CN110102336A - A kind of composite catalyst and its preparation method and application for methane non oxidative aromatization synthesis benzene - Google Patents

A kind of composite catalyst and its preparation method and application for methane non oxidative aromatization synthesis benzene Download PDF

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CN110102336A
CN110102336A CN201910502663.6A CN201910502663A CN110102336A CN 110102336 A CN110102336 A CN 110102336A CN 201910502663 A CN201910502663 A CN 201910502663A CN 110102336 A CN110102336 A CN 110102336A
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catalyst
methane
base solid
benzene
molecular sieve
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孙建平
王磊
张国权
张生军
闵小建
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Shaanxi Coal and Chemical Technology Institute Co Ltd
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Shaanxi Coal and Chemical Technology Institute Co Ltd
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    • 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
    • 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
    • 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
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • 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

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  • Crystallography & Structural Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The present invention provides a kind of composite catalyst and the preparation method and application thereof for methane aromatizing synthesis benzene.Including Mo base solid catalyst and hydrogen-absorbing material, Mo base solid catalyst includes molecular sieve carrier, and the active component Mo, the auxiliary agent M that are supported on molecular sieve carrier1With auxiliary agent M2；M1For Fe, Co, Ni or Ru, M2For Mg, Mn, Cu or Rh；Hydrogen-absorbing material is Zr, Ti or ZrTi alloy.According to mass percentage, Mo, M in Mo base solid catalyst1And M2Content be respectively 2%~10%, 0.1%~1.5% and 0.05%~0.5%, the mass ratio of Mo base solid catalyst and hydrogen-absorbing material is 1:(1~3).Catalyst of the present invention significantly improves the conversion ratio of methane and the yield of product benzene.

Description

A kind of composite catalyst and its preparation side for methane non oxidative aromatization synthesis benzene Method and application
Technical field
The invention belongs to technical field of chemical engineering catalysts, and in particular to a kind of catalyst for methane aromatization, Relate more specifically to a kind of composite catalyst and its preparation method and application for methane non oxidative aromatization synthesis benzene.
Background technique
In recent years, shale gas, coal bed gas flourish in the whole world, after from the research of shale gas geological conditions, " dessert area " Competition and the probing of evaluation well and exploration and development early-stage preparations, to marine facies shale gas industrialization Mining Test, transitional facies and land Phase shale gas exploration assessment two develops on a large scale the stage, just orderly to marine facies shale gas scale exploitation, transitional facies and terrestrial facies page Rock gas industrializes Mining Test progress step by step；And coal gas industry experienced breakthrough period at -2009 years 2001, from 2010 years to The present enters fast-developing initial stage, has preliminarily formed the big industrial base of Qinshui basin and Eastern Margin of Ordos Basin etc. two at present.
The concern of various countries is also increasingly caused as shale gas and the effective use of the methane of coal bed gas main component.Working as Modern Energy situation is sharply in the case where upheaval, and the optimization based on low-carbon economy considers and the requirement of ecological environmental protection, further It efficiently utilizes and has important practical significance containing methane resource.
It is well known that benzene and downstream aromatic compound are important basic chemical industry raw material, occupy in economy important Status.Currently, benzene and downstream aromatic compound mainly pass through petroleum catalytic reforming, naphtha cracking, toluene disproportionation, first The techniques such as benzene hydrogenation dealkylation are made；It is obtained on a small quantity from the techniques such as coke furnace light oil and coal tar oil extract coking benzene.As it can be seen that benzene Source it is single, the synthesis path for innovating benzene is one of important topic that chemical industry faces.
