the calcination temperature in step (iv) is preferably between 300°C and 800°C, such as between 300°C and 500°C or between 350°C and 450°C. A calcination time of 2–6 hours is generally sufficient, although this can vary depending on scale.

[0039] Example raw materials SGN SZ31164 is a commercial zirconia extrusion (1.2 mm diameter) from NorPro Saint Gobain.

[0040] ZOH-85 is a commercial Zr(OH)4 from Zircomet.

[0041] Z-3186 is a commercial ZrO2 product from Daiichi Kigenso Kagaku Kogyo Co. Ltd.

[0042] RC-100 is a commercial ZrO2 product from Daiichi Kigenso Kagaku Kogyo Co. Ltd.

[0043] XZO 631 / 01 is a commercial Zr(OH)4 from MEL Chemicals.

[0044] General procedures for manufacturing carriers The raw material (ZrO2 or Zr(OH)4) is dried and mixed with a lubricant (microcrystalline cellulose, hydroxymethyl cellulose, or magnesium stearate). In the case of an extruded catalyst, an additive solution (5% ammonia, 5% nitric acid, zirconium nitrate solution, or zirconium acetate solution) is added, and the mixture is extruded into lobes with an average diameter of 1.3 mm or cylinders with a diameter of 1.6 mm. In the case of a granular catalyst, the mixture of raw material and lubricant is granulated into flakes with a diameter of 3.3 mm. The material is dried (120°C) and then calcined under specified conditions.

[0045] Program for measuring crushing strength Radial crushing strength was measured using an Engineering Systems CT6 instrument. A crushing rate of 22 mm / min and a 50 kg force sensor were used. Twenty individual particles were analyzed and averaged.

[0046] Program for measuring total pore volume and BET surface area Surface area was measured using a Micromeritics 2420 ASAP physical adsorption analyzer by applying the BET method according to ASTM Method D 3663-03, "Standard Tests for Surface Area". Nitrogen gas was used as the adsorbate, and measurements were taken at liquid nitrogen temperature. The cross-sectional area of ​​nitrogen molecules was taken as 16.2 Å. 2 Prior to analysis, the sample was degassed by purging with dry nitrogen at the optimal temperature for at least 1 hour. (At 0.05 P / P) o Up to 0.20 P / P o (including 0.05 P / P) o and 0.20 P / P o Five relative pressure / volume data pairs were obtained within a relative pressure range. The equilibration time for each point was 10 seconds. Surface area was reported based on the weight of the degassed sample. Complete adsorption / desorption isotherms were measured within a relative pressure range of 0.05 to 0.995 and back to 0.05. The final point on the adsorption isotherm (0.995 P / P) was used. o The total pore volume is determined at point ().

[0047] Program for measuring acidic site density The particles were ground into powder and loaded into a Micromeritics AutoChem 2950HP thermal analyzer. A helium flow of 40 mL / min was passed through the particles at atmospheric pressure while heating to 400°C at a rate of 20°C / min. The temperature of 400°C was maintained for 10 minutes, followed by cooling to 120°C. After reaching 120°C, a helium flow of 40 mL / min and a helium flow of 5% v / v ammonia were passed through the particles for 30 minutes. Physically adsorbed ammonia was purged with a helium flow of 40 mL / min for 30 minutes. The particle temperature was then increased to 700°C at a rate of 5°C / min and maintained for 30 minutes, during which time the desorption of ammonia from the particles was monitored using a TCD detector. The total amount of desorbed ammonia was calculated by integrating the desorption profile, which had been calibrated using a known amount of ammonia-containing helium. This value was then normalized to the sample BET surface area (measured according to the BET surface area procedure) to obtain the total amount of ammonia in µL. NH3 / m 2 The density of acidic sites was calculated.

[0048] Program for measuring the density of basic sites The program is based on the article " Evaluation of Surface Acid-Basic Properties of Inorganic-Based Solids by Model Catalytic Alcohol Reaction Networks ( Catalyst Reviews , 48:315-362, 2006) and " Synthesis and Characterization of ZrO 2 as Acid-Basic Catalysts: Reactivity of 2-Methyl-3-butyn-2-ol ” ( Journal of Catalysis The procedure described in 183, 240-250 (1999)).

