CN112206811A - 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 PDF

Info

Publication number
CN112206811A
CN112206811A CN201910624307.1A CN201910624307A CN112206811A CN 112206811 A CN112206811 A CN 112206811A CN 201910624307 A CN201910624307 A CN 201910624307A CN 112206811 A CN112206811 A CN 112206811A
Authority
CN
China
Prior art keywords
molecular sieve
solution
catalyst
type zsm
aqueous solution
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.)
Granted
Application number
CN201910624307.1A
Other languages
Chinese (zh)
Other versions
CN112206811B (en
Inventor
徐亚荣
魏书梅
樊金龙
陈蓝天
冯丽梅
贺春梅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Petrochina Co Ltd
Original Assignee
Petrochina Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Petrochina Co Ltd filed Critical Petrochina Co Ltd
Priority to CN201910624307.1A priority Critical patent/CN112206811B/en
Publication of CN112206811A publication Critical patent/CN112206811A/en
Application granted granted Critical
Publication of CN112206811B publication Critical patent/CN112206811B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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 methanol conversion, a preparation method and application thereof. The preparation method of the catalyst for preparing propylene by methanol conversion comprises the steps of mixing a tetrapropyl ammonium bromide aqueous solution, a water glass aqueous solution and a sodium metaaluminate aqueous solution to obtain a mixed solution; crystallizing the mixed solution at 150-210 ℃ for at least 6 hours, and washing, drying and roasting a crystallized product to obtain a Na-type ZSM-5 molecular sieve; and (3) carrying out ion exchange on the Na-type ZSM-5 molecular sieve and an ion exchange solution, and then washing, drying and roasting to prepare 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, which is obtained by the preparation method, has the characteristics of high propylene selectivity and good catalytic stability.

Description

Catalyst for preparing propylene by methanol conversion and preparation method and application thereof
Technical Field
The invention relates to a propylene production technology, in particular to a catalyst for preparing propylene by methanol conversion, a preparation method and application thereof.
Background
Propylene is used as an important chemical basic raw material, is widely used for producing chemicals such as polypropylene, acrylonitrile, propylene oxide and the like, and is a base stone in the modern petrochemical industry. In recent years, driven by the rapid increase of the demand of propylene downstream product derivatives, particularly polypropylene, the consumption of propylene is greatly increased, and the market potential is huge.
At present, propylene mainly comes from naphtha steam cracking co-production and catalytic cracking by-products in China. However, petroleum resources in China are deficient, the propylene capacity can not meet the requirement of the domestic market on propylene, and the search for a novel propylene production process is reluctant. Among them, a process route of using coal, natural gas, biomass and the like as raw materials, preparing Methanol from synthesis gas, and then producing propylene (MTP) from Methanol is widely concerned by people. The process has wide raw material source and low price, 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 most hopeful to replace the petroleum route.
It has been considered that the reaction process for preparing hydrocarbon by converting methanol on an acidic molecular sieve catalyst 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 low-carbon olefin which mainly comprises 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, cycloparaffin, aromatic hydrocarbon and even coke. Meanwhile, the produced higher olefins can also be converted into corresponding lower hydrocarbons by cracking reaction or the like. In the above process route, the catalyst plays an important role. Therefore, how to inhibit the generation of byproducts and improve the selectivity and the catalytic stability of propylene becomes the key for the development of MTP catalysts.
The ZSM-5 molecular sieve is the first choice of the MTP catalyst due to the proper pore channel structure and the wide-range adjustable acid property. However, due to the diffusion limitation effect on larger molecules, the catalytic stability of the molecular sieve still needs to be improved, so that the multistage pore ZSM-5 molecular sieve is produced. 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 obviously improved.
The synthesis of the multistage hole ZSM-5 molecular sieve mainly comprises a soft template agent method, a hard template agent method, post-treatment methods such as desiliconization and dealuminization. Among them, the soft template method usually requires the use of additional, expensive template and has many steps; the hard template method usually requires high-temperature roasting to remove the synthesized template, but the high-temperature roasting may 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 feasible compared with the first two methods, but the change of the silicon-aluminum ratio of the molecular sieve caused by chemical dissolution is uncontrollable. Although the multi-stage hole 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 the MTP catalyst is a problem to be solved at present, and the new process is beneficial to realizing industrial scale production on the premise of ensuring that the prepared MTP catalyst has higher propylene selectivity and catalytic stability.
Disclosure of Invention
Aiming at the defects, the invention provides the method for preparing the propylene catalyst by methanol conversion, which is suitable for industrial mass production, and the prepared propylene catalyst by methanol conversion has the characteristics of high propylene selectivity and good catalytic stability.
The invention also provides a catalyst for preparing propylene by methanol conversion, which is prepared by adopting the preparation method. The catalyst for preparing propylene by methanol conversion has the characteristics of high propylene selectivity and good catalytic stability.
The invention also provides application of the catalyst for preparing propylene by methanol conversion in preparing propylene by methanol.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a catalyst for converting methanol to propylene, comprising:
mixing a tetrapropyl ammonium bromide aqueous solution, a water glass aqueous solution and a sodium metaaluminate aqueous solution to obtain a mixed solution, wherein the mass ratio of tetrapropyl ammonium bromide to silicon dioxide to sodium metaaluminate is (0.33-30): (1-10): 1;
crystallizing the mixed solution at 150-210 ℃ for at least 6 hours, and washing, drying and roasting a crystallized product to obtain a Na-type ZSM-5 molecular sieve;
and (2) carrying out ion exchange on the Na-type ZSM-5 molecular sieve and an ion exchange solution, washing, drying and roasting 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, the H-type ZSM-5 molecular sieve is simply referred to as a catalyst I).
According to the preparation method provided by the invention, tetrapropylammonium bromide is used as a template agent, and the dosage of the template agent and the silicon-aluminum ratio (SiO) in raw materials are controlled reasonably2With Al2O3In a specific molar ratio), and then carrying out specific crystallization treatment to obtain the Na-type ZSM-5 molecular sieve. The Na-type ZSM-5 molecular sieve is further characterized as a hierarchical molecular sieve. Finally, the Na-type ZSM-5 molecular sieve is converted into the H-type ZSM-5 molecular sieve by ion exchange. When 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 of simple overall process flow and good repeatability, and the used raw materials are common industrial raw materials and low in price, so that the preparation method is very favorable for being amplified to industrial production scale.