In the nineties in last century, the Dalian Chemistry and Physics Institute reports methane for the first time can be highly selective on Mo/HZSM-5 catalyst One step of ground generates the aromatic compounds such as benzene (Catalysis Letters, 1993,21 (1/2): 35), a large amount of to make full use of Methane resource provides a new approach.For reaction temperature at 1073K, product is mainly H2, benzene, naphthalene and a small amount of C2With Toluene, wherein the selectivity of benzene and naphthalene can respectively reach 60-70% and 10-20%, C2And the selectivity of toluene is 5% or so, Remaining mainly carbon deposit.The process directly converts liquid aromatic hydrocarbons compound products for methane by catalytic dehydrogenation, while secondary The hydrogen for producing high added value all has great importance in industry and scientific research.But the reaction is limited by thermodynamics, methane turns Rate is low, and in order to solve this problem, researchers attempt to add activity and stabilization of the various metal promoters to improve catalyst Property, such as Xu Yide report methane in patent document CN1167653 and are being added to the second component R (R=La, Ce, Pr, Nd) Mo-R/HZSM-5 catalyst action under carry out aromatization process, but thermodynamic (al) limitation can not be broken, methane conversion is still It is lower.
Currently, having carried out a large amount of work to the research of pure methane aromatisation both at home and abroad, but it is not involved with compound urge The report of agent.Therefore, develop it is a kind of for methane non oxidative aromatization synthesis benzene composite catalyst to Gas Industry have There is important realistic meaning.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of for the compound of methane non oxidative aromatization synthesis benzene Type catalyst and its preparation method and application breaks the yield that thermodynamical equilibrium substantially increases methane conversion and benzene.
The present invention is to be achieved through the following technical solutions:
A kind of composite catalyst for methane non oxidative aromatization synthesis benzene, comprising: Mo base solid catalyst and suction hydrogen Material；Mo base solid catalyst includes molecular sieve carrier, and the active component Mo, the auxiliary agent M that are supported on molecular sieve carrier1With Auxiliary agent M2；M1For Fe, Co, Ni or Ru, M2For Mg, Mn, Cu or Rh；Hydrogen-absorbing material is Zr, Ti or ZrTi alloy.
Preferably, according to mass percentage, Mo, M in Mo base solid catalyst1And M2Content be respectively 2%~ 10%, 0.1%~1.5% and 0.05%~0.5%, the mass ratio of Mo base solid catalyst and hydrogen-absorbing material is 1:(1~3).
Preferably, molecular sieve carrier ZSM-5, ZSM-11, MCM-22 or MCM-49.
Composite catalyst according to claim 1 or 2 for methane non oxidative aromatization synthesis benzene, feature exist In M1For Fe or Co；M2For Mg or Mn；Hydrogen storage material TiZr alloy.
A kind of preparation method of the composite catalyst for methane non oxidative aromatization synthesis benzene, including walk as follows It is rapid:
1) molecular sieve carrier roasts to 5 at 400~700 DEG C~for 24 hours；
2) by the carrier impregnation handled by step 1 to (NH4)6Mo7O24And M1And M2Nitrate aqueous solution in, stir Mix 8~for 24 hours, obtain catalyst precursor；
3) catalyst precursor for obtaining step 2 is dry, then obtains Mo base solid phase in 400~700 DEG C of 1~12h of roasting Catalyst.
4) the pre- 10~60min of carbonization treatment of the Mo base solid catalyst obtained step 3.
5) that the Mo base solid catalyst for the pre- carbonization that step 4 obtains is obtained aromatisation with hydrogen-absorbing material physical mixed is compound Type catalyst.
Preferably, in step 3), drying is specifically: in 90~120 DEG C of dry 4~16h.
Preferably, in step 4), CH is used4Pre- carbonization treatment is carried out, the condition being carbonized in advance are as follows: 550~750 DEG C of temperature, Air speed is 2~15L/gh.
Application of the composite catalyst in oxygen-free aromatization reaction of methane.
Preferably, the reaction condition of methane non oxidative aromatization are as follows: air speed is 5~15L/gh, reaction temperature 600~900 DEG C, reaction pressure is 0.1~3.0MPa.