[0049] Six g of granules, along with 15 mL of 2-methyl-3-butyn-2-ol (MBOH) and a single drop of water, were loaded into a static 45 mL autoclave. The autoclave was placed in an oven at 200 °C for 18 hours, then cooled to room temperature. The concentrations of 2-methyl-1-buten-3-yne (Mbyne), isopropylidene acetone (MO), 2-methyl-3-butyn-2-ol (MBOH), 3-methyl-2-butenal (Prenal), 3-hydroxy-3-methyl-2-butanone (HMB), and 4-hydroxy-4-hydroxy-4-methyl-2-pentanone (DAA) in the reaction liquid were analyzed by gas chromatography using external standard. A certain amount of acetone and 4-hydroxy-4-hydroxy-4-methyl-2-pentanone (DAA) were added, and the result was divided by the BET surface area of ​​the granules (6 g) to obtain the wt.% 碱性产物 / m 2 The density of basic sites was calculated.

[0050] General co-impregnation process for manufacturing HDO catalysts The supports S1 and S3 to S7 described in Table 1 were converted into HDO catalysts C1 and C3 to C7 using the following procedure. Zirconia extrudate was loaded into a rotary drum. An impregnation solution was prepared by dissolving ammonium molybdate, palladium nitrate solution, tin oxalate, and citric acid in deionized water up to the absorbance volume of the extrudate. The impregnation solution was added to the rotary drum mixer over approximately 2 minutes with gentle rotation (approximately 2 rpm), and the mixture was allowed to tumble for an additional 15 minutes (approximately 2 rpm). The impregnated flakes were transferred to an oven and dried overnight at 105 °C, and then calcined in air at an incline rate of 2 °C / min for 4 hours. The resulting catalyst contained 1 wt% Pd, 2 wt% Mo, and 0.25 wt% Sn, except for S2, which contained 1 wt% Pd, 1 wt% Mo, and 0.25 wt% Sn.

[0051] General sequential impregnation process for manufacturing HDO catalysts The carrier S2 described in Table 1 was converted into HDO catalyst S2 using the following procedure: Zirconia extrudate was loaded into a drum. An impregnation solution was prepared by dissolving ammonium molybdate, tin oxalate, and citric acid in deionized water up to the absorbance volume of the extrudate. The impregnation solution was added to the drum mixer over approximately 2 minutes with gentle rotation (approximately 2 rpm), allowing the mixture to tumble for an additional 15 minutes (approximately 2 rpm). The impregnated extrudate was transferred to an oven and dried overnight at 105°C, and then calcined in air at an incline rate of 2°C / min for 4 hours. The catalyst intermediate was then removed from the oven and loaded into the drum. The palladium nitrate impregnation solution was replenished to the absorbance volume with deionized water. The impregnation solution was added to the drum mixer over approximately 2 minutes with gentle rotation (approximately 2 rpm), allowing the mixture to tumble for an additional 15 minutes (approximately 2 rpm). The impregnated extrudate was transferred to an oven and dried at 105°C overnight, and then calcined in air at 400°C at an incline rate of 2°C / min for 4 hours. The analysis of the data in Table 1 indicates the following: • Good crushing strength can be achieved when Zr(OH)4 or ZrO2 is used as raw material; • The addition of zirconium nitrate (S6) or zirconium acetate (S7) is beneficial to strength, especially zirconium nitrate; Figure 1 The relationship between basic site / BET area and activity is shown. The activity peak of C5 is based on support S5, which has a concentration of 0.0119 wt% / m² from MBOH testing. 2 The density of basic sites.

[0052] Figure 2 The relationship between acidic site / BET area and activity is shown. This relationship is less pronounced compared to the basic site density.

[0053] Effect of calcination temperature The effects of calcination temperature on a variety of properties, including crush strength, BET surface area, number and concentration of acidic and basic sites, were investigated using various carriers and different additives. Results from some selections are shown in Tables 2, 3, and 4.