Specifically, when the mixed solution is prepared, firstly, the tetrapropyl ammonium bromide aqueous solution is added into the water glass aqueous solution, the mixture is stirred for 10-50 min at room temperature to realize the full mixing of the tetrapropyl ammonium bromide aqueous solution and the water glass aqueous solution, then, the sodium metaaluminate aqueous solution is dropwise added into the mixture under the condition of maintaining the stirring, and after the dropwise addition is finished, the mixture is continuously stirred for 2-10 h at room temperature to fully mix the tetrapropyl ammonium bromide aqueous solution and the sodium metaaluminate aqueous solution, so that the mixed solution is.
The dosage and the silicon-aluminum ratio of the template agent tetrapropyl ammonium bromide are reasonably controlled, which is favorable for further improving the performance of the MTP catalyst. In the specific implementation process of the invention, the mass ratio of the tetrapropyl ammonium bromide, the silicon dioxide and the sodium metaaluminate in the mixed solution is generally controlled to be (2-30): (1-10): 1.
wherein the solubility of the tetrapropyl ammonium bromide aqueous solution can be 10-80 wt%, preferably 10-60 wt%; with SiO2In particular, the mass concentration of the water glass aqueous solution can be 10-50 wt%, and preferably 20-50 wt%; the weight ratio of the tetrapropyl ammonium bromide aqueous solution to the water glass aqueous solution can be determined according to the set mass ratio and the concentration of the corresponding aqueous solution, and the weight ratio of the tetrapropyl ammonium bromide aqueous solution to the water glass aqueous solution is 1: 3-10: 1, preferably 1: 4-7: 1, more preferably 1 to 5: 1.
after the preparation of the mixed solution is finished, the mixed solution can be put into a crystallization kettle and crystallized for 6 to 50 hours at the temperature of 150 to 210 ℃. And after crystallization is finished, washing, filtering, drying and roasting the crystallized product at 500-600 ℃ to obtain the Na-type ZSM-5 molecular sieve.
The specific mode of ion exchange is not particularly limited in the invention, and the Na-type ZSM-5 molecular sieve can be converted into the H-type ZSM-5 molecular sieve by adopting the conventional ion exchange process in the field. For example, the Na-type ZSM-5 molecular sieve is subjected to ion exchange with an ion exchange solution at a temperature of 60-100 ℃, preferably 70-90 ℃, and then washed, dried and roasted to prepare the H-type ZSM-5 molecular sieve.
In the specific implementation process of the invention, Na-type ZSM-5 molecular sieve and ion exchange liquid are mixed, treated for at least 1 hour at 60-100 ℃, preferably 70-90 ℃ under the condition of strong stirring, washed, filtered to be neutral and dried; and then 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 roasting can be finished in a muffle furnace, and the roasting temperature can be controlled to be 500-600 ℃ generally.
The ion exchange liquid may be an aqueous solution of an acidic compound, such as an aqueous solution of an acid, an aqueous solution of a strong acid and a 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 0.01-5 mol/L, preferably 0.1-3 mol/L; the weight of the ion exchange liquid is generally more than 5 times of that of the Na-type ZSM-5 molecular sieve, and is usually 5-20 times.
On the basis of 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. Specifically, active metal is loaded on a catalyst I to obtain the modified ZSM-5 molecular sieve (marked as a catalyst II). The inventor researches and discovers that the yield of propylene carbon base is obviously improved and the service life can be prolonged when the obtained modified ZSM-5 molecular sieve is used for preparing propylene by converting methanol by loading a specific active metal on a 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 capacity of the active metal on the H-type ZSM-5 molecular sieve (based on the H-type ZSM-5 molecular sieve) is 0.02-9 wt%, preferably 0.05-5 wt% calculated by the oxide of the active metal.
The invention is not limited to how to realize the loading of the active metal on the H-type ZSM-5 molecular sieve, and the loading mode which is conventional in the field can be adopted, for example, an impregnation method, in particular an equal volume impregnation method can be adopted. The temperature in the dipping process is generally controlled not to exceed 80 ℃, for example, 20 ℃ to 80 ℃, and the dipping time is 2-24 hours. In the specific 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 liquid may be salt solution of active metal, including but not limited to nitrate, acetate or sulfate solution of active metal. The concentration of the dipping solution is generally 0.005-0.6 mol/L, such as 0.01-0.4 mol/L; the mass ratio of the H-type ZSM-5 molecular sieve to the impregnating solution can be controlled to be 1: 1 to 10.
On the basis of 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 methanol conversion, which is to mix the H-type ZSM-5 molecular sieve with composite carrier gel to prepare a corresponding formed catalyst (marked as a catalyst III).
In the prior art, alumina (Al)2O3) Because of having special acid properties and pore structure, it is often used as a catalyst carrier to improve the mechanical strength of the catalyst. However, recent studies have shown that the acidic sites of alumina itself promote the formation of methane and coke, thereby shortening the life of the catalyst. Therefore, the 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 obviously 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; and mixing the sol with magnesium oxide and silica sol, and drying to obtain the composite carrier, wherein the mass ratio of the pseudo-boehmite to the magnesium oxide to the silica sol is (1-8): (1-8): 1, preferably (1-4): (1-2): 1.
in the specific implementation process of the invention, a certain amount of pseudo-boehmite can be taken, added with water and stirred uniformly, then added with a hydrochloric acid aqueous solution dropwise, placed in a water bath at 55-75 ℃ to gelatinize until the pH value is 3-4, stirred continuously for 1-3 hours at room temperature, then added with a certain amount of magnesium oxide, and taken as a binder, stirred uniformly at room temperature, and dried for 2-4 hours at 100-130 ℃ to obtain the composite carrier.
