CN112206811B - Catalyst for preparing propylene by methanol conversion and preparation method and application thereof - Google Patents
Catalyst for preparing propylene by methanol conversion and preparation method and application thereof Download PDFInfo
- Publication number
- CN112206811B CN112206811B CN201910624307.1A CN201910624307A CN112206811B CN 112206811 B CN112206811 B CN 112206811B CN 201910624307 A CN201910624307 A CN 201910624307A CN 112206811 B CN112206811 B CN 112206811B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyst
- solution
- zsm
- type zsm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/06—Propene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/44—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for preparing propylene by converting methanol, a preparation method and application thereof. The preparation method of the propylene catalyst by methanol conversion comprises the steps of mixing tetrapropylammonium bromide aqueous solution, sodium silicate aqueous solution and sodium metaaluminate aqueous solution to obtain mixed solution; crystallizing the mixed solution at 150-210 ℃ for at least 6 hours, and washing, drying and roasting the crystallized product to obtain the Na-type ZSM-5 molecular sieve; and carrying out ion exchange on the Na-type ZSM-5 molecular sieve and the ion exchange liquid, and washing, drying and roasting to obtain the H-type ZSM-5 molecular sieve. The preparation method provided by the invention has the advantages of simple process flow and good repeatability, and is suitable for industrial production; the catalyst for preparing propylene by converting methanol obtained by the preparation method has the characteristics of high propylene selectivity and good catalytic stability.
Description
Technical Field
The invention relates to a propylene production technology, in particular to a catalyst for preparing propylene by converting methanol, a preparation method and application thereof.
Background
Propylene is used as important chemical basic raw material, is widely used for producing chemicals such as polypropylene, acrylonitrile, epoxypropane and the like, and is a basic stone in the modern petrochemical industry. In recent years, the propylene consumption is greatly improved and the market potential is huge driven by the rapid increase of the demand of propylene downstream product derivatives, in particular polypropylene.
At present, propylene in China mainly comes from naphtha steam cracking co-production and catalytic cracking byproducts. However, the petroleum resources in China are deficient, the propylene productivity can not meet the demand of domestic markets for propylene, and the searching of a novel propylene production process is not slow. Among them, the process route of producing Methanol from synthetic gas and then producing propylene (MTP) from Methanol using coal, natural gas and biomass as raw materials has been receiving attention. The process has wide sources and low cost of raw materials, and the process technology for producing the synthesis gas from coal, natural gas and the like is developed quite mature, so the process route is considered as a new process which is hopefully substituted for a petroleum route.
It has been considered that the reaction process for the conversion of methanol over an acidic molecular sieve catalyst to hydrocarbons mainly comprises the following three steps: 1) Dehydrating methanol under the action of a proper acid site to generate Dimethyl Ether (DME) and water; 2) The equilibrium mixture of methanol, dimethyl ether and water is further converted into lower olefins, mainly ethylene and propylene; 3) The low-carbon olefin is subjected to hydrogen transfer, alkylation, cyclization, polycondensation and other reactions to generate alkane, high-carbon olefin, naphthene, arene and even coke. Meanwhile, the produced high-carbon olefin can also produce corresponding low-carbon hydrocarbon through cracking reaction and the like. In the above process route, the catalyst plays an important role. Therefore, how to inhibit the generation of byproducts, so that the propylene selectivity and the catalytic stability are improved, becomes a key for developing an MTP catalyst.
ZSM-5 molecular sieve is the preferred choice of MTP catalyst because of its suitable pore structure and widely adjustable acidity. However, the catalytic stability of the molecular sieve is still to be improved due to the diffusion limiting effect on larger molecules, so that the hierarchical pore ZSM-5 molecular sieve has been developed. The secondary mesopores in the hierarchical pore ZSM-5 molecular sieve not only provide more accessible active sites for reactant molecules, but also provide more sufficient diffusion space for the reactant molecules, so that the catalytic performance is remarkably improved.
The synthesis of the hierarchical pore ZSM-5 molecular sieve mainly comprises a soft template method, a hard template method, a desilication, dealumination and other post-treatment methods. Among them, the soft template method generally requires the use of additional, expensive templates, and has a lot of steps; the hard template method often needs high-temperature roasting to remove the synthesized template, but the high-temperature roasting can cause the damage of the molecular sieve structure, thereby bringing adverse effects on the catalytic performance of the ZSM-5 molecular sieve; the post-treatment method is simple and easy to implement compared with the former two methods, but the change of the silicon-aluminum ratio of the molecular sieve caused by chemical dissolution is uncontrollable. Although the multistage pore ZSM-5 molecular sieve synthesized by the method has better catalytic performance than the traditional ZSM-5 molecular sieve, the synthetic route is not enough to support industrial production application to a great extent. Therefore, how to develop a new process for preparing MTP catalyst, and on the premise of ensuring that the MTP catalyst has higher propylene selectivity and catalytic stability, the industrial mass production is facilitated, which is a problem to be solved at present.
Disclosure of Invention
Aiming at the defects, the invention provides a method for preparing the propylene catalyst by converting methanol, which is suitable for industrial mass production, and the prepared propylene catalyst prepared by converting methanol has the characteristics of high propylene selectivity and good catalytic stability.
The invention also provides a catalyst for preparing propylene by converting methanol, which is prepared by adopting the preparation method. The catalyst for preparing propylene by converting methanol has the characteristics of high propylene selectivity and good catalytic stability.
The invention also provides application of the catalyst for preparing propylene by converting methanol in preparing propylene by using methanol.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a catalyst for producing propylene by converting methanol, comprising:
mixing a tetrapropylammonium bromide aqueous solution, a water glass aqueous solution and a sodium metaaluminate aqueous solution to obtain a mixed solution, wherein the mass ratio of the tetrapropylammonium bromide to the silicon dioxide to the sodium metaaluminate is (0.33-30): (1-10): 1, a step of;
crystallizing the mixed solution at 150-210 ℃ for at least 6 hours, and washing, drying and roasting the crystallized product to obtain the Na-type ZSM-5 molecular sieve;
the Na-type ZSM-5 molecular sieve and the ion exchange liquid are subjected to ion exchange, and then are washed, dried and roasted to prepare the H-type ZSM-5 molecular sieve, wherein the H-type ZSM-5 molecular sieve is used as a catalyst for preparing propylene by converting methanol (for convenience of description, the H-type ZSM-5 molecular sieve is called as a catalyst I for short).
According to the preparation method provided by the invention, tetrapropylammonium bromide is adopted as a template agent, and the dosage of the template agent and the silicon-aluminum ratio (SiO) in the raw materials are reasonably controlled 2 With Al 2 O 3 And then carrying out specific crystallization treatment to obtain the Na-type ZSM-5 molecular sieve. Further characterization shows that the Na-type ZSM-5 molecular sieve is a hierarchical pore molecular sieve. Finally, the Na-type ZSM-5 molecular sieve is converted into an H-type ZSM-5 molecular sieve through ion exchange. When the H-type ZSM-5 molecular sieve is used as a catalyst for preparing propylene by converting methanol, the H-type ZSM-5 molecular sieve has the characteristics of high propylene selectivity and good catalytic stability.
In addition, the preparation method provided by the invention has the advantages that the whole process flow is simpler, the repeatability is good, and the raw materials are common industrial raw materials and the cost is low, so that the preparation method is very favorable for being amplified to the industrial production scale.
Specifically, when preparing the mixed solution, the tetrapropylammonium bromide aqueous solution is firstly added into the sodium silicate aqueous solution, and stirred at room temperature for 10-50 min to realize the full mixing of the tetrapropylammonium bromide aqueous solution and the sodium silicate aqueous solution, then the sodium metaaluminate aqueous solution is dropwise added under the condition of maintaining stirring, and after the dropwise adding is finished, the stirring is continued at room temperature for 2-10 h, so that the three are fully and uniformly mixed, and the mixed solution is obtained.
