CN107952474B - Methane aromatization catalyst and preparation method and application thereof - Google Patents

Methane aromatization catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN107952474B
CN107952474B CN201711238243.9A CN201711238243A CN107952474B CN 107952474 B CN107952474 B CN 107952474B CN 201711238243 A CN201711238243 A CN 201711238243A CN 107952474 B CN107952474 B CN 107952474B
Authority
CN
China
Prior art keywords
catalyst
hmcm
molecular sieve
solution
drying
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
Application number
CN201711238243.9A
Other languages
Chinese (zh)
Other versions
CN107952474A (en
Inventor
陈建刚
龚焱
郭立
李国栋
曾艳艳
管肖肖
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.)
Wuhan Kaidi Engineering Technology Research Institute Co Ltd
Original Assignee
Wuhan Kaidi Engineering Technology Research Institute 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 Wuhan Kaidi Engineering Technology Research Institute Co Ltd filed Critical Wuhan Kaidi Engineering Technology Research Institute Co Ltd
Priority to CN201711238243.9A priority Critical patent/CN107952474B/en
Publication of CN107952474A publication Critical patent/CN107952474A/en
Application granted granted Critical
Publication of CN107952474B publication Critical patent/CN107952474B/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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • 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
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C07C2529/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 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

Abstract

The invention discloses a methane aromatization catalyst and a preparation method and application thereof, wherein the catalyst takes an HMCM-22 molecular sieve as a catalyst carrier, and a Mo and Fe bimetallic component is impregnated and loaded to obtain the methane aromatization catalyst; in the catalyst, the mass content of Mo element is 0.5-10.0%, and the element mass ratio of Mo and Fe is Mo/Fe 0.2-7.0. The preparation method of the catalyst comprises the following steps: 1) preparation of HMCM-22 molecular sieve, or its mixture with CeO2As a catalyst support; 2) impregnating and loading Mo and Fe bimetal components; 3) drying and roasting. The invention also provides the application of the catalyst in preparing aromatic hydrocarbon through methane conversion reaction. The invention has the advantages of obviously improved catalyst structure and methane aromatization performance, relatively simple catalyst preparation and reaction process and favorable industrial application prospect.

