Acidic Zirconium Hydroxide

Abstract

To provide acidic zirconium hydroxides and oxides, production methods of the same, compositions containing acidic zirconium hydroxides and oxides, and the use of these hydroxides and oxides in catalytic and adsorption applications.SOLUTION: The invention relates to a zirconium hydroxide or zirconium oxide containing one or more dopants containing silicon, sulfate, phosphate, tungsten, niobium, aluminum, molybdenum, titanium, or tin in an amount in terms of an oxide of up to 30 wt% and having an acid point, with a majority of the acid point being a Lewis acid point.SELECTED DRAWING: Figure 6a

Description

[Technical Field]

[0001] The present invention relates to an acidic zirconium hydroxide and a method for producing the same, Compositions containing hydroxides and oxides thereof, and their use in catalytic and adsorption applications - Patent Application 20070122997 Concerning the use of things. [Background technology]

[0002] Zirconium hydroxide, due to its known amphoteric properties, is a suitable ion exchange material for phosphates and arsenates. It has a strong ability for selective adsorption of a wide range of different toxic anions.

[0003] Zirconium oxide, with or without stabilizers, is used in environmental, automotive and chemical catalysts. It has found application in many heterogeneous catalysis, including as a catalyst. and important processes such as hydrocarbon synthesis from CO and H2, CO2 and H2, or alcohol dehydration. The catalytic activity of ZrO2 in the reaction has also been studied.

[0004] Zirconium hydroxide has also been widely used as a support for metals. Oxides are also used to stabilize metals or to make the metal more resistant to sintering. The tungstate ion-containing cations have been incorporated into the support to produce The stabilized zirconium hydroxide exhibits super-strong acidic behavior and is effective in isomerizing hydrocarbons or methanol. Zirconium hydroxide has been found to provide high activity for the conversion of alcohol to hydrocarbons. Silicon substitution into hydroxides has been found to increase the acidity of mixed oxides produced from the hydroxides. The resulting material has good catalytic activity at high temperatures and is compatible with liquefied natural gas (LNG) fuel engines. It is currently being tested as a potential methane oxidation catalyst for engines. In the literature for the elemental forms of various dopants, the dopant generally corresponds to zirconium hydroxide. Thus, for example, silicon includes silicates and colloidal silicon. The tungsten includes tungstate and the like.

[0005] The commercial success of zirconium hydroxide materials in catalysis is primarily due to fine processing methods and and other stabilizers can improve their physical and chemical properties. This allows for fine tuning of key parameters of the catalyst support. Different applications require different combinations of properties, but thermal stability, high surface area and Porosity is a requirement for most catalytic applications. Improve product morphology Through improvements in the manufacturing process to achieve this, changes in the balance of acid-base properties may also be observed. These properties are also found in silica, aluminum, sulfate, phosphate, molybdenum, Also notable is the inclusion of dopants such as tin, tungsten, niobium, and titanium. can be significantly affected.

[0006] Thus, porosity is an important but not crucial criterion for effective catalytic behavior. An equally significant role in the final catalytic performance is played by surface acidity. The surface acidity is achieved by, for example, terminal and bridging OH groups in zirconium hydroxide. The strength of the acid sites, as well as their concentration and type (Brönstein's It has been shown that the determination of the β-adaptation (β-adaptation) is important in assessing the suitability of a catalyst for a particular application. The acid characteristics of solid surfaces can be determined by methods including visual color change; spectrophotometry; amine titration, etc. A variety of methods are used to assess sexuality.

[0007] Adsorption of gaseous bases, especially pyridine, combined with infrared (IR) analysis reveals the presence of acid species on the surface. It is accepted as a common method for identifying species for two main reasons: The first reason is that the amount of base adsorbed from the gas phase is related to the concentration and strength of the acid sites on the solid surface. This is because the total concentration of acid sites on the catalyst surface is highly correlated with the surface area of ​​the catalyst. The second reason is that different IR adsorption bands corresponding to the formation of different complexes are By differentiating the properties of the active site.

[0008] Temperature-programmed desorption (TPD) is widely used to characterize acidic / basic sites on oxide surfaces. TPD is another well-known technique that is used to estimate the amount and quality of active sites on zirconium hydroxide. can serve as a measure of strength, which is important for understanding and predicting catalyst performance. is.

[0009] The properties of zirconium hydroxide and zirconium oxide are strongly dependent on the manufacturing method. In the pamphlet of International Publication No. 2004 / 096713, zirconium oxide and A method for producing a zirconium-based mixed oxide is described. In the presence of sulfate anions, zirconium salts are formed by reaction with alkali at temperatures below 50°C. This involves precipitating zirconium hydroxide from an aqueous solution. This produces zirconium oxide that is essentially sulfate-free. In Japanese Patent Application Laid-Open No. 2000-247641 and Japanese Patent Application Laid-Open No. 2000-247641, a base is added to the sulfate slurry. By adding zirconium hydroxide to the sulphate, However, the methods described in these documents do not achieve the improvements of the present invention. Zirconium hydroxide having the desired pore volume, pore size and surface area characteristics is not available. .

[0010] The improved porous properties of amorphous zirconium hydroxide and its preparation are described in International Publication No. WO 2004 / 024990. The hydroxide is described in the pamphlet of 007 / 088326. 00m 2 / g surface area of ​​at least 0.70 cm 3 / g total pore volume, and 5nm to 15 (a) A compound containing sulfate anions and zirconium salts in a specific ratio. (b) cooling the solution to below 25°C; (c) preparing an aqueous solution containing amorphous dibenzofuran; (d) adding alkali to precipitate zinc hydroxide; The ammonium hydroxide is filtered and washed with water or alkali to remove residual sulfates and chlorides. (e) hydrothermally treating the zirconium hydroxide at a pressure of less than 3 barg; and (f) drying the zirconium hydroxide. The hydroxide of ammonium hydroxide is prepared.

