CN104209139B - A kind of methanol conversion produces the Catalysts and its preparation method that propene yield taken into account by gasoline - Google Patents

Abstract

The invention discloses a catalyst for converting methanol into gasoline and taking into consideration the yield of propylene and a preparation method thereof. The catalyst is composed of an active component, a carrier, a modified binder and a metal oxide, wherein the active component is a ZSM-11 molecular sieve, and the ZSM-11 molecular sieve has a hierarchical pore structure of mesopores and micropores and nanorod intercalation Bonding morphology, wherein the volume ratio of mesopores to micropores is (0.2-3.0): 1, the grain size is 50-1900nm, and the silicon-aluminum ratio is 30-300. The agent I and the modified binder II are composed at a mass ratio of 0.1-10:1, the modified binder I is prepared by a metal modification method, and the modified binder II is prepared by a static hydrothermal crystallization method. The catalyst prepared by the present invention can produce gasoline and take into account the yield of propylene when used in methanol conversion reaction, realizes the adjustment of gasoline and propylene yield in the methanol conversion reaction, adapts to the market changes of gasoline and propylene, and improves the production capacity of gasoline and propylene. The ability of methanol conversion technology to resist market risks.

Description

Catalyst for methanol conversion to produce gasoline while taking into account propylene yield and preparation method thereof

technical field

The invention relates to a catalyst for converting methanol to produce gasoline while taking into account the yield of propylene and a preparation method thereof, in particular to a catalyst for converting methanol to produce gasoline while taking into account the yield of propylene containing ZSM-11 molecular sieve active components and a preparation method thereof.

Background technique

The technology of methanol conversion to produce gasoline is a technology that uses methanol as raw material to produce gasoline with the help of catalysts. Compared with catalytic cracking gasoline, the gasoline produced by methanol conversion shows good properties, for example, its olefins, aromatics and S content are all within the range of clean gasoline, which meets the strict restrictions on S content in National IV and National V gasoline standards.

The process of methanol conversion to produce gasoline is developed on the basis of the conversion of methanol to aromatics on the ZSM-5 molecular sieve catalyst developed by Mobil. Mobil methanol conversion to gasoline production technology first uses coal or natural gas as raw material to produce synthesis gas, then uses synthesis gas to produce methanol, and finally converts crude methanol into high-octane gasoline.

The conversion of methanol to propylene technology is based on the production of olefins and other hydrocarbons with the aid of catalysts using methanol as a raw material. It is a technology that can rationally utilize excess methanol while reducing carbon emissions, and has obvious advantages.

At present, ZSM-5 molecular sieve catalyst is a commonly used catalyst in methanol conversion to produce gasoline and propylene, and it shows good catalytic performance in methanol conversion reaction. However, at present, ZSM-5 molecular sieve catalysts cannot simultaneously increase the yield of propylene in gasoline and liquefied gas when used in methanol conversion production reactions due to the limitations of pore structure, acid properties and morphology.

At the same time, in order to meet the strict requirements of the process on the catalyst wear index and particle size distribution, an appropriate binder should be selected, and the binder, as a part of the catalyst, is also closely related to the performance of the catalyst. At present, common binders for preparing semi-synthetic catalysts include aluminum-based binders, silicon-based binders, and silicon-aluminum binders. At the same time, in the prior art, the acidity and metal poisoning resistance of the catalyst can be adjusted by modification such as rare earth, but the price is expensive and the applicability is not great. CN1098130A patent discloses a composite aluminum-based binder, which improves the wear resistance and coke selectivity of semi-synthetic catalysts. The above-mentioned modifications are mostly used in catalytic cracking catalysts, but due to the difference in raw materials, the acid properties and physical properties required for methanol conversion are different from the former. Activity has an important effect.

Contents of the invention

In order to solve the problems in the methanol conversion reaction in the prior art, the embodiments of the present invention provide a catalyst for methanol conversion to produce gasoline while taking into account the yield of propylene and a preparation method thereof. Described technical scheme is as follows:

One aspect of the present invention provides a catalyst for the conversion of methanol to produce gasoline while taking into account the yield of propylene. The catalyst is composed of active components, carriers, modified binders and metal oxides. It is characterized in that the active components Divided into ZSM-11 molecular sieve, the molecular sieve has a stepped pore structure of mesopores and micropores and a nanorod plug-in morphology. The volume ratio of mesopores to micropores is (0.2-3.0): 1, and the grain size is 50 -1900nm, the ratio of silicon to aluminum is 30-300; based on the quality of the catalyst, the mass ratio of the active component, carrier, modified binder and metal oxide of the catalyst is (3-60): (80 -5): (2.0-55): (0.1-50); the modified binder is composed of modified binder Ⅰ and modified binder Ⅱ, and the modified binder Ⅰ adopts metal modification The modified binder II is prepared by the static hydrothermal crystallization method, and the mass ratio of the modified binder I to the modified binder II is 0.1-10:1.

Preferably, based on the mass of the catalyst, the mass ratio of the active component, carrier, modified binder and metal oxide is (10-35): (20-60): (7.0-35): ( 1.0-40).

Preferably, the ZSM-11 molecular sieve has a volume ratio of mesopores to micropores of (0.5-2.0):1, a grain size of 200-1700 nm, and a silicon-aluminum ratio of 30-100.

Specifically, the carrier is selected from at least one of kaolin, MgO, sepiolite, Al ₂ O ₃ , SiO ₂ and diatomaceous earth.

Specifically, the preparation method of the modified binder comprises:

Metal modification treatment: Mix and stir the binder and 2mol/L metal salt solution for 4 hours in a water bath at 60°C, and then let it stand at room temperature for 4-6 hours to obtain modified binder I; among them, the metal salt solution The quality of the metal salt is calculated based on the quality of the corresponding metal oxide of the metal, and the metal oxide is selected from at least one of Zn, W, B, P, Zr, Mg and Mn oxides, and the metal oxide is The mass is 0.5%-15% of the mass of the binder;

Static hydrothermal crystallization treatment: put the binder into a crystallization kettle, statically crystallize at 100°C for 2-8 hours, and then stand at room temperature for 4-6 hours to obtain modified binder II;

The modified binder I and the modified binder II are mixed at a mass ratio of 0.1-10:1, and the modified binder is obtained after uniform stirring.