Description

Methane aromatization catalyst and preparation method and application thereof
Technical Field
The invention relates to a technology for preparing aromatic hydrocarbon by methane conversion, in particular to a methane aromatization catalyst and a preparation method and application thereof.
Background
Aromatic hydrocarbons are important chemical raw materials, and data show that the demand of benzene on the world important organic raw material leaderboard is third, second to ethylene and propylene in 2005-2013, and the demand of the benzene increases year by year. Aromatic hydrocarbons were first obtained from coal tar, but with the development of the petroleum industry, particularly the application of reforming technology, aromatic hydrocarbons can be obtained directly from reformed oil and cracked tar, and petroleum refining is now the main source of aromatic hydrocarbons. However, with the increasing exhaustion of petroleum resources, natural gas resources are one of the most promising alternative energy sources and chemical raw materials in the 21 st century because of their considerable reserves. Methane is the main component of natural gas, and because of its abundant resources, it becomes a main cheap chemical raw material. The research and development of the utilization technology of methane have great strategic significance on the comprehensive utilization of natural gas.
The main pathways for methane conversion are two, direct conversion and indirect conversion. The direct conversion refers to the direct conversion of methane into basic chemical raw materials such as ethylene, aromatic hydrocarbon and oxygen-containing compound under the action of a catalyst. The indirect conversion is carried out by reforming or partially oxidizing methane at high temperature to obtain a mixture of CO and H in a certain ratio2The composed synthesis gas is then further converted into hydrocarbons and oxygen-containing compounds under the action of a catalyst.
At present, Mo-based supported HZSM-5 catalyst is mainly adopted as the catalyst for preparing aromatic hydrocarbon by methane conversion, meanwhile, the research on methane aromatization catalysts with different carrier structures is also carried out by technical personnel, and conventional HMCM-22 molecular sieve supported molybdenum is adopted for methane aromatization reaction in Chinese patent with publication number CN 1271622A.
Carbon deposition is one of key indexes influencing the service life of the catalyst, because the five-membered ring orifice of the traditional ZSM-5 molecular sieve is smaller, secondary reaction is easy to occur, the carbon deposition inactivation of the catalyst is accelerated, and after the framework aluminum is removed by hydrothermal treatment for pore forming, the diffusion of reactants and products is facilitated to a certain extent, the acid loss of the catalyst is caused by damaging the framework structure, the selectivity and the service life can be improved to a certain extent, but still further improvement is needed; generally, the aerobic aromatization means that an oxidant (such as oxygen, etc.) is added, and although the generation of carbon deposit is reduced and the reaction life is prolonged, the selectivity of the target product is reduced. Research shows that carbon deposition on the methane aromatization catalyst seriously affects the service life of the catalyst, and the carbon deposition mainly comprises three components: a) oligomeric fused aromatic hydrocarbons; b) a graphite precursor state; c) mo2C or Mo2OxCy, wherein the third type of carbon deposit is the active species of the reaction, while the first two types of carbon deposits deactivate the catalyst carbon deposit, the first carbon deposit is the main cause of catalyst deactivation, while the oligomeric fused ring aromatic hydrocarbons are mainly formed from relatively unstable aromatic hydrocarbons such as benzene, toluene and the like.
Many research and development institutions and companies have made extensive modification work on HZSM-5 and HMCM-22 molecular sieves in order to obtain better methane aromatization reaction performance on the corresponding Mo-based catalysts. For example, by subjecting the HZSM-5 molecular sieve to appropriate steam treatment, part of the acid centers of the molecular sieve are reduced, which is advantageous for increasing the yield of aromatic hydrocarbons and suppressing the formation of carbon deposits (chem. Commun., (2002): 2048-. With the presence of moderate amounts of oxygen to promote the oxygen-free aromatization reaction (Catalysis Letters, 63(1999) 73). However, these improved processes are very limited in effectiveness due to limitations in the thermodynamic characteristics of the reaction, and the selectivity to aromatics and the lifetime of the methane aromatization catalyst need to be further improved.
Disclosure of Invention
The invention aims to provide a methane aromatization catalyst which has good arene selectivity and is not easy to deposit carbon and deactivate, and a preparation method and application thereof.
In order to achieve the aim, the methane aromatization catalyst provided by the invention is prepared by taking an HMCM-22 molecular sieve as a catalyst carrier and impregnating and loading Mo and Fe bimetallic components; in the catalyst, the mass content of Mo element is 0.5-10.0%, and the element mass ratio of Mo and Fe is Mo/Fe 0.2-7.0.
Preferably, CeO is mixed in the catalyst carrier2The content of the carrier is 0.5 to 10.0 percent of the total weight of the mixed carrier. Adding CeO2By Ce in a reducing atmosphere3+And Ce4+The mutual transformation stores and releases lattice oxygen, and the overflowing lattice oxygen can promote the cracking of methane and the elimination of carbon deposit species, thereby improving the stability and the carbon deposit resistance of the catalyst.
Preferably, in the catalyst carrier, CeO is mixed2The proportion is 1.0 to 6.0 percent of the total weight of the mixed carrier; the methane arylIn the structured catalyst, the mass content of Mo element is 0.5-9.0%, and the element mass ratio of Mo and Fe is 0.78-5.23. By adopting the optimized proportion, the prepared catalyst has better arene selectivity and carbon deposit resistance.
The present invention further provides a method for preparing the aforementioned methane aromatization catalyst, which comprises the steps of:
1) preparing a catalyst carrier, wherein the catalyst carrier is an HMCM-22 molecular sieve or an HMCM-22 molecular sieve and CeO2A mixture of (a);
2) respectively impregnating the catalyst carrier in a Mo impregnation solution and a Fe impregnation solution to load Mo and Fe bimetallic components;
3) and drying and roasting the impregnated catalyst carrier to obtain the methane aromatization catalyst.
Preferably, in the step 2), the impregnation solution of Mo is ammonium molybdate ((NH)4)6Mo7O24) The dipping solution of the Fe is ferric chloride (FeCl)3) Solution or ferric nitrate (Fe (NO)3)3) A solution or a mixture of both.
Preferably, in the step 1), the catalyst carrier is HMCM-22 molecular sieve and CeO2In which CeO is present2The content of (A) is 1.0-6.0% of the total weight of the mixed carrier.
Preferably, in the step 2), the impregnation time of the catalyst carrier in the two impregnation solutions is 12-24 hours respectively; in the step 3), the drying temperature is 90-120 ℃, and the drying time is 12-24 h.
Preferably, in step 1), the step of preparing the HMCM-22 molecular sieve comprises:
1.1) sodium metaaluminate, sodium hydroxide, alkaline silica sol, Hexamethyleneimine (HMI), surfactant C18-6-6(OH)2(cation of the ionic surfactant is C18H37-N+(CH3)2-C6H12-N+(CH3)2-C6H13The anion is OH-) And water according to a certain proportionThe mixture is uniformly mixed according to the proportion, so that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝25～35，NaOH/SiO2＝0.14～0.22，HMI/SiO2＝0.3～0.4，C18-6-6(OH)2/SiO2＝0.02～0.08，H2O/SiO215 to 30 of SiO2The basic silica sol is represented by SiO2Calculated mole number, Al2O3Represents sodium metaaluminate by Al2O3The counted mole number;
1.2) crystallizing, filtering, washing, drying and roasting the obtained mixed solution, and then adopting NH4NO3And (3) carrying out ion exchange on the solution to convert the sodium type molecular sieve into an ammonium type molecular sieve, and filtering, washing, drying and roasting the ammonium type molecular sieve again to obtain the HMCM-22 molecular sieve with a layered structure.
Compared with the conventional MCM-22 molecular sieve, the scheme adds the surfactant C in the synthesis process18-6-6(OH)2The surfactant has the functions of a structure directing agent and a template agent, simultaneously has a hydrophilic group and a hydrophobic group, enhances the solvation effect of hydrothermal reaction, can be embedded into a molecular sieve framework to accelerate the crystallization process of the MCM-22 molecular sieve, can be used for preparing the HMCM-22 molecular sieve with a specific layered structure, and can be used for controlling and synthesizing the molecular sieve with a certain lamellar thickness and lamellar distance by utilizing the advantages of a long carbon chain of the molecule. The molecular sieve has higher relative crystallinity, larger specific surface area and mesoporous pore volume, regular appearance and ordered layer shape, the physical and chemical properties are favorable for dispersing active components Mo and Fe, the methane aromatization reaction is favorably carried out, the carbon deposition resistance and the carbon containing capacity are stronger, the diffusion resistance of reactants and products in a catalyst can be reduced, the occurrence probability of secondary reaction can be reduced, the coking inactivation is slowed down, and the microporous structure is favorable for improving the shape selective selectivity of aromatic hydrocarbon products (particularly benzene).
Preferably, the specific steps of step 1.2) are: A) transferring the mixed solution into a crystallization kettle, and crystallizing for 5-7 days at 150-180 ℃; B) filtering out the solid obtained after crystallization, and washing the solid with deionized water until the solid is neutral; drying at 90-120 ℃ for 12-24 h, and baking at 500-550 DEG CBurning for 6-12 h; C) finally, NH with the concentration of 0.5-2 mol/L is used4NO3Carrying out ion exchange on the solution, wherein the ion exchange condition is that the solution is exchanged for 1-3 h at 80-100 ℃; D) repeating the processes of filtering, washing, drying and roasting according to the same operation and conditions to obtain the HMCM-22 molecular sieve.
The invention also provides the application of the methane aromatization catalyst in preparing aromatic hydrocarbon by methane conversion reaction, in a reactor for preparing aromatic hydrocarbon by methane, the methane aromatization catalyst provided by the invention is adopted to replace the conventional methane aromatization catalyst, and the catalyst is suitable for various reactors such as fixed beds, fluidized beds and the like.
Compared with the prior art, the invention has the beneficial effects that:
1) the methane aromatization catalyst utilizes the characteristic of HMCM-22 layered structure, has larger specific surface area and smaller diffusion resistance, can load more active components, is beneficial to the dispersion of the active components, and has better conversion rate and stability in the process of preparing aromatic hydrocarbon from methane.
2) The methane aromatization catalyst is reasonably prepared by adding the action strength between Mo and an auxiliary agent Fe according to a proportion, the yield of aromatic hydrocarbon, particularly benzene, is obviously improved after Fe modification, and the carbon deposition inactivation rate is obviously slowed down.
3) The invention has the advantages of obviously improved catalyst structure and methane aromatization performance, relatively simple catalyst preparation and reaction process and favorable industrial application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of the HMCM-22 molecular sieve with ordered layers prepared in examples 4-6 and 10-15.
Detailed Description
The present invention is further illustrated in detail by the following specific examples, while giving a conventional MCM-22 supported Mo catalyst as a comparison.
Comparative example
The comparative example prepared a methane aromatization catalyst according to the following steps:
conventional molecular sieves were prepared according to conventional methods: meta-aluminateSodium, sodium hydroxide, alkaline silica sol, hexamethylene imine (HMI) according to a certain molar ratio SiO2/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 7 days at 150 ℃. Filtering the solid obtained after crystallization, washing the solid with deionized water to be neutral, drying the solid at 105 ℃ overnight, and roasting the solid at 550 ℃ for 12 hours. Finally, 1mol/L NH is used4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
