Catalyst for toluene side chain alkylation to prepare styrene microspheres, preparation method and application

Abstract

The application discloses a microspheric catalyst for preparing styrene by toluene side chain alkylation, a preparation method and application. The microspheric catalyst comprises an alkali metal type molecular sieve, a clay filler treated by an alkaline solution, a binder, a catalyst active additive and a forming additive; the mass ratio of the alkali metal type molecular sieve, the clay filler and the binder is 1-10:1-10:1; the mass content of the catalyst active additive is 0.1-5 wt%, and the mass content of the forming additive is 0.1-20 wt%. The microspheric catalyst has a low abrasion index, can meet the demand of a fluidized bed reaction process for preparing styrene by toluene side chain alkylation, and realizes high-efficiency preparation of styrene.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical industry, and in particular to a catalyst for preparing styrene microspheres by alkylation of toluene side chains, a preparation method and application thereof. Background Art

[0002] Styrene (SM), as the most basic aromatic hydrocarbon chemical, is the most widely used chemical product among benzene derivatives. It can be used to manufacture a variety of chemical products such as polystyrene (PS), expanded polystyrene (EPS), acrylonitrile-butadiene-styrene resin (ABS), styrene-acrylonitrile resin (SAN), styrene-butadiene rubber (SBR), unsaturated polyester resin (UPR) and ion exchange resin (IER).

[0003] The one-step production of styrene by toluene side-chain alkylation is the most economically valuable styrene production route. Since its first report in 1967 ("Condensation of toluene and methanol upon synthetic ceolites containing-exchange cations of alkali metals", Dokl Akad Nauk SSSR [J], 1967, 173 (1): 132-134), this process has attracted widespread attention from academia and industry. Compared with the traditional two-step ethylbenzene dehydrogenation process, the toluene side-chain alkylation process can not only reduce equipment investment and operating costs, but also significantly reduce raw material costs. According to calculations by Exelus ("Exelus develops a new styrene production process", Petrochemical Technology and Economics [J], 2007, (3): 12), the toluene side-chain alkylation process can reduce the raw material cost per ton of styrene by approximately US$350 and the energy consumption by approximately US$20 compared with the ethylbenzene dehydrogenation process.

[0004] The side-chain alkylation reaction of toluene is an acid-base synergistic catalytic process. Alkali metal molecular sieves with both acidic and basic sites are currently the most active type of toluene side-chain alkylation catalyst (Side-chain alkylation of toluene with methanol to produce styrene: an overview, Catalysis Science & Technology [J], 2019, (9): 6828-6840). Summary of the Invention

[0005] Alkali metal molecular sieves, when used as catalysts for toluene side-chain alkylation, are prone to carbon deposition and deactivation during the reaction, requiring frequent regeneration. Fluidized bed processes enable continuous catalyst reaction and regeneration, effectively addressing the issue of catalyst deactivation. However, for solid catalysts to be used in fluidized bed processes, they must be prepared as microspheres with a low attrition index. The prior art lacks a method for preparing alkali metal molecular sieves as microspheres, making them unsuitable for fluidized bed reactions for toluene side-chain alkylation to styrene.

[0006] In view of the above problems, the present invention is proposed to provide a catalyst for producing styrene microspheres by alkylation of toluene side chains, a preparation method and application thereof, which overcome the above problems or at least partially solve the above problems.

[0007] An embodiment of the present invention provides a catalyst for producing styrene microspheres by side chain alkylation of toluene, comprising:

[0008] The microsphere catalyst comprises an alkali metal molecular sieve, a clay filler treated with an alkaline solution, a binder, a catalyst activating agent and a molding aid;

[0009] The mass ratio of the alkali metal molecular sieve, clay filler and binder is 1 to 10:1 to 10:1;

[0010] The mass content of the catalyst activating auxiliary agent is 0.1 to 5 wt %, and the mass content of the molding auxiliary agent is 0.1 to 20 wt %.

[0011] In some optional embodiments, the alkali metal molecular sieve includes at least one of an X-type molecular sieve and a Y-type molecular sieve;

[0012] The alkali metal ions in the alkali metal molecular sieve include at least one of Na ions, K ions and Cs ions.

[0013] In some optional embodiments, the clay filler includes at least one of kaolin, chlorite, sepiolite, bentonite, attapulgite, and bentonite.

[0014] In some optional embodiments, the alkaline solution includes at least one of sodium hydroxide, potassium hydroxide and cesium hydroxide.

[0015] In some optional embodiments, the binder includes at least one of silica sol, aluminum sol, zirconium sol and titanium sol.

[0016] In some optional embodiments, the catalyst activating agent includes at least one of copper, zirconium, zinc, chromium, sodium, silver, boron and phosphorus.

[0017] In some optional embodiments, the molding aid includes at least one of magnesium silicate, aluminum silicate and calcium silicate.

[0018] The embodiment of the present invention provides a method for preparing a catalyst for producing styrene microspheres by side chain alkylation of toluene, comprising:

[0019] dispersing the clay filler in an alkaline solution for treatment to obtain a clay filler treated with the alkaline solution;

[0020] The catalyst activating agent, alkali metal molecular sieve, clay filler treated with alkaline solution, binder and molding aid are sequentially added into deionized water, and the mixture is beaten, rubber-milled and defoamed to prepare a slurry with a solid mass content of 5 to 40 wt%;

[0021] The mass ratio of the alkali metal molecular sieve, the clay filler treated with an alkaline solution, and the binder in the slurry is 1 to 10:1 to 10:1, the mass of the catalyst activating agent accounts for 0.1 to 5 wt% of the solid mass in the slurry, and the mass of the molding agent accounts for 0.1 to 20 wt% of the solid mass in the slurry;

[0022] The slurry is spray-dried and formed, and calcined in an air atmosphere at 300-700° C. for 1-10 hours to obtain a microsphere catalyst.

[0023] In some optional embodiments, the step of dispersing the clay filler into an alkaline solution for treatment to obtain the clay filler treated with the alkaline solution comprises:

[0024] The clay filler is dispersed in a 0.01-3 mol / L alkaline solution with a liquid-to-solid ratio of 2-80 mL / g, treated at a temperature of 50-90° C. for 0.5-10 hours, the clay filler is separated from the alkaline solution by centrifugation, and dried at a temperature of 50-200° C. to obtain the alkaline-treated clay filler.

[0025] In some optional embodiments, the clay filler includes at least one of kaolin, chlorite, sepiolite, bentonite, attapulgite, and bentonite;

[0026] The alkaline solution includes at least one of sodium hydroxide, potassium hydroxide and cesium hydroxide.

[0027] In some optional embodiments, the alkali metal molecular sieve includes at least one of an X-type molecular sieve and a Y-type molecular sieve;

[0028] The alkali metal ions in the alkali metal molecular sieve include at least one of Na ions, K ions and Cs ions.

[0029] In some optional embodiments, the binder includes at least one of silica sol, aluminum sol, zirconium sol and titanium sol.

[0030] In some optional embodiments, the catalyst activating agent is a soluble salt comprising at least one of copper, zirconium, zinc, chromium, sodium, silver, boron and phosphorus.

[0031] In some optional embodiments, the molding aid includes at least one of magnesium silicate, aluminum silicate and calcium silicate.

[0032] An embodiment of the present invention provides a method for preparing styrene by side chain alkylation of toluene, wherein the preparation of styrene is achieved using the above-mentioned microsphere catalyst for preparing styrene by side chain alkylation of toluene.

[0033] In some optional embodiments, the above method includes:

[0034] Toluene and methanol with a molar ratio of 0.5 to 10:1 are used as reaction raw materials for 0.2 to 8 hours. -1 The feed mass space velocity is fed into the fluidized bed reactor, and styrene is prepared at a reaction pressure of 0.1 to 5 MPa and a reaction temperature of 350 to 500° C.

[0035] An embodiment of the present invention provides styrene, which is prepared using the above-mentioned method for preparing styrene by alkylation of toluene side chains.

[0036] The beneficial effects of the above technical solutions provided by the embodiments of the present invention include at least:

[0037] The microsphere catalyst and preparation method provided in an embodiment of the present invention are prepared by using an alkali metal molecular sieve, a clay filler treated with an alkaline solution, a binder, a catalyst activating agent, and a molding aid. The clay filler is pretreated with an alkaline solution. The use of the clay filler treated with the alkaline solution to prepare the microsphere catalyst can eliminate the effect of the acidic groups in the clay filler on the alkali metal molecular sieve, making the prepared microsphere catalyst more efficient; thereby, it can meet the fluidized bed reaction process for the side chain alkylation of toluene to produce styrene and efficiently prepare styrene.

[0038] Other features and advantages of the present invention will be described in the following description, and in part will become apparent from the description, or will be understood by practicing the present invention. The purposes and other advantages of the present invention can be realized and obtained by the structures particularly pointed out in the written description, claims, and drawings.

[0039] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation of the present invention. In the accompanying drawings:

[0041] Figure 1 The present invention is a flow chart of a method for preparing a styrene microsphere catalyst by side chain alkylation of toluene in an embodiment of the present invention.

[0042] technical field. DETAILED DESCRIPTION

[0043] Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. Although exemplary embodiments of the present disclosure are shown in the accompanying drawings, it should be understood that the present disclosure can be implemented in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided to enable a more thorough understanding of the present disclosure and to fully convey the scope of the present disclosure to those skilled in the art.

[0044] In the production route of producing styrene by a one-step toluene side chain alkylation reaction, the catalyst problem has always been a difficult problem to achieve industrialization. In order to solve the above-mentioned problems existing in the prior art and meet the requirements of the fluidized bed reaction process for producing styrene by toluene side chain alkylation, an embodiment of the present invention provides a microsphere catalyst for producing styrene by toluene side chain alkylation. The microsphere catalyst has a low wear index and is prepared by a spray drying method based on an alkali metal molecular sieve as the catalyst active component and the addition of a clay filler, a binder, a catalyst activating agent, and a molding aid. This meets the requirements of the fluidized bed reaction process for producing styrene by toluene side chain alkylation.

[0045] The catalyst for producing styrene microspheres by side chain alkylation of toluene provided in an embodiment of the present invention comprises an alkali metal molecular sieve, a clay filler treated with an alkaline solution, a binder, a catalyst activating agent, and a molding aid; wherein the mass ratio of the alkali metal molecular sieve, the clay filler, and the binder is 1 to 10:1 to 10:1; the mass content of the catalyst activating agent is 0.1 to 5 wt%, and the mass content of the molding aid is 0.1 to 20 wt%.

[0046] Optionally, the alkali metal molecular sieve includes at least one of an X-type molecular sieve and a Y-type molecular sieve.

[0047] Optionally, the alkali metal ions in the alkali metal molecular sieve include at least one of Na ions, K ions and Cs ions.

[0048] Optionally, the clay filler includes at least one of kaolin, chlorite, sepiolite, bentonite, attapulgite, and bentonite. The clay filler may contain one or more components, and the content of each component can be selected as needed and is not limited in this application. The alkaline solution used to alkaline-treat the clay filler includes at least one of sodium hydroxide, potassium hydroxide, and cesium hydroxide.

[0049] Optionally, the binder includes at least one of silica sol, aluminum sol, zirconium sol and titanium sol.

[0050] Optionally, the catalyst activating agent includes at least one of copper, zirconium, zinc, chromium, sodium, silver, boron and phosphorus.

[0051] Optionally, the molding aid includes at least one of magnesium silicate, aluminum silicate and calcium silicate.

[0052] Based on the same inventive concept, the present invention provides a method for preparing a catalyst for styrene microspheres by alkylation of toluene side chains, the process of which is as follows: Figure 1 As shown, the following steps are included:

[0053] Step S101: dispersing a clay filler into an alkaline solution for treatment to obtain a clay filler treated with the alkaline solution.

[0054] Preferably, to eliminate the effect of the acidic groups in the clay filler on the alkali metal molecular sieve, the clay filler is pre-treated with an alkaline solution comprising at least one of sodium hydroxide, potassium hydroxide, and cesium hydroxide.

[0055] The alkaline solution treatment process includes: dispersing the clay filler in a 0.01-3 mol / L alkaline solution with a liquid-to-solid ratio of 2-80 ml / g, treating at a temperature of 50-90° C. for 0.5-10 hours, separating the clay filler from the alkaline solution by centrifugal separation, and drying at a temperature of 50-200° C. to obtain the alkaline-treated clay filler.

[0056] Preferably, the mass ratio of the clay filler to the alkaline solution is 9:50-100, and the alkaline solution can be a 0.2 mol / L-0.7 mol / L alkaline solution.

[0057] Step S102: adding a catalyst activating agent, an alkali metal molecular sieve, a clay filler treated with an alkaline solution, a binder and a molding aid into deionized water in sequence to prepare a slurry with a solid mass content of 5 to 40 wt%.

[0058] Accurately weighed catalyst activator, alkali metal molecular sieve, alkaline treated clay filler obtained in step S101, binder and molding aid are sequentially added to deionized water, stirred, beaten, rubber-milled and defoamed to prepare a slurry with a solid mass content of 5 to 40 wt%.

[0059] The mass ratio of the alkali metal molecular sieve, the clay filler treated with an alkaline solution, and the binder in the slurry is 1 to 10:1 to 10:1, the mass of the catalyst activating agent accounts for 0.1 to 5 wt% of the solid mass in the slurry, and the mass of the molding agent accounts for 0.1 to 20 wt% of the solid mass in the slurry;

[0060] The alkali metal molecular sieve used above can be prepared using existing preparation methods. The following Example 1 uses a preparation process and preparation conditions as an example for illustration, and is not limited to the preparation process and preparation conditions in Example 1 in actual application. The alkali metal molecular sieve can be at least one of an X-type molecular sieve and a Y-type molecular sieve, and can be an alkali metal molecular sieve containing at least one alkali metal ion selected from the group consisting of Na ions, K ions, and Cs ions.

[0061] The catalyst activating agent includes at least one of copper, zirconium, zinc, chromium, sodium, silver, boron and phosphorus. Soluble salts containing the above elements may be used in the preparation process.

[0062] Step S103: spray-drying the slurry to obtain a microsphere catalyst, and calcining the slurry in an air environment at 300-700° C. for 1-10 hours.

[0063] Based on the same inventive concept, an embodiment of the present invention further provides a method for preparing styrene by side chain alkylation of toluene, wherein the method uses the above-mentioned catalyst for preparing styrene by side chain alkylation of toluene to achieve the preparation of styrene. The method comprises:

[0064] Toluene and methanol with a molar ratio of 0.5 to 10:1 are used as reaction raw materials for 0.2 to 8 hours. -1 The feed is fed into a fluidized bed reactor at a mass space velocity of 1000 sq. ft., and the reaction pressure is 0.1-5.0 MPa and the reaction temperature is 350-500°C to produce styrene. The catalyst loading in the reaction vessel is 30 g. Preferably, the reaction temperature is 390-450°C.

[0065] An embodiment of the present invention further provides styrene, which is prepared using the above-mentioned method for preparing styrene by alkylation of toluene side chains.

[0066] The preparation and application of the above catalyst are described below through specific examples.

[0067] Unless otherwise specified, all raw materials used in the examples were commercially available, and the instrumentation was performed using the manufacturer's recommended parameters. The attrition index of the microsphere catalysts in the examples and comparative examples was measured according to ASTM-D-5757-00, using the Air Jet Index (AJI)—the percentage of catalyst weight removed by grinding within 5 hours.

[0068] Example 1: Preparation of alkali metal molecular sieves

[0069] Commercially available 13X molecular sieve (Si / Al = 1.23) and NaY molecular sieve (Si / Al = 2.51) powders were used as precursors. The mixtures were exchanged four times with a 0.3 mol / L cesium chloride (CsCl) solution at 80°C. The solid-to-liquid ratio of the 13X or NaY powder to the CsCl solution was 1:10 g / ml. The mixtures were washed with deionized water until no precipitation formed upon addition of silver nitrate solution to the filtrate. The mixtures were then dried at 120°C overnight and calcined in air at 550°C for 5 h. The resulting samples were designated CsX and CsY, respectively.

[0070] Example 2: Clay filler pretreatment

[0071] 1) Preparation of clay filler T-1

[0072] 70 parts by weight of kaolin and 20 parts by weight of bentonite were uniformly mixed and then added to 1000 parts by weight of a 0.3 mol / L sodium hydroxide solution. The mixture was stirred at 80°C for 3 hours, then centrifuged, washed, filtered, and dried at 100°C for 4 hours. The resulting treated clay filler was named T-1.

[0073] 2) Preparation of clay filler T-2

[0074] 70 parts by weight of chlorite and 20 parts by weight of attapulgite were uniformly mixed, then added to 500 parts by weight of a 0.4 mol / L potassium hydroxide solution, stirred at 90°C for 3 hours, then centrifuged, washed, filtered, and dried at 100°C for 4 hours. The treated clay filler was named T-2.

[0075] 3) Preparation of clay filler T-3

[0076] 80 parts by weight of chlorite and 10 parts by weight of sepiolite were uniformly mixed and then added to 500 parts by weight of a 0.2 mol / L cesium hydroxide solution. The mixture was stirred at 70°C for 5 hours, then centrifuged, washed, filtered, and dried at 100°C for 4 hours. The resulting treated clay filler was named T-3.

[0077] 4) Preparation of clay filler T-4

[0078] 70 parts by weight of kaolin and 30 parts by weight of bentonite were uniformly mixed, then added to 700 parts by weight of 0.7 mol / L sodium hydroxide solution. The mixture was stirred at 50°C for 5 hours, then centrifuged, washed, filtered, and dried at 100°C for 4 hours. The treated clay filler was named T-4.

[0079] 5) Preparation of clay filler T-5

[0080] 70 parts by weight of kaolin and 20 parts by weight of bentonite were uniformly mixed and then added to 1000 parts by weight of a 0.01 mol / L sodium hydroxide solution. The mixture was stirred at 80°C for 3 hours, then centrifuged, washed, filtered, and dried at 200°C for 4 hours. The resulting treated clay filler was named T-5.

[0081] 6) Preparation of clay filler T-6

[0082] 70 parts by weight of kaolin and 20 parts by weight of bentonite were uniformly mixed, then added to 1000 parts by weight of 3 mol / L sodium hydroxide solution, stirred at 80°C for 3 hours, then centrifuged, washed, filtered, and dried at 50°C for 4 hours. The treated clay filler was named T-6.

[0083] Example 3 Preparation of microsphere catalyst

[0084] 1) Preparation of microsphere catalyst C-1

[0085] 1 part by weight of copper nitrate, 1 part by weight of chromium nitrate, and 2 parts by weight of sodium borate were added to 500 parts by weight of deionized water and stirred for 10 minutes. Then, 100 parts by weight of CsX, 60 parts by weight of clay filler T-1, and 10 parts by weight of magnesium silicate were added in sequence. After stirring for 10 minutes, 30 parts by weight of aluminum sol (solid content 20.1 wt%) and 40 parts by weight of silica sol (solid content 28.8 wt%) were added. The mixture was then slurried, rubber-milled, defoamed, and spray-dried to form a microsphere. The catalyst was then calcined at 550°C in air for 4 hours to obtain a microsphere catalyst, designated C-1.

[0086] 2) Preparation of microsphere catalyst C-2

[0087] 1 part by weight of copper nitrate, 1 part by weight of chromium nitrate, and 2 parts by weight of sodium borate were added to 500 parts by weight of deionized water and stirred for 10 minutes. Then, 100 parts by weight of CsY, 60 parts by weight of clay filler T-1, and 10 parts by weight of calcium silicate were added in sequence. After stirring for 10 minutes, 30 parts by weight of aluminum sol (solid content 20.1 wt%) and 40 parts by weight of silica sol (solid content 28.8 wt%) were added. The mixture was then slurried, rubber-milled, defoamed, and spray-dried to form a microsphere. The microspheres were calcined at 550°C in air for 4 hours to obtain a catalyst microsphere, designated C-2.

[0088] 3) Preparation of microsphere catalyst C-3

[0089] 1 part by weight of copper nitrate, 0.5 parts by weight of silver nitrate, 2 parts by weight of boric acid, and 1 part by weight of sodium phosphate were added to 500 parts by weight of deionized water and stirred for 10 minutes. Then, 100 parts by weight of CsX, 50 parts by weight of clay filler T-2, 10 parts by weight of magnesium silicate, and 5 parts by weight of aluminum silicate were added in sequence. After stirring for 10 minutes, 40 parts by weight of aluminum sol (solid content 20.1 wt%) and 50 parts by weight of silica sol (solid content 28.8 wt%) were added. The mixture was then slurried, rubber-milled, defoamed, and spray-dried. The mixture was then calcined at 550°C in air for 4 hours to obtain a microsphere catalyst, designated C-3.

[0090] 4) Preparation of microspherical catalyst C-4

[0091] 1 part by weight of copper nitrate, 0.5 parts by weight of zirconium nitrate, 0.5 parts by weight of zinc nitrate, and 3 parts by weight of boron oxide were added to 500 parts by weight of deionized water and stirred for 10 minutes. Then, 100 parts by weight of CsX, 70 parts by weight of clay filler T-3, and 10 parts by weight of aluminum silicate were added in sequence. After stirring for 10 minutes, 50 parts by weight of zirconium sol (solid content 18.3 wt%) and 50 parts by weight of silica sol (solid content 28.8 wt%) were added. The mixture was then slurried, rubber-milled, defoamed, and spray-dried. The mixture was calcined at 550°C in air for 4 hours to obtain a microsphere catalyst, designated C-4.

[0092] 5) Preparation of microspherical catalyst C-5

[0093] 1 part by weight of copper nitrate, 1 part by weight of silver nitrate, and 3 parts by weight of boron oxide were added to 500 parts by weight of deionized water and stirred for 10 minutes. Then, 100 parts by weight of CsX, 60 parts by weight of clay filler T-4, and 10 parts by weight of magnesium silicate were added in sequence and stirred for 10 minutes. Then, 50 parts by weight of zirconium sol (solid content 18.3 wt%), 10 parts by weight of titanium sol (solid content 15.8 wt%), and 40 parts by weight of silica sol (solid content 28.8 wt%) were added. The mixture was then slurried, rubber-milled, defoamed, and spray-dried to form a microsphere. The microspheres were then calcined at 550°C in air for 4 hours to obtain a catalyst microsphere, designated C-5.

[0094] 6) Preparation of microspherical catalyst C-6

[0095] 1 part by weight of copper nitrate, 1 part by weight of chromium nitrate, 1 part by weight of sodium borate, and 1 part by weight of phosphoric acid were added to 500 parts by weight of deionized water and stirred for 10 minutes. Then, 100 parts by weight of CsX, 60 parts by weight of clay filler T-5, and 10 parts by weight of magnesium silicate were added in sequence. After stirring for 10 minutes, 30 parts by weight of aluminum sol (solid content 20.1 wt%) and 40 parts by weight of silica sol (solid content 28.8 wt%) were added. The mixture was then slurried, rubber-milled, defoamed, and spray-dried to form a microsphere. The microspheres were calcined at 300°C in air for 4 hours to obtain a catalyst microsphere, designated C-6.

[0096] 7) Preparation of Microspherical Catalyst C-7

[0097] 1 part by weight of copper nitrate, 1 part by weight of chromium nitrate, 1 part by weight of sodium borate, and 1 part by weight of phosphoric acid were added to 500 parts by weight of deionized water and stirred for 10 minutes. Then, 100 parts by weight of CsX, 60 parts by weight of clay filler T-6, 10 parts by weight of magnesium silicate, and 5 parts by weight of aluminum silicate were added in sequence. After stirring for 10 minutes, 30 parts by weight of aluminum sol (solid content 20.1 wt%) and 40 parts by weight of silica sol (solid content 28.8 wt%) were added. The mixture was then slurried, rubber-milled, defoamed, and spray-dried to form a microsphere. The microspheres were calcined at 700°C in air for 4 hours to obtain a catalyst microsphere, designated C-7.

[0098] Comparative Example

[0099] 1 part by weight of copper nitrate, 1 part by weight of chromium nitrate, and 2 parts by weight of sodium borate were added to 500 parts by weight of deionized water and stirred for 10 minutes. Then, 100 parts by weight of CsX, 45 parts by weight of untreated kaolin, 15 parts by weight of untreated bentonite, and 10 parts by weight of magnesium silicate were added in sequence. After stirring for 10 minutes, 30 parts by weight of aluminum sol (solid content 20.1 wt%) and 40 parts by weight of silica sol (solid content 28.8 wt%) were added. The mixture was then beaten, rubber-milled, defoamed, and spray-dried to form a microsphere catalyst. The catalyst was then calcined at 550°C in air for 4 hours to obtain a microsphere catalyst.

[0100] Example 4: Catalyst Evaluation

[0101] The activity of the microsphere catalysts was evaluated using a fixed fluidized bed reactor. C-1, C-2, C-3, C-4, C-5, C-6, and C-7 obtained in Example 3, as well as the catalysts from the comparative example, were loaded into a fixed fluidized bed reactor with an inner diameter of 35 mm and a catalyst loading of 30 g. Toluene and methanol were introduced via a plunger pump, vaporized in a preheating furnace, and then passed into the reactor.

[0102] During the reaction evaluation, products were analyzed using an Agilent 7890A chromatograph. Hydrocarbon components were separated using an Agilent CP-WAX 25m × 32μm × 1.2μm capillary column and detected by an FID detector. CO, CO2, and H2 were separated using a Porapark Q 4m × 1 / 8″ packed column and detected by a TCD detector.

[0103] In the reaction evaluation, the conversion rate of toluene is X 甲苯 , methanol conversion rate X 甲醇 , styrene selectivity S 苯乙烯 , ethylbenzene selectivity S 乙苯 The calculation method is as follows:

[0104]

[0105]

[0106]

[0107]

[0108] The microsphere catalysts of Example 3 and the comparative example were used for the side chain alkylation of toluene to produce styrene. The reaction evaluation results and wear index are shown in Table 1.

[0109] Table 1

[0110]

[0111]

[0112] In the process of preparing styrene, the reaction is sampled and analyzed 1 time every 1 hour, and the reaction result of above-mentioned Table 1 is the mean value in 5 hours.As can be seen from above-mentioned Table 1, using the microsphere catalyst provided in the embodiment of the application, under identical or similar experimental conditions, the conversion rate of toluene and the selectivity of styrene are significantly improved, that is, the conversion rate of styrene is significantly improved when toluene methanol reaction prepares styrene, and the preparation of styrene can be realized more efficiently, and the microsphere catalyst also has a lower wear index.Wherein experimental conditions include the various relevant experimental conditions such as the raw material ratio and preparation conditions of catalyst, the raw material ratio and preparation of styrene.

[0113] It should be understood that the specific order or hierarchy of steps in the disclosed processes is an example of an exemplary method. Based on design preferences, it should be understood that the specific order or hierarchy of steps in the process can be rearranged without departing from the scope of the present disclosure. The accompanying method claims present elements of the various steps in an exemplary order and are not intended to be limited to the specific order or hierarchy described.

[0114] In the foregoing detailed description, various features are grouped together in a single embodiment to simplify the disclosure. This method of disclosure should not be interpreted as reflecting an intention that embodiments of the claimed subject matter require more features than are expressly recited in each claim. On the contrary, as reflected in the appended claims, the invention comprises less than all the features of any individual disclosed embodiment. The appended claims are therefore hereby expressly incorporated into the detailed description, with each claim standing on its own as a separate preferred embodiment of the invention.

[0115] The foregoing description includes examples of one or more embodiments. Of course, it is not possible to describe all possible combinations of components or methods for the purposes of describing the above embodiments, but one of ordinary skill in the art will recognize that the various embodiments may be further combined and arranged. Therefore, the embodiments described herein are intended to encompass all such changes, modifications and variations that fall within the scope of the appended claims. Furthermore, to the extent the term "comprising" is used in the specification or claims, the term is intended to be encompassed in a manner similar to the term "including," as explained in terms of "including," used as a transitional word in the claims. Furthermore, any use of the term "or" in the specification of the claims is intended to mean a "non-exclusive or."

Claims

1. A catalyst for preparing styrene microspheres by alkylation of toluene side chains, characterized in that: Applicable to fluidized bed reaction processes, including: The microsphere catalyst comprises an alkali metal molecular sieve, a clay filler treated with an alkaline solution, a binder, a catalyst activating agent, and a molding aid; the clay filler treated with an alkaline solution is obtained by dispersing the clay filler in an alkaline solution for treatment; the alkaline solution comprises at least one of sodium hydroxide, potassium hydroxide, and cesium hydroxide; The microsphere catalyst is prepared by sequentially adding a catalyst activating agent, an alkali metal molecular sieve, a clay filler treated with an alkaline solution, a binder, and a molding aid into deionized water to form a slurry having a solid mass content of 5 to 40 wt %. The slurry is spray-dried and formed, and calcined in an air atmosphere at 300 to 700° C. for 1 to 10 hours. The mass ratio of the alkali metal molecular sieve, clay filler and binder is 1 to 10:1 to 10:1; The mass content of the catalyst active agent is 0.1 to 5 wt%, and the mass content of the molding agent is 0.1 to 20 wt%. The catalyst activating agent is a soluble salt containing at least one of copper, zirconium, zinc, chromium, sodium, silver, boron and phosphorus.

2. The microsphere catalyst according to claim 1, wherein The alkali metal molecular sieve includes at least one of an X-type molecular sieve and a Y-type molecular sieve; The alkali metal ions in the alkali metal molecular sieve include at least one of Na ions, K ions and Cs ions.

3. The microsphere catalyst according to claim 1, wherein The clay filler includes at least one of kaolin, chlorite, sepiolite, bentonite, attapulgite and bentonite.

4. The microsphere catalyst according to claim 1, wherein The binder includes at least one of silica sol, aluminum sol, zirconium sol and titanium sol.

5. The microsphere catalyst according to any one of claims 1 to 4, characterized in that The molding aid includes at least one of magnesium silicate, aluminum silicate and calcium silicate.

6. A method for preparing a catalyst for preparing styrene microspheres by side chain alkylation of toluene according to claim 1, characterized in that: include: dispersing the clay filler in an alkaline solution for treatment to obtain a clay filler treated with the alkaline solution; The alkaline solution includes at least one of sodium hydroxide, potassium hydroxide and cesium hydroxide; Adding a catalyst activator, an alkali metal molecular sieve, a clay filler treated with an alkaline solution, a binder, and a molding aid to deionized water in sequence to prepare a slurry with a solid mass content of 5 to 40 wt%; The mass ratio of the alkali metal molecular sieve, the clay filler treated with an alkaline solution, and the binder in the slurry is 1 to 10:1 to 10:1, the mass of the catalyst activator accounts for 0.1 to 5 wt% of the solid mass in the slurry, and the mass of the molding aid accounts for 0.1 to 20 wt% of the solid mass in the slurry; The slurry is spray-dried and formed, and calcined in an air atmosphere at 300-700° C. for 1-10 hours to obtain a microsphere catalyst.

7. The method according to claim 6, wherein The method of dispersing the clay filler into an alkaline solution for treatment to obtain the clay filler treated with the alkaline solution comprises: The clay filler is dispersed in a 0.01-3 mol / L alkaline solution with a liquid-to-solid ratio of 2-80 mL / g, and treated at a temperature of 50-90° C. for 0.5-10 hours. The clay filler is separated from the alkaline solution by centrifugation, and dried at a temperature of 50-200° C. to obtain the alkaline-treated clay filler.

8. The method according to claim 7, wherein The clay filler includes at least one of kaolin, chlorite, sepiolite, bentonite, attapulgite and bentonite.

9. The method according to claim 6, wherein The alkali metal molecular sieve includes at least one of an X-type molecular sieve and a Y-type molecular sieve; The alkali metal ions in the alkali metal molecular sieve include at least one of Na ions, K ions and Cs ions.

10. The method according to claim 6, wherein The binder includes at least one of silica sol, aluminum sol, zirconium sol and titanium sol.

11. The method according to any one of claims 6 to 10, characterized in that: The molding aid includes at least one of magnesium silicate, aluminum silicate and calcium silicate.

12. A method for preparing styrene by side chain alkylation of toluene, characterized in that: The preparation of styrene is achieved by using the catalyst for preparing styrene microspheres by alkylation of toluene side chains as described in any one of claims 1 to 5.

13. The method according to claim 12, wherein: include: Toluene and methanol with a molar ratio of 0.5 to 10:1 are used as reaction raw materials for 0.2 to 8 h. -1 The feed mass space velocity is fed into the fluidized bed reactor, and styrene is prepared at a reaction pressure of 0.1 to 5 MPa and a reaction temperature of 350 to 500°C.

14. Styrene, characterized in that The method for preparing styrene by side chain alkylation of toluene as described in any one of claims 12-13 is used to prepare the same.

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