The usage amount of the template agent tetrapropylammonium bromide and the silicon-aluminum ratio are reasonably controlled, which is beneficial to further improving the performance of the MTP catalyst. In the specific implementation process of the invention, the mass ratio of tetrapropylammonium bromide, silicon dioxide and sodium metaaluminate in the mixed solution is generally controlled to be (2-30): (1-10): 1.
wherein the solubility of the tetrapropylammonium bromide aqueous solution can be specifically 10-80 wt%, preferably 10-60 wt%; in SiO form 2 The mass concentration of the water glass aqueous solution can be specifically 10-50 wt%, preferably 20-50 wt%; the weight ratio of the tetrapropylammonium bromide aqueous solution to the water glass aqueous solution can be specifically determined according to the set mass ratio and the concentration of the corresponding aqueous solution, and the weight ratio of the tetrapropylammonium bromide aqueous solution to the water glass aqueous solution is generally 1: 3-10: 1, preferably 1:4 to 7:1, more preferably 1 to 5:1.
after the mixed solution is prepared, the mixed solution can be put into a crystallization kettle for crystallization for 6 to 50 hours at the temperature of 150 to 210 ℃. After crystallization is completed, washing, filtering, drying and roasting at 500-600 ℃ are carried out on the crystallized product, so that the Na-type ZSM-5 molecular sieve is obtained.
The specific mode of ion exchange is not particularly limited, and the Na-type ZSM-5 molecular sieve can be converted into an H-type ZSM-5 molecular sieve by adopting a conventional ion exchange process in the field. For example, na-type ZSM-5 molecular sieve and ion exchange liquid are subjected to ion exchange at 60-100 ℃, preferably 70-90 ℃, and then washed, dried and roasted to obtain the H-type ZSM-5 molecular sieve.
In the specific implementation process of the invention, na-type ZSM-5 molecular sieve is mixed with ion exchange liquid, and the mixture is treated for at least 1 hour under the conditions of 60-100 ℃, preferably 70-90 ℃ and strong stirring, washed, suction filtered to be neutral and dried; and repeating the steps for at least 1 time, and finally roasting the obtained solid product to obtain the H-type ZSM-5 molecular sieve. Wherein, the drying mode can be heating drying or vacuum dehydration drying; the calcination can be completed in a muffle furnace, and the calcination temperature can be controlled to be 500-600 ℃ generally.
The ion exchange liquid used can be specifically an aqueous solution of an acidic compound, such as an aqueous solution of an acid, an aqueous solution of a strong acid weak base salt, or the like; specifically, the aqueous solution may be one or more of an aqueous hydrochloric acid solution, an aqueous nitric acid solution, an aqueous sulfuric acid solution, an aqueous ammonium chloride solution, an aqueous ammonium nitrate solution, an aqueous ammonium sulfate solution, and the like.
The concentration of the ion exchange liquid is generally 0.01 to 5mol/L, preferably 0.1 to 3mol/L; the weight of the ion exchange liquid is generally 5 times or more, usually 5 to 20 times, the weight of the Na-type ZSM-5 molecular sieve.
Based on the H-type ZSM-5 molecular sieve (namely the catalyst I), the invention also provides a preparation method of another catalyst for preparing propylene by converting methanol. Specifically, active metal is loaded on a catalyst I to obtain a modified ZSM-5 molecular sieve (marked as a catalyst II). The inventor researches and discovers that the yield of propylene carbon-based is obviously improved and the service life is possibly prolonged in the process of preparing propylene by using the obtained modified ZSM-5 molecular sieve in the methanol conversion process by loading specific active metal on the catalyst I.
Specifically, the supported active metal may be selected from at least one of Ce, la, mn, ag and Mg, and particularly may be at least one of Ce, la, and Mn. The loading of the active metal on the H-type ZSM-5 molecular sieve (based on the H-type ZSM-5 molecular sieve) is 0.02 to 9wt%, preferably 0.05 to 5wt%, based on the oxide of the active metal.
The present invention is not particularly limited as to how to achieve loading of the active metal on the H-type ZSM-5 molecular sieve, and may employ a loading method conventional in the art, for example, an impregnation method, especially an isovolumetric impregnation method. The temperature during the impregnation is generally controlled to not exceed 80 c, such as 20 c to 80 c, and the impregnation time is 2 to 24 hours. In the implementation process of the invention, the temperature in the dipping process is controlled to be about 60 ℃, and the dipping time is controlled to be 6-12 hours.
The impregnation fluid used may be, in particular, a salt solution of the active metal, including but not limited to a nitrate solution, an acetate solution or a sulfate solution of the active metal. The concentration of the impregnating solution is generally 0.005 to 0.6mol/L, such as 0.01 to 0.4mol/L; the mass ratio of the H-type ZSM-5 molecular sieve to the impregnating solution can be generally controlled to be 1:1 to 10.
Based on the H-type ZSM-5 molecular sieve (namely the catalyst I), the invention also provides another preparation method of the catalyst for preparing propylene by converting methanol, which is to mix the H-type ZSM-5 molecular sieve with composite carrier gel to prepare a corresponding formed catalyst (denoted as the catalyst III).
In the prior art, alumina (Al 2 O 3 ) It has special acid property and pore canal structure, and is used as catalyst carrier to raise the mechanical strength of catalyst. However, recent studies have shown that the acidic sites of alumina itself promote the formation of methane and coke, thereby shortening the catalyst life. In view of this, the present invention uses a new composite carrier, so that the mechanical strength of the obtained catalyst III is improved compared with that of the catalyst I, the propylene selectivity is maintained, and the catalytic stability is remarkably improved.
Specifically, the preparation process of the composite carrier can be as follows:
peptizing pseudo-boehmite in an acidic aqueous solution at 55-75 ℃ until the pH value is 3-4 to obtain sol; mixing sol with magnesia and silica sol, and drying to obtain composite carrier, wherein the mass ratio of pseudo-boehmite to magnesia to silica sol is (1-8): (1-8): 1, preferably (1 to 4): (1-2): 1.
in the specific implementation process of the invention, a certain amount of pseudo-boehmite can be weighed, water is added and stirred uniformly, then hydrochloric acid aqueous solution is added dropwise, the mixture is placed in a water bath at 55-75 ℃ to form gel until the pH value is 3-4, stirring is continued for 1-3 hours at room temperature, then a certain amount of magnesium oxide is added, silica sol is taken as a binder, and after stirring uniformly at room temperature, the mixture is dried for 2-4 hours at 100-130 ℃ to obtain the composite carrier.
Acidifying the composite carrier to obtain composite carrier gel; kneading, extruding, shaping, drying and roasting the composite carrier gel and the H-type ZSM-5 molecular sieve (catalyst I) to obtain a catalyst (catalyst III) for preparing propylene by converting methanol, wherein the mass ratio of the H-type ZSM-5 molecular sieve to the composite carrier gel is 1: 3-20: 1, preferably 1 to 10:1, more preferably 1.2 to 5:1.
specifically, the composite carrier may be acidified with an acidic solution, wherein: the acidic solution can be specifically selected from one or more of hydrochloric acid aqueous solution, nitric acid aqueous solution, sulfuric acid aqueous solution and phosphoric acid aqueous solution; the concentration of the acid solution is 0.01-0.5 mol/L, and the mass ratio of the composite carrier to the acid solution is 25-225: 1, preferably 60 to 120:1. the temperature of the acidification is usually not more than 40 ℃, such as 10-30 ℃, and the time of the acidification is usually not less than 5min, usually 5-30 min, further 10-30 min.
Based on the modified ZSM-5 molecular sieve (catalyst II), the invention also provides another preparation method of the catalyst for preparing propylene by converting methanol, which comprises the steps of kneading the modified ZSM-5 molecular sieve (catalyst II) with a composite carrier gel, extruding, shaping, drying and roasting to obtain the catalyst (marked as catalyst IV) for preparing propylene by converting methanol. Specifically, the preparation methods of the composite carrier and the composite carrier gel are the same as above, and are not repeated. Specific processes such as kneading, extruding and forming are the same as before, and are not repeated.
In a second aspect, the invention provides a catalyst for preparing propylene by converting methanol, which is prepared by adopting the preparation method. The catalyst for preparing propylene by converting methanol has the characteristics of high propylene selectivity and good catalytic stability.