[0054] Table 2 shows the effect of calcination temperature on the crushing strength, acidic site density, and basic site density of the support prepared from RC-100 (ZrO2). With increasing calcination temperature, the crushing strength increases, while the basicity and BET surface area decrease. Both the acidic and basic site densities increase. Table 3 shows the effect of calcination temperature on the pore volume and BET surface area of ​​the support prepared from XZO 631 / 01 Zr(OH)4. With increasing calcination temperature, both the BET surface area and pore volume decrease. Table 4 shows the effect of the additive on the acidic site density of the support prepared from XZO 631 / 01 Zr(OH)4 under the same calcination conditions. The acidic site density can be adjusted by controlling the strength of the nitric acid used as the additive. The results in Tables 2, 3, and 4 illustrate the following: First, there is a positive correlation between calcination temperature and crushing strength (Table 2). Second, there is a negative correlation between calcination temperature and the number of both acidic and basic sites (Table 2). Third, there is a negative correlation between calcination temperature and both pore volume and BET surface area (Tables 2 and 3). For a given raw material, the properties of the resulting support depend on the calcination temperature. Crushing strength can be increased by selecting an appropriately high calcination temperature, but this will rapidly produce material with an undesirable high concentration of acidic sites. This can be balanced by selecting suitable additives (Table 4).

Claims

1. A zirconium oxide support comprising ≥ 95 wt% ZrO2, wherein: The carrier has a crushing strength of 20 N to 140 N; When measured by N2 physisorption, the support has a total pore volume of 0.10 mL / g to 0.40 mL / g; The carrier has 15 µL NH3 / m 2 Up to 30 µL NH3 / m 2 The density of acidic sites; and The carrier has a concentration of 0.006 wt% / m as measured by the MBOH test. 2 Up to 0.015 wt% / m 2 The density of basic sites.

2. The carrier according to claim 1, wherein the carrier comprises ≥ 98 wt% ZrO2.

3. The carrier according to claim 1, wherein the carrier comprises ≥ 99 wt% ZrO2.

4. The carrier according to any one of claims 1 to 3, wherein the carrier has a crushing strength of 20 N to 80 N.

5. The carrier according to any one of claims 1 to 4, wherein the carrier has a density of 19 µL. NH3 / m 2 Up to 28 µL NH3 / m 2 The density of acidic sites.

6. The carrier according to any one of claims 1 to 5, wherein the carrier has a content of 0.0075 wt% / m 2 Up to 0.014wt% / m 2 The density of basic sites.

7. The carrier according to any one of claims 1 to 6, wherein the carrier is in the form of a trefoil.

8. The carrier according to claim 7, wherein the carrier is in the form of a trefoil having an average diameter of 1.0 mm to 4.0 mm.

9. The carrier according to any one of claims 1 to 8, wherein the carrier comprises: Crushing strength from 20 N to 80 N; Total pore volume from 0.10 mL / g to 0.40 mL / g; 19 µL NH3 / m 2 Up to 28 µL NH3 / m 2 The density of acidic sites; and 0.0075 wt% / m 2 Up to 0.014 wt% / m 2 The density of basic sites.

10. A method for manufacturing a zirconia support, comprising the following steps: (i) Combining raw materials selected from ZrO2 or Zr(OH)4 with lubricants; (ii) The product of step (i) is mixed with an additive selected from acids, bases or zirconium salts, and the mixture is extruded to form a molded article; or the product of step (i) is pressed into a tablet to form a molded article; (iii) Dry the molded body; as well as (iv) Calcining the shaped body.

11. The method according to claim 10, wherein the raw material used in step (i) is ZrO2.

12. The method according to claim 10 or claim 11, wherein the lubricant used in step (i) is microcrystalline cellulose, hydroxymethyl cellulose or metal stearate.

13. The method according to any one of claims 10 to 12, wherein the additive is ammonia.

14. The method according to any one of claims 10 to 12, wherein the additive is an acid.

15. The method of claim 14, wherein the additive is nitric acid.

16. The method according to any one of claims 10 to 12, wherein the additive is a zirconium salt.

17. The method of claim 16, wherein the zirconium salt is zirconium nitrate.

18. The method of claim 16, wherein the zirconium salt is zirconium acetate.

19. The method according to any one of claims 10 to 18, wherein in step (ii), the mixture is compressed into a tablet to form a shaped article.

20. The method according to any one of claims 10 to 18, wherein in step (ii), the mixture is extruded to form a shaped article.

21. The method according to any one of claims 10 to 20, wherein the shaped body has a spherical cross-section.

22. The method according to any one of claims 10 to 20, wherein the shaped body has a trilobal cross section.

23. The method of claim 22, wherein the shaped body has a trilobal cross-section with an average diameter of 1.0 mm to 4.0 mm.

24. The method according to any one of claims 10 to 23, wherein during step (iv), the shaped article is calcined at a temperature of 300°C to 500°C.

25. The method according to any one of claims 10 to 24, wherein the carrier is defined according to any one of claims 1 to 9.

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