And (3) soaking the prepared molecular sieve in an ammonium molybdate aqueous solution in the same volume to obtain the Mo/HMCM-22 with the mass fraction of 4% load, which is named as 4% Mo/HMCM-22 (N). The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
Applying 4% Mo/HMCM-22(N) catalyst in continuous flow micro fixed integral bed reactor for methane aromatization reaction, the catalyst dosage is 0.25g, and the raw material gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. The flow rate of the reaction off-gas was measured by a soap film flow meter.
Example 1
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.02，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the crystallized solid, washing with deionized water to neutral, drying at 105 deg.C for 12 hr, and cooling at 550 deg.CAnd (5) roasting for 12 hours. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Soaking prepared HMCM-22 in ammonium molybdate (NH) in equal volume4)6MoO24·4H2And obtaining the Mo/HMCM-22 with the mass fraction of 0.5 percent of load by using an aqueous solution of O, and naming the Mo/HMCM-22 as 0.5 percent. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
The 0.5% Mo/HMCM-22 catalyst is applied to a continuous flow miniature fixed integral bed reactor for methane aromatization reaction, the catalyst dosage is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. The flow rate of the reaction off-gas was measured by a soap film flow meter.
Example 2
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.02，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the crystallized solid, washing with deionized water to neutrality, drying at 105 deg.C for 12 hr, and calcining at 550 deg.C for 12 hr. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Soaking prepared HMCM-22 in ammonium molybdate (NH) in equal volume4)6MoO24·4H2An aqueous solution of O to obtain a mass fractionWas 4% Mo/HMCM-22, designated 4% Mo/HMCM-22. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
The 4% Mo/HMCM-22 catalyst is applied to a continuous flow micro fixed integral bed reactor for methane aromatization reaction, the catalyst dosage is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. The flow rate of the reaction off-gas was measured by a soap film flow meter.
Example 3
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.02，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the crystallized solid, washing with deionized water to neutrality, drying at 105 deg.C for 12 hr, and calcining at 550 deg.C for 12 hr. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Soaking prepared HMCM-22 in ammonium molybdate (NH) in equal volume4)6MoO24·4H2And obtaining an aqueous solution of O, wherein the mass fraction of the Mo/HMCM-22 is 9 percent of load, and the Mo/HMCM-22 is named as 9 percent. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
Application of 9% Mo/HMCM-22 catalyst in continuous flow micro fixed integral bed reactionCarrying out methane aromatization reaction in a reactor, wherein the dosage of the catalyst is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. The flow rate of the reaction off-gas was measured by a soap film flow meter.
Example 4
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.05，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the crystallized solid, washing with deionized water to neutrality, drying at 105 deg.C for 12 hr, and calcining at 550 deg.C for 12 hr. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Soaking prepared HMCM-22 in ammonium molybdate (NH) in equal volume4)6MoO24·4H2And obtaining the Mo/HMCM-22 with the mass fraction of 0.5 percent of load by using an aqueous solution of O, and naming the Mo/HMCM-22 as 0.5 percent. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
The 0.5% Mo/HMCM-22 catalyst is applied to a continuous flow miniature fixed integral bed reactor for methane aromatization reaction, the catalyst dosage is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. Reaction tailThe flow rate of the gas was measured by a soap film flow meter.
Example 5
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.05，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the crystallized solid, washing with deionized water to neutrality, drying at 105 deg.C for 12 hr, and calcining at 550 deg.C for 12 hr. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Soaking prepared HMCM-22 in ammonium molybdate (NH) in equal volume4)6MoO24·4H2And obtaining the Mo/HMCM-22 with the mass fraction of 4% load by using an aqueous solution of O, and naming the Mo/HMCM-22 as 4%. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
The 4% Mo/HMCM-22 catalyst is applied to a continuous flow micro fixed integral bed reactor for methane aromatization reaction, the catalyst dosage is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. The flow rate of the reaction off-gas was measured by a soap film flow meter.
Example 6
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements:SiO2/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.05，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the crystallized solid, washing with deionized water to neutrality, drying at 105 deg.C for 12 hr, and calcining at 550 deg.C for 12 hr. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Soaking prepared HMCM-22 in ammonium molybdate (NH) in equal volume4)6MoO24·4H2And obtaining an aqueous solution of O, wherein the mass fraction of the Mo/HMCM-22 is 9 percent of load, and the Mo/HMCM-22 is named as 9 percent. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
The 9% Mo/HMCM-22 catalyst is applied to a continuous flow micro fixed integral bed reactor for methane aromatization reaction, the catalyst dosage is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. The flow rate of the reaction off-gas was measured by a soap film flow meter.
Example 7
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.08，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the solid obtained after crystallization, washing the solid with deionized water to be neutral,drying at 105 deg.C for 12 hr, and calcining at 550 deg.C for 12 hr. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Soaking prepared HMCM-22 in ammonium molybdate (NH) in equal volume4)6MoO24·4H2And obtaining the Mo/HMCM-22 with the mass fraction of 0.5 percent of load by using an aqueous solution of O, and naming the Mo/HMCM-22 as 0.5 percent. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