As previously described, the present invention provides four catalysts for the conversion of methanol to propylene, wherein:
the catalyst I is an H-type ZSM-5 molecular sieve obtained by carrying out crystallization treatment, washing, drying and roasting on a mixed solution of a tetrapropyl ammonium bromide aqueous solution, a water glass aqueous solution and a sodium metaaluminate aqueous solution, and then carrying out ion exchange on the obtained Na-type ZSM-5 molecular sieve;
the catalyst II is a modified ZSM-5 molecular sieve obtained by loading at least one active metal of Ce, la, mn, ag and Mg on the basis of the catalyst I, and the propylene selectivity of the catalyst II is obviously higher than that of the catalyst I;
the catalyst III is prepared by adding special composite carrier gel on the basis of the catalyst I, so that the mechanical strength of the catalyst I is improved, the propylene selectivity is maintained, and the catalytic stability is obviously improved;
the catalyst IV is based on the catalyst II, and a special composite carrier gel is added, so that the mechanical strength of the catalyst II is improved, the propylene selectivity is maintained, and the catalytic stability is obviously improved.
The third aspect of the invention provides the application of the catalyst for preparing propylene by converting methanol in preparing propylene by using methanol.
It can be understood that the catalyst for preparing propylene by converting methanol has the characteristics of high propylene selectivity and good catalytic stability, so that the catalyst can be well used in the process for preparing propylene from methanol, can realize full conversion of methanol and can obtain a large amount of propylene products. And the catalyst for preparing propylene by converting methanol has longer service life, so that the propylene production efficiency can be improved.
The preparation method of the catalyst for preparing propylene by converting methanol provided by the invention has the advantages of simple process flow and good repeatability, so that the preparation method is very favorable for being amplified to industrial production scale. And the catalyst for preparing propylene by converting methanol obtained by the preparation method has the characteristics of high propylene selectivity and good catalytic stability. In particular, by further supporting the active metal, propylene selectivity can be further improved; the service life can be further improved by adding the composite carrier gel.
The catalyst for preparing propylene by converting methanol provided by the invention is a multi-level hole ZSM-5 molecular sieve, so that the residence time of product molecules in a pore canal is shortened, side reactions are inhibited, the coking degree is reduced, the single-pass carbon-based yield of propylene is 48.6-58.8 wt%, the service life of the catalyst is 33-110 h, and the conversion rate of methanol is 100%, so that the catalyst for preparing propylene by converting methanol has the characteristics of high propylene selectivity and good catalytic stability. In addition, the raw materials are common industrial raw materials and are low in price, so that the catalyst for preparing propylene by converting methanol has low cost.
Drawings
FIG. 1 is a nitrogen adsorption-desorption isotherm of the Na-type ZSM-5 molecular sieve prepared in step S1 of example 1 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be understood that the following examples do not strictly limit the order of execution of the steps in the preparation method as claimed in the present invention. The individual steps of the preparation method according to the invention can be carried out and carried out in any possible sequence without contradiction.
Example 1
The embodiment provides a catalyst for preparing propylene by methanol conversion and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, adding 10wt% of tetrapropylammonium bromide aqueous solution into SiO 2 Stirring the mixture for 20 minutes at room temperature in 20 weight percent of water glass aqueous solution; then, under the condition of maintaining stirring, dropwise adding a sodium metaaluminate aqueous solution with the concentration of 20wt%, and continuing stirring at room temperature for about 3 hours after the completion of dropwise adding to obtain a mixed solution, wherein the mass ratio of the tetrapropylammonium bromide aqueous solution to the sodium metaaluminate aqueous solution is 1:1:0.2;
After stirring, the mixed solution is put into a crystallization kettle and crystallized for 36 hours at 160 ℃; after crystallization is completed, washing, filtering, drying and roasting the crystallized product for 6 hours in a muffle furnace at 550 ℃ to obtain the Na-type ZSM-5 molecular sieve. The molecular sieve was characterized, and as can be seen from FIG. 1, the Na-type ZSM-5 molecular sieve was a multi-stage pore ZSM-5 molecular sieve.
S2, taking 10g of Na-type ZSM-5 molecular sieve, adding 8g of ammonium nitrate and 100g of water into the mixture, treating the mixture for 2 hours under the conditions of water bath at 80 ℃ and strong stirring, washing and suction filtering the mixture to be neutral, drying the mixture in a baking oven at 120 ℃ for 2 hours, repeating the operation for 2 times, wherein the weight of ammonium nitrate is 0.8 times of that of the Na-type ZSM-5 molecular sieve each time, the mass of water is 10 times of that of the Na-type ZSM-5 molecular sieve, and finally roasting the mixture in a muffle furnace at 550 ℃ for 3 hours to obtain the H-type ZSM-5 molecular sieve.
S3, 0.13g of cerium nitrate Ce (NO) 3 ) 3 ·6H 2 Preparing cerium nitrate aqueous solution with the concentration of about 0.04mol/L by O and 7.5g of water, adding 5.0g of H-type ZSM-5 molecular sieve into the aqueous solution, standing at 60 ℃ for 6 hours, drying overnight in a baking oven at 120 ℃, roasting at 550 ℃ for 2 hours in a muffle furnace, tabletting and grinding to obtain the Ce modified ZSM-5 molecular sieve (catalyst II).
Example 2
The embodiment provides a catalyst for preparing propylene by methanol conversion and a preparation method thereof, wherein the preparation method comprises the following steps:
S1, adding 10wt% of tetrapropylammonium bromide aqueous solution into SiO 2 Stirring the mixture for 20 minutes at room temperature in 20 weight percent of water glass aqueous solution; then dropwise adding a sodium metaaluminate aqueous solution with the concentration of 20wt% under the condition of maintaining stirring, and continuously stirring at room temperature for 3 hours after the completion of dropwise adding to obtain a mixed solution, wherein the mass ratio of the tetrapropylammonium bromide aqueous solution to the sodium metaaluminate aqueous solution is 1:1:0.2;
after stirring, the mixed solution is put into a crystallization kettle and crystallized for 36 hours at 160 ℃; after crystallization is completed, washing, filtering, drying and roasting the crystallized product for 6 hours in a muffle furnace at 550 ℃ to obtain the Na-type ZSM-5 molecular sieve. The Na-type ZSM-5 molecular sieve is a hierarchical pore ZSM-5 molecular sieve.
S2, taking 10g of Na-type ZSM-5 molecular sieve, adding 8g of ammonium nitrate and 100g of water into the mixture, treating the solution for 2 hours under the conditions of water bath at 80 ℃ and strong stirring, washing and suction filtering the solution to be neutral, drying the solution in a baking oven at 120 ℃ for 2 hours, repeating the operation for 2 times, wherein the mass of the ammonium nitrate is 0.8 times of that of the Na-type ZSM-5 molecular sieve each time, the mass of the water is 10 times of that of the Na-type ZSM-5 molecular sieve, and finally roasting the solution in a muffle furnace at 550 ℃ for 3 hours to obtain the H-type ZSM-5 molecular sieve.
S3, preparing a cerium nitrate solution with the concentration of about 0.36mol/L by 1.17g of cerium nitrate and 7.5g of water, adding 5.0g of H-type ZSM-5 molecular sieve into the solution, standing for 8H at 60 ℃, drying overnight in an oven at 120 ℃, and roasting for 2H in a muffle furnace at 550 ℃ to obtain the Ce modified ZSM-5 molecular sieve.
S4, weighing a certain amount of pseudo-boehmite, adding water, uniformly stirring, then dropwise adding a phosphoric acid solution with the concentration of 0.02mol/L, placing in a water bath with the temperature of 65 ℃ to form gel until the pH value is 3.5, stirring at room temperature for 2.5 hours, then adding a certain amount of magnesium oxide, taking silica sol as a binder, uniformly stirring at room temperature, and then drying at the temperature of 120 ℃ for 2 hours to obtain the composite carrier. Wherein, the mass ratio of the pseudo-boehmite, the magnesia and the silica sol is 2:2:1.
s4, acidizing the composite carrier in 0.02mol/L phosphoric acid solution to prepare composite carrier gel, wherein the acidizing conditions are as follows: acidifying at room temperature to 20deg.C for 30min.