Compared with prior art, the invention has the following beneficial technical effects:
Methane aromatizing composite catalyst of the present invention by pre- carbonization treatment Mo base solid catalyst and hydrogen-absorbing material object Reason is mixed with, existing Mo base aromatized catalyst by reaction balance restrict, methane conversion is lower, add hydrogen-absorbing material energy and When adsorbed methane aromatization in the hydrogen that generates, help to break reaction balance, the conversion ratio and benzene of methane be substantially improved Yield.Quick carbon distribution inactivation, addition M1 guarantee that it can effectively be removed in the reaction to existing Mo base solid catalyst in the reaction Carbon distribution extends catalyst life, while the CO generated can increase the yield of benzene；M2 is conducive to maintain and activated centre is promoted to divide High dispersive in son sieve makes activated centre not occur to be aggregated and inactivate, by M1And M2It is modified, it can further make methane Conversion ratio and product benzene yield improve, the service life and improved stability of catalyst.
Methane aromatization is carried out using catalyst of the invention, the conversion ratio of methane and the receipts of benzene can be substantially improved Rate.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and It is not to limit.
A kind of composite catalyst for methane non oxidative aromatization synthesis benzene, catalyst system includes: that Mo base solid phase is urged Agent and hydrogen-absorbing material；Mo base solid catalyst includes molecular sieve carrier, and is supported on molecular sieve carrier and is deposited with oxidation state Active component Mo, auxiliary agent M1And M2Composition, molecular sieve carrier ZSM-5, ZSM-11, MCM-22 or MCM-49, M1For Fe, Co, Ni or Ru, M2For Mg, Mn, Cu or Rh；Hydrogen storage material is Zr, Ti or ZrTi alloy.
According to mass percentage, Mo, M in Mo base solid catalyst1And M2Content be respectively 2%~10%, 0.1% ~1.5% and 0.05%~0.5%, it is labeled as xMoyM1zM2/ ZEO, wherein x, y and z respectively indicate Mo, M1And M2Content, ZEO indicates molecular sieve carrier；Hydrogen-absorbing material alloy designation is aZrbTi, wherein a and b respectively indicates the quality percentage of Zr and Ti Than；The mass ratio of Mo base solid catalyst and hydrogen-absorbing material is 1:(1~3).
A kind of preparation method of the composite catalyst for methane non oxidative aromatization synthesis benzene,
Specifically comprise the following steps:
1) molecular sieve carrier roasts to 5 at 400~700 DEG C~for 24 hours；
2) by the carrier impregnation handled by step 1 to (NH4)6Mo7O24And M1And M2Nitrate aqueous solution in, stir Mix 8~for 24 hours；
3) will by the impregnated catalyst precursor of step 2 at 110 DEG C evaporating water, 90-120 DEG C of drying 4~ 16h, 400~700 DEG C of 1~12h of roasting.
4) catalyst fines that step 3 obtains are subjected to tabletting, broken and screening obtains the Mo base solid phases of 40~60 mesh and urges Catalyst particles.
5) catalyst granules for obtaining step 4 uses CH in fixed bed reactors4Pre- carbonization treatment is carried out, is carbonized in advance Condition are as follows: 550~750 DEG C of temperature, air speed is 2~15L/gh, and the time is 10~60min；
6) catalyst of the pre- carbonization treatment of step 5 is drawn off from fixed bed reactors, then the hydrogen-absorbing material with 40~60 mesh Physical mixed obtains aromatized catalyst.
Application of the methane non oxidative aromatization composite catalyst in conversion of methane in, methane non oxidative aromatization it is anti- Answer condition are as follows: air speed is 5~15L/gh, and 600~900 DEG C of reaction temperature, reaction pressure is 0.1~3.0MPa.
Specific embodiment is as follows.
Embodiment 1
1.1 preparation method
2%Mo1.5%Fe0.05%Mg/ZSM-5 catalyst is prepared using co-impregnation.Firstly, ZSM-5 molecular sieve is existed It is roasted for 24 hours at 400 DEG C；Secondly, the ZSM-5 molecular sieve after roasting is impregnated into (NH4)6Mo7O24、Fe(NO3)3With Mg (NO3)2's In aqueous solution (three's mass ratio is 11.4:
8h 21.3:1) is stirred, is evaporated at 110 DEG C, 90 DEG C of dry 16h；8h is roasted at 400 DEG C finally, being put into Muffle furnace, Obtained catalyst fines obtain the Mo base solid catalyst of 40~60 mesh after tabletting, broken and screening.