The 0.5% Mo/HMCM-22 catalyst is applied to a continuous flow miniature fixed integral bed reactor for methane aromatization reaction, the catalyst dosage is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. The flow rate of the reaction off-gas was measured by a soap film flow meter.
Example 8
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.08，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the crystallized solid, washing with deionized water to neutrality, drying at 105 deg.C for 12 hr, and calcining at 550 deg.C for 12 hr. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Soaking prepared HMCM-22 in ammonium molybdate (NH) in equal volume4)6MoO24·4H2And obtaining the Mo/HMCM-22 with the mass fraction of 4% load by using an aqueous solution of O, and naming the Mo/HMCM-22 as 4%. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
The 4% Mo/HMCM-22 catalyst is applied to a continuous flow micro fixed integral bed reactor for methane aromatization reaction, the catalyst dosage is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. The flow rate of the reaction off-gas was measured by a soap film flow meter.
Example 9
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.08，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the crystallized solid, washing with deionized water to neutrality, drying at 105 deg.C for 12 hr, and calcining at 550 deg.C for 12 hr. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Soaking prepared HMCM-22 in ammonium molybdate (NH) in equal volume4)6MoO24·4H2And obtaining an aqueous solution of O, wherein the mass fraction of the Mo/HMCM-22 is 9 percent of load, and the Mo/HMCM-22 is named as 9 percent. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
9% Mo/HMCM-22 catalyst applicationCarrying out methane aromatization reaction in a continuous flow miniature fixed integral bed reactor, wherein the dosage of the catalyst is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. The flow rate of the reaction off-gas was measured by a soap film flow meter.
Example 10
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.05，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the crystallized solid, washing with deionized water to neutrality, drying at 105 deg.C for 12 hr, and calcining at 550 deg.C for 12 hr. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Soaking prepared HMCM-22 in ammonium molybdate (NH) in equal volume4)6Mo7O24·4H2O and iron nitrate (Fe (NO)3)3·9H2O) to give 4% Mo 0.64% Fe/HMCM-22 with a mass fraction of 4% Mo loading and 0.64% Fe loading, named 4% Mo 0.64% Fe/HMCM-22, wherein the mass ratio Mo/Fe is 6.25. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
The 4% Mo0.64% Fe/HMCM-22 catalyst is applied to a continuous flow miniature fixed integral bed reactor for methane aromatization reaction, the catalyst dosage is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is atFurther dehydrating and deoxidizing before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. The flow rate of the reaction off-gas was measured by a soap film flow meter.
Example 11
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.05，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the crystallized solid, washing with deionized water to neutrality, drying at 105 deg.C for 12 hr, and calcining at 550 deg.C for 12 hr. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Soaking prepared HMCM-22 in ammonium molybdate (NH) in equal volume4)6Mo7O24·4H2O and iron nitrate (Fe (NO)3)3·9H2O) to give 4% Mo 1.3% Fe/HMCM-22 with a mass fraction of 4% Mo loading and 1.3% Fe loading, named 4% Mo 1.3% Fe/HMCM-22, wherein the mass ratio Mo/Fe is 3.08. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
The 4% Mo1.3% Fe/HMCM-22 catalyst is applied to a continuous flow miniature fixed integral bed reactor for methane aromatization reaction, the dosage of the catalyst is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. Reaction ofThe flow rate of the tail gas was measured by a soap film flow meter.
Example 12
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.05，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the crystallized solid, washing with deionized water to neutrality, drying at 105 deg.C for 12 hr, and calcining at 550 deg.C for 12 hr. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Soaking prepared HMCM-22 in ammonium molybdate (NH) in equal volume4)6Mo7O24·4H2O and iron nitrate (Fe (NO)3)3·9H2O) to give 4% Mo 1.72% Fe/HMCM-22 with a mass fraction of 4% Mo loading and 1.72% Fe loading, named 4% Mo 1.72% Fe/HMCM-22, where the mass ratio Mo/Fe is 2.33. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
The 4% Mo1.72% Fe/HMCM-22 catalyst is applied to a continuous flow miniature fixed integral bed reactor for methane aromatization reaction, the catalyst dosage is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. The flow rate of the reaction off-gas was measured by a soap film flow meter.
Example 13
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate and oxyhydrogenSodium hydroxide, alkaline silica sol, hexamethyleneimine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.05，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the crystallized solid, washing with deionized water to neutrality, drying at 105 deg.C for 12 hr, and calcining at 550 deg.C for 12 hr. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Mixing the prepared HMCM-22 and CeO2After mixing homogeneously (CeO)2Equal volume of impregnated ammonium molybdate (NH) (/ total support 1.0%)4)6Mo7O24·4H2O and iron nitrate (Fe (NO)3)3·9H2O) to obtain 4% Mo1.3% Fe/HMCM-22 and CeO with the mass fractions of 4% Mo load and 1.3% Fe load2Composite catalyst named 4% Mo1.3% Fe/HMCM-22&CeO2-1.0, wherein the mass ratio Mo/Fe is 3.08. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
4％Mo1.3％Fe/HMCM-22&CeO2-1.0 catalyst is applied to a continuous flow micro fixed integral bed reactor for methane aromatization reaction, the dosage of the catalyst is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. The flow rate of the reaction off-gas was measured by a soap film flow meter.
Example 14