S5, uniformly mixing 6g of composite carrier gel and 24g of Ce modified ZSM-5 molecular sieve, fully grinding, adding 4g of nitric acid aqueous solution with the concentration of 4wt% into the mixture, kneading, extruding the mixture on a TBL-2 type catalyst molding extrusion device by using a round die with the diameter of 3mm, drying the mixture in an oven at 120 ℃ overnight, and roasting the mixture in a muffle furnace at 600 ℃ for 2 hours to obtain the Ce modified gel ZSM-5 molecular sieve (catalyst IV).
Example 3
The embodiment provides a catalyst for preparing propylene by methanol conversion and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, adding 40wt% of tetrapropylammonium bromide aqueous solution into SiO 2 30wt% of water glass aqueous solution, and stirring for 40min at room temperature; then, under the condition of maintaining stirring, dropwise adding 30wt% sodium metaaluminate aqueous solution, and continuously stirring at room temperature for 3 hours after the completion of dropwise adding to obtain a mixtureThe mass ratio of the tetrapropylammonium bromide aqueous solution, the sodium silicate aqueous solution and the sodium metaaluminate aqueous solution is 2:1:0.1;
after stirring, the mixed solution is put into a crystallization kettle and crystallized for 24 hours at 170 ℃; after crystallization is completed, washing, filtering, drying and roasting the crystallized product for 6 hours in a muffle furnace at 550 ℃ to obtain the Na-type ZSM-5 molecular sieve. Through testing, the Na-type ZSM-5 molecular sieve is a multistage hole ZSM-5 molecular sieve;
s2, taking 10g of Na-type ZSM-5 molecular sieve, adding 8g of ammonium nitrate and 100g of water into the mixture, treating the mixture for 2 hours under the conditions of water bath at 80 ℃ and strong stirring, washing and suction filtering the mixture to be neutral, drying the mixture in a baking oven at 120 ℃ for 2 hours, repeating the operation for 2 times, wherein the mass of ammonium nitrate is 0.8 times of the mass of the molecular sieve each time, the mass of water is 10 times of the mass of the molecular sieve, and finally roasting the mixture in a muffle furnace at 550 ℃ for 3 hours to obtain the H-type ZSM-5 molecular sieve.
S3, 0.09g of manganese sulfate MnSO 4 And 7.5g of water is mixed to prepare a manganese sulfate solution with the concentration of 0.08mol/L, 5.0g of H-type ZSM-5 molecular sieve is added into the water solution, the mixture is kept stand for 9 hours at 60 ℃, is dried overnight in a baking oven at 120 ℃, and is baked for 2 hours in a muffle furnace at 550 ℃ to obtain the Mn modified ZSM-5 molecular sieve.
S4, weighing a certain amount of pseudo-boehmite, adding water, uniformly stirring, then dropwise adding a nitric acid solution with the concentration of 0.02mol/L, placing in a water bath with the temperature of 55 ℃ to form gel until the pH value is 3.5, stirring at room temperature for 1.5 hours, then adding a certain amount of magnesium oxide, taking silica sol as a binder, uniformly stirring at room temperature, and then drying at the temperature of 100 ℃ for 4 hours to obtain the composite carrier. Wherein, the mass ratio of the pseudo-boehmite, the magnesia and the silica sol is 1:1:1.
s4, acidizing the composite carrier in 0.02mol/L nitric acid solution to prepare composite carrier gel, wherein the acidizing conditions are as follows: acidifying at room temperature to 10deg.C for 5min.
S5, uniformly mixing 16g of composite carrier gel and 24g of Mn modified ZSM-5 molecular sieve, fully grinding, adding 4g of nitric acid aqueous solution with concentration of 4wt% into the mixture, kneading, extruding the mixture on a TBL-2 type catalyst molding extrusion device by using a round die with diameter of 3mm, molding, airing, drying in an oven at 120 ℃ overnight, roasting in a muffle furnace at 600 ℃ for 2 hours to obtain a methanol conversion propylene catalyst, tabletting and grinding to obtain the Mn modified gel ZSM-5 molecular sieve (catalyst IV).
Example 4
The embodiment provides a catalyst for preparing propylene by methanol conversion and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, adding 50wt% of tetrapropylammonium bromide aqueous solution into SiO 2 30wt% of water glass solution, and stirring for 40min at room temperature; then dropwise adding a sodium metaaluminate aqueous solution with the concentration of 30wt% under the condition of maintaining stirring, and continuously stirring at room temperature for about 3 hours after the completion of dropwise adding to obtain a mixed solution, wherein the mass ratio of the tetrapropylammonium bromide aqueous solution to the sodium metaaluminate aqueous solution is 2:1:0.5;
after stirring, the mixed solution is put into a crystallization kettle and crystallized for 36 hours at 170 ℃; after crystallization is completed, washing, filtering, drying and roasting the crystallized product for 6 hours in a muffle furnace at 550 ℃ to obtain the Na-type ZSM-5 molecular sieve. Through testing, the Na-type ZSM-5 molecular sieve is a multistage hole ZSM-5 molecular sieve;
s2, taking 10g of Na-type ZSM-5 molecular sieve, adding 8g of ammonium nitrate and 100g of water into the mixture, treating the mixture for 2 hours under the conditions of water bath at 80 ℃ and strong stirring, washing and suction filtering the mixture to be neutral, drying the mixture in a baking oven at 120 ℃ for 2 hours, repeating the operation for 2 times, wherein the mass of ammonium nitrate is 0.8 times of that of the Na-type ZSM-5 molecular sieve each time, the mass of water is 10 times of that of the Na-type ZSM-5 molecular sieve, and finally roasting the mixture in a muffle furnace at 550 ℃ for 3 hours to obtain the H-type ZSM-5 molecular sieve.
S3, 0.13g of manganese acetate Mn (CH) 3 COO) 2 ·4H 2 Preparing manganese acetate solution with the concentration of about 0.07mol/L by O and 7.5g of water, adding 5.0g of H-type ZSM-5 molecular sieve into the water solution, standing at 60 ℃ for 11H, drying overnight in a baking oven at 120 ℃, roasting at 550 ℃ for 2H in a muffle furnace, tabletting and grinding to obtain the Mn modified ZSM-5 molecular sieve (catalyst II).
Example 5
The embodiment provides a catalyst for preparing propylene by methanol conversion and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, adding 60wt% of tetrapropylammonium bromide aqueous solution into SiO 2 30wt% of water glass aqueous solution, and stirring for 40min at room temperature; then dropwise adding a sodium metaaluminate aqueous solution with the concentration of 50wt% under the condition of maintaining stirring, and continuously stirring at room temperature for 3 hours after the completion of dropwise adding to obtain a mixed solution, wherein the mass ratio of the tetrapropylammonium bromide aqueous solution to the sodium metaaluminate aqueous solution is 5:1:0.6;
after stirring, the mixed solution is put into a crystallization kettle and crystallized for 36 hours at 170 ℃; after crystallization is completed, washing, filtering, drying and roasting the crystallized product for 6 hours in a muffle furnace at 550 ℃ to obtain the Na-type ZSM-5 molecular sieve. Through testing, the Na-type ZSM-5 molecular sieve is a multistage hole ZSM-5 molecular sieve;
S2, taking 10g of Na-type ZSM-5 molecular sieve, adding 8g of ammonium nitrate and 100g of water into the mixture, treating the mixture for 2 hours under the conditions of water bath at 80 ℃ and strong stirring, washing and suction filtering the mixture to be neutral, drying the mixture in a baking oven at 120 ℃ for 2 hours, repeating the operation for 2 times, wherein the mass of ammonium nitrate is 0.8 times of that of the Na-type ZSM-5 molecular sieve each time, the mass of water is 10 times of that of the Na-type ZSM-5 molecular sieve, and finally roasting the mixture in a muffle furnace at 550 ℃ for 3 hours to obtain the H-type ZSM-5 molecular sieve.