Above-mentioned Mo base solid catalyst is packed into fixed bed reactors, under conditions of 700 DEG C and air speed are 5L/gh, Pre- carbonization treatment 20min is carried out to catalyst with methane.
The Mo base solid catalyst of above-mentioned pre- carbonization is drawn off, then the metal Zr particle 1:1 in mass ratio with 40~60 mesh Physical mixed is carried out, obtains aromatized catalyst for activity rating.
1.2 evaluation method
It is applied to the catalyst of 1.1 preparations to carry out methane non oxidative aromatization synthesis in the fixed bed reactors of continuous feed The reaction of benzene, catalyst amount 5g, unstripped gas CH4/ Ar (90vol%CH4And 10vol%Ar) gaseous mixture, catalyst exists The composition of catalytic methane aromatization under conditions of 1MPa, 700 DEG C and air speed 5L/gh, reaction product passes through online GC points Analysis.
Embodiment 2
2.1 preparation method
6%Mo0.7%Co0.2%Mn/ZSM-11 catalyst is prepared using co-impregnation.Firstly, by ZSM-11 molecular sieve 12h is roasted at 500 DEG C；Secondly, the ZSM-11 molecular sieve after roasting is impregnated into (NH4)6Mo7O24、Co(NO3)2And Mn (NO3)2Aqueous solution in (three's mass ratio be 16.0:3.3:1) stirring 18h, be evaporated at 110 DEG C, 110 DEG C of dry 12h；Finally, It is put into Muffle furnace and roasts 5h at 500 DEG C, obtained catalyst fines obtain 40-60 purpose after tabletting, broken and screening Mo base solid catalyst.
Above-mentioned Mo base solid catalyst is packed into fixed bed reactors, under conditions of 650 DEG C and air speed are 2L/gh, Pre- carbonization treatment 30min is carried out to catalyst with methane.
The metal Ti particle 1:1.5 in mass ratio of the Mo base solid catalyst of above-mentioned pre- carbonization and 40~60 mesh is subjected to object Reason mixing obtains aromatized catalyst for activity rating.
2.2 evaluation method
It is applied to the catalyst of 2.1 preparations to carry out methane non oxidative aromatization synthesis in the fixed bed reactors of continuous feed The reaction of benzene, catalyst amount 5g, unstripped gas are CH4/Ar (90vol%CH4 and 10vol%Ar) gaseous mixture, and catalyst exists The composition of catalytic methane aromatization under conditions of 2MPa, 800 DEG C and air speed 5L/gh, reaction product passes through online GC points Analysis.
3.1 preparation method
8%Mo1.0%Ni0.1%Cu/MCM-22 catalyst is prepared using co-impregnation.Firstly, by MCM-22 molecular sieve 5h is roasted at 700 DEG C；Secondly, the MCM-22 molecular sieve after roasting is impregnated into (NH4)6Mo7O24、Ni(NO3)2With Cu (NO3)2 Aqueous solution in (three's mass ratio be 50.0:10.6:1) stirring for 24 hours, be evaporated at 110 DEG C, 100 DEG C of dry 4h；Finally, being put into 12h is roasted in Muffle furnace at 700 DEG C, obtained catalyst fines obtain the Mo base of 40-60 mesh after tabletting, broken and screening Solid-phase catalyst.
Above-mentioned Mo base solid catalyst is packed into fixed bed reactors, under conditions of 550 DEG C and air speed are 10L/gh, Pre- carbonization treatment 50min is carried out to catalyst with methane.
By the 30%Zr70%Ti particle 1:2 in mass ratio of the Mo base solid catalyst of above-mentioned pre- carbonization and 40~60 mesh into Row physical mixed obtains aromatized catalyst for activity rating.
3.2 evaluation method
It is applied to the catalyst of 3.1 preparations to carry out methane non oxidative aromatization synthesis in the fixed bed reactors of continuous feed The reaction of benzene, catalyst amount 5g, unstripped gas are CH4/Ar (90vol%CH4 and 10vol%Ar) gaseous mixture, and catalyst exists The composition of catalytic methane aromatization under conditions of 3MPa, 750 DEG C and air speed 10L/gh, reaction product passes through online GC points Analysis.
Embodiment 4
4.1 preparation method
10%Mo0.1%Ru0.5%Rh/MCM-49 catalyst is prepared using co-impregnation.Firstly, by MCM-49 molecular sieve 18h is roasted at 500 DEG C；Secondly, the MCM-49 molecular sieve after roasting is impregnated into (NH4)6Mo7O24、Ru(NO)(NO3)3And Rh (NO3)3Aqueous solution in (three's mass ratio be 55.3:1:4.5) stirring 12h, be evaporated at 110 DEG C, 120 DEG C of dry 8h；Finally, It is put into Muffle furnace and roasts 1h at 500 DEG C, obtained catalyst fines obtain 40-60 purpose after tabletting, broken and screening Mo base solid catalyst.
Above-mentioned Mo base solid catalyst is packed into fixed bed reactors, under conditions of 750 DEG C and air speed are 5L/gh, Pre- carbonization treatment 10min is carried out to catalyst with methane.
By the 50%Zr50%Ti particle 1:3 in mass ratio of the Mo base solid catalyst of above-mentioned pre- carbonization and 40~60 mesh into Row physical mixed obtains aromatized catalyst for activity rating.
4.2 evaluation method
It is applied to the catalyst of 4.1 preparations to carry out methane non oxidative aromatization synthesis in the fixed bed reactors of continuous feed The reaction of benzene, catalyst amount 5g, unstripped gas are CH4/Ar (90vol%CH4 and 10vol%Ar) gaseous mixture, and catalyst exists The composition of catalytic methane aromatization under conditions of 0.1MPa, 600 DEG C and air speed 8L/gh, reaction product passes through online GC Analysis.
Embodiment 5
5.1 preparation method
6%Mo0.5%Fe0.3%Mn/ZSM-5 catalyst is prepared using co-impregnation.Firstly, ZSM-5 molecular sieve is existed It is roasted for 24 hours at 600 DEG C；Secondly, the ZSM-5 molecular sieve after roasting is impregnated into (NH4)6Mo7O24、Fe(NO3)3With Mn (NO3)2's (three's mass ratio is 10.6:2.2:1) stirring for 24 hours, is evaporated, 120 DEG C of dry 12h at 110 DEG C in aqueous solution；Finally, being put into horse 12h is not roasted in furnace at 650 DEG C, the Mo base that obtained catalyst fines obtain 40-60 mesh after tabletting, broken and screening is solid Phase catalyst.
Above-mentioned Mo base solid catalyst is packed into fixed bed reactors, under conditions of 600 DEG C and air speed are 15L/gh, Pre- carbonization treatment 60min is carried out to catalyst with methane.
By the 70%Zr30%Ti particle 1:1 in mass ratio of the Mo base solid catalyst of above-mentioned pre- carbonization and 40~60 mesh into Row physical mixed obtains aromatized catalyst for activity rating.
5.2 evaluation method
It is applied to the catalyst of 5.1 preparations to carry out methane non oxidative aromatization synthesis in the fixed bed reactors of continuous feed The reaction of benzene, catalyst amount 5g, unstripped gas are CH4/Ar (90vol%CH4 and 10vol%Ar) gaseous mixture, and catalyst exists The composition of catalytic methane aromatization under conditions of 0.1MPa, 900 DEG C and air speed 15L/gh, reaction product passes through online GC Analysis.
Embodiment 6
6.1 preparation method
4%Mo0.3%Co0.05%Cu/MCM-22 catalyst is prepared using co-impregnation.Firstly, by MCM-22 molecular sieve 5h is roasted at 500 DEG C；Secondly, the MCM-22 molecular sieve after roasting is impregnated into (NH4)6Mo7O24、Co(NO3)2With Cu (NO3)2 Aqueous solution in (three's mass ratio be 47.0:6.3:1) stirring 18h, be evaporated at 110 DEG C, 120 DEG C of dry 12h；Finally, being put into 5h is roasted in Muffle furnace at 600 DEG C, obtained catalyst fines obtain the Mo base of 40-60 mesh after tabletting, broken and screening Solid-phase catalyst.
Above-mentioned Mo base solid catalyst is packed into fixed bed reactors, under conditions of 700 DEG C and air speed are 5L/gh, Pre- carbonization treatment 30min is carried out to catalyst with methane.
The Mo base solid catalyst of above-mentioned pre- carbonization is drawn off, then presses quality with the 20%Zr80%Ti particle of 40~60 mesh Physical mixed is carried out than 1:2.3, obtains aromatized catalyst for activity rating.
6.2 evaluation method
It is applied to the catalyst of 6.1 preparations to carry out methane non oxidative aromatization synthesis in the fixed bed reactors of continuous feed The reaction of benzene, catalyst amount 5g, unstripped gas CH4/ Ar (90vol%CH4And 10vol%Ar) gaseous mixture, catalyst exists The composition of catalytic methane aromatization under conditions of 1MPa, 750 DEG C and air speed 10L/gh, reaction product passes through online GC points Analysis.
Embodiment 7
7.1 preparation method
6%Mo0.7%Ni0.1%Mg/ZSM-5 catalyst is prepared using co-impregnation.Firstly, ZSM-5 molecular sieve is existed 5h is roasted at 500 DEG C；Secondly, the ZSM-5 molecular sieve after roasting is impregnated into (NH4)6Mo7O24、Ni(NO3)2With Mg (NO3)2's (three's mass ratio is 17.0:3.6:1) stirs 8h in aqueous solution, is evaporated at 110 DEG C, 110 DEG C of dry 16h；Finally, being put into Muffle 12h is roasted in furnace at 500 DEG C, obtained catalyst fines obtain the Mo base solid phase of 40-60 mesh after tabletting, broken and screening Catalyst.
Above-mentioned Mo base solid catalyst is packed into fixed bed reactors, under conditions of 650 DEG C and air speed are 8L/gh, Pre- carbonization treatment 40min is carried out to catalyst with methane.
The Mo base solid catalyst of above-mentioned pre- carbonization is drawn off, then presses quality with the 80%Zr20%Ti particle of 40~60 mesh Physical mixed is carried out than 1:3, obtains aromatized catalyst for activity rating.
7.2 evaluation method
It is applied to the catalyst of 6.1 preparations to carry out methane non oxidative aromatization synthesis in the fixed bed reactors of continuous feed The reaction of benzene, catalyst amount 5g, unstripped gas CH4/ Ar (90vol%CH4And 10vol%Ar) gaseous mixture, catalyst exists The composition of catalytic methane aromatization under conditions of 1MPa, 800 DEG C and air speed 5L/gh, reaction product passes through online GC points Analysis.
Embodiment 8
8.1 preparation method
4%Mo0.7%Fe0.2%Cu/ZSM-5 catalyst is prepared using co-impregnation.Firstly, ZSM-5 molecular sieve is existed 12h is roasted at 500 DEG C；Secondly, the ZSM-5 molecular sieve after roasting is impregnated into (NH4)6Mo7O24、Fe(NO3)3With Cu (NO3)2's (three's mass ratio is 11.7:5.1:1) stirs 18h in aqueous solution, is evaporated at 110 DEG C, 100 DEG C of dry 12h；Finally, being put into horse 5h is not roasted in furnace at 600 DEG C, the Mo base that obtained catalyst fines obtain 40-60 mesh after tabletting, broken and screening is solid Phase catalyst.
Above-mentioned Mo base solid catalyst is packed into fixed bed reactors, under conditions of 650 DEG C and air speed are 12L/gh, Pre- carbonization treatment 25min is carried out to catalyst with methane.
The Mo base solid catalyst of above-mentioned pre- carbonization is drawn off, then presses quality with the 60%Zr40%Ti particle of 40~60 mesh Physical mixed is carried out than 1:3, obtains aromatized catalyst for activity rating.