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate, sodium hydroxide, alkaline silica sol and hexaMethylene imine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.05，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the crystallized solid, washing with deionized water to neutrality, drying at 105 deg.C for 12 hr, and calcining at 550 deg.C for 12 hr. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Mixing the prepared HMCM-22 and CeO2After mixing homogeneously (CeO)2Equal volume of impregnated ammonium molybdate (NH) per total amount of support 3.5%4)6Mo7O24·4H2O and iron nitrate (Fe (NO)3)3·9H2O) to obtain HMCM-22 and CeO with the mass fractions of 4% Mo load and 1.3% Fe load2Composite catalyst named 4% Mo1.3% Fe/HMCM-22&CeO2-3.5, wherein the mass ratio Mo/Fe is 3.08. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
4％Mo1.3％Fe/HMCM-22&CeO2-3.5 catalyst is applied to a continuous flow micro fixed integral bed reactor for methane aromatization reaction, the dosage of the catalyst is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. The flow rate of the reaction off-gas was measured by a soap film flow meter.
Example 15
1) Preparing a layered HMCM-22 molecular sieve: sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine and surfactant C18-6-6(OH)2Uniformly mixing according to a certain proportion to ensure that the mixing molar ratio meets the following requirements: SiO 22/Al2O3＝39，Na/SiO2＝0.18，HMI/SiO2＝0.35，C18-6-6(OH)2/SiO2＝0.05，H2O/SiO219.8, transferring the mixture to a crystallization kettle for crystallization for 5 days at 150 ℃. Filtering the crystallized solid, washing with deionized water to neutrality, drying at 105 deg.C for 12 hr, and calcining at 550 deg.C for 12 hr. Finally using 1mol/L NH4NO3And (3) carrying out ion exchange on the solution, and repeating the processes of filtering, washing, drying and roasting to obtain the HMCM-22.
2) Mixing the prepared HMCM-22 and CeO2After mixing homogeneously (CeO)2Equal volume of impregnated ammonium molybdate (NH) (-) 6.0% total support4)6Mo7O24·4H2O and iron nitrate (Fe (NO)3)3·9H2O) to obtain HMCM-22 and CeO with the mass fractions of 4% Mo load and 1.3% Fe load2Composite catalyst named 4% Mo1.3% Fe/HMCM-22&CeO2-6, wherein the mass ratio Mo/Fe is 3.08. The impregnated sample is dried in a water bath, dried in air at 120 ℃ for 12h and finally calcined in a muffle furnace. And tabletting, grinding and sieving the roasted sample to obtain 20-40 mesh particles for activity test.
4％Mo1.3％Fe/HMCM-22&CeO2-6 catalysts are applied to a continuous flow micro fixed integral bed reactor for methane aromatization reaction, the dosage of the catalysts is 0.25g, and the feed gas is CH4(99.995%) and Ar (99.995%). CH (CH)4And Ar is further dehydrated and deoxidized before entering the reactor. The catalyst was raised in Ar to a reaction temperature of 700 ℃ at a rate of 6 ℃/min, CH4The flow rate was fixed at 8.0ml/min and the reaction pressure was atmospheric. The flow rate of the reaction off-gas was measured by a soap film flow meter.
Effect verification:
the HMCM-22 molecular sieve prepared in the step 1) of the embodiments 4-6 and 10-15 is observed under a scanning electron microscope, and an obtained photo is shown in figure 1, and as can be seen from figure 1, the HMCM-22 molecular sieve is regular in shape and is in an ordered layered shape, so that the dispersion of active components is facilitated, and the shape selectivity, carbon deposition resistance and carbon capacity of the catalyst are increased.
The BET data of the methane aromatization catalyst prepared in the examples was tested as follows: the specific surface area and pore volume, pore size, etc. of the sample were measured on a micromeriticsASAP-2000. And (3) carrying out vacuum pretreatment on the powder sample at 393K, and carrying out isothermal adsorption on liquid nitrogen to obtain an adsorption-desorption isothermal line. And calculating parameters such as specific surface area, pore volume, pore diameter and the like of the sample by adopting a BET multilayer adsorption theory, and calculating by using a BJH equation. The results obtained are shown in Table 1 below.
TABLE 1 BET data for the catalysts in the examples
Figure BDA0001489404950000181
Figure BDA0001489404950000191
Analyzing results of methane aromatization reaction of comparative example and each example to obtain CH4Conversion, and C in the product6H6、CH3-C6H5、C2H4And C2H6The results obtained are shown in table 2 below.
TABLE 2 reaction performance for producing aromatic hydrocarbons from methane in each comparative example
Figure BDA0001489404950000192
Figure BDA0001489404950000201
Note: CH in Table 24conv refers to methane conversion and selectivity refers to the ratio of the amount of methane consumed by the products in the methane aromatization reaction to the total amount of methane consumed by the products in the list.
As can be seen from the data in tables 1 and 2, compared with the conventional Mo/MCM-22, the molecular sieve sample added with the surfactant has larger specific surface area and pore volume, especially the mesoporous volume is obviously increased, and the anti-carbon deposition and carbon holding capacity of the catalyst are favorably improved.
After further loading of the bimetallic component, the methane conversion and benzene selectivity were further improved, with 4% Mo1.3% Fe/HMCM-22 (example 11) at 160min of reaction having a methane conversion of 13.79% and benzene selectivity of 97.33%, which was clearly better than the comparative example.
Further HMCM-22 and CeO24% Mo1.3% Fe/HMCM-22 prepared after loading the bimetallic component on the support&CeO2-3 (example 14), at 700min of reaction, the methane conversion is 11.02%, the benzene selectivity is 97.51%, and the catalyst prepared performs the best methane aromatization reaction. Further illustrates the use of a layered MCM-22 molecular sieve and CeO2The catalyst which is a dual-carrier and loads Mo and Fe double-metal components well improves methane aromatization reaction, can obviously improve methane conversion rate and benzene selectivity, and the MoFe/HMCM-22 and CeO2The composite catalyst system can obviously slow down carbon deposition in the reaction process and improve the stability of the catalyst. The application of the catalyst in a circulating fluidized bed reactor can conveniently realize the regeneration of the deactivated catalyst, so the process has good industrial application prospect.