S3, 0.07g of silver nitrate AgNO 3 And 7.5g of water to prepare a silver nitrate solution with the concentration of about 0.055mol/L, 5.0g of H-type ZSM-5 molecular sieve is added into the solution, the mixture is kept stand for 12 hours at 60 ℃, is dried overnight in a baking oven at 120 ℃, is baked for 2 hours in a muffle furnace at 550 ℃, and finally is tabletted and ground to obtain the Ag modified ZSM-5 molecular sieve (catalyst II).
Example 6
The embodiment provides a catalyst for preparing propylene by methanol conversion and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, adding 60wt% of tetrapropylammonium bromide aqueous solution into SiO 2 30wt% of water glass aqueous solution, and stirring for 40min at room temperature; then dropwise adding 50wt% sodium metaaluminate water solution under the condition of maintaining stirring, and continuously stirring at room temperature for 3 hours after the completion of dropwise adding to obtain a mixed solution, wherein tetrapropylammonium bromide is water-soluble The mass ratio of the liquid, the water glass aqueous solution and the sodium metaaluminate aqueous solution is 5:1:0.6;
after stirring, the mixed solution is put into a crystallization kettle and crystallized for 36 hours at 170 ℃; after crystallization is completed, washing, filtering, drying and roasting the crystallized product for 6 hours in a muffle furnace at 550 ℃ to obtain the Na-type ZSM-5 molecular sieve. Through testing, the Na-type ZSM-5 molecular sieve is a multistage hole ZSM-5 molecular sieve;
s2, taking 10g of Na-type ZSM-5 molecules, adding 8g of ammonium nitrate and 100g of water into the mixture, treating the mixture for 2 hours under the conditions of water bath at 80 ℃ and strong stirring, washing and suction filtering the mixture to be neutral, drying the mixture in a baking oven at 120 ℃ for 2 hours, repeating the operation for 2 times, wherein the mass of the ammonium nitrate is 0.8 times of the mass of the molecular sieve each time, the mass of the water is 10 times of the mass of the molecular sieve, and finally roasting the mixture in a muffle furnace at 550 ℃ for 3 hours to obtain the H-type ZSM-5 molecular sieve.
S3, preparing a lanthanum nitrate solution with the concentration of about 0.0985mol/L by 0.32g of lanthanum nitrate and 7.5g of water, adding 5.0g of H-type ZSM-5 molecular sieve into the lanthanum nitrate solution, standing for 8H at 60 ℃, drying overnight in a baking oven at 120 ℃, and roasting for 2H in a muffle furnace at 550 ℃ to obtain the Mg-modified ZSM-5 molecular sieve.
S4, weighing a certain amount of pseudo-boehmite, adding water, uniformly stirring, then dropwise adding a sulfuric acid solution with the concentration of 0.02mol/L, placing in a water bath with the temperature of 60 ℃ to form gel until the pH value is 3.5, stirring for 2 hours at room temperature, then adding a certain amount of magnesium oxide, taking silica sol as a binder, uniformly stirring at the room temperature, and then drying at the temperature of 110 ℃ for 3 hours to obtain the composite carrier. Wherein, the mass ratio of the pseudo-boehmite, the magnesia and the silica sol is 1:2:1.
S4, acidizing the composite carrier in 0.02mol/L sulfuric acid solution to prepare composite carrier gel, wherein the acidizing conditions are as follows: acidifying at room temperature to 25deg.C for 20min.
S5, uniformly mixing 10g of composite carrier gel and 24g of La modified ZSM-5 molecular sieve, fully grinding, adding 4g of nitric acid aqueous solution with concentration of 4wt% into the mixture, kneading, extruding the mixture on a TBL-2 type catalyst molding extrusion device by using a round die with diameter of 3mm, drying the mixture in an oven at 120 ℃ overnight, and roasting the mixture in a muffle furnace at 600 ℃ for 2 hours to obtain the La modified gel ZSM-5 molecular sieve (catalyst IV).
Example 7
The embodiment provides a catalyst for preparing propylene by methanol conversion and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, adding 60wt% of tetrapropylammonium bromide aqueous solution into SiO 2 30wt% of water glass aqueous solution, and stirring for 40min at room temperature; then dropwise adding a sodium metaaluminate aqueous solution with the concentration of 50wt% under the condition of maintaining stirring, and continuously stirring at room temperature for 3 hours after the completion of dropwise adding to obtain a mixed solution, wherein the mass ratio of the tetrapropylammonium bromide aqueous solution to the sodium metaaluminate aqueous solution is 5:1:0.6;
After stirring, the mixed solution is put into a crystallization kettle and crystallized for 36 hours at 170 ℃; after crystallization is completed, washing, filtering, drying and roasting the crystallized product for 6 hours in a muffle furnace at 550 ℃ to obtain the Na-type ZSM-5 molecular sieve. Through testing, the Na-type ZSM-5 molecular sieve is a multistage hole ZSM-5 molecular sieve;
s2, taking 10g of Na-type ZSM-5, adding 8g of ammonium nitrate and 100g of water into the mixture, treating the mixture for 2 hours under the conditions of water bath at 80 ℃ and strong stirring, washing and suction filtering the mixture to be neutral, drying the mixture in a baking oven at 120 ℃ for 2 hours, repeating the operation for 2 times, wherein the mass of ammonium nitrate is 0.8 times that of a molecular sieve each time, the mass of water is 10 times that of the molecular sieve, and finally roasting the mixture in a muffle furnace at 550 ℃ for 3 hours to obtain the H-type ZSM-5 molecular sieve.
And tabletting and grinding the roasted H-type ZSM-5 molecular sieve to obtain the catalyst (catalyst I) for preparing propylene by converting methanol.
Example 8
The embodiment provides a catalyst for preparing propylene by methanol conversion and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, adding 60wt% of tetrapropylammonium bromide aqueous solution into SiO 2 30wt% of water glass solution, and stirring for 40min at room temperature; then dropwise adding a sodium metaaluminate aqueous solution with the concentration of 50wt% under the stirring condition, and continuously stirring at room temperature for 3 hours after the completion of dropwise adding; wherein, the water solution of tetrapropylammonium bromide, water glass water solution and aluminum metasilicate The mass ratio of the sodium acid aqueous solution is 5:1:0.6; after stirring, the mixed solution is put into a crystallization kettle and crystallized for 36 hours at 170 ℃; after crystallization is completed, washing, filtering, drying and roasting the crystallized product for 6 hours in a muffle furnace at 550 ℃ to obtain the Na-type ZSM-5 molecular sieve. Through testing, the Na-type ZSM-5 molecular sieve is a multistage pore ZSM-5 molecular sieve.
S2, taking a Na-type ZSM-5 molecular sieve, adding 8g of ammonium nitrate and 100g of water into the molecular sieve, treating the molecular sieve for 2 hours under the conditions of 80 ℃ water bath and strong stirring, washing and suction filtering the molecular sieve to be neutral, drying the molecular sieve in a baking oven at 120 ℃ for 2 hours, repeating the operation for 2 times, wherein the mass of the ammonium nitrate is 0.8 times of that of the molecular sieve each time, the mass of the water is 10 times of that of the molecular sieve, and finally roasting the molecular sieve in a muffle furnace at 550 ℃ for 3 hours to obtain the H-type ZSM-5 molecular sieve.
S3, weighing a certain amount of pseudo-boehmite, adding water, uniformly stirring, then dropwise adding 1mol/L hydrochloric acid solution, placing in a 65 ℃ water bath to form gel until the pH value is 3, stirring at room temperature for 2 hours, then adding a certain amount of magnesium oxide, taking silica sol as a binder, uniformly stirring at room temperature, and then drying at 120 ℃ for 2 hours, wherein the mass ratio of the pseudo-boehmite to the magnesium oxide to the silica sol is 2:1:1, obtaining the composite carrier.