8.2 evaluation method
It is applied to the catalyst of 6.1 preparations to carry out methane non oxidative aromatization synthesis in the fixed bed reactors of continuous feed The reaction of benzene, catalyst amount 5g, unstripped gas CH4/ Ar (90vol%CH4And 10vol%Ar) gaseous mixture, catalyst exists The composition of catalytic methane aromatization under conditions of 2MPa, 700 DEG C and air speed 5L/gh, reaction product passes through online GC points Analysis.
Embodiment 9
9.1 preparation method
6%Mo1.5%Co0.5%Mg/MCM-22 catalyst is prepared using co-impregnation.Firstly, by MCM-22 molecular sieve 5h is roasted at 600 DEG C；Secondly, the MCM-22 molecular sieve after roasting is impregnated into (NH4)6Mo7O24、Co(NO3)2With Mg (NO3)2 Aqueous solution in (three's mass ratio be 3.4:1.5:1) stirring 18h, be evaporated at 110 DEG C, 110 DEG C of dry 16h；Finally, being put into horse 8h is not roasted in furnace at 550 DEG C, the Mo base that obtained catalyst fines obtain 40-60 mesh after tabletting, broken and screening is solid Phase catalyst.
Above-mentioned Mo base solid catalyst is packed into fixed bed reactors, under conditions of 750 DEG C and air speed are 5L/gh, Pre- carbonization treatment 10min is carried out to catalyst with methane.
The Mo base solid catalyst of above-mentioned pre- carbonization is drawn off, then presses quality with the 40%Zr60%Ti particle of 40~60 mesh Physical mixed is carried out than 1:2.8, obtains aromatized catalyst for activity rating.
9.2 evaluation method
It is applied to the catalyst of 9.1 preparations to carry out methane non oxidative aromatization synthesis in the fixed bed reactors of continuous feed The reaction of benzene, catalyst amount 5g, unstripped gas CH4/ Ar (90vol%CH4And 10vol%Ar) gaseous mixture, catalyst exists The composition of catalytic methane aromatization under conditions of 3MPa, 900 DEG C and air speed 10L/gh, reaction product passes through online GC points Analysis.
Embodiment 10
10.1 preparation methods
4%Mo0.5%Ni0.05%Mn/MCM-22 catalyst is prepared using co-impregnation.Firstly, by MCM-22 molecular sieve 18h is roasted at 500 DEG C；Secondly, the MCM-22 molecular sieve after roasting is impregnated into (NH4)6Mo7O24、Ni(NO3)2And Mn (NO3)2Aqueous solution in (three's mass ratio be 42.6:9.6:1) stirring 18h, be evaporated at 110 DEG C, 90 DEG C of dry 16h；Finally, It is put into Muffle furnace and roasts 10h at 650 DEG C, obtained catalyst fines obtain 40-60 purpose after tabletting, broken and screening Mo base solid catalyst.
Above-mentioned Mo base solid catalyst is packed into fixed bed reactors, under conditions of 550 DEG C and air speed are 10L/gh, Pre- carbonization treatment 35min is carried out to catalyst with methane.
The Mo base solid catalyst of above-mentioned pre- carbonization is drawn off, then with the Zr particle 1:1.1 in mass ratio of 40~60 mesh into Row physical mixed obtains aromatized catalyst for activity rating.
10.2 evaluation methods
It is applied to the catalyst of 10.1 preparations to carry out methane non oxidative aromatization conjunction in the fixed bed reactors of continuous feed At the reaction of benzene, catalyst amount 5g, unstripped gas CH4/ Ar (90vol%CH4And 10vol%Ar) gaseous mixture, catalyst exists The composition of catalytic methane aromatization under conditions of 2MPa, 750 DEG C and air speed 12L/gh, reaction product passes through online GC points Analysis.