Claims (9)

1. A methane aromatization catalyst characterized by: the catalyst is HMCM-22 molecular sieve or mixed with CeO2The HMCM-22 molecular sieve is a catalyst carrier, and the methane aromatization catalyst is obtained by impregnating and loading Mo and Fe bimetallic components; in the catalyst, the mass content of Mo element is 0.5-10.0%, and the element mass ratio of Mo to Fe is 0.2-7.0;
the preparation method of the HMCM-22 molecular sieve comprises the following steps:
1.1) mixing sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine HMI and surfactant C18-6-6(OH)2Mixing with water to ensure that the mixed molar ratio satisfies the following condition: c18-6-6(OH)2/SiO20.02-0.08; the surfactant C18-6-6(OH)2The cation of (A) is C18H37-N+(CH3)2-C6H12-N+(CH3)2-C6H13The anion is OH-；
1.2) crystallizing, filtering, washing, drying and roasting the obtained mixed solution, and then adopting NH4NO3And (3) carrying out ion exchange on the solution to convert the sodium type molecular sieve into an ammonium type molecular sieve, and filtering, washing, drying and roasting the ammonium type molecular sieve again to obtain the HMCM-22 molecular sieve with a layered structure.
2. A methane aromatization catalyst according to claim 1 characterized in that: when the catalyst carrier is mixed with CeO2When being CeO2The content of (A) is 0.5-10.0% of the total weight of the mixed carrier.
3. A methane aromatization catalyst according to claim 2 characterized in that: in the catalyst carrier, mixed CeO2The proportion is 1.0 to 6.0 percent of the total weight of the mixed carrier; in the methane aromatization catalyst, the mass content of Mo element is 0.5-9.0%, and the element mass ratio of Mo to Fe is 0.78-5.23.
4. A method of preparing a methane aromatization catalyst according to claim 1 wherein: the method comprises the following steps:
1) preparing a catalyst carrier, wherein the catalyst carrier is an HMCM-22 molecular sieve or an HMCM-22 molecular sieve and CeO2A mixture of (a); wherein, the preparation steps of the HMCM-22 molecular sieve comprise:
1.1) mixing sodium metaaluminate, sodium hydroxide, alkaline silica sol, hexamethyleneimine HMI and surfactant C18-6-6(OH)2Mixing with water to ensure that the mixed molar ratio satisfies the following condition: c18-6-6(OH)2/SiO20.02-0.08; the surfactant C18-6-6(OH)2The cation of (A) is C18H37-N+(CH3)2-C6H12-N+(CH3)2-C6H13The anion is OH-；
1.2) crystallizing, filtering, washing, drying and roasting the obtained mixed solution, and then adopting NH4NO3Performing ion exchange on the solution to convert the sodium molecular sieve into an ammonium molecular sieve, and filtering, washing, drying and roasting the ammonium molecular sieve again to obtain the HMCM-22 molecular sieve with a layered structure;
2) respectively impregnating the catalyst carrier in a Mo impregnation solution and a Fe impregnation solution to load Mo and Fe bimetallic components;
3) and drying, roasting and forming the impregnated catalyst carrier to obtain the methane aromatization catalyst.
5. The method of producing a methane aromatization catalyst according to claim 4 characterized in that: in the step 2), the Mo impregnation solution is an ammonium molybdate solution, and the Fe impregnation solution is an iron chloride solution or an iron nitrate solution or a mixture of the iron chloride solution and the iron nitrate solution.
6. The method of producing a methane aromatization catalyst according to claim 4 characterized in that: in the step 1), the catalyst carrier is HMCM-22 molecular sieve and CeO2In which CeO is present2The content of (A) is 1.0-6.0% of the total weight of the mixture.
7. The method of producing a methane aromatization catalyst according to claim 4 characterized in that: in the step 3), the drying temperature is 90-120 ℃, and the drying time is 12-24 h.
8. The method for producing a methane aromatization catalyst according to any one of claims 4 to 7 wherein: the specific steps of step 1.2) are as follows: A) transferring the mixed solution into a crystallization kettle, and crystallizing for 5-7 days at 150-180 ℃; B) filtering out the solid obtained after crystallization, and washing the solid with deionized water until the solid is neutral; drying at 90-120 deg.C for 12-24 hr, and then at 500-550 deg.CRoasting for 6-12 h; C) finally, NH with the concentration of 0.5-2 mol/L is used4NO3Carrying out ion exchange on the solution, wherein the ion exchange condition is that the solution is exchanged for 1-3 h at 80-100 ℃; D) repeating the processes of filtering, washing, drying and roasting according to the same operation and conditions to obtain the HMCM-22 molecular sieve.
9. The methane aromatization catalyst according to claim 1 or 2 is applied to the methane conversion reaction to prepare aromatic hydrocarbon.
CN201711238243.9A 2017-11-30 2017-11-30 Methane aromatization catalyst and preparation method and application thereof Active CN107952474B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711238243.9A CN107952474B (en) 2017-11-30 2017-11-30 Methane aromatization catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711238243.9A CN107952474B (en) 2017-11-30 2017-11-30 Methane aromatization catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN107952474A CN107952474A (en) 2018-04-24
CN107952474B true CN107952474B (en) 2020-09-01