S3, acidizing the composite carrier in a nitric acid solution with the concentration of 1mol/L to prepare composite carrier gel, wherein the acidizing conditions are as follows: acidifying at room temperature to 20deg.C for 10min.
Uniformly mixing 15g of composite carrier gel and 24g of H-type ZSM-5 molecular sieve, fully grinding, adding 4g of nitric acid aqueous solution with the concentration of wt% into the mixture, kneading the mixture, extruding the mixture on a TBL-2 type catalyst molding extrusion device by using a round die with the diameter of 3mm to form a molded shape, airing the molded shape, drying the molded shape in an oven at 120 ℃ overnight, and roasting the molded shape in a muffle furnace at 600 ℃ for 2 hours to obtain the catalyst (catalyst III) for preparing propylene by converting methanol.
Example 9
The embodiment provides a catalyst for preparing propylene by methanol conversion and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, adding a tetrapropylammonium bromide aqueous solution with the concentration of 50wt% into SiO 2 30 wt.% water glassStirring the mixture in the aqueous solution at room temperature for 40min; then dropwise adding a sodium metaaluminate aqueous solution with the concentration of 30wt% into the mixture under the stirring condition, and continuously stirring the mixture at room temperature for 3 hours after the completion of dropwise adding; wherein, the mass ratio of the tetrapropylammonium bromide aqueous solution, the sodium silicate aqueous solution and the sodium metaaluminate aqueous solution is 2:1:0.5; after stirring, the mixed solution is put into a crystallization kettle and crystallized for 40 hours at 165 ℃; after crystallization is completed, washing, filtering, drying and roasting the crystallized product at 550 ℃ to obtain the hierarchical pore Na-ZSM-5 molecular sieve.
S2, taking a Na-type ZSM-5 molecular sieve, adding 8g of ammonium nitrate and 100g of water into the molecular sieve, treating the molecular sieve for 2 hours under the conditions of 80 ℃ water bath and strong stirring, washing and suction filtering the molecular sieve to be neutral, drying the molecular sieve in a baking oven at 120 ℃ for 2 hours, repeating the operation for 2 times, wherein the mass of the ammonium nitrate is 0.8 times of that of the molecular sieve each time, the mass of the water is 10 times of that of the molecular sieve, and finally roasting the molecular sieve in a muffle furnace at 550 ℃ for 3 hours to obtain the H-type ZSM-5 molecular sieve.
S3, 0.13g of manganese acetate Mn (CH) 3 COO) 2 ·4H 2 Preparing manganese acetate solution with the concentration of about 0.07mol/L by O and 7.5g of water, adding 5.0g of H-type ZSM-5 molecular sieve into the solution, standing at 60 ℃ for 8H, drying overnight in a baking oven at 120 ℃, and roasting at 550 ℃ for 2H to obtain the Mn modified ZSM-5 molecular sieve.
S4, weighing a certain amount of pseudo-boehmite, adding water, uniformly stirring, then dropwise adding 1mol/L hydrochloric acid solution, placing in a 65 ℃ water bath to form gel until the pH value is 3, stirring at room temperature for 2 hours, then adding a certain amount of magnesium oxide, taking silica sol as a binder, uniformly stirring at room temperature, and then drying at 120 ℃ for 2 hours to obtain the composite carrier. Wherein, the mass ratio of the pseudo-boehmite, the magnesia and the silica sol is 2:1:1.
acidifying the composite carrier in 1mol/L nitric acid solution to prepare composite carrier gel, wherein the acidifying conditions are as follows: acidifying at room temperature to 20deg.C for 10min.
S5, uniformly mixing 10g of composite carrier gel and 24g of Mn modified ZSM-5 molecular sieve, fully grinding, adding 4g of nitric acid aqueous solution with concentration of 4wt% into the mixture, kneading, extruding the mixture on a TBL-2 type catalyst molding extrusion device by using a circular mold with diameter of 3mm, drying the mixture overnight in an oven at 120 ℃, and roasting the dried mixture in a muffle furnace at 600 ℃ for 2 hours to obtain the Mn modified gel ZSM-5 methanol conversion propylene catalyst (catalyst IV).
Example 10
The embodiment provides a catalyst for preparing propylene by methanol conversion and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, adding 50wt% of tetrapropylammonium bromide aqueous solution into SiO 2 30wt% of water glass solution, and stirring for 40min at room temperature; then dropwise adding a sodium metaaluminate aqueous solution with the concentration of 30wt% under the condition of maintaining stirring, and continuously stirring at room temperature for about 3 hours after the completion of dropwise adding to obtain a mixed solution, wherein the mass ratio of the tetrapropylammonium bromide aqueous solution to the sodium metaaluminate aqueous solution is 2:1:0.5;
after stirring, the mixed solution is put into a crystallization kettle and crystallized for 36 hours at 170 ℃; after crystallization is completed, washing, filtering, drying and roasting the crystallized product for 6 hours in a muffle furnace at 550 ℃ to obtain the Na-type ZSM-5 molecular sieve. Through testing, the Na-type ZSM-5 molecular sieve is a multistage hole ZSM-5 molecular sieve;
S2, taking 10g of Na-type ZSM-5 molecular sieve, adding 8g of ammonium nitrate and 100g of water into the mixture, treating the mixture for 2 hours under the conditions of water bath at 80 ℃ and strong stirring, washing and suction filtering the mixture to be neutral, drying the mixture in a baking oven at 120 ℃ for 2 hours, repeating the operation for 2 times, wherein the mass of ammonium nitrate is 0.8 times of that of the Na-type ZSM-5 molecular sieve each time, the mass of water is 10 times of that of the Na-type ZSM-5 molecular sieve, and finally roasting the mixture in a muffle furnace at 550 ℃ for 3 hours to obtain the H-type ZSM-5 molecular sieve.
S3, 0.13g of manganese acetate Mn (CH) 3 COO) 2 ·4H 2 O and 7.5g of water are prepared into a manganese acetate solution with the concentration of about 0.07mol/L, 5.0g of H-type ZSM-5 molecular sieve is added into the water solution, the mixture is stood for 11 hours at 60 ℃, dried overnight in an oven at 120 ℃, and roasted for 2 hours in a muffle furnace at 550 ℃ to obtain the Mn modified ZSM-5 molecular sieve.
S4, weighing a certain amount of pseudo-boehmite, adding water, uniformly stirring, then dropwise adding a hydrochloric acid solution with the concentration of 0.02mol/L, placing in a water bath with the temperature of 75 ℃ to form gel until the pH value is 4, stirring at room temperature for 3 hours, then adding a certain amount of magnesium oxide, taking silica sol as a binder, uniformly stirring at room temperature, and then drying at the temperature of 110 ℃ for 3 hours to obtain the composite carrier. Wherein, the mass ratio of the pseudo-boehmite, the magnesia and the silica sol is 1:1:1.
s4, acidizing the composite carrier in 0.02mol/L hydrochloric acid solution to prepare composite carrier gel, wherein the acidizing conditions are as follows: acidifying at room temperature to 20deg.C for 20min.
S5, uniformly mixing 6g of composite carrier gel and 24g of Mn modified ZSM-5 molecular sieve, fully grinding, adding 4g of nitric acid aqueous solution with the concentration of 4wt% into the mixture, kneading, extruding the mixture on a TBL-2 type catalyst molding extrusion device by using a circular mold with the diameter of 3mm, drying the mixture overnight in an oven at 120 ℃, and roasting the mixture in a muffle furnace at 600 ℃ for 2 hours to obtain the Mn modified gel ZSM-5 molecular sieve.
Screening the catalyst for preparing propylene by converting methanol in the above examples, and taking particles with the particle size of 40-60 meshes in examples 1, 4 and 7 for micro-inverse evaluation; the catalysts of examples 2-3, 5-6 and 8-10 were cut into about 2mm catalyst particles for microreplication evaluation. The specific micro-inverse evaluation method comprises the following steps:
based on mass fraction>The performance evaluation was carried out on 99wt% pure methanol as a raw material in a micro fixed bed reactor at 450℃with a nitrogen flow rate of 20mL/min at normal pressure. Wherein, for the catalyst in example 7, the loading was 1g and the mass space velocity was 9.6h -1 The method comprises the steps of carrying out a first treatment on the surface of the For the catalysts of the other examples, the loading was 3g and the mass space time was 3.2h -1 。
The evaluation results in examples 1 to 10 are shown in Table 1. Wherein the yield of the product is based on the hydrocarbon content after dehydration of the methanol; catalyst life refers to the reaction time corresponding to a reduction in methanol conversion to 95 wt%.