[0011] Improvements to the amorphous materials described in WO 2007 / 088326 Despite the enhanced porous properties, the improved thermal stability of the fired material and the tailored porous / crystalline structure The design of the structure (including the possibility of forming pores of a certain size and phase content) and the specific surface (acid / base) properties are desired. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] International Publication No. 2004 / 096713 Pamphlet [Patent Document 2] Japanese Patent Publication No. 11-292538 [Patent Document 3] Patent Publication No. 2000-247641 [Patent Document 4] The present invention is further described by reference to the following drawings, which are not intended to limit the scope of the invention as claimed. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a graph showing nitrogen adsorption isotherms for the acidic zirconium hydroxides of Comparative Example 2 and Preparation Example 2. [Figure 2a] FIG. 2a shows the NH3-TPD profiles for the acidic zirconium oxides of Comparative Examples 1 and 2 and Preparation Examples 1 and 2 when calcined at 600°C / 2 hours. [Figure 2b] FIG. 2b shows the CO2-TPD profiles for the acidic zirconium oxides of Comparative Examples 1 and 2 and Preparation Examples 1 and 2 when calcined at 600°C / 2 hours. [Figure 3] FIG. 3 shows the XRD data of the acidic zirconium hydroxides of Comparative Examples 1 and 2 and Preparation Examples 1-4 when dried at 110°C. [Figure 4] FIG. 4 shows the XRD data for the acidic zirconium oxides of Comparative Examples 1 and 2 and Preparation Examples 1 and 2 when calcined at 450° C. for 2 hours. [Figure 5] FIG. 5 shows TPD-MS data showing the intensity at 41 amu as a function of temperature for a) the virgin materials of Comparative Examples 1, 2, and 5 and Preparative Examples 1 and 2, and b) the calcined doped materials of Comparative Examples 4 and 8 and Preparative Examples 5, 6, and 7. [Figure 6]FIG. 6 shows the DRIFT spectra of pyridine-saturated acidic zirconia samples recorded in vacuum at 100° C. for a) freshly calcined samples of zirconium hydroxide materials from Preparative Examples 1 and 2 and Comparative Examples 1, 2, and 5, and b) calcined doped zirconium oxides from Preparative Examples 5-7 and Comparative Examples 4, 5, and 8. [Figure 7] FIG. 7 is a diagram showing the NH3-TPD profiles for the tungsten-stabilized zirconium oxides of Comparative Examples 3 and 4 and Preparation Examples 5 and 8 when calcined at 700°C for 2 hours. [Figure 8] FIG. 8 shows XRD data for the tungsten-stabilized zirconium oxides of Comparative Examples 3 and 4 and Preparation Examples 5 and 8 when fired at 700° C. for 2 hours. [Figure 9] FIG. 9 shows the NH3-TPD profiles for the silica-stabilized zirconium oxides of Comparative Examples 7 and 8 and Preparative Examples 7 and 10 when calcined at 850°C for 2 hours. [Figure 10] FIG. 10 shows the XRD data of the silica-stabilized zirconium oxides of Comparative Examples 7 and 8 and Preparative Examples 7 and 10 when calcined at 850° C. for 2 hours. [Figure 11] FIG. 11 is a diagram showing the NH3-TPD profiles for the sulfate-stabilized zirconium oxides of Comparative Examples 5 and 6 and Preparation Examples 6, 9, 11 and 12 when calcined at 600°C for 2 hours. [Figure 12] FIG. 12 shows XRD data for the sulfate-stabilized zirconium oxides of Comparative Examples 5 and 6 and Preparation Examples 6 and 9 when calcined at 600° C. for 2 hours. [Figure 13] FIG. 13 shows the TG-DTA profiles for the acidic zirconium hydroxides of Comparative Examples 1 and 2 and Preparation Examples 1 and 2 when dried at 110°C. DETAILED DESCRIPTION OF THE INVENTION

[0014] Presentation of the invention According to the present invention, there is provided a zirconium hydroxide or zirconium oxide as defined in the following embodiments of the invention. For all embodiments of the invention, the zirconium hydroxide or zirconium oxide can be defined as acidic. The majority of the acid sites of the zirconium hydroxide and zirconium oxide can also be Lewis acid sites. This is the case for a Lewis acid site with a valence of about 1600-1620 cm. -1 and approximately 1440-1450cm -1 1700~1400cm -1 This can be indicated by the highest intensity peak in the DRIFT spectrum of zirconium hydroxide in the range of about 1600-1620 cm. More specifically, zirconium hydroxide and zirconium oxide may have more Lewis acid sites than Bronsted acid sites. This can be indicated by the highest intensity peak in the DRIFT spectrum of zirconium hydroxide in the range of about 1600-1620 cm. -1 and approximately 1440-1450cm -1 The peak in the DRIFT spectrum of zirconium hydroxide is approximately 1630-1640 cm -1 and approximately 1530-1550 nm -1 In the context of the present invention, the term "acid site" is used to refer to acid species available for reaction. Acid sites can include Bronsted acid sites, i.e., proton donors (e.g., protons on terminal surface OH groups, SO3H groups, or other surface groups), and Lewis acid sites, i.e., electron acceptors (e.g., Zr atoms). Zirconium oxides or zirconium hydroxides can contain up to 30% by weight, more specifically up to 16% by weight, based on the oxide, of dopants including one or more of silicon, sulfate, phosphate, tungsten, niobium, aluminum, molybdenum, titanium, or tin. All zirconium oxides and zirconium hydroxides can contain up to 30% by weight, more specifically up to 16% by weight, based on the oxide, of dopants including one or more of silicon, sulfate, phosphate, tungsten, niobium, aluminum, molybdenum, titanium, or tin. Mu hydroxy acid It should be noted that the oxide contains about 1.5 to 2% by weight of hafnium oxide or hydroxide as an impurity, based on the oxide, which is not included in the amount of "unavoidable impurities" described below.

[0015] According to one aspect of the present invention, silicon, sulfate, phosphate, tungsten, Dopants containing one or more of niobium, aluminum, molybdenum, titanium, or tin are added at 0. and providing a zirconium hydroxide containing less than 1% by weight of zirconium hydroxide, the zirconium hydroxide being porous. and for pores with a pore diameter of up to 155 nm, At least 70% have pore diameters between 3.5 and 155 nm as measured using the BJH method. In particular, zirconium hydroxide has a silicon content on an oxide basis. , sulfates, phosphates, tungsten, niobium, aluminum, molybdenum, titanium, tin , rare earth metals, or yttrium. More specifically, for pores with a pore diameter of up to 155 nm, the pore volume At least 75% of the pores have a pore diameter between 3.5 and 155 nm as measured using the BJH method. In particular, pores having a pore diameter of up to 155 nm. With respect to the pore volume, less than 30%, more specifically less than 25%, is obtained using the BJH method. This can be provided by pores having a pore diameter of less than 3.5 nm as measured by a pore size measuring instrument. In this context, pore diameters between 3.5 and 155 nm are considered to be mesoporous / macroporous. pore diameters less than 3.5 nm are defined as microporous.

[0016] In particular, zirconium hydroxide has a concentration of at least 0.01% as measured by N2 physisorption. 75cm 3 / g, more specifically at least 0.80 cm 3 / g total pore volume In particular, the zirconium hydroxide has a diameter of at least 6.0 nm, more particularly at least It may have an average pore diameter of 6.5 nm.

[0017] In particular, zirconium oxide was measured by XRD (X At least 80% by weight, more specifically at least 82% by weight, as measured by X-ray diffraction % of the monoclinic phase.

[0018] In particular, zirconium hydroxide has at least Also, zirconium hydroxide may have an acid loading of 1300 μmol / g. has a T below 365°C as measured by propylamine TPD max , and even more Specifically, T below 360°C max may have:

[0019] This aspect of the invention also generally involves calcining (e.g., at temperatures above 450°C) the above-mentioned Zirconium obtained or obtainable from the defined zirconium hydroxide More specifically, silicon, sulfate, phosphate, tungsten, niobium, aluminum Dopants containing one or more of aluminum, molybdenum, titanium, or tin are 0% on an oxide basis. and contains less than 0.1 wt. % of cellulose and has a solubility of at least 5% after firing at 600°C for 2 hours in air. 0m 2 / g, and more specifically a surface area of ​​at least 52 m 2 / g surface area More specifically, zirconium oxide is provided in the presence of silicon, sulfate, Salt, phosphate, tungsten, niobium, aluminum, molybdenum, titanium, tin, rare earth Dopants containing one or more of the following metals or yttrium are contained in an amount of less than 0.1% by weight on an oxide basis. In particular, zirconium oxide can be produced by firing at 600°C for 2 hours in an air atmosphere. have an acid loading of at least 100 μmol / g as measured by propylamine TPD More specifically, zirconium oxide can be calcined in an air atmosphere at 600°C for 2 hours. A total pore volume of at least 0.35 cm3 / g as measured by N2 physisorption after In particular, the zirconium oxide may have the following properties after calcination at 600° C. for 2 hours in an air atmosphere: It may have an average pore diameter of at least 25.0 nm. More specifically, The ammonium oxide exhibits basicity, and when measured by TPD (temperature programmed desorption), it has a temperature of 400-600°C. ℃, and more specifically in air atmosphere After calcination at 600 °C for 2 h, the material was characterized by a CO2 uptake of at least 16 μmol / g. Let's say.

[0020] Additionally, this aspect of the invention provides a method for producing a metal oxide containing silicon, sulfate, phosphate, tungsten, niobium, aluminum, or the like. A dopant containing one or more of aluminum, molybdenum, titanium, titanium or tin is added to the oxide. After firing at 900°C for 2 hours in an air atmosphere, the content is less than 0.1% by weight. 15m 2 / g, and even more specifically at least 16m 2 Zirconium dioxide with a surface area of ​​1 / g In particular, zirconium oxide is sintered in air at 900°C for 2 hours. After formation, the surface area is at least 0.10 cm as measured by N2 physisorption. 3 / g total fineness More specifically, zirconium oxide is heated to 900° C. in an air atmosphere. After calcining at rt for 2 hours, the porous silica may have an average pore diameter of at least 26.0 nm.

[0021] More specifically, zirconium hydroxide or zirconium oxide is, on an oxide basis, at least 98% by weight purity, and even more particularly at least 99% by weight purity (as defined above). hafnium oxide or hydroxide impurities).

[0022] Zirconium hydroxide or the corresponding calcined oxide is also preferred, especially in the range of 3.5 to 5 They exhibit useful physical properties such as high pore volume associated with pore diameters in the 0 nm range. , zirconium hydroxide, or the corresponding calcined oxide, with P / P0>0.6 The nitrogen isotherm of type IV hysteresis loop of H3 with mesoporosity can be shown.

[0023] According to a second aspect of the present invention, 0.1 to 30% by weight of silicon hydroxide or A doped zirconium oxide containing silicon oxide is provided, wherein the zirconium The aluminum oxides, measured by TPD after calcination at 850°C for 2 hours, are at least It has an NH3 uptake of 3.5 μmol / l. More specifically, it is silicon-doped. Zirconium oxide was calcined in air at 850°C for 2 hours and then measured by TPD. When measuring, it is at least 4.0 μmol / m 2 , and more specifically at least 4.25 μmol / m 2 In particular, silicon doped The zirconium oxide was calcined in air at 850°C for 2 hours and then analyzed by TPD. At least 330 μmol / m when measured by 2 , more specifically, at least 360 μmol / m 2 In particular, silicon-doped di- The vanadium oxide was calcined in air at 850°C for 2 hours and then treated with NHTPD. When measuring, T max , more specifically a T of at least 285°C max As mentioned above, this oxide is generally obtained by calcination (e.g., 45 at temperatures above 0°C) from the corresponding zirconium hydroxide, or It is possible.

[0024] In particular, silicon-doped zirconium oxide was calcined at 850°C for 2 hours in an air atmosphere. and an acid charge of at least 170 μmol / m3 as measured by propylamine TPD. It may have a filling.

[0025] Additionally, embodiments of the present invention also provide a method for producing a cellulose acetate solution having a cellulose acetate content of at least 54% by weight as measured by N2 physisorption. 0m 2 / g surface area of ​​at least 0.90 cm 3 / g total pore volume Regarding zirconium hydroxide, when calcined in an air atmosphere at 850°C for 2 hours, TPD At least 3.5 μmol / m 2 There is NH3 uptake.

[0026] More specifically, silicon-doped zirconium hydroxide or silicon-doped zirconate The oxides are present in an amount of 1 to 10% by weight, more specifically 1 to 5% by weight, based on the oxides. Specifically, it may contain 2.5 to 4.5% by weight of silicon hydroxide or silicon oxide. The residue of the boron-doped zirconium oxide is, on an oxide basis, zirconium oxide and 0. It may contain up to 3% by weight of unavoidable impurities.

[0027] According to a third aspect of the present invention, at least 400 m 2 / g of surface area of ​​the oxide group Doped zirconia containing 0.1 to 30 wt. % tungsten hydroxide or oxide as a standard. More specifically, tungsten-doped zirconium hydroxide is provided. The monster is at least 450m 2 / g, and even more specifically at least 500m 2 / g It can have a surface area.

[0028] In particular, tungsten-doped zirconium hydroxide exhibited excellent solubility when measured by the N2 physical adsorption method. In this case, at least 0.7 cm 3 / g, more specifically at least 0.8 cm 3 / g total pores It can have a volume.

[0029] In particular, this aspect of the invention generally involves calcining (e.g., at temperatures above 450°C) the above-mentioned tungsten-doped zirconium hydroxide as defined above, or obtained from The present invention also relates to a tungsten-doped zirconium oxide that can be used for the purpose of the present invention. When measured by TPD after firing at 700°C for 2 hours in an oxygen atmosphere, the oxide content was 0. 1 to 30% by weight, at least 4.30 μmol / m 2 Tungsten with NH3 uptake and providing a tungsten-doped zirconium oxide containing tungsten hydroxide or oxide. More specifically, tungsten-doped zirconium oxide was heated in an air atmosphere for 7 At least 420 μmol / g as measured by TPD after baking at 00°C for 2 hours , and even more specifically may have an NH3 uptake of at least 460 μmol / g .

[0030] In particular, tungsten-doped zirconium oxide was found to be oxidized at 700°C for 2 hours in an air atmosphere. At least 260 μmol / L as measured by propylamine TPD after baking for 1 hour. g, and more specifically, it can have an acid filling amount of at least 280 μmol / l.

[0031] More specifically, tungsten-doped zirconium hydroxide or tungsten-doped zirconium oxide may have 12 - 20% by weight, and even more specifically 14 - 18% by weight of tungsten hydroxide or oxide based on the oxide. In particular, the residue of tungsten-doped zirconium oxide may contain zirconium oxide and up to 0.3% by weight of unavoidable impurities.

[0032] According to a fourth aspect of the present invention, there is provided a doped zirconium hydroxide having 0.1 - 30% by weight, more specifically 1 - 12% by weight, and even more specifically 1 - 10% by weight of sulfate based on the oxide, and having a surface area of at least 375 m 2 / g. More specifically, the sulfate-doped zirconium hydroxide may have a surface area of at least 400 m m 2 / g.

[0033] In particular, when the sulfate-doped zirconium hydroxide is measured by the N2 physical adsorption method, it may have a total pore volume of at least 0.50 cm 3 / g, more specifically at least 0.60 cm 3 / g. In particular, the sulfate-doped zirconium hydroxide may have an average pore diameter of at least 5.5 nm, and more specifically at least 6.0 nm. In particular, an aspect of the present invention generally provides, or can provide, a sulfate-doped zirconium hydroxide as defined above obtained by firing (e.g., at a temperature of 450 °C or higher).

[0034] ​ The present invention also relates to a sulfate-doped zirconium oxide that can be produced by heating at 600°C in an air atmosphere. After baking at 2°C for 2 hours, the concentration is at least 800 μmol / l, and better, as measured by TPD. More particularly at least 850 μmol / l, even more particularly at least 900 μmol / l mol / l NH3 uptake, containing 0.1-30 wt.% sulfate on an oxide basis In particular, sulfate-doped zirconium oxide is provided. The rhenium oxide is 1 to 12% by weight of sulfate, more specifically 1 to 10% by weight of sulfate, based on the oxide. % by weight of sulfates.

[0035] In particular, sulfate-doped zirconium oxide was sintered at 600°C for 2 hours in an air atmosphere. At least 800 μmol / g as determined by propylamine TPD after synthesis , more specifically, it can have an acid loading of 900 μmol / g.

[0036] More specifically, sulfate-doped zirconium oxide is heated at 600°C in an air atmosphere. After baking for 2 hours at 40°C, the 2 / g surface area, and more specifically less Both 150m 2 In particular, zirconium oxide can have a surface area of ​​1 / g. When measuring by physical adsorption, after calcining at 600°C for 2 hours in an air atmosphere, 0.30cm 3 / g, more specifically at least 0.32 cm 3 / g total pore volume More specifically, zirconium oxide can be heated in an air atmosphere at 600°C for 2 hours. After baking for a short time, the average surface roughness is at least 8.5 nm, and even more specifically at least 9.0 nm. It may have a uniform pore diameter.

[0037] The present invention provides a method for producing a polymer having controlled acidic and basic properties both in the bulk and on the surface. This invention relates to the acidic zirconium hydroxide and acidic zirconium oxide.

[0038] In some embodiments, silicon, tungsten, sulfate, phosphate, niobium, aluminum Zirconium hydroxide or oxide doped with aluminum, molybdenum, titanium, or tin The compound may contain additional dopants, particularly to help stabilize the bulk morphology. The additional dopant may be a rare earth hydroxide or oxide, or yttrium hydroxide or oxide, or any other transition metal hydroxide or oxide not already mentioned. This further dopant is present in an amount of less than 25% by weight, more particularly 0.1 to 10% by weight, based on the oxide. It may be present in a concentration of 25% by weight, in particular zirconium hydroxide or zirconium oxide. The total zirconium content will not be less than 50% by weight on an oxide basis. In an embodiment, the zirconium hydroxide of the present invention contains less than 5% by weight of cerium hydroxide, more particularly Specifically, less than 2% by weight cerium hydroxide, and even more specifically less than 1% by weight cerium hydroxide. In some embodiments, the zirconium hydroxide contains substantially no cerium. Not at all.

[0039] As mentioned above, zirconium hydroxide or a further stabilized or doped zirconium hydroxide may be used. The zirconium hydroxide can be calcined to the corresponding oxide. These oxides generally exhibit acidic properties, but some also exhibit strong basic properties. The temperature at which the composition is heated depends on the dopants added to the composition. Regarding the above, a very high firing temperature may lead to the loss of the dopant from the composition. For example, in the case of a composition containing sulfate, the firing temperature is less than 650°C, more specifically The firing temperature should be between 400 and 650°C. For compositions containing tungsten, the firing temperature should be between 8 and 100°C. It should be below 50°C, more specifically 400-800°C. For other compositions The firing temperature may be 400 to 1000°C, more specifically 450 to 800°C.

[0040] In particular, the zirconium hydroxide was substantially amorphous as determined by XRD. More specifically, zirconium hydroxide may be measured by laser light scattering. If so, the d is less than 100 μm, more specifically 10 to 50 μm. 50 It may have a particle size .

[0041] To be useful in catalytic or adsorption applications, the compositions defined herein contain 250 ppm less than 250 ppm Na and / or less than 250 ppm K, more particularly less than 200 ppm, and More specifically, it may contain less than 125 ppm of Na and / or K. The content of Na and / or K may be less than 50 ppm.

[0042] According to a fifth aspect of the present invention, the above zirconium hydroxide and / or zirconium acid A catalyst, catalyst support or adsorbent comprising any of the compounds is provided.

[0043] According to a further aspect of the present invention, there is provided a method for producing zirconium hydroxide, the method comprising the steps of: The method comprises the following steps: (a) dissolving a zirconium salt in an aqueous acid; (b) adding one or more complexing agents to the resulting solution or sol; The complexing agent is an organic compound containing at least one of the following functional groups: amine, organic sulfate, sulfonate, hydroxyl, ether or carboxylic acid groups, That is, (c) heating the solution or sol formed in step (b); (d) adding a sulfating agent; (e) adding a base to form zirconium hydroxide; and (f) optionally adding a dopant.

[0044] When zirconium hydroxide, optionally containing a dopant, is produced in this manner, the resulting The material has a higher percentage of mesopores than previously achieved. For undoped zirconium hydroxide calcined at 1000 K, improved thermal stability was achieved. The undoped zirconium hydroxide also has a higher proportion of the monoclinic phase. It can be shown that:

[0045] In some embodiments, the zirconium salt is zirconium basic carbonate or zirconium carbonate. In certain embodiments, zirconium basic carbonate can be a mineral acid. It is readily soluble, commercially available, and the produced carbonate anion is fugitive, and the Zirconium basic carbonate (ZBC) is preferred because the carbonate anion does not participate in complex post-reactions. Some alternative anions may be less desirable from an environmental point of view. In some embodiments, the aqueous acid may be hydrochloric acid, sulfuric acid, nitric acid, or acetic acid, particularly aqueous acid. The preferred acid is nitric acid. Without wishing to be bound by any theory, other acids may be used. However, the nitrate ions provided by nitric acid react particularly well with the zirconium ions in the aqueous solution. It is thought that it coordinates well with

[0046] In particular, in step (a), the zirconium ions in the solution or the sol are The molar ratio of nium ions is 1:0.8 to 1:2, and particularly 1:0.8 to 1:1.5. Ugh.

[0047] In the context of the present invention, the term complexing agent means a ligand that binds to zirconium. In some embodiments, in step (b), the complexing agent is carboxylic acids, dicarboxylic acids, alpha hydroxycarboxylic acids, amino acids, organic sulfates, or polycarboxylic acids In particular, the complexing agent may be a polydentate ligand, more particularly a bidentate ligand. The polyol may be a polysaccharide, such as starch. In particular, the complexing agent may be an alpha hydroxyl group. The complexing agent generally has a polar group (i.e., amine, organic sulfate, sulfonate, hydroxyl, ether, or carboxylic acid group), and In some embodiments, the one or more hydrocarbon groups are It may contain one or more aromatic substituents, more particularly one or more phenyl substituents. Without wishing to be bound by theory, it is believed that multidentate ligands effectively coordinate to metal ions. The combination of different functional groups within the same molecule interacts with different coordination environments on the metal ion. It is advantageous for the pore size to function and can provide both steric and electronic effects. Depending on the size and nature of the pore network, complexing agents with different hydrocarbon groups are used. For example, the alpha hydroxycarboxylic acid may be an aromatic (e.g., phenyl) or non-aromatic alpha hydroxycarboxylic acids, more specifically mandelic acid or benzilic acid Or it may be lactic acid, and even more particularly mandelic acid.

[0048] In particular, in step (a), the solution formed may be heated. °C, more specifically at least 40°C, even more specifically at least 50°C More specifically, the melt may be heated to a temperature in the range of 50 to 70°C. The liquid may be heated to about 60°C.

[0049] Optionally, in step (a), increasing the pH of the solution by adding a base This increase in pH is due to the reduction in free acidity. In particular, the pH increase should be carried out before heating the solution. More specifically, the base may be sodium hydroxide, sodium carbonate, sodium bicarbonate, or the like. Sodium, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, potassium hydroxide The soluble solids may be potassium carbonate, potassium bicarbonate, and / or potassium hydrogen carbonate.

[0050] In particular, step (b) further comprises adding water, typically deionized water, to the heated solution. More specifically, in step (b), after the addition of the complexing agent, the solution contains ZrO2 5 to 25% by weight, more specifically 10 to 20% by weight, and even more specifically has an equivalent zirconium content of 12-16 wt. % expressed as ZrO2. The equivalent zirconium content, expressed as 2, is, for example, 100 g of a 15 wt. % solution is 15 g This means that it has the same zirconium content as ZrO2.

[0051] More specifically, in step (c), the heating is performed by heating the solution or sol to 60 to 100°C, More specifically, it may include heating at a temperature of 80 to 100°C for 1 to 15 hours. The heating may be carried out for 1 to 5 hours. More specifically, in step (c), The temperature of the solution or sol can be increased at a rate of 0.1 to 1.5°C / min. In this context, linear (i.e., constant) heating rates are used, as well as nonlinear heating rates (e.g., fast The heating rate refers to a heating rate that includes both a fast initial heating rate followed by a slower heating rate. The process usually provides the optimal polymer / oligomer size for mesoporous powder preparation. This is done to assist.

[0052] In particular, in step (d), the solution or sol is allowed to cool before adding the sulfating agent. More specifically, the solution or sol can be cooled to a temperature below 40°C, or More specifically, it can be cooled to a temperature below 30°C. Suitable sulfating agents are the water-soluble salts of sulfates, bisulfates, sulfites, and bisulfites. The oxidizing agent can be sulfuric acid. The sulfating agent can be a molar ratio of zirconium ions to sulfate ions of The ratio of sulfur dioxide to sulfur dioxide in step (d) can be 1:0.05 to 1:1. After the addition of the acid salt, the method of the present invention involves removing from the solution or sol, for example by filtering, There may be a step of isolating the solid.

[0053] In step (e), the pH of the solution or sol is adjusted to pH > The base can be sodium hydroxide, sodium carbonate, sodium bicarbonate, Sodium, ammonium hydroxide, ammonium carbonate, ammonium bicarbonate, potassium hydroxide More specifically, the step ( In e), the addition of a base forms a precipitate of zirconium hydroxide. The pH to which the sol can be adjusted depends on the base used. either ammonium hydroxide or alkali metal hydroxide, more specifically sodium hydroxide In the case of ammonium hydroxide, the maximum achievable pH is typically about pH 10.5-1. In the case of alkali metal hydroxides, the pH can be adjusted to 11 to 13 or higher. Cut.

[0054] Step (e) is performed at any temperature at which the solution or sol does not freeze, i.e., −5° C. to 95° C. More specifically, it can be carried out at 10°C to 80°C.

[0055] In some embodiments, the method of the present invention further comprises adding a dopant after step (e). This may include a step (f) of forming a silicon dioxide film by doping the dopant in step (e). This invention is advantageous in that it is added after step (e) rather than being co-precipitated with the ammonium hydroxide. This is a novel feature of the method of the invention. In particular, the dopant may be, for example, a surface stabilizer or a bulk stabilizer. The agent can be any material that stabilizes the tetragonal phase of zirconia. The dopant phase can provide improved catalytic performance. More specifically, the dopants can be silicon, sulfate, phosphate, titanium, etc. containing one or more of the following: tin, niobium, aluminum, molybdenum, titanium, or tin Even more specifically, the dopant may be one of sulfate, silicon, or tungsten. The sulfate may comprise one or more of sulfuric acid, ammonium sulfate, sodium sulfate, or other sulfates. It can be added in the form of a salt; silicon can be added as aqueous colloidal silica or sodium silicate. and tungsten can be added in the form of silica, such as tungsten. It is added in the form of a tungstate such as sodium tungstate or ammonium metatungstate. Step (f) can be performed after step (e) and after the drying step described below. This can be done at any point during manufacturing before the cap.

[0056] In some embodiments, the method of the present invention further comprises, after step (e), and after step (f). The method may further comprise a step (g) of heat treating the zirconium hydroxide before or after the step (g). The treatment may be hydrothermal treatment. The hydrothermal treatment is carried out by heating the solution or sol in an autoclave for 0.5 to 24 hours. The method may further comprise heating to a temperature of 50 to 250°C, particularly 100 to 250°C, for a short time.

[0057] More specifically, between step (e) and step (g) and / or during step (g) After step (f), and before or after step (f), the method of the present invention may be carried out by simply filtering, for example. The method may further comprise the steps of separating the zirconium hydroxide and / or washing the zirconium hydroxide. These steps may be carried out by adding chloride ions, sulfate ions, phosphate ions, nitrate ions, Acetate ions, sodium ions, potassium ions, ammonium ions and / or organic residues This can be done to remove residues. Sulfates or phosphates are added as dopants. In the case of compositions without added ions, the amount of sulfate or phosphate ions is 0.3% by weight or less; More specifically, it can be reduced to 0.1% by weight or less. The amount of chloride ions is 0.05% by weight or less, more specifically 0.01% by weight or less. % or less, and even more specifically, each can be reduced to 0.005% by weight or less.

[0058] The alkali metal ions are obtained by reslurrying the washed zirconium hydroxide and adding mineral acid. In particular, the mineral acid may be nitric acid or sulfuric acid, more particularly Specifically, it can be nitric acid. The nitric acid concentration can be about 10% by weight to 60% by weight. The pH of the solution is generally adjusted to less than 9, preferably between 6.5 and 9. After the filtration step, the method of the present invention involves redispersing the precipitate in an aqueous medium and The resulting dispersed slurry or wet cake (wet cake-like substance) is heated to 100°C to 350°C, particularly There may be an optional step of heating to 100°C to 200°C. The reaction temperature can be up to 100° C. in a closed reaction vessel such as a reactor or in an open vessel.

[0059] In some embodiments, the method of the present invention comprises step (e), step (f) or If step (g) is performed, it may be performed after step (e) or after step (f) or Step (g) may be followed by step (h) of drying the zirconium hydroxide. In particular, step (h) may be by oven drying, spray drying or vacuum drying. Drying should be carried out in an oxidizing, inert (e.g., N2) or reducing atmosphere. More specifically, zirconium hydroxide is dried at a temperature of 50 to 200°C. If a vacuum is used, the drying temperature may be at the lower end of this range. If not, temperatures at the higher end of this range, for example 100-150°C, may be required.

[0060] In some embodiments, the method of the present invention further comprises step (f) and / or step (g). If step (g) is not performed, or step (e) or step (f) ), followed by a step (h) of calcining the zirconium hydroxide to form zirconium oxide. More specifically, the firing step may be performed at a temperature of 400 to 1100°C, and more preferably Specifically, the firing step can be carried out at a temperature of 600 to 850°C. It can be performed for 15 hours, more specifically 2 to 8 hours, and even more specifically 2 to 3 hours. The calcination step can be carried out in any gas atmosphere, especially a reducing or Although a neutral atmosphere can be used, the firing step can be carried out in a static or flowing air atmosphere. The method of the present invention may be carried out in air, as this can assist in the removal of organic species. A neutral atmosphere is generally preferred. A neutral atmosphere generally does not oxidize or reduce the composition in that atmosphere. This is defined as the absence of air or oxygen from the atmosphere. A further example of a neutral atmosphere is a nitrogen atmosphere. The atmosphere may be that of combustion gases produced from a gas-fired kiln. The time may depend on the thermal mass to be fired and the required degree of crystallinity, homogeneity , and a sufficient time at that temperature to ensure acidity and development of the solid microstructure. After calcination, zirconium oxide (which is doped) is The composition may be formed or compressed, for example, by granulation, pelleting, tableting or extrusion. These forming or pressing steps may include the addition of a binder. may optionally include

[0061] The method of the present invention deagglomerates or pulverizes zirconium hydroxide or zirconium oxide. An optional additional step may be to add zirconium hydroxide or oxide powder. Zirconium in the form of powder or a slurry (e.g., wet) in an aqueous or non-aqueous liquid. This step can be performed on the hydroxide or oxide of the silica. , using known methods such as opposed air pulverization, impact pulverization, ball mill pulverization, and bead mill pulverization. It can be implemented.

[0062] The present invention also relates to compositions obtained by the above method, as well as methods for using the obtained materials. Applications include, but are not limited to, catalysts, catalyst supports or precursors, binders, functional materials, and the like. Functional binders, coatings and adsorbents. [Example]

[0063] The present invention will be described below with reference to examples.

[0064] Comparative Example 1 A solution of basic zirconium sulfate in deionized water containing 200 g of ZrO2 equivalent was prepared. A 28% by weight aqueous solution of sodium hydroxide was added until the pH of the solution reached 13. The solution was added dropwise to the solution, and the precipitated zirconium hydroxide product was then filtered. The wet cake was reslurried in deionized water and washed to obtain 2000 g of A slurry was obtained which was hydrothermally treated at 1 barg for 1 hour and then dried at 110°C.

[0065] Comparative Example 2 Samples were prepared according to the method described in EP 1984301 That is, 394.84 g of 20% by weight aqueous sulfuric acid solution, 18.28 g of deionized water, and 9 66.18 g of zirconium oxychloride (20.7 wt. % ZrO), and The solution was cooled to -2°C. Then, 10% by weight of sodium hydroxide was added until the pH of the solution reached 8. The solution was titrated with 28% by weight of sodium hydroxide until the pH of the solution reached 13. The precipitated zirconium hydroxide product was then filtered and The wet cake was reslurried in deionized water and washed at 1 barg for 1 hour. The mixture was then hydrothermally treated for 1 h and then dried at 110°C.

[0066] Comparative Example 3 Before the hydrothermal treatment of 2000 g of the slurry, the oxide group in the obtained zirconium hydroxide was 8 wt% sodium tungstate to target 15.8 wt% WO3 as standard. A sample was prepared according to Comparative Example 1, except that an aqueous solution was added. After adjusting the pH to 6.7, the resulting slurry was filtered and washed with deionized water.

[0067] Comparative Example 4 Before the hydrothermal treatment, the obtained zirconium hydroxide contained 15.8 wt. % W on an oxide basis. Add 328g of 8% by weight sodium tungstate aqueous solution to target O3 A sample was prepared according to Comparative Example 2, except that the slurry was adjusted to pH 6 with nitric acid. After adjusting to 0.7, the resulting slurry was filtered and washed with deionized water.

[0068] Comparative Example 5 Prior to hydrothermal treatment, 390 g of the wet cake was slurried in deionized water and the resulting In order to target 10 wt. % SO3 on an oxide basis in the zirconium hydroxide added, A sample was prepared according to Comparative Example 1, except that 127.1 g of a 20 wt % aqueous sulfuric acid solution was added. Made.

[0069] Comparative Example 6 Prior to hydrothermal treatment, 977 g of the wet cake was slurried in deionized water and the resulting In the zirconium hydroxide, 180% SO3 was targeted on an oxide basis. A sample was prepared according to Comparative Example 2, except that 0.9 g of 20 wt % aqueous sulfuric acid solution was added. .

[0070] Comparative Example 7 Before the hydrothermal treatment, 24.17 g of colloidal silica solution (Ludox AS-30) was added The solution was added to 1761.22 g of the slurry prepared according to Comparative Example 1. When the solution reached a pH of 11, A 28 wt % aqueous solution of sodium hydroxide was added dropwise until the precipitated mixed zirconia was dissolved. The aluminum hydroxide product was filtered and washed. The wet cake was reslurried to give It was hydrothermally treated at 1 barg for 5 hours and then dried at 110°C.

[0071] Comparative Example 8 Prior to hydrothermal treatment, 900 g of the washed wet cake was slurried in deionized water. 22.6 g of 30 wt % colloidal silica solution (Ludox AS-30) was added. Otherwise, the samples were prepared according to Comparative Example 2.

[0072] Preparation Example 1 537.63 g of basic zirconium carbonate (containing 37.2% ZrO2) was dissolved in 49% dilute nitric acid. 0.81 g of HCl (to achieve a target NO3 / Zr ratio of 1.2). The mixture was heated to 60°C. 2.759 g of mandelic acid was added to the solution along with 390.8 g of water. The solution was then heated again at 94°C for 2 hours.

[0073] The resulting solution was mixed with 465.31 g of deionized water, followed by a 20% by weight aqueous solution of sulfuric acid. 394.84 g of ethanol was added to the mixture. The pH of the resulting solution was then adjusted to 100 with dilute sodium hydroxide. The pH was adjusted to 13.0 with sodium hydroxide solution. The resulting slurry was then filtered and washed. The wet cake was hydrothermally treated at 1 barg for 1 hour and then dried at 110°C.

[0074] Preparation Example 2 537.63 g of basic zirconium carbonate (containing 37.2% ZrO2) was dissolved in 49% dilute nitric acid. 0.81 g of ZnO (to achieve a target NO3 / Zr ratio of 1.45). The solution was heated. 2.759 g of mandelic acid was added to the solution along with 390.8 g of water. The solution was then heated again at 94°C for 2 hours.

[0075] The resulting solution was mixed with 564.01 g of deionized water, followed by a 20 wt % aqueous solution of sulfuric acid. 394.84 g of ethanol was added to the mixture. The pH of the resulting solution was then adjusted to 100 with dilute sodium hydroxide. The pH was adjusted to 13.0 with an aqueous sodium hydroxide solution. The resulting slurry was then filtered and washed. The wet cake was hydrothermally treated at 1 barg for 1 hour and then dried at 110°C.

[0076] Preparation Example 3 The sample was prepared according to the procedure described in Preparation Example 1, except that a small amount of mandelic acid (1. 226g) was used to prepare the samples.

[0077] Preparation Example 4 The sample was prepared according to the procedure described in Preparation Example 2, except that a small amount of mandelic acid (1. 226g) was used to prepare the samples.

[0078] Preparation Example 5 Prior to hydrothermal treatment, 1891.2 g of the slurry was dissolved in 258 g of aqueous sodium tungstate. The resulting zirconium hydroxide contained 15.8% by weight of WO3 on an oxide basis. The sample was prepared according to Preparation Example 1, except that the target was The pH was adjusted to 6.7 with dilute nitric acid, and the resulting slurry was then filtered and washed with deionized water. .

[0079] Preparation Example 6 The same procedure as in Preparation Example 1 was repeated except that dilute sulfuric acid was added after the hydrothermal treatment and before drying. The samples were prepared according to the procedure. The samples were then dried at 110°C and analyzed on an oxide basis. The target SO3 content of 10 wt% was achieved.

[0080] Preparation Example 7 A sample of zirconium hydroxide wet cake was prepared according to Preparation Example 1. Prior to treatment, 30 wt% colloidal silica solution (Ludox AS-30) 12.46 The sample was then dried at 110°C to achieve the target SiO2 content on an oxide basis. It got 3.5%.

[0081] Preparation Example 8 The sample was prepared according to the procedure described in Preparation Example 5, where NO3 / Zr=1.4 Different ratios of initial reagents were used to give 5.

[0082] Preparation Example 9 Prepare the sample according to the procedure described in Preparation Example 6, and the NO3 / Zr ratio will be 1.45. Different ratios of initial reagents were used as shown.

[0083] Preparation Example 10 Prepare a sample according to the procedure described in Preparation Example 7, with NO3 / Zr = 1.45. Different ratios of initial reagents were used as shown.

[0084] Preparation Example 11 Before the hydrothermal treatment, 1812.7 g of the washed slurry was adjusted to pH 6.5 with dilute sulfuric acid. The sample was prepared according to the procedure described in Preparation Example 1, with the exception of the oxide A SO3 content of 6.5 wt% was obtained on the basis.

[0085] Preparation Example 12 A 28 g sample prepared according to the procedure described in Preparation Example 1 was mixed with dilute sulfuric acid. This was then further dried at 110°C for 3 hours to achieve the target SO3 content of 10% by weight on an oxide basis. obtained.

[0086] Materials and Methods The samples prepared in the various examples were analyzed as prepared, except that for analytical purposes To determine the Na content, samples were calcined in static air at various temperatures for 2 hours. In this case, the concentration is less than 200 ppm by liquid ion chromatography (Methro m IC 761).

[0087] SO3 content was measured using the Eltra Carbon Sulfur Analyzer CS. 800 was measured.

[0088] Porosity characteristics Surface area, pore diameter, and total pore volume measurements were performed using a Micromeritics TriSt The analysis was carried out by liquid nitrogen adsorption at -196°C using an AR 3020 analyzer. The sample was degassed under vacuum at 90°C for 30 minutes. Surface area: The surface area was measured by BET multipoint measurements. Total pore volume: The pore volume measurement was performed during desorption at p / p° = 0.9814. Pore ​​size distribution and average pore diameter: The pore size distribution was measured to determine the average pore size in the range of 1.7 to 300 nm. The BJH method (desorption branch) was used to calculate the average width vs. incremental pore volume. The percentage of micropores (%) was calculated based on the BJH pore size distribution plot.

[0089] Particle size Particle size distribution was measured by light scattering using a Microtrac X100 equipped with an ASVR unit. To confirm the validity of the measurement results, a standard sample was run prior to analysis. The ASVR unit was pre-loaded with 0.05% Nopcosant K dispersant. The oven automatically filled to the desired level, approximately 0.100 g of dry sample was added, and then the oven was turned on to 40 W. The internal ultrasonic probe was set to treat for 60 seconds. The pre-circulation time was 30 seconds, and the operating time was The time was set to 50 seconds. The sample was measured three times (according to Mie scattering theory) and the average result was obtained and reported. He declared.

[0090] Thermogravimetric analysis (TGA) TG-DTA (thermogravimetric analysis-differential thermal analysis) experiments (sample weight loss (TG) and exothermic D Measurement of TA signals (e.g., crystallization temperature) was performed using a Setsys-EVO-DTA instrument. 50 mg of sample was placed in a 100 μl Pt crucible and heated in a 20% O2 / He atmosphere. The temperature was raised from 20 to 1000°C at a heating rate of 10°C / min in an atmosphere (flow rate: 20 ml / min). The experimental progress and data analysis were carried out by Data Acquisition System. This was performed using etsys-1750 CS Evol software.

[0091] X-ray diffraction (XRD) Powder XRD phase analysis of zirconia-based materials was performed using a Bruker D8 Advance X-ray diffusion system (Diffrac. EVA software, Bragg-Brenta no geometry, LYNXEYE detector, C in the 2θ range from 10° to 70° u radiation (λ=1.5418Å), 0.015° per unit step, The test was performed under the following conditions: time of 0.2 seconds, 0.02 mm Ni filter, applied power 40 mV / 40 mA Diffraction of the zirconia sample was measured using TOPAS software (version 4.2). Quantitative phase analysis was performed on the patterns. Reference materials were used for peak identification (B Tetragonal zirconia / monoclinic zirconia loaded by ruker). Data evaluation. included peak search, manual / automatic background subtraction and data smoothing. The determination of the particle size was carried out by the Scherrer method, K=0.9.

[0092] Loss of Intake (LOI) Loss on ignition (LOI) was measured using a Vecsrar unit under a constant flow of air. The sample (2 g) was heated at a rate of 3°C / min to the desired temperature (typically 1000°C, but For the fluorine-doped samples, the temperature is increased to 800°C. The sample was then held at that temperature for at least 60 minutes until no weight change over time was observed. .

[0093] Acidity measurement (for pre-calcined samples) NH3 / CO2-Temperature Programmed Desorption (TPD)-Measurements were performed using an AMI200 instrument. A 0.2g sample was heated in a flow of argon (20ml / min) from ambient temperature to the maximum temperature of the experiment. Temperature (undoped sample = 600 °C; sulfate = 544 °C; tungstate = 700 °C; The sample was then heated to a temperature of 800°C (silica doped) at a ramp rate of 20°C / min. After 45 minutes at this temperature, the mixture was cooled to 100°C and diluted with 5% NH3 / He (or 5% CO2 / He) is flowed over the sample at 100°C for 30 minutes (20 ml / min). The pool was exposed to a helium stream at 100 °C for 1 h to remove any unadsorbed NH3 / C O2 was removed from the system and a stable baseline was obtained with a thermal conductivity detector (TCD). The temperature was increased from 100°C to the maximum temperature in the experiment at 10°C / min in a helium flow (20 ml / min) with a residence time of 100°C. TPD experiments were performed up to 100°C. NH3 or CO2 uptake was monitored based on the TCD response. Quantitative analysis is performed based on pulse calibration, whereby 5% NH3 / He or a series of pulses of known volumes (527 microliters) of 5% CO2 / He The sputum was injected into the carrier stream and the TCD response was recorded.

[0094] Propylamine adsorption / thermogravimetric analysis / mass spectrometry (TGA-MS) - this analysis is performed on samples This was done by exposing the filter to propylamine overnight. Mett equipped with a um ThermoStar™ GSD 301 T3 mass spectrometer Temperature-programmed desorption on a Toledo TGA / DSC 2 STARe System Before the procedure, excess physisorbed propylamine was removed under vacuum at 30°C. Considering the mass change of the acid, the mass loss was calculated based on the temperature range of 200-800°C. The number of points was calculated.

[0095] Ex-situ pyridine adsorption - This analysis is performed by impregnating the sample with the appropriate pyridine. The excess physisorbed pyridine was removed in a vacuum oven at 30°C overnight. The sample was then placed in an environmental cell used for diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. Before filling the tube, the sample was diluted (10 wt. % in KBr). The film was vacuum dried at 100°C for 15 min to remove moisture that had been physically adsorbed during exposure to air.

[0096] result The test results are shown in Tables 1 to 7 below. The tables show the following: Table 1 - Various properties of acidic zirconium hydroxide Table 2 - Acidity measured by NH3 / CO2-TPD after baking at 600°C for 2 hours Surface properties of zirconium hydroxide. Table 3 - XRD phase ratio analysis of sample calcined at 450°C for 2 hours Table 4 - Propylamine - Fresh and at 600°C as measured by TPD Surface properties of acidic zirconium hydroxide calcined for 2 hours Table 5 - Tungsten measured by NH3-TPD after firing at 700°C for 2 hours Surface properties of stabilized zirconium hydroxide. Table 6 - Silica stabilization measured by NH3-TPD after calcination at 850°C for 2 hours Surface properties of zirconium hydroxide. Table 7 - Sulfate stabilization measured by NH3-TPD after calcination at 600°C for 2 hours Surface properties of zirconium hydroxide.

[0097] According to the method route of the present invention, undoped zirconia after firing at high temperature (900°C) The results show improved thermal stability and predominantly mesoporous structure compared to the hydroxides and corresponding oxides. It is shown that the calcined undoped zirconium hydrate retains good porosity. Oxide materials show a greater influence from the monoclinic phase, which may be important for certain applications of the material. The porosity of the doped hydroxides can also be compared to the benchmarks tested. For both types of materials (undoped / doped), the acidity (acid point There is generally a significant increase in the intensity of

[0098] Regarding acidity: The concentration, strength and type of acid sites were determined by propylamine adsorption / TGA-M This was confirmed by S (Fig. 5) and ex-situ pyridine adsorption (DFTIR) (Fig. 6). From the data (peak areas) shown in Figure 5a, it is clear that commercially available sulfated zirconia - a known ultra-strong Compared to the acid, the undoped zirconium hydroxide sample has a significantly higher acid loading. In addition, the strong acidity of all samples was observed at the propene release temperature (41 The acid strength is evidenced by the acidity of Sample 1 and Sample 2 (comparison, about 36 8°C) to the sample 3 (352°C) and sample 4 (346°C) of the present invention. ℃), exceeding the standard benchmark (423℃). The data obtained demonstrate that the materials of the present invention are strongly acidic even without the addition of stabilizing dopants. It has been demonstrated that the material of the present invention can be obtained without the addition of a stabilizing dopant. This makes it unique over other known zirconias.

[0099] The drift spectrum of the pyridine-impregnated sample (Figure 6) shows a peak at 1446 cm -1 and 160 4cm -1 The presence of an absorbance peak in the test sample – the main characteristic of a Lewis acid site This proves the Lewis acid properties of the compound.

[0100] Doped materials (such as sulfate, tungsten, or silica) contribute to the acidity and porosity properties. The same trend was observed for the standard commercial grades. The porosity increased by 30% and the acidity (measured by NH3-TPD) increased by 25% (Tables 5, 6 and and 7), which has a positive impact on catalyst activity, making them more popular in the heterogeneous catalyst market. Become competitive.

[0101] [Table 1]

[0102] [Table 2]

[0103] [Table 3]

[0104] [Table 4]

[0105] [Table 5]

[0106] [Table 6]

[0107] [Table 7]

Claims

1. A porous zirconium hydroxide containing less than 0.1 wt. % of a dopant, including a sulfate, based on the oxide, the porous zirconium hydroxide is at least 99% pure by weight, on an oxide basis, excluding hafnium oxide or hydroxide impurities; 1. A porous zirconium hydroxide, wherein, with respect to pores having a pore diameter of up to 155 nm, at least 70% of the pore volume of said porous zirconium hydroxide is provided by pores having a pore diameter of 3.5 to 155 nm, as measured using the BJH method.

2. 2. The porous zirconium hydroxide of claim 1, wherein, with respect to pores having a pore diameter up to 155 nm, at least 75% of the pore volume of said porous zirconium hydroxide is provided by pores having a pore diameter of 3.5 to 155 nm, as measured using the BJH method.

3. 3. The porous zirconium hydroxide of claim 1, wherein, for pores having a pore diameter of up to 155 nm, less than 30% of the pore volume of the porous zirconium hydroxide is provided by pores having a pore diameter of less than 3.5 nm, as measured using the BJH method.

4. 4. The porous zirconium hydroxide according to claim 1, wherein, with respect to pores having a pore diameter of up to 155 nm, less than 25% of the pore volume of the porous zirconium hydroxide is provided by pores having a pore diameter of less than 3.5 nm, as measured using the BJH method.

5. N ２ At least 0.75 cm as measured by physical adsorption ３ The porous zirconium hydroxide according to any one of claims 1 to 4, having a total pore volume of 1 / g.

6. N ２ At least 0.80 cm as measured by physical adsorption ３ 6. The porous zirconium hydroxide of claim 5, having a total pore volume of 1 / g.

7. 7. The porous zirconium hydroxide according to claim 1, having an average pore diameter of at least 6.0 nm.

8. 8. The porous zirconium hydroxide of claim 7, having an average pore diameter of at least 6.5 nm.

9. 9. The porous zirconium hydroxide of any one of claims 1 to 8, having an acid loading of at least 1300 μmol / g as measured by propylamine TPD.

10. 10. The porous zirconium hydroxide of any one of claims 1 to 9, having a Tmax of less than 365°C as measured by propylamine TPD.

11. 11. The porous zirconium hydroxide of claim 10, having a Tmax of less than 360°C as measured by propylamine TPD.

12. After firing at 600°C for 2 hours in an air atmosphere, ２ The porous zirconium hydroxide according to any one of claims 1 to 11, having a surface area of ​​1 / g.

13. 13. The porous zirconium hydroxide according to any one of claims 1 to 12, comprising one or more additional dopants selected from rare earth hydroxides or oxides, yttrium hydroxide or oxide, or other transition metal hydroxides or oxides, such that the total zirconium content of the zirconium hydroxide or zirconium oxide is at least 50% by weight on an oxide basis.

14. A catalyst, catalyst support or precursor, binder, functional binder, coating or adsorbent comprising the porous zirconium hydroxide of any one of claims 1 to 13.

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