Family

ID=61962760

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711238243.9A Active CN107952474B (en) 2017-11-30 2017-11-30 Methane aromatization catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN107952474B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1491747A (en) * 2002-10-25 2004-04-28 中国科学院大连化学物理研究所 Metal load type molecular sieve catalyst and preparing method and use
CN101618337A (en) * 2009-08-03 2010-01-06 大连理工大学 Method for improving catalytic property of methane aromatization catalyst

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6552243B2 (en) * 2000-07-27 2003-04-22 Conoco Phillips Company Catalyst and process for aromatic hydrocarbons production from methane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1491747A (en) * 2002-10-25 2004-04-28 中国科学院大连化学物理研究所 Metal load type molecular sieve catalyst and preparing method and use
CN101618337A (en) * 2009-08-03 2010-01-06 大连理工大学 Method for improving catalytic property of methane aromatization catalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Cooperative Structure Direction of Diammonium Surfactants and Sodium Ions to Generate MFI Zeolite Nanocrystals of Controlled Thickness;Youngjin Kim et al.;《CHEMISTRY OF MATERIALS》;20170131;第29卷;第1752–1757页 *
One-pot synthesis of MWW zeolite nanosheets using a rationally designed organic structure-directing agent;Helen Y. Luo et al.;《Chemical Science》;20150722;第6卷;第6320–6324页 *

Also Published As

Publication number Publication date
CN107952474A (en) 2018-04-24

Similar Documents

Publication Publication Date Title
CN110614116A (en) Non-noble metal low-carbon alkane dehydrogenation catalyst, preparation method thereof and method for preparing low-carbon olefin by low-carbon alkane dehydrogenation
CN107899619B (en) A kind of preparing propylene by dehydrogenating propane composite alumina support catalyst and preparation method thereof
CN105502433B (en) A kind of preparing gasoline by methanol catalyst nano Zn ZSM 5 preparation method
CN115007197B (en) Multistage hole ZSM-5 molecular sieve encapsulated Ni metal catalyst with micropores and mesopores, and preparation method and application thereof
CN114558612A (en) Hierarchical pore ZSM-5 molecular sieve packaged Pt-Ni bimetallic catalyst and preparation method and application thereof
CN114570415B (en) Pt @ hierarchical pore zeolite catalyst for preparing propylene by propane dehydrogenation and preparation method thereof
CN106391106B (en) A kind of preparation method of the core-shell structure molecular sieve containing metal
CN117225400B (en) Modified alumina carrier, preparation method and application
CN110694673A (en) Aromatization catalyst of waste edible oil and preparation method and application thereof
Sumi et al. Mg and Zn co-doped mesoporous ZSM-5 as an ideal catalyst for ethane dehydroaromatization reaction
CN108014795A (en) A kind of propane dehydrogenation catalyst and its preparation method and application
Zhao et al. Effect of calcination temperature on structure, composition and properties of S 2 O 8 2−/ZrO 2 and its catalytic performance for removal of trace olefins from aromatics
CN114073976B (en) Modified ZSM-5 molecular sieve and preparation method and application thereof
CN103159578A (en) Method using molecular sieve catalyst immobilized with gold to transform low-carbon hydrocarbon into aromatic hydrocarbon
CN111250096A (en) Non-noble metal isobutane dehydrogenation catalyst with hexagonal mesoporous material as carrier and preparation method and application thereof
CN107952474B (en) Methane aromatization catalyst and preparation method and application thereof
CN106669652B (en) A kind of catalysis ethanol prepares the catalyst and its preparation process and application method of low-carbon alkene
CN110170333B (en) Catalyst for preparing ethylene from ethane in carbon dioxide atmosphere and preparation method thereof
CN106391100B (en) A kind of modified IM-5 molecular sieve and its preparation method and application
CN109569703B (en) Catalyst for producing gasoline component from naphtha and methanol, preparation method and application
CN112108180A (en) Catalyst for preparing low-carbon olefin by directly converting synthesis gas and preparation method thereof
CN111135852A (en) Non-noble metal isobutane dehydrogenation catalyst with rodlike mesoporous molecular sieve as carrier and preparation method and application thereof
US11097263B2 (en) Aromatization catalyst, preparation method, regeneration method thereof, and aromatization method
CN109529911B (en) Platinum-tin-based mesoporous catalyst for propane anaerobic dehydrogenation and preparation and application thereof
CN110871106B (en) Preparation method of ethane and propane conversion catalyst capable of running stably

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