TABLE 1
As can be seen from Table 1, the methanol conversion rate of the catalyst for producing propylene by using the methanol conversion catalyst provided by the example of the invention reaches 100%, and the catalyst has very high propylene carbon-based yield and very long service life. Presumably, the catalyst for preparing propylene by converting methanol is a multi-stage hole ZSM-5 molecular sieve, and in the reaction process of catalyzing the conversion of methanol into propylene, the residence time of product molecules in a pore canal can be shortened, so that side reactions are inhibited, the coking degree is reduced, the single-pass carbon-based yield of propylene is 48.6-58.8 wt%, the service life of the catalyst is 33-110 hours, and the conversion rate of methanol is 100%.
Compared with the catalyst I in the example 7, the propylene carbon-based yield of the catalysts in the examples 1 and 4-5 is obviously improved, which proves that the loading of proper active metal on the H-type ZSM-5 molecular sieve is beneficial to improving the catalytic activity of the catalyst and promoting the conversion of methanol to propylene. In addition, by loading the proper active metal on the H-type ZSM-5 molecular sieve, the catalytic stability of the catalyst can be improved, for example, compared with the active metal Ag loaded in the embodiment 5, the service life of the catalyst is obviously prolonged when other active metals are loaded in the embodiment 1 and the embodiment 4.
As can be seen from comparative examples 1, 4-5 and examples 2-3, 6, 8-10, in general, the addition of the composite support gel to the catalyst (either catalyst I or catalyst II) resulted in a slight decrease or substantial maintenance of the propylene carbon-based yield, while the catalyst life was significantly improved, and in particular, as can be seen from the comparison of examples 4 and 10, the catalyst life was significantly prolonged and the change in catalytic activity was not significant after the addition of the composite support gel, and therefore, the composite support gel had an important role in the preparation of a methanol-to-propylene catalyst.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. The preparation method of the catalyst for preparing propylene by converting methanol is characterized by comprising the following steps:
mixing a tetrapropylammonium bromide aqueous solution, a water glass aqueous solution and a sodium metaaluminate aqueous solution to obtain a mixed solution, wherein the mass ratio of the tetrapropylammonium bromide to the silicon dioxide to the sodium metaaluminate is (0.33-30): (1-10): 1, a step of;
Crystallizing the mixed solution at 150-210 ℃ for at least 6 hours, and washing, drying and roasting the crystallized product to obtain the Na-type ZSM-5 molecular sieve;
carrying out ion exchange on the Na-type ZSM-5 molecular sieve and ion exchange liquid, and washing, drying and roasting to obtain an H-type ZSM-5 molecular sieve;
peptizing pseudo-boehmite in an acidic aqueous solution at 55-75 ℃ until the pH value is 3-4 to obtain sol;
mixing the sol with magnesia and silica sol, and drying to obtain a composite carrier, wherein the mass ratio of pseudo-boehmite to magnesia to silica sol is (1-8): (8-1): 1, a step of;
acidifying the composite carrier to obtain composite carrier gel;
kneading, extruding, shaping, drying and roasting the composite carrier gel and the H-shaped ZSM-5 molecular sieve to obtain a catalyst for preparing propylene by converting methanol, wherein the mass ratio of the H-shaped ZSM-5 molecular sieve to the composite carrier gel is 1: 3-20: 1.
2. the preparation method of claim 1, wherein the Na-type ZSM-5 molecular sieve and the ion exchange liquid are subjected to ion exchange at 60-100 ℃, and then are washed, dried and roasted to obtain the H-type ZSM-5 molecular sieve; wherein the concentration of the ion exchange liquid is 0.01-5 mol/L; the weight of the ion exchange liquid is 5-20 times of that of the Na-type ZSM-5 molecular sieve.
3. The method according to claim 1, wherein the ion exchange liquid is one or more selected from the group consisting of aqueous hydrochloric acid, aqueous nitric acid, aqueous sulfuric acid, aqueous ammonium chloride, aqueous ammonium nitrate and aqueous ammonium sulfate.
4. The method according to claim 2, wherein the ion exchange liquid is one or more selected from the group consisting of aqueous hydrochloric acid, aqueous nitric acid, aqueous sulfuric acid, aqueous ammonium chloride, aqueous ammonium nitrate and aqueous ammonium sulfate.
5. The method according to any one of claims 1 to 4, further comprising: loading active metal on the H-type ZSM-5 molecular sieve, and drying, roasting and pressing to form the modified ZSM-5 molecular sieve, wherein the modified ZSM-5 molecular sieve is used as a catalyst for preparing propylene by methanol conversion;
wherein the active metal is selected from at least one of Ce, la, mn, ag and Mg, and the loading amount of the active metal on the H-type ZSM-5 molecular sieve is 0.02-9 wt% based on the oxide of the active metal.
6. The preparation method according to claim 5, wherein an impregnation method is adopted to load active metal on the H-type ZSM-5 molecular sieve, and the temperature in the impregnation process is controlled to be not more than 80 ℃, and the impregnation time is 2-24 hours;
The used impregnating solution is selected from nitrate solution, acetate solution or sulfate solution of active metal, the concentration of the impregnating solution is 0.005-0.6 mol/L, and the mass ratio of the H-type ZSM-5 molecular sieve to the impregnating solution is 1:1 to 10.
7. The method of claim 1, wherein the composite support is acidified with an acidic solution, wherein:
the acidic solution is selected from one or more of hydrochloric acid aqueous solution, nitric acid aqueous solution, sulfuric acid aqueous solution and phosphoric acid aqueous solution; the concentration of the acidic solution is 0.01-0.5 mol/L, and the mass ratio of the composite carrier to the acidic solution is 25-225: 1, a step of;
the temperature of the acidification treatment is not more than 40 ℃ and the time is not less than 5min.
8. A catalyst for the conversion of methanol to propylene, characterized in that it is obtained by the preparation method according to any one of claims 1 to 7.
