阅读说明：本技术 硫酸化氧化锆催化剂及其制备方法和应用 (Sulfated zirconia catalyst, preparation method and application thereof ) 是由 刘波 吕建刚 许烽 周海春 金萍 于 2019-10-24 设计创作，主要内容包括：本发明公开了硫酸化氧化锆催化剂及其制备方法和应用。该制备方法以简单锆盐、其它金属硫酸盐为前驱体,经简单研磨、焙烧制得的氧化锆固体超强酸催化剂,具有步骤少、不产生废水、不消耗水、能耗少等优点。该正丁烷异构化催化剂的活性组分包括铝与镓中的一种或两种和硫。本发明的正构烷烃异构化催化剂不含易流失的卤素,同时催化剂对原料中的氧、硫等杂质含量不敏感,在正丁烷骨架异构化反应中显现较高的催化活性,具有较好的应用前景。(The invention discloses a sulfated zirconia catalyst, a preparation method and application thereof. The preparation method takes simple zirconium salt and other metal sulfates as precursors, and the zirconium oxide solid super acidic catalyst is prepared by simple grinding and roasting, and has the advantages of few steps, no waste water generation, no water consumption, low energy consumption and the like. The active component of the n-butane isomerization catalyst comprises sulfur and one or two of aluminum and gallium. The normal paraffin isomerization catalyst does not contain halogen which is easy to lose, is insensitive to the content of impurities such as oxygen, sulfur and the like in the raw materials, shows higher catalytic activity in the normal butane skeletal isomerization reaction, and has better application prospect.)

1. A method of preparing a sulfated zirconia catalyst, comprising the steps of:

s2, mixing IIIA transition metal sulfate, zirconium salt and optional sugar powder to obtain a mixture;

s3, roasting the mixture obtained in the step S2, and forming to obtain a sulfated zirconia catalyst;

and an optional step S1 of pulverizing the IIIA group transition metal sulfate, the zirconium salt, and the optional sugar to obtain a powder.

2. The method of claim 1, wherein the group iiia transition metal is selected from one or more of aluminum and gallium, preferably including aluminum and gallium;

and/or the zirconium salt is selected from one or more of zirconium nitrate and zirconium oxychloride, preferably zirconium nitrate;

and/or, the sugar is selected from one or more of glucose, fructose and sucrose, preferably glucose.

3. The method of claim 1 or 2, wherein the sugar is present in an amount of 0.5% to 2.0% by weight based on the total weight of the group iiia transition metal sulfate and zirconium salt;

and/or the atomic molar ratio of the IIIA group transition metal in the IIIA group transition metal sulphate to the zirconium in the zirconium salt is (0.01-40):100, preferably (2-20): 100.

4. A method according to any one of claims 1 to 3, wherein the roasting air flow rate is 10 to 100mL/min, preferably 50 to 100 mL/min; and/or the roasting temperature is 500-800 ℃, preferably 600-700 ℃; and/or the time of calcination is 1 to 5 hours.

5. A catalyst prepared according to the process of any one of claims 1 to 4, comprising 0.5 to 3.0% by weight of one or more of aluminium and gallium in the range 1.0 to 6.0% by weight and 0.5 to 2.5% by weight of sulphur.

6. A method of activating a catalyst prepared by the method of any one of claims 1 to 4 or the catalyst of claim 5, comprising the step of heating the catalyst in a stream of air prior to use.

7. The method as claimed in claim 6, wherein the activation temperature is 380 ℃ and 480 ℃, and/or the activation time is 2-4h, and/or the air flow rate is 30-60 mL/min.

8. Use of a catalyst prepared according to the process of any of claims 1 to 4 or a catalyst according to claim 5 in a n-butane skeletal isomerization reaction.

9. Use according to claim 8, wherein the n-butane skeletal isomerization reaction is carried out under hydrogen conditions.

10. The process according to claim 9, wherein the n-butane skeletal isomerization reaction temperature is 180 ℃ and/or the pressure is 0.5 to 1.5MPa and/or the butane volume space velocity is 0.2 to 2h^-1And/or a hydrogen to hydrocarbon molar ratio of 0.1 to 1.0.

Technical Field

The invention belongs to the field of heterogeneous catalyst preparation, and relates to a sulfated zirconia catalyst, and a preparation method and application thereof.

Background

Industrially, n-butane is mainly derived from catalytic cracking units. In 2016, the yield of catalytic cracking by-product liquefied petroleum gas in China reaches 3504 ten thousand tons, about 35 percent of resources supply carbon four for deep processing, and the n-butane resources are rich. The alkylate oil production scale is largest in the C four industry chain at present, and is used for the MTBE production scale. With the vigorous popularization of urban natural gas, the consumption of liquefied gas in cities is greatly reduced, the price falls back, and the liquefied gas becomes a prime power for driving the carbon four deep processing project.

With the increasing strictness of the environmental protection requirement, the upgrading pace of gasoline quality is quickened in China, and the national V-standard gasoline is completely supplied in China from 1 month and 1 day in 2017. The main content of the gasoline standard upgrading in China is to meet the requirements of 'desulfurization, manganese reduction and olefin reduction' of gasoline under the condition of ensuring the octane number. The octane number of the gasoline is difficult to reach the standard by reducing the olefin and the aromatic hydrocarbon, so the development of high-octane number clean components for blending the gasoline is very key. The hydrocarbon alkylation oil has the advantages of higher octane number, low volatility, no aromatic hydrocarbon and olefin, almost no sulfur and the like, and is very suitable for oil blending. One of the feedstocks for the production of hydrocarbon alkylate oil is isobutane, and therefore the development of a catalyst for the production of isobutane by skeletal isomerization of n-butane is of great importance for clean gasoline production.

The isomerization catalyst is generally of the platinum halide/alumina type, with gamma-Al₂O₃As a carrier, and a proper amount of chloride auxiliary agent is required to be continuously added into the raw materials in the operation process. The main problems of the technology are that the content of water and sulfur in the raw materials is strictly required to be less than 0.1ppm, and meanwhile, chlorine-containing substances generated in the reaction process are corrosive to equipment, so that the material cost and the maintenance cost of the equipment are increased, and the environment is polluted.

The n-butane skeletal isomerization catalyst using zirconia as a carrier does not contain chlorine, has loose requirements on the moisture content and the sulfur content of raw materials, can be regenerated, and is the development direction of the isomerization catalyst. As is known, the preparation process of the catalyst generally produces 'three wastes' pollution, which not only brings environmental protection pressure, but also increases the cost of the catalyst, so that the simple, convenient, efficient and clean preparation of the catalyst is an important proposition of industrial catalysis. The following patents disclose the preparation of zirconium oxide catalysts for isomerization of alkanes such as n-butane.

Patent CN1660973A discloses an isomerization method of C5, C6 alkane, the preparation process of the catalyst comprises: reacting the zirconium salt solution with an alkali solution to prepare zirconium hydroxide; mixing zirconium hydroxide and silica sol, and drying; containing SO₄ ^2-Dipping and drying the solution; dipping in metal salt solution, drying and roasting.

Patent CN106732676A discloses a n-butane isomerization catalyst, which is prepared by coprecipitation of zirconium salt, gallium salt solution and ammonia water or urea aqueous solution, filtration, washing and drying to obtain a precursor, then impregnating other component solutions, drying and roasting to finally obtain ZrO₂A catalyst.

Patents CN106140197A and CN106101797B disclose a solid super acidic catalyst, a preparation method thereof, and an isomerization method of light normal paraffin, wherein the catalyst is prepared by coprecipitation of ammonia water and a metal salt solution, filtering, washing, drying, impregnation step by step, drying, and finally roasting.

From the above publications, it is known that SO is currently used for butane isomerization₄ ^2-/ZrO₂The catalyst is prepared through the reaction of zirconium salt and ammonia water to produce zirconium hydroxide precipitate, filtering, washing and drying to obtain catalyst precursor, and soaking in SO-containing solution₄ ^2-Solution and metal salt solution, and finally drying and roasting to obtain the catalyst. The method has multiple preparation steps and long flow, alkaline wastewater containing ammonia and the like is generated, a large amount of water is consumed when the precipitate is washed to be neutral, and the energy consumption is high after multiple drying.

Disclosure of Invention

In order to achieve the above object, a first aspect of the present invention provides a method for preparing a sulfated zirconia catalyst, comprising the steps of:

s2, mixing IIIA transition metal sulfate, zirconium salt and optional sugar powder to obtain a mixture;

and S3, roasting the mixture obtained in the step S2, and forming to obtain the sulfated zirconia catalyst.

According to some embodiments of the present invention, there is further included a step S1 of pulverizing the group iiia transition metal sulfate, the zirconium salt, and optionally the sugar to obtain a powder.

According to some embodiments of the invention, the group iiia transition metal is selected from one or more of aluminum and gallium.

According to some embodiments of the invention, the group iiia transition metal comprises aluminum and gallium.

According to some embodiments of the invention, the zirconium salt is selected from one or more of zirconium nitrate and zirconium oxychloride.

According to some embodiments of the invention, the zirconium salt is zirconium nitrate.

According to some embodiments of the invention, the sugar is selected from one or more of glucose, fructose, sucrose.

According to some embodiments of the invention, the sugar is glucose.

According to some embodiments of the invention, the sugar is present in an amount of 0.5% to 2.0% by weight of the total weight of the group iiia transition metal sulfate and zirconium salt.

According to some embodiments of the invention, the atomic molar ratio of the group IIIA transition metal in the group IIIA transition metal sulfate to the zirconium in the zirconium salt is (0.01-40): 100.

According to some embodiments of the invention, the atomic molar ratio of the group IIIA transition metal in the group IIIA transition metal sulfate to the zirconium in the zirconium salt is (2-20): 100.

According to some preferred embodiments of the present invention, the atomic molar ratio of the group IIIA transition metal in the group IIIA transition metal sulfate to the zirconium in the zirconium salt is (9-12): 100.

According to some preferred embodiments of the invention, the atomic molar ratio of aluminum and gallium in the group IIIA transition metal sulfate to zirconium in the zirconium salt is (4-8):2: 100.

According to some embodiments of the invention, the air flow rate of the calcination is 10-100 mL/min.

According to some embodiments of the invention, the air flow rate of the calcination is 50-100 mL/min.

According to some embodiments of the present invention, the firing temperature is 500-800 ℃.

According to some embodiments of the present invention, the firing temperature is 600-700 deg.C,

according to some embodiments of the invention, the calcination is for a time period of 1 to 5 hours.

The second aspect of the present invention provides a catalyst obtained by the production method according to the first aspect.

According to some embodiments of the invention, the catalyst comprises, by weight, 0.5 to 3.0% of aluminum and one or more of 1.0 to 6.0% of gallium and 0.5 to 2.5% of sulfur.

A third aspect of the invention provides a method for activation treatment of the catalyst obtained by the production method according to the first aspect or the catalyst according to the second aspect, comprising a step of heating the catalyst in an air flow before use.

According to some embodiments of the present invention, the activation temperature is 380-.

According to some embodiments of the invention, the activation time is 2-4 h.

According to some embodiments of the invention, the air flow rate is 30-60 mL/min.

The fourth aspect of the present invention provides a catalyst obtained by the production method according to the first aspect or the catalyst of the second aspect for use in a n-butane skeletal isomerization reaction.

According to some embodiments of the invention, the n-butane skeletal isomerization reaction is carried out under hydro-thermal conditions.

According to some embodiments of the invention, the n-butane skeletal isomerization reaction temperature is 180-220 ℃.

According to some embodiments of the invention, the n-butane skeletal isomerization reaction pressure is from 0.5 to 1.5 MPa.

According to some embodiments of the invention, the n-butane skeletal isomerization reaction butane volume space velocity is from 0.2 to 2 hours^-1。

According to some embodiments of the invention, the n-butane skeletal isomerization reaction hydrogen to hydrocarbon molar ratio is from 0.1 to 1.0.

The invention has the beneficial effects that:

the invention provides a normal butane skeletal isomerization catalyst and a simple and clean preparation method thereof, the catalyst is a zirconia solid super acidic catalyst which is prepared by taking simple zirconium salt and other metal sulfates as precursors and simply grinding and roasting, and the preparation method has the advantages of less steps, no waste water generation, no water consumption, less energy consumption and the like.

Detailed Description

The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.

[ example 1 ]

Respectively adding 128.8g of Zr (NO)₃)₄·5H₂O、6g Al₂(SO₄)₃·18H₂Grinding O and 1.3g of glucose into fine powder, mixing the powder together, grinding the mixture evenly, and then roasting the mixture for 4 hours at the air flow rate of 50mL/min and the temperature of 650 ℃ to obtain the n-butane skeletal isomerization catalyst SZ-1. The catalyst SZ-1 comprises the following components: the mass percentage of Al is 1.2 percent, and the mass percentage of S is 1.8 percent.

[ example 2 ]

Respectively adding 128.8g of Zr (NO)₃)₄·5H₂O、10g Al₂(SO₄)₃·18H₂Grinding O and 1.4g of glucose into fine powder, mixing the powder together, grinding the mixture evenly, and then roasting the mixture for 4 hours at the air flow rate of 50mL/min and the temperature of 650 ℃ to obtain the n-butane skeletal isomerization catalyst SZ-2. The catalyst SZ-2 comprises the following components: the mass percentage of Al is 1.9 percent, and the mass percentage of S is 2.8 percent.

[ example 3 ]

Respectively adding 128.8g of Zr (NO)₃)₄·5H₂O、2g Al₂(SO₄)₃·18H₂Grinding O and 1.3g of glucose into fine powder, mixing the powder together, grinding the mixture evenly, and then roasting the mixture for 4 hours at the air flow rate of 50mL/min and the temperature of 650 ℃ to obtain the n-butane skeletal isomerization catalyst SZ-3. The catalyst SZ-3 comprises the following components: the mass percentage of Al is 0.4 percent, and the mass percentage of S is 0.6 percent.

[ example 4 ]

Respectively adding 128.8g of Zr (NO)₃)₄·5H₂O、8g Al₂(SO₄)₃·18H₂Grinding O and 2.0g of glucose into fine powder, mixing the powder together, grinding the mixture evenly, and then roasting the mixture for 3 hours at the air flow rate of 50mL/min and the temperature of 700 ℃ to obtain the n-butane skeletal isomerization catalyst SZ-4. The catalyst SZ-4 comprises the following components: the mass percentage of Al is 1.5 percent, and the mass percentage of S is 2.4 percent.

[ example 5 ]

Respectively adding 128.8g of Zr (NO)₃)₄·5H₂O、1.3g Ga₂(SO₄)₃2.0g of glucose is ground into fine powder, then the fine powder is mixed and ground evenly, and then the mixture is roasted for 4 hours under the conditions that the air flow rate is 50mL/min and the temperature is 650 ℃, thus obtaining the n-butane skeletal isomerization catalyst SZ-5. The catalyst SZ-5 comprises the following components: the mass percentage of Ga is 1 percent, and the mass percentage of S is 0.6 percent.

[ example 6 ]

Respectively adding 128.8g of Zr (NO)₃)₄·5H₂O、3.9g Ga₂(SO₄)₃And 2g of glucose are ground into fine powder, then the fine powder and the glucose are mixed together and ground uniformly, and then the mixture is roasted for 5 hours under the conditions that the air flow rate is 50mL/min and the temperature is 600 ℃, so that the n-butane skeletal isomerization catalyst SZ-6 is obtained. The catalyst SZ-6 comprises the following components: the mass percentage of Ga is 3 percent, and the mass percentage of S is 1.7 percent.

[ example 7 ]

Respectively adding 128.8g of Zr (NO)₃)₄·5H₂O、6.5g Ga₂(SO₄)₃2g of glucose is ground into fine powder, then the fine powder is mixed and ground evenly, and then the mixture is roasted for 3 hours under the conditions that the air flow rate is 50mL/min and the temperature is 700 ℃, thus obtaining the n-butane skeletal isomerization catalyst SZ-7. The catalyst SZ-7 comprises the following components: the mass percentage of Ga is 4.7 percent, and the mass percentage of S is 2.7 percent.

[ example 8 ]

Respectively adding 128.8g of Zr (NO)₃)₄·5H₂O、5.2g Ga₂(SO₄)₃2g of glucose is ground into fine powder, then the fine powder and the glucose are mixed and ground uniformly, and then the mixture is roasted for 4 hours under the conditions that the air flow rate is 50mL/min and the temperature is 650 ℃, so that the n-butane skeletal isomerization catalyst SZ-8 is obtained. The catalyst SZ-8 comprises the following components: the mass percentage of Ga is 3.8 percent, and the mass percentage of S is 2.2 percent.

[ example 9 ]

Respectively adding 128.8g of Zr (NO)₃)₄·5H₂O、2g Al₂(SO₄)₃·18H₂O、1.3g Ga₂(SO₄)₃2g of glucose is ground into fine powder, then the fine powder and the glucose are mixed and ground uniformly, and then the mixture is roasted for 4 hours under the conditions that the air flow rate is 50mL/min and the temperature is 650 ℃, so that the n-butane skeletal isomerization catalyst SZ-9 is obtained. The catalyst SZ-9 comprises the following components: the mass percentage of Al is 0.4%, the mass percentage of Ga is 1.0%, and the mass percentage of S is 1.2%.

[ example 10 ]

Respectively adding 128.8g of Zr (NO)₃)₄·5H₂O、6g Al₂(SO₄)₃·18H₂O、1.3g Ga₂(SO₄)₃2g of glucose is ground into fine powder, then the fine powder is mixed and ground evenly, and then the mixture is roasted for 4 hours under the conditions that the air flow rate is 50mL/min and the temperature is 650 ℃, thus obtaining the n-butane skeletal isomerization catalyst SZ-10. The catalyst SZ-10 comprises the following components: the mass percentage of Al is 1.1%, the mass percentage of Ga is 1%, and the mass percentage of S is 2.3%.

[ COMPARATIVE EXAMPLE 1 ]

Respectively adding 128.8g of Zr (NO)₃)₄·5H₂O、10g Al₂(SO₄)₃·18H₂Grinding O into fine powder, mixing the powder together, grinding uniformly, and roasting for 4 hours at the air flow rate of 50mL/min and the temperature of 650 ℃ to obtain the n-butane skeletal isomerization catalyst SZ-11. The catalyst SZ-11 comprises the following components: the mass percentage of Al is 1.9 percent, and the mass percentage of S is 2.7 percent.

The performance evaluation of the n-butane skeletal isomerization catalyst was carried out on a fixed bed continuous flow reaction system, the specification of the reaction tube was 5mm × 40cm, the catalyst loading was 5mL, the particle size was 20-40 mesh, and the catalyst was placed in a constant temperature zone of the furnace. The reaction temperature is 200 ℃, the hydrogen pressure is 1MPa, and the butane volume space velocity is 1h^-1The molar ratio of hydrogen to hydrocarbon is 1:1, and the reaction product is analyzed on line by adopting gas chromatography. The results of the catalyst performance evaluation are shown in Table 1.

TABLE 1

As can be seen from Table 1, the catalyst prepared by the invention has better activity for catalyzing skeletal isomerization of n-butane.

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.