Specifically, the binder is selected from at least one of silica sol, aluminum sol and water glass.

Specifically, when the binder is silica sol, its quality is based on the mass of silica, wherein the mass fraction of silica in the silica sol is 40.0%; when the binder is water glass, Its quality is based on the mass of silicon dioxide, wherein the mass fraction of silicon dioxide in the water glass is 27.5%; when the binder is aluminum sol, its quality is based on the quality of alumina monohydrate, wherein one The mass fraction of hydrated alumina in the aluminum sol is 20.0%.

Specifically, the metal oxide is selected from at least one of Zn, Ce, P, Co, B, K, Cs, Ca, Mg, Sr and Ba oxides.

Another aspect of the present invention provides a kind of method for preparing above-mentioned catalyst, described method comprises the following steps:

Mix the active component, carrier and modified binder with deionized water in a prescribed order, and stir them evenly to make a catalyst gel;

Add the metal salt solution to the catalyst gel, dry at 120°C for 6-8h, roast at 700°C for 2h, and sieve out 80-200μm catalyst particles after cooling. The mass of the metal salt in the metal salt solution is based on the To calculate the mass of the metal oxide corresponding to the metal, the amount of the metal salt solution is generally selected according to the following principle: 70 g of the metal salt solution is required to prepare 50 g of catalyst particles.

A third aspect of the present invention provides a method for preparing the above-mentioned catalyst, the method comprising the following steps:

Mix the active component, carrier and modified binder with deionized water in a prescribed order, and stir them evenly to make a catalyst gel; dry the above catalyst gel at 120°C for 6-8h, and bake at 700°C for 2h , after cooling, sieve out 80-200 μm intermediate shaped catalyst particles;

At normal temperature, impregnate the metal salt solution on the above-mentioned intermediate shaped catalyst particles, then dry at 140°C for 8-10h, and roast at 700°C for 2h to obtain catalyst particles; To calculate the mass of the metal oxide, the amount of the metal salt solution is generally selected according to the following principles: 70 g of the metal salt solution is required to impregnate 50 g of the catalyst particles formed in the middle.

In the preparation method of the above-mentioned catalyst, the active component, the carrier and the modified binder are mixed with deionized water according to the specified order and specifically prepared according to the following specified sequence:

When using pseudo-boehmite to prepare Al ₂ O ₃ as a carrier, first mix pseudo-boehmite, water and hydrochloric acid, and mechanically stir for 0.5h to form a gel. Add active components and carriers to the above solution, then add modified binder and deionized water, and mechanically stir evenly to obtain the catalyst gel.

When other carriers are selected, first add deionized water to the modified binder, then add the carrier, mechanically stir at room temperature, then add active components and deionized water, and mechanically stir evenly to obtain the catalyst gel.

In the above method for preparing the catalyst of the present invention, the metal salt solution is prepared according to the following method: Weigh the required mass of metal salt according to the mass ratio, and dissolve it in deionized water to prepare the metal salt solution.

In the above-mentioned preparation method of the catalyst of the present invention, at normal temperature, the specific operation of impregnating the metal salt solution on the intermediate shaped catalyst particles is as follows: drop the metal salt solution dropwise onto the intermediate shaped catalyst particles with a dropper, After all the incipient wetness is dried, repeat the operation 3-4 times until all the metal salt solution is used up.

A preferred embodiment of the present invention is: a catalyst for methanol conversion to produce gasoline while taking into account the yield of propylene, the catalyst is composed of an active component, a carrier, a modified binder and a metal oxide, and the active component is ZSM -11 molecular sieve, the ZSM-11 molecular sieve has a volume ratio of mesopores to micropores (0.5-2.0): 1, crystal grains of 200-1700nm, and a silicon-aluminum ratio of 30-100; based on the quality of the catalyst , the mass ratio of the active component of the catalyst, the carrier, the modified binder and the metal oxide is: (10-35): (20-60): (7.0-35): (1.0-40), The preparation method of the catalyst is: firstly weigh the active component, the carrier, the modified binder and the metal oxide according to the mass ratio of each component, and at normal temperature, the active component, the The carrier and modified binder are mixed with deionized water in the prescribed order, and mechanically stirred evenly to make a catalyst gel, and then the catalyst gel is dried at 120°C for 6-8h, roasted at 700°C for 2h, and screened out after cooling. Intermediate shaped catalyst particles of 80-200 μm; dissolving metal oxides in water to prepare a corresponding metal salt solution, impregnating the above-mentioned metal salt solution on the intermediate shaped catalyst particles at room temperature, drying at 140°C for 8-10h, Calcined at 700°C for 2 hours to obtain catalyst particles.

Principle of the present invention is as follows:

In the conventional methanol conversion reaction, the yield of gasoline and the yield of propylene belong to a pair of contradictions, that is, only one high-yield product can be obtained, and it is impossible to produce more gasoline while taking into account the yield of propylene, or to produce more propylene At the same time, take into account the yield of gasoline. However, the embodiment of the present invention provides a catalyst for methanol conversion reaction, which can produce propylene while taking into account the yield of gasoline or produce gasoline while taking into account the yield of propylene, which subverts the conventional thinking in the field of liquefied gas production and provides a new development direction .

The active component of the catalyst described in the embodiment of the present invention is ZSM-11 molecular sieve, and the ZSM-11 molecular sieve has a stepped pore structure of mesopores and micropores and a nanorod insertion morphology, and the ZSM-11 molecular sieve The grain size of the ZSM-11 molecular sieve is 50-1900nm, the silicon-aluminum ratio is 30-300, and the volume ratio of the medium pores to the micropores of the ZSM-11 molecular sieve is (0.2-3.0):1.

A ZSM-11 molecular sieve with a hierarchical pore structure of micropores and mesopores and a nanorod plug-in morphology was used as the active component of the catalyst, and a ZSM-11 molecular sieve was prepared by adjusting the grain size, morphology, and silicon-aluminum ratio of the ZSM-11 molecular sieve. A series of catalysts are used to realize the purpose of methanol conversion reaction to produce more gasoline while taking into account the yield of propylene, and can properly adjust the yield of gasoline and propylene in the product. The hierarchical pore structure of the micropores and mesopores of the ZSM-11 molecular sieve effectively reduces molecular diffusion resistance, prevents secondary reactions from further occurring, and is beneficial to the improvement of olefin selectivity.

The nano-rod insertion morphology of the ZSM-11 molecular sieve means that the molecular sieve has a uniform spherical shape self-assembled from rod-shaped microcrystals, which overcomes the defects of mesoporous molecular sieves and the cumbersome post-treatment process.

The volume ratio of mesopores and micropores of the ZSM-11 molecular sieve is related to the selectivity of the product. The larger the proportion of mesopores, the easier it is for macromolecular substances to diffuse inside the molecular sieve, and the higher the yield of gasoline obtained; at the same time, the content of intermediate species and low-carbon olefins is also different if the proportion of mesopores is different.

The crystal grains of the ZSM-11 molecular sieve will affect the catalytic activity and selectivity. Smaller molecular sieve grain size can increase the outer surface, and expose more internal micropores to contact with reactants, shorten the residence time of low-carbon olefin intermediates on the catalytic active center of molecular sieves, and inhibit the formation of by-products. Improving the selectivity of the target product is beneficial to improving the activity and life of the catalyst.

The silicon-aluminum ratio of the ZSM-11 molecular sieve will affect the acid distribution and acid strength on the surface of the molecular sieve. When the silicon-alumina ratio is low, the number of acid sites will increase, secondary reactions will easily occur, and the selectivity of olefins will decrease. If the silicon-aluminum ratio is too high, the acid density will decrease, and the conversion rate will decrease significantly.

When the grain size of the ZSM-11 molecular sieve is 200-1700nm, the silicon-aluminum ratio is 30-100, and the ratio of mesopore volume to micropore volume is (0.5-2.0): 1, the activity of the catalyst obtained and the selection of the target product Sex is the highest.

The carrier of the catalyst provided in the embodiment of the present invention mainly plays the role of dispersing and supporting the active components in the catalyst, and provides the catalyst with certain mechanical strength and thermal and hydrothermal stability. Depending on the content of the active component, the content of the carrier in the catalyst is also different.

The binder mainly binds the active components and the carrier together to meet the technical requirements on catalyst wear index and particle size distribution. In addition, as a component of the catalyst, it can also play a certain role in modulating the reaction performance of the catalyst. The embodiments of the present invention provide catalysts with modified binders. The acid properties of the catalyst can be adjusted by using the modified binder. According to the content of the active component and carrier in the catalyst, the content of the modified binder in the catalyst is also different.

In order to adjust the acidity of the ZSM-11 molecular sieve grain surface, metal oxides are added to the catalyst to reduce the acidity of the catalyst, thereby improving the selectivity of olefin products in the methanol conversion reaction of the catalyst. According to the content of the active component, the content of the oxide of the alkali metal or alkaline earth metal in the catalyst is also different.

The beneficial effects brought by the technical solution provided by the embodiments of the present invention are:

Use ZSM-11 molecular sieve as the active component and match the catalyst with suitable carrier and modified binder to carry out methanol conversion reaction, which can produce gasoline while taking into account the yield of propylene or produce propylene while taking into account the yield of gasoline, realizing the methanol conversion reaction The adjustment of gasoline and propylene yields in the middle adapts to the market changes of gasoline and propylene, and improves the ability of methanol conversion technology to resist market risks.

detailed description

In order to make the purpose, technical solution and advantages of the present invention clearer, the implementation manners of the present invention will be further described in detail below.

The catalyst that the embodiment of the present invention provides is prepared according to the following method:

First, based on the mass of the catalyst, calculate and weigh the active components, carrier, and modified binder according to the mass ratio (3-60): (80-5): (2.0-55): (0.1-50) and metal oxide, adding the active component, carrier and modified binder into 50-100g deionized water, mechanically stirring at normal temperature to make a catalyst gel; dissolving the metal oxide in deionized water to prepare To form a metal salt solution, the amount of the metal salt solution is generally selected according to the following principles: 70 g of the metal salt solution needs to be prepared to prepare 50 g of catalyst particles; the metal salt solution is added to the catalyst gel, dried at 120°C for 6-8 hours, and then dried at 700°C Calcined for 2 hours, cooled and sieved to obtain catalyst particles with a diameter of 80-200 μm.

The catalyst provided by the embodiments of the present invention can also be prepared according to the following method:

First, based on the mass of the catalyst, calculate and weigh the active components, carrier, and modified binder according to the mass ratio (3-60): (80-5): (2.0-55): (0.1-50) and metal oxides, the active component, carrier, and binder are added to 50-100g of deionized water, and mechanically stirred at room temperature to make it uniform, and then the catalyst gel is dried at 120°C for 6-8h, and roasted at 700°C After cooling for 2 hours, sieve out 80-200μm intermediate shaped catalyst particles; dissolve metal oxides in deionized water to make metal salt solution, generally select the amount of metal salt solution according to the following principles: impregnate 50g of intermediate shaped catalyst Particles need to prepare 70g of metal salt solution; then impregnate the above metal salt solution on the intermediate shaped catalyst particles, and finally dry at 140°C for 8-10h, and bake at 700°C for 2h.

Specifically, the active component is ZSM-11 molecular sieve, and the active component ZSM-11 molecular sieve used in the examples of the present invention was synthesized by the inventor himself, and the specific synthesis method refers to patent CN102557071A.

Specifically, the carrier is at least one of kaolin, MgO, sepiolite, Al ₂ O ₃ , SiO ₂ and diatomaceous earth. The purity and manufacturer of the carriers used in the examples of the present invention are shown in the following table.

Specifically, the preparation method of the modified binder comprises:

Metal modification treatment: Mix and stir the binder and 2mol/L metal salt solution for 4 hours in a water bath at 60°C, and then let it stand at room temperature for 4-6 hours to obtain modified binder I; among them, the metal salt solution The quality of the metal salt is calculated based on the quality of the corresponding metal oxide of the metal, and the metal oxide is selected from at least one of Zn, W, B, P, Zr, Mg and Mn oxides, and the metal oxide is The mass is 0.5%-15% of the mass of the binder;

Static hydrothermal crystallization treatment: Put the binder into the crystallization kettle, statically crystallize at 100°C for 2-8 hours, and then stand at room temperature for 4-6 hours to obtain modified binder II;

The modified binder I and the modified binder II are mixed at a mass ratio of 0.1-10:1, and the modified binder is obtained after uniform stirring.

The binder is at least one of silica sol, aluminum sol and water glass. When binding agent is silica sol, the quality of described silica sol is based on the mass of silicon dioxide, and the massfraction of silicon dioxide in described silica sol is 40.0%; When binding agent is water glass, described water glass The quality of the silica is based on the mass of silica, and the mass fraction of silica in the water glass is 27.5%; when the binding agent is aluminum sol, the quality of the aluminum sol is based on the mass of alumina monohydrate, which The mass fraction in the aluminum sol is 20.0%. The purity and manufacturer of the binder used in the embodiments of the present invention are shown in the table below.

Specifically, the metal oxide is at least one of Zn, Ce, P, Co, B, K, Cs, Ca, Mg, Sr and Ba oxides.

The purity and the manufacturer of the metal salt used in the embodiments of the present invention are as follows:

Example 1

Preparation of modified silica sol: first mix 20g of silica sol with 5mL 2mol/L zinc nitrate solution in a 60°C water bath and stir for 4h, then let it stand at room temperature for 6h to obtain modified silica sol Ⅰ; then mix 20g of silica sol Put it into a crystallization kettle, statically crystallize at 100°C for 6 hours, and then stand at room temperature for 4 hours to obtain modified silica sol II; finally, modify silica sol I and modified silica sol II at a mass ratio of 1:1 The ratio is mixed, and the modified silica sol is obtained after stirring evenly.

Example 2

Preparation of modified aluminum sol: first mix 10g of water glass with 8mL of 2mol/L magnesium nitrate solution in a 60°C water bath and stir for 4h, then leave it at room temperature for 4h to obtain modified aluminum sol I; then mix 30g of water glass with Put it into a crystallization kettle, statically crystallize at 100°C for 4 hours, and then stand at room temperature for 4 hours to obtain modified aluminum sol II; finally, modify aluminum sol I and modified aluminum sol II in a mass ratio of 1:3 The ratio is mixed, and the modified aluminum sol is obtained after stirring evenly.

Example 3

Preparation of modified water glass: first, 50 g of water glass was mixed and stirred with 30 mL of 2mol/L ammonium dihydrogen phosphate solution under 60° C. water bath conditions for 4 h, and then left to stand at room temperature for 4 h to obtain modified water glass Ⅰ; then 10 g Put the water glass into a crystallization kettle, statically crystallize it at 100°C for 4 hours, and then let it stand at room temperature for 4 hours to obtain modified water glass II; : 1 ratio is mixed, obtains described modified water glass after stirring.

The modified silica sol used in the following examples 4-23 is provided by embodiment 1, the modified aluminum sol used is provided by embodiment 2, and the modified water glass used is provided by embodiment 3.

Example 4

Add 50 g of deionized water to 13.75 g of modified silica sol, then add 48.5 g of kaolin, and stir evenly. Add 46g of ZSM-11 molecular sieve powder of 1100nm, Si/Al of 100, and mesopore volume ratio of 2.0 to the above solution, then add 12.5g of deionized water, stir evenly, dry at 120°C for 6-8h, and then dry at 700°C Calcined at ℃ for 2h, crushed after cooling and sieved out to 80-200μm as intermediate shaped catalyst. Weigh 2.56g of Ba(NO ₃ ) ₂ , dissolve it in 70g of deionized water to make an aqueous solution of Ba(NO ₃ ) ₂ , impregnate the solution on 50g of the intermediate shaped catalyst, and then dry at 140°C for 8-10h , roasted at 700°C for 2h, and set aside.

Example 5

Add 50 g of deionized water to 38.75 g of modified silica sol, then add 64.5 g of kaolin, and stir evenly. Add 20g of 1100nm, Si/Al35, ZSM-11 molecular sieve powder with a mesopore volume ratio of 1.5 to the above solution, then add 12.5g of deionized water, stir evenly, dry at 120°C for 6-8h, and then roast at 700°C 2h, after cooling, pulverize and sieve out 80-200μm catalyst as intermediate shaped catalyst. Weigh 6.92g of CsNO ₃ , dissolve it in 70g of deionized water to make an aqueous solution of CsNO ₃ , impregnate the solution on 50g of the intermediate shaped catalyst, then dry at 140°C for 8-10h, and bake at 700°C for 2h. spare.

Example 6

Add 50 g of deionized water to 5.0 g of modified silica sol, then slowly add 70.0 g of kaolin, and stir evenly. Add 28g of ZSM-11 molecular sieve powder of 1700nm, Si/Al100, and mesopore volume ratio of 1.5 to the above solution, then add 12.5g of deionized water to dissolve, and mechanically stir evenly. Then it was dried at 120°C for 6-8 hours, calcined at 700°C for 2 hours, and after cooling, it was crushed and sieved to obtain an intermediate shaped catalyst of 80-200 μm. Weigh 29.28g of Ca(NO ₃ ) ₂ , dissolve it in 70g deionized water to make an aqueous solution of Ca(NO ₃ ) ₂ , impregnate the solution on 50g of the intermediate shaped catalyst, then dry at 140°C for 8 -10h, roast at 700°C for 2h, set aside.

Example 7

Add 50 g of deionized water to 50.0 g of modified silica sol, then slowly add 60.0 g of kaolin, and stir evenly. Add 20g of ZSM-11 molecular sieve powder of 1700nm, Si/Al35, and mesopore volume ratio of 1.5 to the above solution, then add 12.5g of deionized water to dissolve, and mechanically stir evenly. Then it was dried at 120°C for 6-8 hours, calcined at 700°C for 2 hours, and after cooling, it was crushed and sieved to obtain an intermediate shaped catalyst of 80-200 μm. Weigh 21.44g of KNO ₃ , dissolve it in 70g of deionized water to make an aqueous solution of KNO ₃ , impregnate the solution on 50g of the intermediate shaped catalyst, then dry at 140°C for 8-10h, and bake at 700°C for 2h. spare.

Example 8

Add 50 g of deionized water to 100.0 g of modified silica sol, then slowly add 10.0 g of sepiolite, and stir evenly. Add 50g of ZSM-11 molecular sieve powder with 1700nm, Si/Al35, and mesopore volume ratio of 2.0 to the above solution, then add 12.5g of deionized water to dissolve, and stir evenly to obtain catalyst gel. Weigh 34.91g of Zn(NO ₃ ) ₂ ·6H ₂ O, dissolve it in 70g of deionized water to make an aqueous solution of Zn(NO ₃ ) ₂ , add it to the catalyst gel, and then dry it at 120°C for 6- 8h, calcination at 700°C for 2h, after cooling, crush and sieve shaped catalyst particles of 80-200μm.

Example 9

Add 50 g of deionized water to 105.0 g of modified aluminum sol, then add 46.5 g of kaolin slowly, and stir evenly. Add 32.5g of ZSM-11 molecular sieve powder with 500nm, Si/Al100, and mesopore volume ratio of 1.5 to the above solution, then add 12.5g of deionized water to dissolve, and mechanically stir evenly. Then it was dried at 120°C for 6-8 hours, calcined at 700°C for 2 hours, and after cooling, it was crushed and sieved to obtain an intermediate shaped catalyst of 80-200 μm. Weigh 10.21g of Sr(NO ₃ ) ₂ , dissolve it in 70g deionized water to make an aqueous solution of Sr(NO ₃ ) ₂ , impregnate the solution on 50g of the intermediate shaped catalyst, then dry at 140°C for 8 -10h, roast at 700°C for 2h, set aside.

Example 10

Add 50 g of deionized water to 135.0 g of modified aluminum sol, then add 52.5 g of kaolin slowly, and stir evenly with a machine. Add 20.5g of ZSM-11 molecular sieve powder with 1700nm, Si/Al100, and mesopore volume ratio of 1.0 to the above solution, then add 12.5g of deionized water to dissolve, and mechanically stir evenly. Then it was dried at 120°C for 6-8 hours, calcined at 700°C for 2 hours, and after cooling, it was crushed and sieved to obtain an intermediate shaped catalyst of 80-200 μm. Weigh 8.52g of Ba(NO ₃ ) ₂ , dissolve it in 70g of deionized water and stir evenly to make an aqueous solution of Ba(NO ₃ ) ₂ , impregnate the solution on 50g of the intermediate shaped catalyst, and then in 140°C Dry for 8-10 hours, bake at 700°C for 2 hours, and set aside.

Example 11

Add 50 g of deionized water to 62.5 g of modified silica sol, then add 43.5 g of kaolin slowly, and stir evenly. Add 31.5g of ZSM-11 molecular sieve powder with 500nm, Si/Al35, and mesopore volume ratio of 1.5 to the above solution, then add 12.5g of deionized water to dissolve, and mechanically stir evenly. Dry at 120°C for 6-8h, then calcined at 700°C for 2h, after cooling, crush and sieve out 80-200μm catalyst as intermediate shaped catalyst. Weigh 11.63g of Zn(NO ₃ ) ₂ 6H ₂ O, dissolve it in 70g deionized water and stir evenly to make an aqueous solution of Zn(NO ₃ ) ₂ , impregnate the solution on the 50g described intermediate shaped catalyst, Then dry at 140°C for 8-10h. Then weigh 8.46g of NH ₄ Ce(NO ₃ ) ₆ , dissolve it in 70g of deionized water and stir well to make an aqueous solution of NH ₄ Ce(NO ₃ ) ₆ , and impregnate the above-mentioned Zn(NO ₃ ) ₂ aqueous solution The dried catalyst is impregnated with an aqueous solution of NH ₄ Ce(NO ₃ ) ₆ , dried at 140° C. for 8-10 hours, calcined at 700° C. for 2 hours, and set aside.

Example 12

Add 50 g of deionized water to 38.75 g of modified silica sol, then add 52.5 g of kaolin slowly, and stir evenly. Add 32g of ZSM-11 molecular sieve powder with 1100nm, Si/Al65, and mesopore volume ratio of 0.5 to the above solution, then add 12.5g of deionized water to dissolve, and mechanically stir evenly. Dry at 120°C for 6-8h, then calcined at 700°C for 2h, after cooling, pulverize and sieve out 80-200μm catalyst as intermediate shaped catalyst. Weigh 18.40g of Mg(NO ₃ ) ₂ 6H ₂ O, dissolve it in 70g deionized water and stir evenly to make an aqueous solution of Mg(NO ₃ ) ₂ , impregnate the solution on 50g of the intermediate shaped catalyst, Then dry at 140°C for 8-10h, and bake at 700°C for 2h, and set aside.

Example 13

Add 50 g of deionized water to 61.25 g of modified silica sol, then add 45.5 g of kaolin slowly, and stir evenly. Add 30g of ZSM-11 molecular sieve powder of 500nm, Si/Al65, and mesopore volume ratio of 1.0 to the above solution, then add 12.5g of deionized water to dissolve, and mechanically stir evenly. Dry at 120°C for 6-8h, then calcined at 700°C for 2h, after cooling, crush and sieve out 80-200μm catalyst as intermediate shaped catalyst. Weigh 14.64g of Ca(NO ₃ ) ₂ , dissolve it in 70g of deionized water and stir evenly to make an aqueous solution of Ca(NO ₃ ) ₂ , impregnate the solution on 50g of the intermediate shaped catalyst, and then in 140°C Dry for 8-10 hours, bake at 700°C for 2 hours, and set aside.

Example 14

Add 50 g of deionized water into 20.00 g of modified water glass, then slowly add 58.5 g of sepiolite, and stir evenly with a machine. Add 36g of ZSM-11 molecular sieve powder of 500nm, Si/Al35, and mesopore volume ratio of 0.5 to the above solution, then add 12.5g of deionized water to dissolve, and mechanically stir evenly. Dry at 120°C for 6-8h, then calcined at 700°C for 2h, after cooling, crush and sieve out 80-200μm catalyst as intermediate shaped catalyst. Weigh 11.63g of Zn(NO ₃ ) ₂ 6H ₂ O, dissolve it in 70g deionized water and stir evenly to make an aqueous solution of Zn(NO ₃ ) ₂ , impregnate the solution on the 50g described intermediate shaped catalyst, Then dry at 140°C for 8-10h, and bake at 700°C for 2h, and set aside.

Example 15

Add 50 g of deionized water to 26.25 g of modified silica sol, then slowly add 63.5 g of MgO, and stir evenly. Add 26g of ZSM-11 molecular sieve powder with 500nm, Si/Al100, and mesopore volume ratio of 1.0 to the above solution, then add 12.5g of deionized water to dissolve, and mechanically stir evenly. Dry at 120°C for 6-8h, then calcined at 700°C for 2h, after cooling, crush and sieve out 80-200μm catalyst as intermediate shaped catalyst. Weigh 8.04g of KNO ₃ (calculated according to the mass of its oxide as 5g), dissolve it in 70g of deionized water and stir well to make an aqueous solution of KNO ₃ , impregnate the solution on 50g of the intermediate shaped catalyst, and then heat it at 140°C Dry for 8-10 hours. Then weigh 12.21g of Co(NO ₃ ) ₂ ·6H ₂ O, dissolve it in 70g of deionized water and stir evenly to make an aqueous solution of Co(NO ₃ ) ₂ ·6H ₂ O, and soak the above KNO ₃ An aqueous solution of Co(NO ₃ ) ₂ ·6H ₂ O was impregnated on the dried catalyst. Then dry at 140°C for 8-10h, and bake at 700°C for 2h, and set aside.

Example 16

Add 180 g of deionized water to 44.08 g of pseudoboehmite, stir evenly, add 28.2 g of hydrochloric acid, and stir for 0.5 h to form a gel. Add 30g of 1700nm, Si/Al65, ZSM-11 and 35g of kaolin powder with a volume ratio of mesopores of 1.5 to the above solution, then add 12.5g of modified silica sol and 20g of water, mechanically stir evenly, and dry at 120°C for 6- 8h, followed by calcination at 700°C for 2h, after cooling, crush and sieve out 80-200μm catalyst as intermediate shaped catalyst. Weigh 3.79g of ammonium dihydrogen phosphate, dissolve it in 70g of deionized water and stir evenly to make an aqueous solution of ammonium dihydrogen phosphate, impregnate the solution on 50g of the intermediate shaped catalyst, and then dry at 140°C for 8-10h, Roast at 700°C for 2h, set aside.

Example 17

Add 180 g of deionized water to 44.08 g of pseudoboehmite, stir evenly, add 28.2 g of hydrochloric acid, and stir for 0.5 h to form a gel. Add 25g of 1100nm, Si/Al100, ZSM-11 with mesopore volume ratio of 1.5 and 30g of kaolin powder to the above gel, then add 37.5g of modified silica sol and 20g of water, mechanically stir evenly, and dry at 120°C for 6 -8h, followed by calcination at 700°C for 2h, after cooling, crush and sieve out 80-200μm catalyst as intermediate shaped catalyst. Weigh 6.50g of CsNO ₃ , dissolve it in 70g of deionized water and stir evenly to make an aqueous solution of CsNO ₃ , impregnate the solution on 50g of the intermediate shaped catalyst, then dry at 140°C for 8-10h, and bake at 700°C for 2h ,spare.

Example 18

Add 180 g of deionized water to 29.39 g of pseudo-boehmite, stir evenly, add 18.8 g of hydrochloric acid, and stir for 0.5 h to form a gel. Add 20g of 500nm, Si/Al65, ZSM-11 with mesopore volume ratio of 0.5 and 50g of kaolin powder to the above gel, then add 25.0g of modified silica sol and 20g of water, mechanically stir evenly, and dry at 120°C for 6 -8h, followed by calcination at 700°C for 2h, after cooling, crush and sieve out 80-200μm catalyst as intermediate shaped catalyst. Weigh 8.52g of Ba(NO ₃ ) ₂ , dissolve it in 70g of deionized water and stir evenly to make Ba(NO ₃ ) ₂ aqueous solution, impregnate the solution on 50g of the intermediate shaped catalyst, and then dry at 140°C 8-10h, roast at 700°C for 2h, set aside.

Example 19

Add 180 g of deionized water to 51.42 g of pseudoboehmite, stir evenly, add 32.99 g of hydrochloric acid, and stir for 0.5 h to form a gel. Add 20g of 500nm, Si/Al35, ZSM-11 with mesopore volume ratio of 1.0 and 35g of kaolin powder to the above gel, then add 25.0g of modified silica sol and 20g of water, mechanically stir evenly, and dry at 120°C for 6 -8h, followed by calcination at 700°C for 2h, after cooling, crush and sieve out 80-200μm catalyst as intermediate shaped catalyst. Take by weighing 20.0 Mg(NO ₃ ) ₂ 6H ₂ O, dissolve it in 70g deionized water and stir evenly to make an impregnated Mg(NO ₃ ) ₂ aqueous solution, impregnate the solution on the 50g described intermediate shaped catalyst, and then Dry at 140°C for 8-10h, bake at 700°C for 2h, and set aside.

Example 20

Add 180 g of deionized water to 36.73 g of pseudo-boehmite, stir evenly, add 37.51 g of hydrochloric acid, and stir for 0.5 h to form a gel. Add 25g of 1100nm, Si/Al100, ZSM-11 with mesopore volume ratio of 1.0 and 32.5g of kaolin powder to the above gel, then add 43.75g of modified silica sol and 20g of water, mechanically stir evenly, and dry at 120°C 6-8h, followed by roasting at 700°C for 2h, after cooling, pulverize and sieve out 80-200μm catalyst as intermediate shaped catalyst. Weigh 10.21g of Sr(NO ₃ ) ₂ , dissolve it in 70g of deionized water and stir evenly to make an aqueous solution of Sr(NO ₃ ) ₂ , impregnate the solution on 50g of the intermediate shaped catalyst, and then dry at 140°C 8-10h, roast at 700°C for 2h, set aside.

Example 21

Add 180 g of deionized water to 47.75 g of pseudo-boehmite, stir evenly, add 23.50 g of hydrochloric acid, and stir for 0.5 h to form a gel. Add 40g of 500nm, Si/Al65, ZSM-11 with mesopore volume ratio of 2.0 and 15g of kaolin powder to the above gel, then add 31.25g of modified silica sol and 20g of water, mechanically stir evenly, and dry at 120°C for 6 -8h, followed by calcination at 700°C for 2h, after cooling, crush and sieve out 80-200μm catalyst as intermediate shaped catalyst. Weigh 10.72g of KNO ₃ , dissolve it in 70g of deionized water and stir well to make an aqueous solution of KNO ₃ , impregnate the solution on 50g of the intermediate shaped catalyst, then dry at 140°C for 8-10h, and roast at 700°C 2h, spare.

Example 22

Add 180 g of deionized water to 22.04 g of pseudoboehmite, stir evenly, add 14.10 g of hydrochloric acid, and stir for 0.5 h to form a gel. Add 35g of 1100nm, Si/Al35, ZSM-11 with mesopore volume ratio of 2.0 and 30g of kaolin powder to the above gel, then add 50.0g of modified silica sol and 20g of water, mechanically stir evenly, and dry at 120°C for 6 -8h, followed by calcination at 700°C for 2h, after cooling, crush and sieve out 80-200μm catalyst as intermediate shaped catalyst. Take by weighing 12.21g of Co(NO ₃ ) ₂ 6H ₂ O, dissolve it in 70g deionized water and stir evenly, make Co(NO ₃ ) ₂ aqueous solution, impregnate this solution on the described intermediate shaped catalyst of 50g, then Dry at 140°C for 8-10h, bake at 700°C for 2h, and set aside.

Example 23

Add 180 g of deionized water to 44.08 g of pseudoboehmite, stir evenly, add 28.2 g of hydrochloric acid, and stir for 0.5 h to form a gel. Add 20g of 1100nm, Si/Al65, ZSM-11 with mesopore volume ratio of 1.5 and 35g of kaolin powder to the above gel, then add 37.5g of modified silica sol and 20g of water, mechanically stir evenly, and dry at 120°C for 6 -8h, followed by calcination at 700°C for 2h, after cooling, crush and sieve out 80-200μm catalyst as intermediate shaped catalyst. Weigh 11.63g of Zn(NO ₃ ) ₂ ·6H ₂ O (calculated according to the mass of its oxide as 5g), dissolve it in 70g of deionized water and stir well to make a Zn(NO ₃ ) ₂ aqueous solution, and add The shaped catalyst is impregnated with the solution, and then dried at 140°C for 8-10 hours. Then weigh 8.46g of NH ₄ Ce(NO ₃ ) ₆ , dissolve it in 70g of deionized water and stir to make NH ₄ Ce(NO ₃ ) ₆ aqueous solution, impregnate the above-mentioned Zn(NO ₃ ) ₂ aqueous solution and The dried catalyst is impregnated with NH ₄ Ce(NO ₃ ) ₆ aqueous solution, then dried at 140°C for 8-10 hours, calcined at 700°C for 2 hours, and set aside.

Catalyst performance test: The catalytic performance of the catalysts provided in the examples of the present invention in the methanol conversion reaction was tested according to the following conditions: using pure methanol with a mass fraction of 99% as a raw material, the catalysts prepared in Examples 4 to 23 were tested in Performance evaluation was carried out on a micro-fixed-bed reactor with a reaction temperature of 450°C, a catalyst loading of 2g, a nitrogen flow rate of 21mL/min, and a mass space time of 6h ^-1 . Evaluation results (product distribution of continuous feeding for 10 minutes) are shown in attached tables 1 to 4, and product selectivity is based on the amount of hydrocarbons after methanol dehydration.

Table 1 pure methanol reaction product selectivity on the catalyst of Examples 4-8, C% (wt)

Table 4 Reaction product selectivity of pure methanol on catalysts of Examples 19-23, C% (wt)

As can be seen from Tables 1-4, the reaction performance evaluation results of the catalysts provided by Examples 4-23 of the present invention show that gasoline conversion, propylene conversion and P/E are respectively 26.51-66.31%, 8.54-41.35%, 1.23 The range of -5.35 is flexible and variable, so as to realize the adjustment of gasoline and propylene yield in the methanol conversion reaction, adapt to the market changes of gasoline and propylene, and improve the ability of methanol conversion technology to resist market risks.

Comparative example 1

He Changqing et al. used diethylamine as a template to synthesize silicon phosphorus aluminum molecular sieve SAPO-34 in the methanol conversion reaction. The yield of propylene was 39.42%, and the yield of gasoline was 0. See Table 5.

Comparative example 2

Cao Yongkun et al. found that when HZSM-5 molecular sieve was used for methanol conversion reaction, the yield of propylene was 0, and the yield of gasoline was 87%, see Table 5.

It can be seen that when SAPO-34 and HZSM-5 molecular sieves are used as catalysts for methanol conversion reactions, only propylene or gasoline can be obtained, and the adjustment of gasoline and propylene yields in methanol conversion reactions cannot be realized, so it is difficult to adapt to gasoline and gasoline. Changes in the propylene market have brought pressure on methanol conversion technology to resist market risks.

References for comparative examples 1-2 are as follows:

He Changqing, Liu Zhongmin, Cai Guangyu, et al. Synthesis of silicon phosphorus aluminum molecular sieves with diethylamine as template[P].CN1096496A.1994-12-21.

Cao Yongkun.Methanol to gasoline, methanol to olefins technology progress and industrial application[J].Coal Chemical Industry,2010,4:25-27.

Table 5 Reaction product selectivity of pure methanol on comparative catalyst, C% (wt)

The serial numbers of the above embodiments of the present invention are for description only, and do not represent the advantages and disadvantages of the embodiments.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection of the present invention. within range.

Claims (10)

1. A catalyst for the conversion of methanol to produce gasoline while taking into account the yield of propylene, the catalyst is composed of an active component, a carrier, a modified binding agent and a metal oxide, and it is characterized in that the active component is ZSM- 11 Molecular sieve, the molecular sieve has a hierarchical pore structure of mesopores and micropores and nanorod insertion morphology, wherein the volume ratio of mesopores to micropores is (0.2-3.0): 1, the grain size is 50-1900nm, silicon The aluminum ratio is 30-300; based on the quality of the catalyst, the mass ratio of the catalyst's active component, carrier, modified binder and metal oxide is (3-60): (80-5): (2.0-55): (0.1-50); the modified binder is composed of modified binder I and modified binder II, and the modified binder I is prepared by a metal modification method, The modified binder II is prepared by static hydrothermal crystallization, and the mass ratio of the modified binder I to the modified binder II is 0.1-10:1. 2. catalyzer as claimed in claim 1 is characterized in that, taking the quality of catalyzer as benchmark, the mass ratio of described active component, carrier, modified binder and metal oxide is (10-35):( 20-60): (7.0-35): (1.0-40). 3. The catalyst according to claim 1, characterized in that, the volume ratio of the mesopore and the micropore of the ZSM-11 molecular sieve is (0.5-2.0): 1, the crystal grain is 200-1700nm, and the silicon-aluminum ratio is 30-100. 4. The catalyst according to claim 1, wherein the carrier is at least one selected from kaolin, MgO, sepiolite, Al ₂ O ₃ , SiO ₂ and diatomaceous earth. 5. catalyzer as claimed in claim 1 is characterized in that, the preparation method of described modified binding agent comprises: Metal modification treatment: Mix and stir the binder and 2mol/L metal salt solution for 4 hours in a water bath at 60°C, and then let it stand at room temperature for 4-6 hours to obtain modified binder I; among them, the metal salt solution The quality of the metal salt is calculated based on the quality of the corresponding oxide of the metal, and the corresponding oxide of the metal is selected from at least one of Zn, W, Zr, Mg and Mn oxides, and the quality of the corresponding oxide of the metal is 0.5%-15% of the above binder mass; Static hydrothermal crystallization treatment: put the binder into a crystallization kettle, statically crystallize at 100°C for 2-8 hours, and then stand at room temperature for 4-6 hours to obtain modified binder II; The modified binder I and the modified binder II are mixed at a mass ratio of 0.1-10:1, and the modified binder is obtained after uniform stirring. 6. The catalyst according to claim 5, wherein the binder is selected from at least one of silica sol, aluminum sol and water glass. 7. catalyzer as claimed in claim 6 is characterized in that, when described binding agent is silica sol, its quality is in the mass fraction of silicon dioxide, and wherein the massfraction of silicon dioxide in described silica sol is 40.0 %; when the binder is water glass, its quality is based on the mass of silicon dioxide, wherein the mass fraction of silicon dioxide in the water glass is 27.5%; when the binder is aluminum sol, its The mass is based on the mass of alumina monohydrate, wherein the mass fraction of alumina monohydrate in the aluminum sol is 20.0%. 8. The catalyst according to claim 1, wherein the metal oxide is selected from at least one of Zn, Ce, Co, K, Cs, Ca, Mg, Sr and Ba oxides. 9. A method for preparing the catalyst according to claim 1, characterized in that the method comprises the following steps: Mix the active component, carrier and modified binder with deionized water in a prescribed order, and mechanically stir evenly to make a catalyst gel; Add the metal salt solution to the catalyst gel, dry at 120°C for 6-8h, roast at 700°C for 2h, and sieve out 80-200μm catalyst particles after cooling. The mass of the metal salt in the metal salt solution is based on the Calculate the mass of the metal corresponding to the metal oxide. 10. A method for preparing the catalyst according to claim 1, characterized in that the method comprises the following steps: Mix the active component, carrier and modified binder with deionized water in a prescribed order, and stir them evenly to make a catalyst gel; dry the above catalyst gel at 120°C for 6-8h, and bake at 700°C for 2h , after cooling, sieve out 80-200 μm intermediate shaped catalyst particles; At normal temperature, impregnate the metal salt solution on the above-mentioned intermediate shaped catalyst particles, then dry at 140°C for 8-10h, and roast at 700°C for 2h to obtain catalyst particles; Mass calculation of metal oxides.