9. The use of the catalyst for preparing propylene by converting methanol according to claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910624307.1A CN112206811B (en) | 2019-07-11 | 2019-07-11 | Catalyst for preparing propylene by methanol conversion and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910624307.1A CN112206811B (en) | 2019-07-11 | 2019-07-11 | Catalyst for preparing propylene by methanol conversion and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112206811A CN112206811A (en) | 2021-01-12 |
| CN112206811B true CN112206811B (en) | 2023-06-30 |
Family
ID=74047545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910624307.1A Active CN112206811B (en) | 2019-07-11 | 2019-07-11 | Catalyst for preparing propylene by methanol conversion and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112206811B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113023746B (en) * | 2021-03-17 | 2022-09-27 | 宁夏大学 | Lanthanum modified molecular sieve and preparation method and application thereof |
| CN113289674B (en) * | 2021-05-27 | 2022-10-11 | 复旦大学 | Bifunctional catalyst for preparing light aromatic hydrocarbon from synthesis gas and preparation method thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006008655A (en) * | 2003-12-12 | 2006-01-12 | Mitsubishi Chemicals Corp | Method for producing propylene |
| CN1724161A (en) * | 2005-07-13 | 2006-01-25 | 清华大学 | Process for preparing load type silicon phoshporus aluminium molecular sieve |
| CN101172246A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Process for preparation of propylene catalysts with methanol conversion |
| CN101491779A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Catalyst for hydrogen selective catalyst combustion reaction with hydrothermal stability |
| CN101837298A (en) * | 2010-05-14 | 2010-09-22 | 广西壮族自治区化工研究院 | Small-grain ZSM-5 molecular sieve catalyst used for preparing ethylene from bioethanol and preparation method thereof |
| CN102302945A (en) * | 2011-10-04 | 2012-01-04 | 大连理工大学 | Method for preparing propene by catalytic cracking |
| CN102335612A (en) * | 2010-07-22 | 2012-02-01 | 中国石油天然气股份有限公司 | Selective hydrodesulfurization catalyst and preparation method thereof |
| CN102989501A (en) * | 2012-12-11 | 2013-03-27 | 神华集团有限责任公司 | Preparation method of H-ZSM-5 molecular sieve based catalyst and prepared catalyst |
| CN104098108A (en) * | 2013-04-03 | 2014-10-15 | 中国石油天然气股份有限公司 | Rectangular-morphology ZSM-5 molecular sieve and preparation method thereof |
| CN104324746A (en) * | 2014-10-13 | 2015-02-04 | 浙江工业大学 | Metal modified ZSM-5 molecular sieve catalyst and its application |
| CN104624226A (en) * | 2013-11-13 | 2015-05-20 | 中国石油天然气股份有限公司 | ZSM-5 and ZSM-11 eutectic zeolite molecular sieve and preparation method and application thereof |
| CN105498854A (en) * | 2015-12-31 | 2016-04-20 | 沈阳三聚凯特催化剂有限公司 | High-precision desulfurization and denitrification catalyst carrier and preparation method thereof |
| CN105776245A (en) * | 2014-12-22 | 2016-07-20 | 中触媒有限公司 | Synthesis method of ZSM-5 molecular sieve and application of ZSM-5 molecular sieve in methanol synthesis to prepare propylene |
| WO2018219365A1 (en) * | 2017-06-02 | 2018-12-06 | 中国科学院大连化学物理研究所 | Catalyst, and method for direct conversion of syngas to prepare light olefins |
| CN109420520A (en) * | 2017-08-28 | 2019-03-05 | 中国科学院上海硅酸盐研究所 | A kind of multilevel structure ZSM-5 zeolite molecular sieve catalyst and its preparation method and application |
-
2019
- 2019-07-11 CN CN201910624307.1A patent/CN112206811B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006008655A (en) * | 2003-12-12 | 2006-01-12 | Mitsubishi Chemicals Corp | Method for producing propylene |
| CN1724161A (en) * | 2005-07-13 | 2006-01-25 | 清华大学 | Process for preparing load type silicon phoshporus aluminium molecular sieve |
| CN101172246A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Process for preparation of propylene catalysts with methanol conversion |
| CN101491779A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Catalyst for hydrogen selective catalyst combustion reaction with hydrothermal stability |
| CN101837298A (en) * | 2010-05-14 | 2010-09-22 | 广西壮族自治区化工研究院 | Small-grain ZSM-5 molecular sieve catalyst used for preparing ethylene from bioethanol and preparation method thereof |
| CN102335612A (en) * | 2010-07-22 | 2012-02-01 | 中国石油天然气股份有限公司 | Selective hydrodesulfurization catalyst and preparation method thereof |
| CN102302945A (en) * | 2011-10-04 | 2012-01-04 | 大连理工大学 | Method for preparing propene by catalytic cracking |
| CN102989501A (en) * | 2012-12-11 | 2013-03-27 | 神华集团有限责任公司 | Preparation method of H-ZSM-5 molecular sieve based catalyst and prepared catalyst |
| CN104098108A (en) * | 2013-04-03 | 2014-10-15 | 中国石油天然气股份有限公司 | Rectangular-morphology ZSM-5 molecular sieve and preparation method thereof |
| CN104624226A (en) * | 2013-11-13 | 2015-05-20 | 中国石油天然气股份有限公司 | ZSM-5 and ZSM-11 eutectic zeolite molecular sieve and preparation method and application thereof |
| CN104324746A (en) * | 2014-10-13 | 2015-02-04 | 浙江工业大学 | Metal modified ZSM-5 molecular sieve catalyst and its application |
| CN105776245A (en) * | 2014-12-22 | 2016-07-20 | 中触媒有限公司 | Synthesis method of ZSM-5 molecular sieve and application of ZSM-5 molecular sieve in methanol synthesis to prepare propylene |
| CN105498854A (en) * | 2015-12-31 | 2016-04-20 | 沈阳三聚凯特催化剂有限公司 | High-precision desulfurization and denitrification catalyst carrier and preparation method thereof |
| WO2018219365A1 (en) * | 2017-06-02 | 2018-12-06 | 中国科学院大连化学物理研究所 | Catalyst, and method for direct conversion of syngas to prepare light olefins |
| CN109420520A (en) * | 2017-08-28 | 2019-03-05 | 中国科学院上海硅酸盐研究所 | A kind of multilevel structure ZSM-5 zeolite molecular sieve catalyst and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| Exploring Si/Mg composite supported Ziegler-Natta Ti-based catalysts for propylene polymerization;Zhu W等;《Chinese Journal of Polymer Science》;20171119;第35卷(第12期);1474-1487 * |
| 刘建周主编.金属改性.《工业催化工程》.中国矿业大学出版社,2018,第168页. * |
| 拟薄水铝石载体材料的研发及其在加氢精制催化剂中的应用;南军等;《第十五届全国工业催化技术及应用年会论文集》;20180811;95-102 * |
| 载体酸碱性对高硫合成气制甲硫醇的K-Mo-Co催化剂结构和性能的影响;陈爱平等;《石油化工》;20080515(第10期);990-994 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112206811A (en) | 2021-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108927213A (en) | A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane | |
| CN112206811B (en) | Catalyst for preparing propylene by methanol conversion and preparation method and application thereof | |
| CN105983435B (en) | A kind of isomerization of butene catalyst and its preparation method and application | |
| CN113694961B (en) | Nano hierarchical pore BETA structure molecular sieve catalyst, and preparation method and application thereof | |
| CN106391106B (en) | A kind of preparation method of the core-shell structure molecular sieve containing metal | |
| CN101279284B (en) | Catalyst for preparing ethylene propylene from catalytic pyrolysis | |
| CN109433252B (en) | CO (carbon monoxide)2Oxide C2H6Dehydrogenation to C2H4And a process for preparing the same | |
| CN108569707B (en) | Multi-stage pore SAPO-34 molecular sieve and application thereof in methanol-to-olefin reaction | |
| CN112774663A (en) | Hierarchical pore catalyst for directly preparing ethylene from methane and preparation method and application thereof | |
| CN104326483B (en) | A kind of low silicon composite molecular sieve and synthetic method and application | |
| CN102040444B (en) | Method for preparing propylene by butylene and ethene | |
| CN103418425B (en) | Catalyst of preparing propylene by methanol transformation and preparation method thereof | |
| CN110180530B (en) | Catalyst for preparing olefin by dehydrogenating low-carbon alkane and preparation method thereof | |
| CN111036284B (en) | Catalyst, preparation method thereof and method for preparing light olefins from synthesis gas | |
| CN107952469B (en) | Bifunctional catalyst and preparation method and application thereof | |
| CN102872900A (en) | Catalyst for dry gas and benzene alkylation to prepare ethylbenzene | |
| CN100475337C (en) | Catalyst of naphtha catalytic pyrolysis preparing ethylene and propylene | |
| CN114289061A (en) | Catalyst for converting disubstituted alkyl anthracene into monosubstituted alkyl anthracene and preparation method and application thereof | |
| CN106890669A (en) | A kind of catalyst for producing methyl acetate, its preparation method and application | |
| CN106861751B (en) | The preparation method and product of the nucleocapsid catalyst of the beta-molecular sieve containing H and application | |
| CN116159591A (en) | Oxide-molecular sieve composite catalyst and preparation method and application thereof | |
| CN101869834B (en) | Selective hydrogen burning catalyst for internal heating of petroleum hydrocarbon cracking raw materials and application thereof | |
| CN113200554A (en) | Nano mordenite molecular sieve and preparation method and application thereof | |
| CN108568310B (en) | Embedded microporous-mesoporous composite molecular sieve methanation catalyst and application thereof | |
| CN111977663A (en) | Hierarchical pore structure zeolite molecular sieve and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |