CN109701633B

CN109701633B - Fluidized bed catalyst, preparation method and application thereof

Info

Publication number: CN109701633B
Application number: CN201711016750.8A
Authority: CN
Inventors: 吴思操; 刘红星; 顾松园; 殷喜平; 张少钢
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2017-10-26
Filing date: 2017-10-26
Publication date: 2022-04-05
Anticipated expiration: 2037-10-26
Also published as: CN109701633A

Abstract

The invention relates to a fluidized bed catalyst and a preparation method thereof, and mainly solves the problems of poor wear resistance and serious catalyst loss in the reaction process of the conventional fluidized bed catalyst. The BET specific surface area of the catalyst prepared by the invention is 220-280 m²(ii) a pore diameter of 1.0 to 1.7 nm. The method adopted by the invention comprises the following steps: (a) preparing a mixed solution containing a molecular sieve, a binder, a carrier material, a dilute acid solution and a liquid medium in proportion; (b) shearing the mixed solution at a high speed to obtain a suspension; (c) spray drying the suspension to form a fluidized bed catalyst; (d) roasting the fluidized bed catalyst to obtain the finished product of the catalyst for preparing the olefin from the methanol. The method has wide applicability, has no special requirements on the existing fluidized bed catalyst production device, and can be used for the industrialized production process of various fluidized bed catalysts.

Description

Fluidized bed catalyst, preparation method and application thereof

Technical Field

The invention relates to a fluidized bed catalyst, a preparation method and application thereof, in particular to preparation of a microspherical fluidized bed catalyst, and especially preparation of a high-wear-resistance fluidized bed catalyst.

Background

Ethylene and propylene are important basic organic chemical raw materials in the chemical industry, and play a very important role in the modern petroleum and chemical industries. Ethylene is used to make various polyethylene plastics and other chemicals, and propylene is used primarily to make various polypropylene plastics and other chemicals. With the rapid development of economy in China, the demand of the development of chemical industry on light olefins is rising day by day, and the contradiction between supply and demand is more and more prominent. At present, more than 98 percent of ethylene in the world mainly comes from steam cracking technology, more than 60 percent of propylene comes from byproducts of ethylene production by steam cracking, and 30 percent of propylene comes from byproducts of gasoline and diesel oil produced by catalytic cracking in oil refineries. As the demand for petroleum continues to increase, and as petroleum is not renewable, the contradiction in the supply and demand of olefins is not solved, and the development of a technology for producing ethylene and propylene from unconventional petroleum resources is imminent.

Methanol is a common chemical raw material, can be produced by taking coal, natural gas, biomass and solid waste as raw materials, and has wide raw material sources. Natural gas is subjected to a partial oxidation method and a steam reforming method to obtain synthesis gas (CO + H)₂) Then in CuO/ZnO/Al₂O₃Producing methanol under the action of a catalyst. The industrial production of methanol from coal or natural gas through synthesis gas is realized, the scale is continuously enlarged, and the technology is also perfected day by day. The resources of coal and natural gas in China are relatively rich, and the technology for preparing olefin from methanol by using coal or natural gas to produce basic chemical raw materials is an effective way for realizing the extension development of the coal chemical industry or the natural gas chemical industry to the petrochemical industry. The development of the technology for preparing the olefin from the methanol has profound significance for ensuring national energy safety, economy, rapidness and sustainable development.

The SAPO-34 molecular sieve has the best performance as the catalyst for the methanol-to-olefin reaction so far. Because the molecular sieve has too fine granularity, poor caking property, difficult molding and higher manufacturing cost, 100 percent of the molecular sieve is not generally adopted to prepare the catalyst for the industrial process. In the fixed bed reactor, the catalyst is required to have a certain crushing strength, to prevent the catalyst from being crushed by impact during the catalyst filling process, and to prevent the catalyst filled in the lower layer from being crushed by pressure. In the fluidized bed reactor, because the catalyst continuously and circularly flows in the reactor, the catalyst particles, the catalyst and the wall of the reactor, the catalyst and a conveying pipeline and the catalyst and a regeneration system are continuously collided and rubbed. Therefore, in addition to good activity and selectivity, the catalyst is also required to have good particle size distribution and strong attrition resistance.

At present, the fluidized bed catalyst applied to preparing low-carbon olefin is mainly prepared by fully mixing a molecular sieve, a matrix, a binder and a structural auxiliary agent to prepare slurry, and then forming by a spray drying means. CN1132533A reports a preparation method of an abrasion-resistant catalyst for converting methanol into low-carbon olefin, and the abrasion-resistant effect of the catalyst is improved by reducing the content of a molecular sieve in the catalyst. USP5248647 reports a fluidized bed catalyst prepared by slurrying SAPO-34 molecular sieve, kaolin, silica sol, followed by spray drying.

Patent CN 20111019576.7 reports an MTO fluidized bed catalyst and a preparation method thereof. The preparation process mainly uses silica sol as a binder, then a small amount of aluminum-containing compound is added, the wear resistance of the catalyst is improved under the condition of not changing the acidity of the catalyst, and the wear index of the obtained catalyst is less than 2.0. Wherein the aluminum-containing compound comprises alumina sol, pseudo-boehmite, active alumina, aluminum chlorohydrate and aluminum trioxide hydrate.

Patent CN102527445A discloses a preparation method of a low-abrasion fluidized bed microspherical catalyst, which comprises preparing a slurry from a molecular sieve, an adhesive, a dispersant and water, shearing, spray-drying, re-dispersing the prepared microspherical particles in water, shearing, spraying again, and roasting the microspherical particles to obtain the low-abrasion fluidized bed catalyst.

Patent 103769237a discloses a method for improving the wear resistance of a fluidized bed catalyst, which comprises uniformly mixing fine catalyst powder with an average particle size of less than 80 μm with a molecular sieve, a binder, a carrier material and a liquid medium to form a suspension, shearing the suspension at a high speed, and spray-drying to effectively improve the wear resistance of the finished catalyst.

Patent CN101157057A discloses a method for in-situ synthesis of molecular sieve to prepare a low-abrasion catalyst, which comprises preparing porous microspheres by spray forming, and then performing hydrothermal synthesis treatment on the microspheres to generate an ordered molecular sieve structure inside the porous microspheres, thereby obtaining a low-abrasion microspherical catalyst.

Patent CN 200780041945.6 reports a process for the preparation of FCC catalysts, which process essentially comprises spray drying an aqueous slurry of zeolite, clay and polyaluminium chloride, followed by calcination. Among them, polyaluminium chloride is also called aluminum hydroxychloride, aluminum oxychloride and aluminum decachloride. By adding the polyaluminium chloride, the abrasion resistance of the catalyst is greatly improved. However, chlorine ions in the polyaluminium chloride remain in the catalyst and affect the reaction performance of the catalyst.

US 4946814 reports a method for improving the attrition resistance of a catalyst by first formulating a silica-alumina binder, then adding a matrix material (such as kaolin) and a molecular sieve to form a slurry, and finally adding a fluorine-containing anionic surfactant to improve the attrition resistance of the resulting catalyst. However, the adopted surfactant is expensive, and the fluorine ions have great influence on the environment, so that the method is not beneficial to industrial production.

Although some patents have been directed to improving the attrition resistance of fluidized bed catalysts, the attrition resistance of the fluidized bed catalysts is still low and needs to be further improved.

Disclosure of Invention

One of the technical problems to be solved by the invention is the problem of poor abrasion resistance of the fluidized bed catalyst in the prior art, and provides a fluidized bed catalyst, in particular a high-abrasion-resistance fluidized bed catalyst; the catalyst has the advantage of high abrasion resistance. The second technical problem to be solved by the invention is how to prepare the catalyst with high activity and high wear resistance strength, and the preparation method realizes the obvious improvement of the wear resistance of the fluidized bed catalyst and reduces the wear of the catalyst in the fluidized bed reaction process.