Acidizing the composite carrier to obtain composite carrier gel; and (3) kneading, extruding, forming, drying and roasting the composite carrier gel and an 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 may be specifically selected from one or more of an aqueous hydrochloric acid solution, an aqueous nitric acid solution, an aqueous sulfuric acid solution and an aqueous phosphoric acid 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 treatment is usually not more than 40 ℃, for example, 10 to 30 ℃, and the time of the acidification treatment is usually not less than 5min, usually 5 to 30min, and further 10 to 30 min.
On the basis of the modified ZSM-5 molecular sieve (catalyst II), the invention also provides another preparation method of the catalyst for preparing propylene by methanol conversion, which comprises the steps of kneading the modified ZSM-5 molecular sieve (catalyst II) and composite carrier gel, extruding, molding, drying and roasting to obtain the catalyst (marked as catalyst IV) for preparing propylene by methanol conversion. Specifically, the preparation methods of the composite carrier and the composite carrier gel are the same as above, and are not described again. The specific processes of kneading, extruding and forming are the same as those of the previous process, and are not described again.
The second aspect of 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 methanol conversion has the characteristics of high propylene selectivity and good catalytic stability.
As described above, the present invention provides four catalysts for converting 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 to obtain a Na-type ZSM-5 molecular sieve and then carrying out ion exchange on the 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 added with the specially-made 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 added with the specially-made composite carrier gel on the basis of the catalyst II, 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 is to provide an application of the catalyst for preparing propylene by methanol conversion in preparing propylene by methanol.
The catalyst for preparing propylene by methanol conversion 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 by methanol, the methanol can be fully converted, and a large amount of propylene products can be obtained. And the catalyst for preparing propylene by methanol conversion has longer service life, so that the production efficiency of propylene can be improved.
The preparation method of the catalyst for preparing propylene by methanol conversion 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. Moreover, 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, the selectivity of propylene can be further improved by further loading active metal; by adding the composite carrier gel, the service life can be further prolonged.
The catalyst for preparing propylene by methanol conversion provided by the invention is a multi-stage pore ZSM-5 molecular sieve, so that the retention time of product molecules in a pore channel is shortened, side reactions are inhibited, the coking degree is reduced, the one-way 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 methanol conversion has the characteristics of high propylene selectivity and good catalytic stability. In addition, the used raw materials are common industrial raw materials and are low in price, so that the catalyst for preparing propylene by methanol conversion also has low cost.
Drawings
FIG. 1 is a nitrogen adsorption-desorption isotherm of a Na-type ZSM-5 molecular sieve prepared in step S1 of example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be understood that the following examples do not strictly limit the order of execution of the steps of the claimed manufacturing process. The individual steps of the preparation method of the invention can be carried out and carried out in any possible order 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 10 wt% tetrapropylammonium bromide water solution to SiO2Stirring the mixture for 20min at room temperature in 20 wt% water glass solution; then, under the condition of maintaining stirring, dripping 20 wt% sodium metaaluminate aqueous solution, and continuing to stir at room temperature for about 3 hours after finishing dripping to obtain a mixed solution, wherein the mass ratio of the tetrapropyl ammonium bromide aqueous solution, the water glass aqueous solution and the sodium metaaluminate aqueous solution is 1: 1: 0.2;
after stirring, putting the mixed solution into a crystallization kettle, and crystallizing at 160 ℃ for 36 hours; and after crystallization is finished, washing, filtering, drying and roasting the crystallized product in a muffle furnace at 550 ℃ for 6 hours to obtain the Na-type ZSM-5 molecular sieve. The molecular sieve is characterized, and as can be seen from FIG. 1, 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 Na-type ZSM-5 molecular sieve, treating the mixture for 2 hours in a water bath at 80 ℃ under the condition of strong stirring, washing and filtering the mixture to be neutral, drying the mixture for 2 hours in an oven at 120 ℃, repeating the operation for 2 times, wherein the weight of the ammonium nitrate is 0.8 time 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 mixture for 3 hours in a muffle furnace at 550 ℃ to obtain the H-type ZSM-5 molecular sieve.
S3, 0.13g of cerium nitrate Ce (NO)3)3·6H2Preparing a cerium nitrate aqueous solution with the concentration of about 0.04mol/L by using O and 7.5g of water, adding 5.0g of H-type ZSM-5 molecular sieve into the aqueous solution, standing for 6 hours at 60 ℃, drying overnight in a 120 ℃ oven, roasting for 2 hours in a 550 ℃ 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 10 wt% tetrapropylammonium bromide water solution to SiO2Stirring the mixture for 20min at room temperature in 20 wt% water glass solution; then, under the condition of maintaining stirring, dropwise adding a 20 wt% sodium metaaluminate aqueous solution, and continuing to stir at room temperature for 3 hours after dropwise adding is completed to obtain a mixed solution, wherein the mass ratio of the tetrapropyl ammonium bromide aqueous solution to the water glass aqueous solution to the sodium metaaluminate aqueous solution is 1: 1: 0.2;
after stirring, putting the mixed solution into a crystallization kettle, and crystallizing at 160 ℃ for 36 hours; and after crystallization is finished, washing, filtering, drying and roasting a crystallized product in a muffle furnace at 550 ℃ for 6 hours 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 Na-type ZSM-5 molecular sieve, treating the solution for 2 hours under the conditions of water bath at 80 ℃ and strong stirring, washing, filtering to be neutral, drying the solution in an oven at 120 ℃ for 2 hours, repeating the operation for 2 times, wherein the mass of the ammonium nitrate is 0.8 time 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 in an oven at 120 ℃ overnight, and roasting in a muffle furnace at 550 ℃ for 2H to obtain the Ce modified ZSM-5 molecular sieve.
S4, weighing a certain amount of pseudo-boehmite, adding water, stirring uniformly, then dropwise adding 0.02mol/L phosphoric acid solution, placing in a water bath at 65 ℃ for gelling until the pH value is 3.5, stirring at room temperature for 2.5h, then adding a certain amount of magnesium oxide, taking silica sol as a binder, stirring uniformly at room temperature, and drying at 120 ℃ for 2h to obtain the composite carrier. Wherein the mass ratio of the pseudo-boehmite, the magnesium oxide and the silica sol is 2: 2: 1.
s4, acidifying the composite carrier in 0.02mol/L phosphoric acid solution to prepare composite carrier gel, wherein the acidification conditions are as follows: acidifying for 30min at room temperature to 20 deg.C.
S5, mixing 6g of composite carrier gel and 24g of Ce modified ZSM-5 molecular sieve uniformly, grinding fully, adding 4g of nitric acid aqueous solution with the concentration of 4 wt% into the mixture, kneading, extruding and molding the mixture on a TBL-2 type catalyst molding and extruding device by using a round mold with the diameter of 3mm, airing, placing the dried mixture in an oven at 120 ℃ for drying overnight, and roasting the dried 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 40 wt% tetrapropylammonium bromide water solution to SiO2Stirring the mixture for 40min at room temperature in 30 wt% water glass solution; then, under the condition of keeping stirring, a sodium metaaluminate aqueous solution with the concentration of 30 wt% is droppedAnd after the dropwise addition is finished, continuously stirring for 3 hours at room temperature to obtain a mixed solution, wherein the mass ratio of the tetrapropyl ammonium bromide aqueous solution to the water glass aqueous solution to the sodium metaaluminate aqueous solution is 2: 1: 0.1;
after stirring, putting the mixed solution into a crystallization kettle, and crystallizing at 170 ℃ for 24 hours; and after crystallization is finished, washing, filtering, drying and roasting a crystallized product in a muffle furnace at 550 ℃ for 6 hours to obtain the Na-type ZSM-5 molecular sieve. Tests show that 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 Na-type ZSM-5 molecular sieve, treating the mixture for 2 hours in a water bath at 80 ℃ under a strong stirring condition, washing and filtering the mixture to be neutral, drying the mixture for 2 hours in an oven at 120 ℃, repeating the operation for 2 times, wherein the mass of the ammonium nitrate is 0.8 time 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 mixture for 3 hours in a muffle furnace at 550 ℃ to obtain the H-type ZSM-5 molecular sieve.
S3, adding 0.09g of manganese sulfate MnSO4Preparing a manganese sulfate solution with the concentration of 0.08mol/L with 7.5g of water, adding 5.0g of H-type ZSM-5 molecular sieve into the aqueous solution, standing for 9H at 60 ℃, drying overnight in a 120 ℃ oven, and roasting for 2H in a 550 ℃ muffle furnace to obtain the Mn modified ZSM-5 molecular sieve.
S4, weighing a certain amount of pseudo-boehmite, adding water, stirring uniformly, then dropwise adding 0.02mol/L nitric acid solution, placing in a water bath at 55 ℃ for gelling until the pH value is 3.5, stirring at room temperature for 1.5h, then adding a certain amount of magnesium oxide, taking silica sol as a binder, stirring uniformly at room temperature, and drying at 100 ℃ for 4h to obtain the composite carrier. Wherein the mass ratio of the pseudo-boehmite, the magnesium oxide and the silica sol is 1: 1: 1.
s4, acidifying the composite carrier in 0.02mol/L nitric acid solution to prepare composite carrier gel, wherein the acidification conditions are as follows: acidifying for 5min at room temperature to 10 deg.C.
S5, mixing 16g of composite carrier gel and 24g of Mn modified ZSM-5 molecular sieve uniformly, grinding fully, adding 4g of nitric acid aqueous solution with the concentration of 4 wt% into the mixture, kneading, extruding the mixture on a TBL-2 type catalyst forming and extruding device by using a round die with the diameter of 3mm, airing, placing the dried mixture in an oven at 120 ℃ for drying overnight, roasting the dried mixture in a muffle furnace at 600 ℃ for 2h to obtain a catalyst for propylene preparation through methanol conversion, 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 50 wt% tetrapropylammonium bromide water solution to SiO2Stirring the mixture for 40min at room temperature in 30 wt% water glass solution; then, dropwise adding a sodium metaaluminate aqueous solution with the concentration of 30 wt% under the condition of maintaining stirring, and continuing to stir at room temperature for about 3 hours after the dropwise adding is finished to obtain a mixed solution, wherein the mass ratio of the tetrapropyl ammonium bromide aqueous solution, the water glass aqueous solution and the sodium metaaluminate aqueous solution is 2: 1: 0.5;
after stirring, putting the mixed solution into a crystallization kettle, and crystallizing at 170 ℃ for 36 hours; and after crystallization is finished, washing, filtering, drying and roasting a crystallized product in a muffle furnace at 550 ℃ for 6 hours to obtain the Na-type ZSM-5 molecular sieve. Tests show that 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 Na-type ZSM-5 molecular sieve, treating the mixture for 2 hours in a water bath at 80 ℃ under the condition of strong stirring, washing and filtering the mixture to be neutral, drying the mixture for 2 hours in an oven at 120 ℃, repeating the operation for 2 times, wherein the mass of the ammonium nitrate is 0.8 time 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 mixture for 3 hours in a muffle furnace at 550 ℃ to obtain the H-type ZSM-5 molecular sieve.
S3, adding 0.13g of manganese acetate Mn (CH)3COO)2·4H2Preparing a manganese acetate solution with the concentration of about 0.07mol/L by using O and 7.5g of water, adding 5.0g of H-type ZSM-5 molecular sieve into the aqueous solution, standing for 11H at 60 ℃, drying overnight in a 120 ℃ oven, roasting for 2H in a 550 ℃ 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 60 wt% tetrapropylammonium bromide water solution to SiO2Stirring the mixture for 40min at room temperature in 30 wt% water glass solution; then, under the condition of maintaining stirring, dropwise adding a sodium metaaluminate aqueous solution with the concentration of 50 wt%, and continuing to stir at room temperature for 3 hours after dropwise adding is completed to obtain a mixed solution, wherein the mass ratio of the tetrapropyl ammonium bromide aqueous solution to the water glass aqueous solution to the sodium metaaluminate aqueous solution is 5: 1: 0.6;
after stirring, putting the mixed solution into a crystallization kettle, and crystallizing at 170 ℃ for 36 hours; and after crystallization is finished, washing, filtering, drying and roasting a crystallized product in a muffle furnace at 550 ℃ for 6 hours to obtain the Na-type ZSM-5 molecular sieve. Tests show that 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 Na-type ZSM-5 molecular sieve, treating the mixture for 2 hours under the conditions of water bath at 80 ℃ and strong stirring, washing and filtering the mixture to be neutral, drying the mixture in an oven at 120 ℃ for 2 hours, repeating the operation for 2 times, wherein the mass of the ammonium nitrate is 0.8 time 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 mixture for 3 hours in a muffle furnace at 550 ℃ to obtain the H-type ZSM-5 molecular sieve.
S3, mixing 0.07g of silver nitrate AgNO3Preparing silver nitrate solution with the concentration of about 0.055mol/L with 7.5g of water, adding 5.0g of H-type ZSM-5 molecular sieve into the solution, standing for 12 hours at 60 ℃, drying in a 120 ℃ oven overnight, roasting in a 550 ℃ muffle furnace for 2 hours, tabletting and grinding 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 60 wt% tetrapropylammonium bromide water solution to SiO2Stirring the mixture for 40min at room temperature in 30 wt% water glass solution; then dripping 50 wt% sodium metaaluminate aqueous solution under the condition of keeping stirring, and continuing stirring at room temperature after finishing drippingAnd stirring for 3 hours to obtain a mixed solution, wherein the mass ratio of the tetrapropyl ammonium bromide aqueous solution to the water glass aqueous solution to the sodium metaaluminate aqueous solution is 5: 1: 0.6;
after stirring, putting the mixed solution into a crystallization kettle, and crystallizing at 170 ℃ for 36 hours; and after crystallization is finished, washing, filtering, drying and roasting a crystallized product in a muffle furnace at 550 ℃ for 6 hours to obtain the Na-type ZSM-5 molecular sieve. Tests show that the Na-type ZSM-5 molecular sieve is a hierarchical pore ZSM-5 molecular sieve;
s2, taking 10g of Na-type ZSM-5 molecules, adding 8g of ammonium nitrate and 100g of water into the Na-type ZSM-5 molecules, treating the mixture for 2 hours in a water bath at 80 ℃ under a strong stirring condition, washing and filtering the mixture to be neutral, drying the mixture for 2 hours in an oven at 120 ℃, repeating the operation for 2 times, wherein the mass of the ammonium nitrate is 0.8 time 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 mixture for 3 hours in a muffle furnace at 550 ℃ to obtain the H-type ZSM-5 molecular sieve.
S3, preparing a lanthanum nitrate solution with the concentration of about 0.0985mol/L from 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 in an oven at 120 ℃ overnight, and roasting in a muffle furnace at 550 ℃ for 2H to obtain the Mg modified ZSM-5 molecular sieve.
S4, weighing a certain amount of pseudo-boehmite, adding water, stirring uniformly, then dropwise adding 0.02mol/L sulfuric acid solution, placing in a water bath at 60 ℃ for gelling until the pH value is 3.5, stirring at room temperature for 2h, then adding a certain amount of magnesium oxide, taking silica sol as a binder, stirring uniformly at room temperature, and drying at 110 ℃ for 3h to obtain the composite carrier. Wherein the mass ratio of the pseudo-boehmite, the magnesium oxide and the silica sol is 1: 2: 1.
s4, acidifying the composite carrier in 0.02mol/L sulfuric acid solution to prepare composite carrier gel, wherein the acidification conditions are as follows: acidifying at room temperature to 25 deg.C for 20 min.
S5, mixing 10g of composite carrier gel and 24g of La modified ZSM-5 molecular sieve uniformly, grinding fully, adding 4g of nitric acid aqueous solution with the concentration of 4 wt% into the mixture, kneading, extruding the mixture on a TBL-2 type catalyst forming and extruding device by using a round die with the diameter of 3mm, airing, placing the dried mixture in an oven at 120 ℃ for drying overnight, and roasting the dried mixture in a muffle furnace at 600 ℃ for 2h 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 60 wt% tetrapropylammonium bromide water solution to SiO2Stirring the mixture for 40min at room temperature in 30 wt% water glass solution; then, under the condition of maintaining stirring, dropwise adding a sodium metaaluminate aqueous solution with the concentration of 50 wt%, and continuing to stir at room temperature for 3 hours after dropwise adding is completed to obtain a mixed solution, wherein the mass ratio of the tetrapropyl ammonium bromide aqueous solution, the water glass aqueous solution and the sodium metaaluminate aqueous solution is 5: 1: 0.6;
after stirring, putting the mixed solution into a crystallization kettle, and crystallizing at 170 ℃ for 36 hours; and after crystallization is finished, washing, filtering, drying and roasting a crystallized product in a muffle furnace at 550 ℃ for 6 hours to obtain the Na-type ZSM-5 molecular sieve. Tests show that the Na-type ZSM-5 molecular sieve is a hierarchical pore ZSM-5 molecular sieve;
s2, taking Na-type ZSM-510 g, adding 8g of ammonium nitrate and 100g of water into the Na-type ZSM-510 g, processing the mixture for 2 hours in a water bath at 80 ℃ under the condition of strong stirring, washing and filtering the mixture to be neutral, drying the mixture for 2 hours in an oven at 120 ℃, repeating the operation for 2 times, wherein the mass of the ammonium nitrate is 0.8 time 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 mixture for 3 hours in a muffle furnace at 550 ℃ to obtain the H-type ZSM-5 molecular sieve.
Tabletting and grinding the roasted H-type ZSM-5 molecular sieve to obtain the catalyst (catalyst I) for preparing the propylene by converting the 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 60 wt% tetrapropylammonium bromide water solution to SiO2Stirring the mixture for 40min at room temperature in 30 wt% water glass solution; then, under the condition of stirring, dropwise adding a sodium metaaluminate aqueous solution with the concentration of 50 wt%, and continuously stirring for 3 hours at room temperature after dropwise adding is finished; it is composed ofIn the method, the mass ratio of the tetrapropyl ammonium bromide aqueous solution, the water glass aqueous solution and the sodium metaaluminate aqueous solution is 5: 1: 0.6; after stirring, putting the mixed solution into a crystallization kettle, and crystallizing at 170 ℃ for 36 hours; and after crystallization is finished, washing, filtering, drying and roasting a crystallized product in a muffle furnace at 550 ℃ for 6 hours to obtain the Na-type ZSM-5 molecular sieve. Tests show that the Na-type ZSM-5 molecular sieve is a hierarchical pore ZSM-5 molecular sieve.
S2, adding 8g of ammonium nitrate and 100g of water into a Na-type ZSM-5 molecular sieve, treating for 2 hours in a water bath at 80 ℃ under a strong stirring condition, washing, performing suction filtration to be neutral, drying for 2 hours in an oven at 120 ℃, repeating the operation for 2 times, wherein the mass of the ammonium nitrate is 0.8 time 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 for 3 hours in a muffle furnace at 550 ℃ to obtain the H-type ZSM-5 molecular sieve.
S3, weighing a certain amount of pseudo-boehmite, adding water, stirring uniformly, then dropwise adding 1mol/L hydrochloric acid solution, placing in a water bath at 65 ℃ for gelling until the pH value is 3, stirring for 2h at room temperature, then adding a certain amount of magnesium oxide, taking silica sol as a binder, stirring uniformly at room temperature, and drying for 2h at 120 ℃, 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, acidifying the composite carrier in 1mol/L nitric acid solution to prepare composite carrier gel, wherein the acidification conditions are as follows: acidifying for 10min at room temperature to 20 deg.C.
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, extruding the mixture into a shape by using a circular mold with the diameter of 3mm on a TBL-2 type catalyst forming and extruding device, airing, placing the shape in an oven at 120 ℃ for drying overnight, and roasting the 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 tetrapropylammonium bromide with a concentration of 50 wt%Aqueous solution, added to SiO2Stirring the mixture for 40min at room temperature in 30 wt% water glass solution; then under the condition of stirring, dropwise adding a sodium metaaluminate aqueous solution with the concentration of 30 wt%, and continuing to stir at room temperature for 3 hours after dropwise adding is finished; wherein the mass ratio of the tetrapropyl ammonium bromide aqueous solution, the water glass aqueous solution and the sodium metaaluminate aqueous solution is 2: 1: 0.5; after stirring, putting the mixed solution into a crystallization kettle, and crystallizing at 165 ℃ for 40 hours; and after crystallization is finished, washing, filtering, drying and roasting the crystallized product at 550 ℃ to obtain the hierarchical porous Na-ZSM-5 molecular sieve.
S2, adding 8g of ammonium nitrate and 100g of water into a Na-type ZSM-5 molecular sieve, treating for 2 hours in a water bath at 80 ℃ under a strong stirring condition, washing, performing suction filtration to be neutral, drying for 2 hours in an oven at 120 ℃, repeating the operation for 2 times, wherein the mass of the ammonium nitrate is 0.8 time 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 for 3 hours in a muffle furnace at 550 ℃ to obtain the H-type ZSM-5 molecular sieve.
S3, adding 0.13g of manganese acetate Mn (CH)3COO)2·4H2Preparing a manganese acetate solution with the concentration of about 0.07mol/L by using O 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 Mn modified ZSM-5 molecular sieve.
S4, weighing a certain amount of pseudo-boehmite, adding water, stirring uniformly, then dropwise adding 1mol/L hydrochloric acid solution, placing in a water bath at 65 ℃ for gelling until the pH value is 3, stirring at room temperature for 2h, then adding a certain amount of magnesium oxide, taking silica sol as a binder, stirring uniformly at room temperature, and drying at 120 ℃ for 2h to obtain the composite carrier. Wherein the mass ratio of the pseudo-boehmite, the magnesium oxide and the silica sol is 2: 1: 1.
acidizing the composite carrier in 1mol/L nitric acid solution to prepare composite carrier gel, wherein the acidizing conditions are as follows: acidifying for 10min at room temperature to 20 deg.C.
S5, mixing 10g of composite carrier gel and 24g of Mn modified ZSM-5 molecular sieve uniformly, grinding fully, adding 4g of nitric acid aqueous solution with the concentration of 4 wt% into the mixture, kneading, extruding and molding the mixture on a TBL-2 type catalyst molding and extruding device by using a round mold with the diameter of 3mm, airing, placing the dried mixture in an oven at 120 ℃ for drying overnight, 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 50 wt% tetrapropylammonium bromide water solution to SiO2Stirring the mixture for 40min at room temperature in 30 wt% water glass solution; then, dropwise adding a sodium metaaluminate aqueous solution with the concentration of 30 wt% under the condition of maintaining stirring, and continuing to stir at room temperature for about 3 hours after the dropwise adding is finished to obtain a mixed solution, wherein the mass ratio of the tetrapropyl ammonium bromide aqueous solution, the water glass aqueous solution and the sodium metaaluminate aqueous solution is 2: 1: 0.5;
after stirring, putting the mixed solution into a crystallization kettle, and crystallizing at 170 ℃ for 36 hours; and after crystallization is finished, washing, filtering, drying and roasting a crystallized product in a muffle furnace at 550 ℃ for 6 hours to obtain the Na-type ZSM-5 molecular sieve. Tests show that 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 Na-type ZSM-5 molecular sieve, treating the mixture for 2 hours in a water bath at 80 ℃ under the condition of strong stirring, washing and filtering the mixture to be neutral, drying the mixture for 2 hours in an oven at 120 ℃, repeating the operation for 2 times, wherein the mass of the ammonium nitrate is 0.8 time 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 mixture for 3 hours in a muffle furnace at 550 ℃ to obtain the H-type ZSM-5 molecular sieve.
S3, adding 0.13g of manganese acetate Mn (CH)3COO)2·4H2Preparing a manganese acetate solution with the concentration of about 0.07mol/L by using O and 7.5g of water, adding 5.0g of H-type ZSM-5 molecular sieve into the aqueous solution, standing for 11H at 60 ℃, drying overnight in an oven at 120 ℃, and roasting for 2H 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, stirring uniformly, then dropwise adding 0.02mol/L hydrochloric acid solution, placing in a water bath at 75 ℃ for gelling until the pH value is 4, stirring at room temperature for 3h, then adding a certain amount of magnesium oxide, taking silica sol as a binder, stirring uniformly at room temperature, and drying at 110 ℃ for 3h to obtain the composite carrier. Wherein the mass ratio of the pseudo-boehmite, the magnesium oxide and the silica sol is 1: 1: 1.
s4, acidifying the composite carrier in 0.02mol/L hydrochloric acid solution to prepare composite carrier gel, wherein the acidification conditions are as follows: acidifying at room temperature to 20 deg.C for 20 min.
S5, mixing 6g of composite carrier gel and 24g of Mn modified ZSM-5 molecular sieve uniformly, grinding fully, adding 4g of nitric acid aqueous solution with the concentration of 4 wt% into the mixture, kneading, extruding and molding the mixture on a TBL-2 type catalyst molding and extruding device by using a circular mold with the diameter of 3mm, airing, placing the dried mixture in an oven at 120 ℃ for drying overnight, and roasting the dried 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 embodiment, taking the particles with the particle size of 40-60 meshes in the embodiments 1, 4 and 7 for micro-reverse evaluation; the catalysts of examples 2-3, 5-6 and 8-10 were cut into catalyst particles of about 2mm for a microreaction evaluation. The specific method for micro-reverse evaluation comprises the following steps:
by mass fraction of>99 wt% pure methanol is used as raw material, performance evaluation is carried out on a miniature fixed bed reaction device, the reaction temperature is 450 ℃, the nitrogen flow rate is 20mL/min, and the pressure is normal. Wherein for the catalyst in example 7, the loading was 1g and the mass space velocity was 9.6h-1(ii) a For the catalysts in the other examples, the loading was 3g and the mass space time was 3.2h-1。
The evaluation results of examples 1 to 10 are shown in Table 1. Wherein the yield of the product is based on the amount of the carbon hydrogen after the dehydration of the methanol; catalyst life refers to the reaction time corresponding to a decrease in methanol conversion to 95 wt.%.
TABLE 1
Figure BDA0002126552660000161
Figure BDA0002126552660000171
As can be seen from table 1 above, the catalyst for preparing propylene by converting methanol provided in the embodiment of the present invention has a methanol conversion rate of 100%, and has a very high propylene carbon-based yield and a very long lifetime. Presumably, the catalyst for preparing propylene by methanol conversion is a multi-stage pore ZSM-5 molecular sieve, and in the reaction process of catalyzing the conversion of methanol into propylene, the retention time of product molecules in the pore channels can be shortened, so that side reactions are inhibited, and the coking degree is reduced, so that the yield of propylene per pass carbon 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 embodiment 7, the yield of propylene carbon group of the catalysts in the embodiments 1 and 4-5 is obviously improved, which shows that the proper active metal is loaded on the H-type ZSM-5 molecular sieve, which is beneficial to improving the catalytic activity of the catalyst and promoting the conversion of methanol to propylene. In addition, the catalyst stability can be improved by loading appropriate active metal on the H-type ZSM-5 molecular sieve, for example, compared with the active metal Ag loaded in the example 5 and other active metals loaded in the examples 1 and 4, the service life of the catalyst is obviously prolonged.
Comparing examples 1, 4-5 and examples 2-3, 6, 8-10, it can be seen that, overall, when the composite carrier gel is added to the catalyst (whether catalyst I or catalyst II), the yield of propylene carbon groups is slightly reduced or substantially maintained, and the service life of the catalyst is significantly improved, especially, when the composite carrier gel is added, the service life of the catalyst is significantly prolonged and the change of catalytic activity is not significant, so that the composite carrier gel has an important function for preparing the methanol-to-propylene catalyst, as can be seen in comparison of examples 4 and 10.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A preparation method of a catalyst for preparing propylene by methanol conversion is characterized by comprising the following steps:
mixing a tetrapropyl ammonium bromide aqueous solution, a water glass aqueous solution and a sodium metaaluminate aqueous solution to obtain a mixed solution, wherein the mass ratio of tetrapropyl ammonium bromide to silicon dioxide to sodium metaaluminate is (0.33-30): (1-10): 1;
crystallizing the mixed solution at 150-210 ℃ for at least 6 hours, and washing, drying and roasting a crystallized product to obtain a Na-type ZSM-5 molecular sieve;
and carrying out ion exchange on the Na-type ZSM-5 molecular sieve and an ion exchange solution, washing, drying and roasting 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.
2. The preparation method of claim 1, wherein the Na-type ZSM-5 molecular sieve is subjected to ion exchange with an ion exchange solution at 60-100 ℃, and then washed, dried and calcined to prepare the H-type ZSM-5 molecular sieve; wherein the concentration of the ion exchange solution 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 production method according to claim 1 or 2, wherein the ion exchange liquid is selected from 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, and an aqueous ammonium sulfate solution.
4. The production method according to any one of claims 1 to 3, further comprising: loading active metal on the H-type ZSM-5 molecular sieve, drying, roasting and pressing to form to obtain a modified ZSM-5 molecular sieve, wherein the modified ZSM-5 molecular sieve is used as a catalyst for preparing propylene by methanol conversion;
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% calculated by the oxide of the active metal.
5. The preparation method according to claim 4, characterized in that an impregnation method is adopted, active metal is loaded on the H-type ZSM-5 molecular sieve, the temperature in the impregnation process is controlled not to exceed 80 ℃, and the impregnation time is 2-24 hours;
the impregnation liquid is selected from nitrate solution, acetate solution or sulfate solution of active metal, the concentration of the impregnation liquid is 0.005-0.6 mol/L, and the mass ratio of the H-type ZSM-5 molecular sieve to the impregnation liquid is 1: 1 to 10.
6. The production method according to any one of claims 1 to 3, further comprising:
peptizing pseudo-boehmite in an acidic aqueous solution at 55-75 ℃ until the pH value is 3-4 to obtain sol;
and mixing and drying the sol, magnesium oxide and silica sol to obtain the composite carrier, wherein the mass ratio of the pseudo-boehmite to the magnesium oxide to the silica sol is (1-8): (8-1): 1;
acidizing the composite carrier to obtain composite carrier gel;
and (2) kneading, extruding, forming, drying and roasting the composite carrier gel and the H-type ZSM-5 molecular sieve to obtain the catalyst 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.
7. the production method according to claim 4 or 5, characterized by further comprising:
peptizing pseudo-boehmite in an acidic aqueous solution at 55-75 ℃ until the pH value is 3-4 to obtain sol;
and mixing and drying the sol, magnesium oxide and silica sol to obtain the composite carrier, wherein the mass ratio of the pseudo-boehmite to the magnesium oxide to the silica sol is (1-8): (1-8): 1;
acidizing the composite carrier to obtain composite carrier gel;
and (2) carrying out mixing kneading, strip extrusion molding, drying and roasting on the composite carrier gel and the modified ZSM-5 molecular sieve to obtain the catalyst for preparing propylene by methanol conversion, wherein the mass ratio of the H-type ZSM-5 molecular sieve to the composite carrier gel is 1: 3-20: 1.
8. the method according to claim 6 or 7, wherein the composite carrier is subjected to an acidification treatment using an acidic solution, wherein:
the acid 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 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;
the temperature of the acidification treatment is not more than 40 ℃, and the time is not less than 5 min.
9. A catalyst for propylene production by methanol conversion, which is obtained by the production method according to any one of claims 1 to 8.
10. The use of the methanol-to-propylene catalyst of claim 9 in the preparation of propylene from methanol.
CN201910624307.1A 2019-07-11 2019-07-11 Catalyst for preparing propylene by methanol conversion and preparation method and application thereof Active CN112206811B (en)

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 true CN112206811A (en) 2021-01-12
CN112206811B 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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113023746A (en) * 2021-03-17 2021-06-25 宁夏大学 Lanthanum modified molecular sieve and preparation method and application thereof
CN113289674A (en) * 2021-05-27 2021-08-24 复旦大学 Bifunctional catalyst for preparing light aromatic hydrocarbon from synthesis gas and preparation method thereof

Citations (15)

* Cited by examiner, † Cited by third party
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 ZSM-5 molecular sieve with rectangular morphology 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 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

Patent Citations (15)

* Cited by examiner, † Cited by third party
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 ZSM-5 molecular sieve with rectangular morphology 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 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)

* Cited by examiner, † Cited by third party
Title
ZHU W等: "Exploring Si/Mg composite supported Ziegler-Natta Ti-based catalysts for propylene polymerization", 《CHINESE JOURNAL OF POLYMER SCIENCE》 *
刘建周主编: "《工业催化工程》", 30 June 2018, 中国矿业大学出版社 *
南军等: "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", 《第十五届全国工业催化技术及应用年会论文集》 *
陈爱平等: "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", 《石油化工》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113023746A (en) * 2021-03-17 2021-06-25 宁夏大学 Lanthanum modified molecular sieve and preparation method and application thereof
CN113289674A (en) * 2021-05-27 2021-08-24 复旦大学 Bifunctional catalyst for preparing light aromatic hydrocarbon from synthesis gas and preparation method thereof

Also Published As

Publication number Publication date
CN112206811B (en) 2023-06-30

Similar Documents

Publication Publication Date Title
KR20130082273A (en) Catalyst for oxidative coupling reaction of methane, method for preparing the same, and method for oxidative coupling reaction of methane using the same
CN106362791B (en) One kind is for compound duct molecular sieve catalyst of the preparing propylene transformed mesoporous-micropore of dehydrogenating propane and preparation method thereof
CN101940958B (en) Method for preparing low-carbon olefin catalyst by loading iron-based synthetic gas
CN114272950A (en) CH (physical channel)4、CO2Catalyst for reforming preparation of synthesis gas and preparation method and application thereof
CN102698761A (en) Preparation method of catalyst for hexone synthesis by acetone hydrogenation and application
CN112206811A (en) Catalyst for preparing propylene by methanol conversion and preparation method and application thereof
CN109433252B (en) CO (carbon monoxide)2Oxide C2H6Dehydrogenation to C2H4And a process for preparing the same
CN102040444B (en) Method for preparing propylene by butylene and ethene
CN110170333B (en) Catalyst for preparing ethylene from ethane in carbon dioxide atmosphere and preparation method thereof
CN111036284B (en) Catalyst, preparation method thereof and method for preparing light olefins from synthesis gas
CN105582933B (en) Catalyst for double-bond isomerization
CN110329992A (en) Low-temperature methanol steam reforming catalyst for preparing hydrogen and preparation method thereof
CN106890669A (en) A kind of catalyst for producing methyl acetate, its preparation method and application
CN113198527B (en) Composite hierarchical pore molecular sieve catalyst for preparing aromatic hydrocarbon from low-carbon alkane and preparation method thereof
CN114130420B (en) Benzene hydroalkylation catalyst and preparation method and application thereof
CN111939966B (en) Alkaline molecular sieve catalyst, preparation method thereof and application thereof in synthesis of N-methylmorpholine oxide
CN114433220B (en) Preparation method of benzene and synthesis gas alkylation catalyst
KR20180116000A (en) Catalysts for methanation of carbon dioxide and the manufacturing method of the same
CN114289061A (en) Catalyst for converting disubstituted alkyl anthracene into monosubstituted alkyl anthracene and preparation method and application thereof
KR101633985B1 (en) Supported mixed metal oxide catalyst for dehydrogenation of buthane and preparing method of the same
CN104549295A (en) Olefin isomerization catalyst
CN114425411B (en) Supported Fe-based catalyst and preparation and application thereof
JP2012157794A (en) Catalyst for dehydrating glycerin, method for preparing the same and method for producing acrolein using the same
CN104815688B (en) Iron-based molecular sieve catalyst and preparation method and application thereof
CN114433217B (en) Benzene and synthesis gas alkylation catalyst 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