Nano-zirconium hydroxide, its preparation methods and applications, and catalytic methods for n-butane skeletal isomerization.

Abstract

This invention relates to a nano-zirconium hydroxide, its preparation method, and its application in a catalytic method for n-butane skeletal isomerization. The nano-zirconium hydroxide has a spherical and / or near-spherical morphology with a particle size distribution of 10-30 nm. The nano-zirconium hydroxide described in this invention is particularly suitable as a catalyst support, especially as a support for n-butane isomerization catalysts, and can improve the single-pass conversion of n-butane and the selectivity of isobutane.

Description

Technical Field

[0001] This invention relates to a nano-zirconium hydroxide, its preparation method, and its application in a butane skeleton isomerization catalysis method. Background Technology

[0002] Zirconium hydroxide is an amphoteric hydroxide that is insoluble in water and has a slightly strong alkaline nature. It is non-toxic and odorless, insoluble or slightly soluble in water, insoluble in alcohols, alkalis, and ammonium salt solutions, but readily soluble in inorganic acids such as hydrochloric acid. It decomposes into zirconium dioxide and water at 500℃. Due to its amphoteric nature, it reacts with acids and alkalis, forming crystalline orthozirconates upon melting with strong bases. The zirconium hydroxide initially obtained by reacting an aqueous solution of zirconium salt with an aqueous solution of caustic soda (or ammonia) is called α-zirconic acid, which is soluble in dilute acids. The precipitate formed under heating conditions is called β-zirconic acid, which is sparingly soluble in water and acids.

[0003] Zirconium hydroxide is used in the manufacture of other zirconium compounds, pigments, dyes, and glass. It is primarily used in the preparation of zirconium and zirconium compounds, and also as a filler, catalyst, deodorant, and pigment in the plastics, rubber, and ion exchange resin industries. It is used as an analytical reagent, in the preparation of chromium compounds and the formulation of pigments; and as an intermediate for other zirconium products.

[0004] CN111422904A discloses a method for producing zirconium hydroxide, which includes simultaneously adding zirconium oxychloride solution and alkaline solution into a reaction tank to generate zirconium hydroxide precipitate.

[0005] CN107500351A describes the preparation of zirconium hydroxide by bubbling ammonia gas through a zirconium solution.

[0006] However, the production methods described in these technologies do not disclose how to prepare nano-sized zirconium hydroxide or nano-zirconium hydroxide with regular morphology. Existing technologies also rarely mention how to prepare nano-sized zirconium hydroxide, mostly focusing on how to prepare nano-zirconia. For example, CN101913649B describes the preparation of nano-zirconia by adding a template agent and hydrothermal treatment at 115℃~160℃. This method, using hydrothermal treatment at high temperatures of 115℃~160℃, directly yields crystalline zirconium oxide from solution, but cannot produce amorphous zirconium hydroxide. CN101049965A describes obtaining a zirconium oxalate precursor precipitate using oxalic acid as a precipitant, followed by calcination at 600℃ to decompose and obtain nano-zirconia with an average particle size distribution of 10~30nm. This method also does not involve a zirconium hydroxide intermediate.

[0007] The catalytic performance of zirconium hydroxide is influenced by the atomic arrangement and the number of unsaturated bonds on its surface. The particle size and morphology of zirconium hydroxide significantly affect its surface atomic arrangement and the number of unsaturated bonds, thus impacting its catalytic performance and the preparation of other catalysts based on zirconium hydroxide, such as the solid superacid SO42-. 2-—ZrO2. Preparation of active SO4 2- One of the important conditions for ZrO2 solid superacids is generally considered to be that amorphous hydrated zirconium oxide should be treated with a liquid sulfation reagent, as sulfation of zirconium oxide crystals is ineffective. Summary of the Invention

[0008] The purpose of this invention is to provide a nano-zirconium hydroxide, its preparation method, and its application in the catalytic method of n-butane skeleton isomerization. The nano-zirconium hydroxide described in this invention has a spherical and / or near-spherical morphology, making it suitable for use as a catalyst support.

[0009] To achieve the above objectives, the first aspect of the present invention provides a nano-zirconium hydroxide having a spherical and / or near-spherical morphology and a particle size distribution of 10-30 nm.

[0010] A second aspect of the present invention provides a method for preparing the nano-zirconium hydroxide described herein, the method comprising:

[0011] (1) Mix the template agent with an alkaline solution; the template agent includes benzenesulfonic acid compounds;

[0012] (2) The solution obtained in step (1) is mixed with a zirconium salt aqueous solution to form a precipitate;

[0013] (3) The product obtained in step (2) is subjected to a hydrothermal reaction;

[0014] (4) Cool the product obtained in step (3), separate it to obtain a solid, and dry it to obtain spherical and / or near-spherical nano-zirconium hydroxide.

[0015] A third aspect of the present invention provides the application of the nano-zirconium hydroxide described herein in a catalyst support.

[0016] A fourth aspect of the present invention provides a catalytic method for the skeletal isomerization of n-butane, the catalytic method comprising: contacting a gas containing n-butane with a catalyst and H2, wherein the catalyst contains the nano-zirconium hydroxide described in the present invention.

[0017] Through the above technical solution, the present invention provides nano-zirconium hydroxide with a spherical and / or near-spherical morphology and a particle size distribution of 10-30 nm; in a preferred embodiment of the present invention, the nano-zirconium hydroxide has a narrow particle size distribution.

[0018] The preparation method of nano-zirconium hydroxide described in this invention has the advantages of simple process and easy operation and control.

[0019] The nano-zirconium hydroxide described in this invention is particularly suitable as a catalyst support, especially as a support for isomerization catalysts, and can improve the single-pass conversion of n-butane and the selectivity of isobutane. Attached Figure Description

[0020] Figure 1 This is a scanning electron microscope (SEM) image of the nano-zirconium hydroxide prepared in Example 1;

[0021] Figure 2 This is a transmission electron microscope (TEM) image of the nano-zirconium hydroxide prepared in Example 1;

[0022] Figure 3 This is a scanning electron microscope (SEM) image of the zirconium hydroxide prepared in Comparative Example 1;

[0023] Figure 4 This is a scanning electron microscope (SEM) image of the nano-zirconium hydroxide prepared in Comparative Example 2. Detailed Implementation

[0024] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0025] The first aspect of the present invention provides a nano-zirconia, which has a spherical and / or near-spherical morphology and a particle size distribution of 10-30 nm.

[0026] The nano-zirconia has a narrow particle size distribution. According to a preferred embodiment of the present invention, more than 85% of the nano-zirconia particles are distributed in the 15-25 nm range.

[0027] In this invention, the specific surface area of ​​the nano-zirconium hydroxide can be selected from a wide range. According to a preferred embodiment of this invention, the specific surface area of ​​the nano-zirconium hydroxide is 350-390 m². 2 / g.

[0028] In this invention, the total pore volume of the nano-zirconia hydroxide can be selected within a wide range. According to a preferred embodiment of this invention, the total pore volume of the nano-zirconia hydroxide is 0.42-0.72 cm³. 3 / g.

[0029] In this invention, the average pore size of the nano-zirconia hydroxide can be selected from a wide range. According to a preferred embodiment of this invention, the average pore size of the nano-zirconia hydroxide is 5.4-8.2 nm.

[0030] Nano-zirconium hydroxide possessing the aforementioned properties can achieve the objectives of this invention. This invention does not place particular requirements on the preparation method of the catalytic oxidation catalyst. According to a preferred embodiment of this invention, this invention provides a method for preparing the nano-zirconium hydroxide described herein, the method comprising: the preparation method of the nano-zirconium hydroxide, the method comprising:

[0031] (1) Mix the template agent with an alkaline solution; the template agent includes benzenesulfonic acid compounds;

[0032] (2) The solution obtained in step (1) is mixed with a zirconium salt aqueous solution to form a precipitate;

[0033] (3) The product obtained in step (2) is subjected to a hydrothermal reaction;

[0034] (4) The product obtained in step (3) is cooled, separated to obtain a solid, and dried to obtain spherical and / or near-spherical nano-zirconium hydroxide. The preparation method of nano-zirconium hydroxide described in this invention has the advantages of simple process and easy operation and control.

[0035] In this invention, the range of benzenesulfonic acid compounds is relatively wide. According to a preferred embodiment of this invention, the benzenesulfonic acid compounds are selected from one of the compounds shown in formula (I).

[0036]

[0037] R1, R2, and R3 are each independently selected from hydrogen, amino, hydroxyl, or C1-C12 alkyl groups;

[0038] X is selected from H, Na, or NH4.

[0039] According to a preferred embodiment of the present invention, in formula (I), R1 and R3 are hydrogen; R2 is selected from at least one of hydrogen, amino, hydroxyl, methyl, ethyl and dodecyl.

[0040] According to a preferred embodiment of the present invention, the benzenesulfonic acid compound is selected from at least two of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and 4-hydroxybenzenesulfonic acid, preferably a mixture of p-toluenesulfonic acid and dodecylbenzenesulfonic acid, and more preferably the molar ratio of toluenesulfonic acid to dodecylbenzenesulfonic acid is 0.5-2:1. This enables the support to achieve high activity and selectivity as a catalyst, particularly the activity and selectivity of the isomerization catalyst.

[0041] In this invention, the ratio of the alkaline substance to the zirconium salt in step (2) can be selected over a wide range. According to a preferred embodiment of this invention, the alkaline substance is expressed as OH in molar ratio. - Zirconium salts are calculated as zirconium, OH - Zr = 2:1 - 4.6:1.

[0042] In this invention, the ratio of template agent to zirconium salt in step (2) can be selected over a wide range. According to a preferred embodiment of this invention, the molar ratio of template agent to Zr is 3 to 40: 100.

[0043] In this invention, in step (2), the zirconium salt solution can have a wide range of selectable concentrations. According to a preferred embodiment of this invention, the concentration of zirconium salt in the zirconium salt solution is 10-50 wt%.

[0044] In this invention, in step (2), the mixing temperature can be selected within a wide concentration range. According to a preferred embodiment of this invention, the mixing temperature is 35 to 60°C.

[0045] In this invention, the hydrothermal reaction conditions in step (3) can be selected from a wide range. According to a preferred embodiment of this invention, the hydrothermal conditions include: a temperature of 90℃ to 115℃, preferably 95℃ to 115℃; and / or a time of 8 to 72 hours.

[0046] According to a preferred embodiment of the present invention, in step (4), the product obtained in step (3) is cooled to below 35°C.

[0047] In this invention, there is no particular limitation on the drying conditions in step (4). Conventional drying conditions in the art can achieve the purpose of this invention. The following is an illustrative description, but it does not limit the scope of this invention. According to one embodiment of this invention, the drying conditions include: a drying temperature of 110-120°C; and a drying time that can be determined according to actual needs, preferably 12-24 hours.

[0048] In this invention, the alkaline substance in step (1) can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to one embodiment of this invention, the alkaline substance is selected from at least one of ammonia, sodium hydroxide, sodium carbonate and ammonium carbonate, preferably ammonia.

[0049] In this invention, in step (2), there are many types of zirconium salts that can be selected. According to a preferred embodiment of this invention, the zirconium salt is selected from zirconium oxychloride and / or zirconium nitrate.

[0050] According to a preferred embodiment of the present invention, in step (2), the solution obtained in step (1) is added dropwise to the zirconium salt aqueous solution at a constant flow rate, preferably 10-100 mL / min.

[0051] According to a preferred embodiment of the present invention, in step (3), a hydrothermal reaction is carried out under constant temperature conditions.

[0052] According to a preferred embodiment of the present invention, the method for preparing nano-zirconium hydroxide includes:

[0053] (1) Mix the benzenesulfonic acid compound template agent with ammonia water;

[0054] (2) The solution obtained in step (1) is added dropwise to the zirconium salt aqueous solution at a constant flow rate to generate a precipitate;

[0055] (3) The product obtained in step (2) is subjected to a hydrothermal reaction; the hydrothermal conditions include: temperature of 90℃~115℃; time of 8~72 hours;

[0056] (4) Cool the product obtained in step (3) to obtain a solid, and dry it at 110℃~120℃ to obtain spherical and / or near-spherical nano-zirconium hydroxide.

[0057] A third aspect of this invention provides the application of the nano-zirconium hydroxide described herein in a catalyst support, preferably in the preparation of isomerization catalysts. The nano-zirconium hydroxide described herein is particularly suitable as a catalyst support, especially as a support for n-butane isomerization catalysts, and can improve the single-pass conversion of n-butane and the selectivity of isobutane.

[0058] A fourth aspect of this invention provides a catalytic method for the skeletal isomerization of n-butane, the method comprising: contacting a n-butane-containing feedstock with a catalyst and H2, wherein the catalyst contains the nano-zirconium hydroxide described in this invention. The nano-zirconium hydroxide described in this invention is particularly suitable as a catalyst support, used as a support for a n-butane isomerization catalyst, and can improve the single-pass conversion of n-butane and the selectivity of isobutane.

[0059] In this invention, there is no particular limitation on the type of catalyst, which can be a conventional catalyst active component in the art. Preferably, the catalyst active component is copper oxide and / or aluminum oxide.

[0060] According to a preferred embodiment of the present invention, in the catalyst, the elemental molar ratio is Al:Cu:Zr = (0.4-7):(0.4-7):100.

[0061] In this invention, the catalyst preparation method includes: impregnating aluminum salt and / or copper salt onto the nano-zirconium hydroxide of this invention, followed by drying and calcination.

[0062] In this invention, the contact conditions are not particularly limited and can be conventional n-butane skeleton isomerization catalytic conditions in the art. According to a preferred embodiment of the present invention, the contact conditions include: a temperature of 180-220°C and a pressure of 0.5-1.5 MPa.

[0063] According to a preferred embodiment of the present invention, the hydrogen-hydrogen molar ratio is 0.1-1.

[0064] According to a preferred embodiment of the present invention, the volume hourly space velocity (VHSV) of n-butane is 0.2-2 h⁻¹. -1 .

[0065] The present invention will be described in detail below through embodiments. However, these embodiments do not in any way limit the scope of the present invention.

[0066] In the following examples, the specific surface area, average pore size, and pore volume were measured using a Micrometrics Tristar 3000 specific surface area analyzer.

[0067] Method for testing the particle size of nano-zirconium hydroxide: Based on the obtained electron micrograph, the particle size is calculated according to the TEM image.

[0068] Example 1

[0069] (1) Add 17.2g of p-toluenesulfonic acid to 612g of 10wt% ammonia water, stir to dissolve, and obtain an alkaline solution;

[0070] (2) Add 322.2g of zirconium oxychloride octahydrate to 1000mL of deionized water and stir to dissolve to obtain zirconium solution. At 50℃, add the prepared alkaline solution dropwise (dropping rate is 20mL / min) to the zirconium solution while stirring at a stirring speed of 300rpm.

[0071] (3) After all the ingredients are added, continue stirring for 1 hour, then transfer to a crystallization kettle, heat to 100°C, and keep at a constant temperature for 24 hours.

[0072] (4) Cool the product obtained in step (3) to room temperature, filter, wash with water, and dry the resulting solid in an oven at 120°C for 24 hours; the final supported zirconium hydroxide is numbered ZH-1, and the SEM image is shown below. Figure 1 TEM image Figure 2 The BET characterization data are shown in Table 1.

[0073] The zirconium hydroxide has a spherical and / or near-spherical morphology with a particle size of 10–30 nm, of which 87% is distributed in the range of 15–25 nm. The remaining 13% is distributed in the ranges of ≥10 nm and <15 nm and >25 nm and ≤30 nm.

[0074] Example 2

[0075] (1) Add 23.2g of 4-hydroxybenzenesulfonic acid to 300g of 20wt% sodium hydroxide aqueous solution, stir to dissolve, and obtain an alkaline solution;

[0076] (2) Add 143.1g of zirconium nitrate pentahydrate to 966mL of deionized water and stir to dissolve to obtain zirconium solution. At 35℃, add the prepared alkaline solution dropwise (dropping rate is 100mL / min) to the zirconium solution while stirring at a stirring speed of 300rpm.

[0077] (3) After all the ingredients are added, continue stirring for 1 hour, then transfer to a crystallization kettle, heat to 95°C, and keep at a constant temperature for 72 hours.

[0078] (4) Cool the product obtained in step (3) to room temperature, filter, wash with water, and dry the obtained solid in an oven at 110°C for 24 hours; the final support zirconium hydroxide is numbered ZH-2. The SEM and TEM characterization results are similar to those of ZH-1. The BET characterization data are shown in Table 1.

[0079] The zirconium hydroxide has a spherical and / or near-spherical morphology with a particle size of 10–30 nm. 87% of the zirconium hydroxide is distributed in the range of 15–25 nm. The remaining 13% is distributed in the ranges of ≥10 nm and <15 nm and >25 nm and ≤30 nm.

[0080] Example 3

[0081] (1) Add 10.3g of ammonium dodecylbenzenesulfonate to 533g of ammonia water with a concentration of 10wt%, stir to dissolve, and then add 19.2g of ammonium carbonate to the solution and stir to dissolve to obtain an alkaline solution;

[0082] (2) Add 322.2 g of zirconium oxychloride octahydrate to 322.2 mL of deionized water and stir to dissolve to obtain a zirconium solution. At 60 °C, add the prepared alkaline solution dropwise (dropping rate is 10 mL / min) to the zirconium solution while stirring at a stirring speed of 300 rpm.

[0083] (3) After all the ingredients are added, continue stirring for 1 hour, then transfer to a crystallization kettle, heat to 115°C, and keep at a constant temperature for 8 hours.

[0084] (4) Cool the product obtained in step (3) to room temperature, filter, wash with water, and dry the obtained solid in an oven at 120°C for 24 hours; finally, the carrier zirconium hydroxide was obtained as ZH-3. The SEM and TEM characterization results were similar to those of ZH-1. The BET characterization data are shown in Table 1.

[0085] The zirconium hydroxide has a spherical and / or near-spherical morphology with a particle size of 10–30 nm. 85% of the zirconium hydroxide is distributed in the range of 15–25 nm. The remaining 15% is distributed in the ranges of ≥10 nm and <15 nm and >25 nm and ≤30 nm.

[0086] Example 4

[0087] (1) Add 34.8g of sodium dodecylbenzenesulfonate to 612g of ammonia water with a concentration of 10wt%, stir to dissolve, and obtain an alkaline solution;

[0088] (2) Add 322.2g of zirconium oxychloride octahydrate to 1000mL of deionized water and stir to dissolve to obtain zirconium solution. At 50℃, add the prepared alkaline solution dropwise (dropping rate is 30mL / min) to the zirconium solution while stirring at a stirring speed of 300rpm.

[0089] (3) After all the ingredients are added, continue stirring for 1 hour, then transfer to a crystallization kettle, heat to 110°C, and keep at a constant temperature for 24 hours.

[0090] (4) Cool the product obtained in step (3) to room temperature, filter, wash with water, and dry the obtained solid in an oven at 120°C for 24 hours; the final support zirconium hydroxide is numbered ZH-4. The SEM and TEM characterization results are similar to those of ZH-1. The BET characterization data are shown in Table 1.

[0091] The zirconium hydroxide has a spherical and / or near-spherical morphology with a particle size of 10–30 nm. 86% of the zirconium is distributed in the 15–25 nm range. The remaining 14% is distributed in the ≥10 nm and <15 nm and >25 nm and ≤30 nm ranges.

[0092] Example 5

[0093] The method of Example 1 was followed, except that the template agent was a mixture of 8.6 g of p-toluenesulfonic acid and 16.3 g of dodecylbenzenesulfonic acid; the other conditions were the same as in Example 1. The zirconium hydroxide had a spherical and / or near-spherical morphology with a particle size of 10–30 nm. BET characterization data are shown in Table 1.

[0094] Example 6

[0095] The method is the same as in Example 1, except that the hydrothermal isothermal temperature in step (3) is 90°C; the other conditions are the same as in Example 1. The zirconium hydroxide has a spherical and / or near-spherical morphology with a particle size of 10–30 nm. BET characterization data are shown in Table 1.

[0096] Example 7

[0097] The method of Example 1 was followed, except that the template agent was p-aminobenzenesulfonic acid; the other conditions were the same as in Example 1. The zirconium hydroxide had a spherical and / or near-spherical morphology with a particle size of 10–30 nm. BET characterization data are shown in Table 1.

[0098] Comparative Example 1

[0099] The method of Example 1 was followed, except that in step (1), p-toluenesulfonic acid template agent was not added when preparing the alkaline solution; the other conditions were the same as in Example 1. The final zirconium hydroxide was designated ZH-A, and its SEM image is shown below. Figure 3 Zirconium hydroxide has an irregular morphology and consists of large particles; BET characterization data are shown in Table 1.

[0100] Comparative Example 2

[0101] The method of Example 1 is followed, except that p-toluenesulfonic acid is added to the zirconium oxychloride aqueous solution in step (2) instead of the ammonia solution in step (1); specifically as follows:

[0102] (1) Measure 612g of ammonia water with a concentration of 10wt% as an alkaline solution;

[0103] (2) Add 17.2g of p-toluenesulfonic acid and 322.2g of zirconium oxychloride octahydrate to 1000mL of deionized water and stir to dissolve to obtain a zirconium solution. At 50℃, add the prepared alkaline solution dropwise (dropping rate is 20mL / min) to the zirconium solution while stirring at a stirring speed of 300rpm.

[0104] (3) After all the ingredients are added, continue stirring for 1 hour, then transfer to a crystallization kettle, heat to 100°C, and keep at a constant temperature for 24 hours.

[0105] (4) Cool the product obtained in step (3) to room temperature, filter, wash with water, and dry the resulting solid in an oven at 120°C for 24 hours; finally, zirconium hydroxide, designated ZH-B, was obtained. SEM image is shown below. Figure 4 Zirconium hydroxide has an irregular morphology and consists of large particles; BET characterization data are shown in Table 1.

[0106] Table 1

[0107]

[0108] Examples 8-14

[0109] The zirconium hydroxide prepared in Examples 1-7 was used as a support to prepare catalysts for the isomerization of n-butane.

[0110] Catalyst preparation: 6.3 g of aluminum sulfate octadechydrate and 4.7 g of copper sulfate pentahydrate were placed in a beaker and dissolved in an appropriate amount of water. The prepared aqueous solution was added dropwise to 50 g of zirconium hydroxide while stirring (initial wet impregnation method). After all the solution was added, stirring was continued for a period of time to ensure uniform mixing. After standing at room temperature for 24 h, the mixture was dried in an oven at 130 °C for 24 h. Finally, it was calcined in a muffle furnace at 600 °C for 4 h to obtain the n-butane isomerization catalyst.

[0111] Catalyst evaluation method: The performance evaluation of the n-butane skeletal isomerization catalyst was carried out in a fixed-bed reactor with a reaction tube size of 5 mm × 40 cm, a catalyst loading of 5 mL, and a particle size of 20-40 mesh. The reactor was placed in the constant temperature zone of the furnace. The reaction temperature was 200℃, the hydrogen pressure was 1 MPa, and the butane volume hourly space velocity was 1 h⁻¹. -1 The hydrogen-to-hydrogen molar ratio was 1:1. The catalyst required activation before use. Activation was performed by heating in a nitrogen stream containing 10% hydrogen by volume at 350°C for 8 hours. The catalyst performance evaluation results are shown in Table 2.

[0112] Comparative Examples 3-4

[0113] The method of Example 8 was followed, except that the zirconium hydroxide prepared in Comparative Examples 1-2 was used to prepare the catalysts, while the other conditions were the same as in Example 8. The catalyst performance evaluation results are shown in Table 2.

[0114] Table 2

[0115]

[0116]

[0117] As can be seen from the results in Table 2, the n-butane isomerization catalyst prepared using zirconium hydroxide as a support according to the present invention has better activity.

[0118] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A nano-zirconium hydroxide, characterized in that, The nano-zirconia has a spherical and / or near-spherical morphology with a particle size distribution of 10-30 nm; more than 85% of the nano-zirconia particles have a particle size distribution of 15-25 nm; and the total pore volume of the nano-zirconia is 0.42-0.72 cm³. 3 / g; the average pore size of the nano-zirconium hydroxide is 5.4-8.2nm.

2. The nano-zirconium hydroxide according to claim 1, wherein, The specific surface area of ​​the nano-zirconium hydroxide is 350-390 m². 2 / g.

3. A method for preparing nano-zirconium hydroxide as described in claim 1 or 2, characterized in that, The method includes: (1) Mix the template agent with an alkaline solution; the template agent includes benzenesulfonic acid compounds; (2) The solution obtained in step (1) is mixed with an aqueous solution of zirconium salt to form a precipitate; (3) The product obtained in step (2) is subjected to a hydrothermal reaction; (4) Cool the product obtained in step (3), separate it to obtain a solid, and dry it to obtain spherical and / or near-spherical nano-zirconium hydroxide; The benzenesulfonic acid compound is selected from one of the compounds shown in formula (I); （I） Formula (I), R1 and R3 are hydrogen; R2 is selected from at least one of hydrogen, amino, hydroxyl, methyl, ethyl and dodecyl, and X is selected from one of H, Na or NH4; In step (3), the hydrothermal conditions include a temperature of 90℃-115℃.

4. The preparation method according to claim 3, wherein, The benzenesulfonic acid compound is selected from at least two of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and 4-hydroxybenzenesulfonic acid.

5. The preparation method according to claim 4, wherein, The benzenesulfonic acid compound is a mixture of p-toluenesulfonic acid and dodecylbenzenesulfonic acid, with a molar ratio of toluenesulfonic acid to dodecylbenzenesulfonic acid of 0.5-2:

1.

6. The preparation method according to claim 3 or 4, wherein, In molar ratio, alkaline substances are expressed as OH- - Zirconium salts are calculated as zirconium, OH - Zr = 2-4.6:1; and / or On a molar ratio, template agent: Zr = 3-40:100; and / or The concentration of zirconium salt in the aqueous solution is 10-50 wt%; and / or In step (2), the mixing temperature is 35-60℃; and / or In step (3), the hydrothermal conditions include: a temperature of 90℃-115℃ and a time of 8-72 hours; and / or In step (4), the product obtained in step (3) is cooled to below 35°C; and / or In step (4), the drying conditions include a drying temperature of 110-120℃.

7. The preparation method according to claim 3 or 4, wherein, In step (1), the alkaline substance is selected from at least one of ammonia, sodium hydroxide, sodium carbonate, and ammonium carbonate; and / or In step (2), the zircon salt is selected from zirconium oxychloride and / or zirconium nitrate; In step (2), the solution obtained in step (1) is added dropwise to the zirconium salt aqueous solution at a constant flow rate; and / or In step (3), the hydrothermal reaction is carried out under constant temperature conditions.

8. The preparation method according to claim 7, wherein, In step (1), the alkaline substance is ammonia; and / or In step (2), the solution obtained in step (1) is added dropwise to the zirconium salt aqueous solution at a constant flow rate of 10-100 mL / min.

9. The application of the nano-zirconium hydroxide as described in claim 1 or 2 in a catalyst support.

10. The application according to claim 9, wherein, The application of the aforementioned nano-zirconium hydroxide in the preparation of isomerization catalysts.

11. A catalytic method for the skeletal isomerization of n-butane, characterized in that, The method includes contacting a n-butane-containing feedstock with a catalyst and H2, wherein the catalyst contains the nano-zirconium hydroxide as described in claim 1 or 2.

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