In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a fluidized bed catalyst comprises a SAPO molecular sieve and a binder; the catalyst is characterized in that the BET specific surface area of the catalyst is 220-280 m²/g。

In the preparation scheme, the BET specific surface area of the obtained finished catalyst is 230-260 m²/g。

In the preparation scheme, the most probable pore diameter of the finished catalyst is 1.0-1.7 nm.

In the technical scheme, the optimal pore diameter of the catalyst is 1.1-1.5 nm.

In the technical scheme, the optimal pore diameter of the catalyst is 1.1-1.3 nm.

In the preparation scheme, the molecular sieve is selected from at least one of SAPO-34, SAPO-44, SAPO-47, SAPO-5 or SAPO-56.

To solve the second technical problem, the invention adopts the following technical scheme: a preparation method of a fluidized bed catalyst comprises the following steps: (a) preparing a mixed solution containing a molecular sieve, a binder, a carrier material, a dilute acid solution and a liquid medium in proportion; (b) shearing the mixed solution at a high speed to obtain a suspension; (c) spray-drying the suspension to obtain a fluidized bed catalyst; (d) roasting the fluidized bed catalyst to obtain the finished product of the catalyst for preparing the olefin from the methanol. To solve the second technical problem, the invention can adopt the following technical scheme:

to solve the second technical problem, another technical solution adopted by the present invention is as follows: a preparation method of a fluidized bed catalyst comprises the following steps: (a) preparing a mixed solution containing a molecular sieve, a binder, a carrier material and a dilute acid solution according to a proportion; (b) adding a liquid medium in the process of shearing the mixed solution at a high speed and uniformly stirring to obtain a suspension; (c) spray-drying the suspension to obtain a fluidized bed catalyst; (d) roasting the fluidized bed catalyst to obtain the finished product of the catalyst for preparing the olefin from the methanol.

In the above technical solution, preferably, the fluidized bed catalyst of the present invention can be obtained by treating with MTO catalyst, which is currently used in industry. The specific surface area of the MTO catalyst for industrial use is reduced or the most probable pore size of the MTO catalyst for industrial use is reduced by the treatment.

In the preparation scheme, the binder is selected from at least one of silica sol, aluminum sol and pseudo-boehmite sol.

In the above technical scheme, the dilute acid solution is at least one selected from dilute hydrochloric acid, dilute nitric acid or dilute phosphoric acid.

In the technical scheme, the concentration of the dilute acid solution is 5-60 wt%, and more preferably, the concentration of the dilute acid solution is 30-40 wt%.

In the above technical scheme, the proportion in step (a) is as follows: 10-50 parts of molecular sieve, 20-50 parts of binder, 10-50 parts of carrier material, 2-20 parts of dilute acid solution and 40-60 parts of liquid medium.

In the technical scheme, preferably, the weight part of the dilute acid solution is 6-14 parts; more preferably, the diluted acid solution is 12-14 parts by weight.

And (3) performing high-speed circulating shearing on a mixed solution consisting of the molecular sieve, the binder, the carrier material, the dilute acid solution and the liquid medium for 20-40 min by using a colloid mill to form suspension slurry, wherein the average particle size of the obtained slurry particles is less than 5 microns, and the diameter of 90% of the particles is less than 6 microns. And (3) carrying out spray drying on the slurry, wherein the conditions of spray drying are that the air inlet temperature is 250-320 ℃, the air outlet temperature is 150-200 ℃, collecting solid powder particles below a spray drying tower, and roasting the solid powder particles to obtain the finished product of the fluidized bed catalyst.

In the technical scheme, the preferable particle size distribution of the fluidized bed catalyst is 20-150 μm.

In the technical scheme, the preferable average particle size of the fluidized bed catalyst is 55-85 μm; more preferably, the average particle size of the fluidized bed catalyst is 70-80 μm.

In the above technical solution, preferably, the attrition index of the finished fluidized bed catalyst is less than 0.6 wt%/h, and more preferably, the attrition index is less than 0.3 wt%/h.

In the above technical solution, preferably, the fluidized bed catalyst further contains rhenium oxide; preferably, the content of rhenium oxide is 0.1-1% by weight of the fluidized bed catalyst.

In the technical scheme, the finished product fluidized bed catalyst is applied to the reaction of preparing ethylene/propylene from methanol, the reaction temperature is 400-550 ℃, the reaction pressure is 0.1-0.5 MPa, and the airspeed of the raw material methanol is 2.0-6.0 h^-1Then (c) is performed. Ethylene selectivity is greater than 50% and propylene selectivity is greater than 30%, more preferably, ethylene selectivity is greater than 54% and propylene selectivity is greater than 33%.

By adopting the technical scheme of the invention and the catalyst containing the SAPO molecular sieve with the specific surface and the pore channel structure, the applicant surprisingly finds that the catalyst adopting the SAPO molecular sieve with the specific surface and the pore channel structure has stronger abrasion and better catalytic performance when the catalyst is applied to the reaction of preparing olefin from methanol, and obtains good technical effect.

The present invention is further illustrated in detail by the following specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention.

The experimental procedures under specific conditions not specified in the patent examples were generally carried out under conventional conditions.

Drawings

Curve 1 in FIG. 1 is a plot of the pore size distribution for a shaped conventional catalyst prepared by the method of comparative example 1.

Curve 2 in FIG. 1 is the pore size distribution plot for the shaped catalyst prepared by the method of example 1.

Curve 3 in FIG. 1 is the pore size distribution plot for the shaped catalyst prepared by the method of example 2.

Detailed Description

[ COMPARATIVE EXAMPLE 1 ]

According to the parts by weight, 30 parts of SAPO-34 molecular sieve, 20 parts of kaolin, 30 parts of alumina sol and 50 parts of deionized water are fully mixed and subjected to circulating colloid milling for 40 minutes to obtain a suspension. The average particle size of the suspension particles was 3.8 μm as determined by a laser particle sizer. Spray-drying the suspension, wherein the frequency of an atomizer is 20HZ, the air inlet temperature is 300 ℃, the feeding speed is 300g/min, collecting the solid at the bottom of the drying tower and the powder product in a collecting tank of a cyclone separator, and roasting the solid and the powder product in a muffle furnace for 8 hours at the temperature of 600 ℃ to obtain a finished product of the fluidized bed catalyst, wherein the abrasion index of the catalyst is 0.8 weight percent/hour. BET surface area of the resulting catalyst of 278m²The mode pore diameter is 1.63 nm. The catalyst is applied to a reaction system for preparing olefin from methanol, the reaction temperature is 500 ℃, the reaction pressure is 0.1MPa, and the airspeed of the raw material methanol is 4.0h^-1The ethylene selectivity was 51.35% and the propylene selectivity was 31.83%. The pore size distribution of the shaped conventional catalyst prepared by the method is shown in figure 1.

[ example 1 ]

According to the parts by weight, 30 parts of SAPO-34 molecular sieve, 20 parts of kaolin, 30 parts of alumina sol, 5 parts of dilute hydrochloric acid with the weight concentration of 40% and 45 parts of deionized water are fully mixed and subjected to circulating colloid milling for 40 minutes to obtain suspension. The average particle size of the suspension particles was 3.9 μm as determined by a laser particle sizer. Spray-drying the suspension, wherein the frequency of an atomizer is 20Hz, the air inlet temperature is 300 ℃, the feeding speed is 300g/min, collecting the solid at the bottom of the drying tower and the powder product in a collecting tank of a cyclone separator, and roasting the solid and the powder product in a muffle furnace at the temperature of 600 ℃ for 8 hours to obtain a finished product of the fluidized bed catalyst, wherein the abrasion index of the catalyst is 0.32 weight percent/hour. BET surface area 245m of the resulting catalyst²The mode pore diameter is 1.28 nm. The finished catalyst is applied to a reaction system for preparing olefin from methanol, the reaction temperature is 500 ℃, the reaction pressure is 0.1MPa, and the space velocity of the raw material methanol is 4.0h^-1When the catalyst is used, the selectivity of ethylene reaches 55.07 percent, and the selectivity of propylene reaches 31.76 percent. The pore size distribution of the shaped catalyst prepared by the method is shown in figure 1.

[ example 2 ]

According to the parts by weight, 30 parts of SAPO-34 molecular sieve, 20 parts of kaolin, 30 parts of alumina sol, 5 parts of 40% diluted phosphoric acid and 45 parts of deionized water are fully mixed and subjected to circulating colloid milling for 40 minutes to obtain suspension. The average particle size of the suspension particles was 3.9 μm as determined by a laser particle sizer. Spray-drying the suspension, wherein the frequency of an atomizer is 20Hz, the air inlet temperature is 300 ℃, the feeding speed is 300g/min, collecting the solid at the bottom of the drying tower and the powder product in a collecting tank of a cyclone separator, and roasting the solid and the powder product in a muffle furnace at the temperature of 600 ℃ for 8 hours to obtain a finished product of the fluidized bed catalyst, wherein the abrasion index of the catalyst is 0.35 weight percent/hour. BET surface area of 258m of the resulting catalyst²The mode pore diameter is 1.16 nm. The finished catalyst is applied to a reaction system for preparing olefin from methanol, the reaction temperature is 500 ℃, the reaction pressure is 0.1MPa, and the space velocity of the raw material methanol is 4.0h^-1When the catalyst is used, the selectivity of ethylene reaches 54.07 percent, and the selectivity of propylene reaches 32.89 percent. The pore size distribution of the shaped catalyst prepared by the method is shown in figure 1.

[ example 3 ]

According to the parts by weight, 30 parts of SAPO-34 molecular sieve and kaolin20 parts of silica sol, 30 parts of silica sol, 5 parts of diluted phosphoric acid with the concentration of 40 percent and 45 parts of deionized water are fully mixed and subjected to circulating colloid milling for 40 minutes to obtain suspension. The average particle size of the suspension particles was 3.9 μm as determined by a laser particle sizer. Spray-drying the suspension, wherein the frequency of an atomizer is 20Hz, the air inlet temperature is 300 ℃, the feeding speed is 300g/min, collecting the solid at the bottom of the drying tower and the powder product in a collecting tank of a cyclone separator, and roasting the solid and the powder product in a muffle furnace at the temperature of 600 ℃ for 8 hours to obtain a finished product of the fluidized bed catalyst, wherein the abrasion index of the catalyst is 0.44 weight percent/hour. BET surface area of the resulting catalyst 256m²The mode pore diameter is 1.14 nm. The finished catalyst is applied to a reaction system for preparing olefin from methanol, the reaction temperature is 500 ℃, the reaction pressure is 0.1MPa, and the space velocity of the raw material methanol is 4.0h^-1When the catalyst is used, the selectivity of ethylene reaches 53.95 percent, and the selectivity of propylene reaches 32.76 percent.

[ example 4 ]

According to the parts by weight, 30 parts of SAPO-34 molecular sieve, 20 parts of kaolin, 30 parts of pseudo-boehmite sol, 5 parts of diluted phosphoric acid with the concentration of 40% and 45 parts of deionized water are fully mixed and subjected to circulating colloid milling for 40 minutes to obtain suspension. The average particle size of the suspension particles was 3.9 μm as determined by a laser particle sizer. Spray-drying the suspension, wherein the frequency of an atomizer is 20Hz, the air inlet temperature is 300 ℃, the feeding speed is 300g/min, collecting the solid at the bottom of the drying tower and the powder product in a collecting tank of a cyclone separator, and roasting the solid and the powder product in a muffle furnace at the temperature of 600 ℃ for 8 hours to obtain a finished product of the fluidized bed catalyst, wherein the abrasion index of the catalyst is 0.46 weight percent/hour. BET surface area of the resulting catalyst of 253m²The mode pore diameter is 1.13 nm. The finished catalyst is applied to a reaction system for preparing olefin from methanol, the reaction temperature is 500 ℃, the reaction pressure is 0.1MPa, and the space velocity of the raw material methanol is 4.0h^-1When the catalyst is used, the selectivity of ethylene reaches 54.01 percent, and the selectivity of propylene reaches 32.83 percent.

[ example 5 ]

According to the parts by weight, 30 parts of SAPO-5 molecular sieve, 20 parts of kaolin, 20 parts of alumina sol, 10 parts of pseudo-boehmite sol, 5 parts of diluted phosphoric acid with the concentration of 40% and 45 parts of deionized water are fully mixed and subjected to circulating colloid milling for 40 minutes to obtain suspension. The average particle diameter of the suspension particles is measured by a laser particle sizer to be3.9 μm. Spray-drying the suspension, wherein the frequency of an atomizer is 20Hz, the air inlet temperature is 300 ℃, the feeding speed is 300g/min, collecting the solid at the bottom of the drying tower and the powder product in a collecting tank of a cyclone separator, and roasting the solid and the powder product in a muffle furnace at the temperature of 600 ℃ for 8 hours to obtain a finished product of the fluidized bed catalyst, wherein the abrasion index of the catalyst is 0.42 weight percent/hour. BET surface area of 255m for the catalyst obtained²The mode pore diameter is 1.4 nm. The finished catalyst is applied to a reaction system for preparing olefin from methanol, the reaction temperature is 500 ℃, the reaction pressure is 0.1MPa, and the space velocity of the raw material methanol is 4.0h^-1When the catalyst is used, the selectivity of ethylene reaches 53.95 percent, and the selectivity of propylene reaches 32.78 percent.

[ example 6 ]

According to the parts by weight, 30 parts of SAPO-5 molecular sieve, 20 parts of kaolin, 30 parts of alumina sol, 5 parts of 40% diluted phosphoric acid and 45 parts of deionized water are fully mixed and subjected to circulating colloid milling for 40 minutes to obtain suspension. The average particle size of the suspension particles was 3.9 μm as determined by a laser particle sizer. Spray-drying the suspension, wherein the frequency of an atomizer is 20Hz, the air inlet temperature is 300 ℃, the feeding speed is 300g/min, collecting the solid at the bottom of the drying tower and the powder product in a collecting tank of a cyclone separator, and roasting the solid and the powder product in a muffle furnace at the temperature of 600 ℃ for 8 hours to obtain a finished product of the fluidized bed catalyst, wherein the abrasion index of the catalyst is 0.37 weight percent/hour. BET surface area of the resulting catalyst of 250m²The mode pore diameter is 1.13 nm. The finished catalyst is applied to a reaction system for preparing olefin from methanol, the reaction temperature is 500 ℃, the reaction pressure is 0.1MPa, and the space velocity of the raw material methanol is 4.0h^-1When the catalyst is used, the selectivity of ethylene reaches 52.16 percent, and the selectivity of propylene reaches 31.39 percent.

[ example 7 ]

According to the weight parts, 15 parts of SAPO-34 molecular sieve, 15 parts of SAPO-5 molecular sieve, 20 parts of kaolin, 30 parts of alumina sol, 5 parts of 40% diluted phosphoric acid and 30 parts of deionized water are fully mixed and subjected to cyclic colloid milling for 40 minutes, and 15 parts of deionized water is added in the process of shearing the mixed solution at a high speed and is uniformly stirred to obtain a suspension. The average particle size of the suspension particles was 3.9 μm as determined by a laser particle sizer. Spray-drying the suspension at an atomizer frequency of 20Hz, an inlet air temperature of 300 ℃ and a feed rate of 300g/min, collecting the solids at the bottom of the drying towerThe powder product in the cyclone collection tank was calcined in a muffle furnace at 600 ℃ for 8 hours to obtain a finished fluidized bed catalyst with a attrition index of 0.36 wt%/hour. BET surface area of the resulting catalyst 252m²The mode pore diameter is 1.12 nm. The finished catalyst is applied to a reaction system for preparing olefin from methanol, the reaction temperature is 500 ℃, the reaction pressure is 0.1MPa, and the space velocity of the raw material methanol is 4.0h^-1When the catalyst is used, the selectivity of ethylene reaches 53.42 percent, and the selectivity of propylene reaches 32.27 percent.

[ examples 8 to 11 ]

The procedure and experimental conditions were exactly the same as those in example 1, but the types of the diluted acid solutions used were changed to obtain the final catalyst with abrasion index, specific surface area, maximum pore diameter and ethylene and propylene selectivity shown in Table 1.

TABLE 1

[ examples 12 to 18 ]

The procedure and experimental conditions were exactly the same as those in example 2, but the dilute phosphoric acid concentration was changed to obtain the final catalyst with attrition index, specific surface area, maximum pore diameter and ethylene and propylene selectivity as shown in Table 2.

TABLE 2

[ examples 19 to 25 ]

The procedure and experimental conditions were exactly the same as those in example 2, except that the liquid medium and the diluted phosphoric acid were changed in parts, to obtain the final catalyst having the abrasion index, specific surface area, maximum pore size and ethylene/propylene selectivity as shown in Table 3.

TABLE 3

[ examples 26 to 35 ]

The performance of the finished catalyst prepared in example 2 was evaluated under different reaction conditions. The reaction conditions and the evaluation results are shown in Table 4.

TABLE 4

[ example 36 ]

According to the parts by weight, 30 parts of SAPO-34 molecular sieve, 20 parts of kaolin, 30 parts of alumina sol, 5 parts of dilute hydrochloric acid with the concentration of 40 percent by weight, 0.2 part of ammonium perrhenate (containing 50 percent of rhenium oxide) and 45 parts of deionized water are fully mixed and subjected to circulating colloid milling for 40 minutes to obtain suspension. The average particle size of the suspension particles was 3.9 μm as determined by a laser particle sizer. Spray-drying the suspension, wherein the frequency of an atomizer is 20Hz, the air inlet temperature is 300 ℃, the feeding speed is 300g/min, collecting the solid at the bottom of the drying tower and the powder product in a collecting tank of a cyclone separator, and roasting the solid and the powder product in a muffle furnace at the temperature of 600 ℃ for 8 hours to obtain a finished product of the fluidized bed catalyst, wherein the abrasion index of the catalyst is 0.32 weight percent/hour. BET surface area of the resulting catalyst 246m²The mode pore diameter is 1.26 nm. The finished catalyst is applied to a reaction system for preparing olefin from methanol, the reaction temperature is 500 ℃, the reaction pressure is 0.1MPa, and the space velocity of the raw material methanol is 4.0h^-1When the catalyst is used, the selectivity of ethylene reaches 56.0 percent, and the selectivity of propylene reaches 34.5 percent.

[ example 37 ]

According to the parts by weight, 30 parts of SAPO-34 molecular sieve, 20 parts of kaolin, 30 parts of alumina sol, 5 parts of dilute hydrochloric acid with the concentration of 40 percent by weight, 0.8 part of ammonium perrhenate (containing 50 percent of rhenium oxide) and 45 parts of deionized water are fully mixedAnd a circulating colloid mill was performed for 40 minutes to obtain a suspension. The average particle size of the suspension particles was 3.9 μm as determined by a laser particle sizer. Spray-drying the suspension, wherein the frequency of an atomizer is 20Hz, the air inlet temperature is 300 ℃, the feeding speed is 300g/min, collecting the solid at the bottom of the drying tower and the powder product in a collecting tank of a cyclone separator, and roasting the solid and the powder product in a muffle furnace at the temperature of 600 ℃ for 8 hours to obtain a finished product of the fluidized bed catalyst, wherein the abrasion index of the catalyst is 0.33 weight percent/hour. BET surface area of the resulting catalyst 247m²The mode pore diameter is 1.29 nm. The finished catalyst is applied to a reaction system for preparing olefin from methanol, the reaction temperature is 500 ℃, the reaction pressure is 0.1MPa, and the space velocity of the raw material methanol is 4.0h^-1When the catalyst is used, the selectivity of ethylene reaches 57.5 percent, and the selectivity of propylene reaches 35.6 percent.

[ example 38 ]

According to the parts by weight, 30 parts of SAPO-34 molecular sieve, 20 parts of kaolin, 30 parts of alumina sol, 5 parts of dilute hydrochloric acid with the concentration of 40 percent by weight, 1.0 part of ammonium perrhenate (containing 50 percent of rhenium oxide) and 45 parts of deionized water are fully mixed and subjected to circulating colloid milling for 40 minutes to obtain suspension. The average particle size of the suspension particles was 3.9 μm as determined by a laser particle sizer. Spray-drying the suspension, wherein the frequency of an atomizer is 20Hz, the air inlet temperature is 300 ℃, the feeding speed is 300g/min, collecting the solid at the bottom of the drying tower and the powder product in a collecting tank of a cyclone separator, and roasting the solid and the powder product in a muffle furnace at the temperature of 600 ℃ for 8 hours to obtain a finished product of the fluidized bed catalyst, wherein the abrasion index of the catalyst is 0.32 weight percent/hour. BET surface area 243m of the resulting catalyst²The mode pore diameter is 1.26 nm. The finished catalyst is applied to a reaction system for preparing olefin from methanol, the reaction temperature is 500 ℃, the reaction pressure is 0.1MPa, and the space velocity of the raw material methanol is 4.0h^-1When the catalyst is used, the selectivity of ethylene reaches 56.8 percent, and the selectivity of propylene reaches 35.4 percent.

Claims

1. A fluidized bed catalyst comprises a SAPO molecular sieve and a binder; characterized in that the BET specific surface area of the catalyst is 237-²The mode pore diameter of the catalyst is 1.11-1.5 nm.

2. The fluid bed catalyst of claim 1, wherein the catalyst has a mode pore size of 1.11-1.3 nm.

3. The fluid bed catalyst of claim 1, wherein the SAPO molecular sieve is selected from one or at least one of SAPO-34, SAPO-44, SAPO-47, SAPO-5 or SAPO-56.

4. The method for preparing the fluidized bed catalyst according to claim 1, comprising the steps of: (a) preparing mixed solution containing dilute acid solution, liquid medium, molecular sieve, binder and carrier material according to a proportion; (b) shearing the mixed solution at a high speed to obtain a suspension; (c) spray drying the suspension to form a fluidized bed catalyst; (d) and roasting the fluidized bed catalyst to obtain the finished product fluidized bed catalyst.

5. The method of claim 4, wherein the dilute acid solution is at least one selected from dilute hydrochloric acid, dilute nitric acid, and dilute phosphoric acid.

6. The method for preparing a fluidized bed catalyst according to claim 4, wherein the binder is at least one selected from the group consisting of silica sol, aluminum sol, and pseudo-boehmite sol.

7. The method for preparing the fluidized bed catalyst according to claim 4, wherein the concentration of the dilute acid solution is 5-60 wt%.

8. The method for preparing the fluidized bed catalyst according to claim 4, wherein the ratio in the step (a) is as follows: 10-50 parts of molecular sieve, 20-50 parts of binder, 10-50 parts of carrier material, 2-20 parts of dilute acid solution and 40-60 parts of liquid medium.

9. The fluid catalyst of claim 1 wherein the fluid catalyst attrition index is less than 0.5 wt%/hour.

10. The fluid catalyst of claim 1 wherein the fluid catalyst attrition index is less than 0.3 wt%/hour.

11. A method for preparing olefin from methanol, wherein the fluidized bed catalyst of any one of claims 1 to 3 is applied to the reaction process of preparing ethylene/propylene from methanol, the reaction temperature is 400-550 ℃, the reaction pressure is 0.1-0.5 MPa, and the weight space velocity of the raw material methanol is 1.0-10 h < -1 >.