Embodiment 11
11.1 preparation methods
6%Mo0.1%Ru0.3%Mn/ZSM-11 catalyst is prepared using co-impregnation.Firstly, by ZSM-11 molecular sieve 5h is roasted at 500 DEG C；Secondly, the ZSM-11 molecular sieve after roasting is impregnated into (NH4)6Mo7O24、Ru(NO)(NO3)3And Mn (NO3)2Aqueous solution in (three's mass ratio be 33.2:1:3.1) stirring 18h, be evaporated at 110 DEG C, 110 DEG C of dry 4h；Finally, It is put into Muffle furnace and roasts 12h at 500 DEG C, obtained catalyst fines obtain 40-60 purpose after tabletting, broken and screening Mo base solid catalyst.
Above-mentioned Mo base solid catalyst is packed into fixed bed reactors, under conditions of 700 DEG C and air speed are 7L/gh, Pre- carbonization treatment 60min is carried out to catalyst with methane.
The Mo base solid catalyst of above-mentioned pre- carbonization is drawn off, then is carried out with the Ti particle 1:2 in mass ratio of 40~60 mesh Physical mixed obtains aromatized catalyst for activity rating.
11.2 evaluation methods
It is applied to the catalyst of 11.1 preparations to carry out methane non oxidative aromatization conjunction in the fixed bed reactors of continuous feed At the reaction of benzene, catalyst amount 5g, unstripped gas CH4/ Ar (90vol%CH4And 10vol%Ar) gaseous mixture, catalyst exists The composition of catalytic methane aromatization under conditions of 1MPa, 600 DEG C and air speed 8L/gh, reaction product passes through online GC points Analysis.
Embodiment 12
12.1 preparation methods
10%Mo0.5%Co0.1%Rh/MCM-49 catalyst is prepared using co-impregnation.Firstly, by MCM-49 molecular sieve It is roasted for 24 hours at 500 DEG C；Secondly, the MCM-49 molecular sieve after roasting is impregnated into (NH4)6Mo7O24、Co(NO3)2And Rh (NO3)3Aqueous solution in (three's mass ratio be 61.7:5.5:1) stirring 18h, be evaporated at 110 DEG C, 110 DEG C of dry 12h；Finally, It is put into Muffle furnace and roasts 1h at 600 DEG C, obtained catalyst fines obtain 40-60 purpose after tabletting, broken and screening Mo base solid catalyst.
Above-mentioned Mo base solid catalyst is packed into fixed bed reactors, under conditions of 700 DEG C and air speed are 5L/gh, Pre- carbonization treatment 10min is carried out to catalyst with methane.
The Mo base solid catalyst of above-mentioned pre- carbonization is drawn off, then presses quality with the 20%Zr80%Ti particle of 40~60 mesh Physical mixed is carried out than 1:2.5, obtains aromatized catalyst for activity rating.
12.2 evaluation methods
It is applied to the catalyst of 12.1 preparations to carry out methane non oxidative aromatization conjunction in the fixed bed reactors of continuous feed At the reaction of benzene, catalyst amount 5g, unstripped gas CH4/ Ar (90vol%CH4And 10vol%Ar) gaseous mixture, catalyst exists The composition of catalytic methane aromatization under conditions of 0.1MPa, 750 DEG C and air speed 5L/gh, reaction product passes through online GC Analysis.
Each embodiment oxygen-free aromatization reaction of methane is analyzed as a result, obtaining CH4C in conversion ratio and product6H6Yield, Acquired results see the table below 1.
The reactivity worth of each embodiment methane non oxidative aromatization benzene of table 1
As it can be seen from table 1 when catalyst prepared by the present invention prepares benzene for catalytic methane oxygen-free aromatization reaction, CH4C in conversion ratio and product6H6Yield it is higher.

Claims (9)

1. a kind of composite catalyst for methane non oxidative aromatization synthesis benzene characterized by comprising Mo base solid catalysis Agent and hydrogen-absorbing material；Mo base solid catalyst includes molecular sieve carrier, and be supported on molecular sieve carrier active component Mo, Auxiliary agent M1With auxiliary agent M2；M1For Fe, Co, Ni or Ru, M2For Mg, Mn, Cu or Rh；Hydrogen-absorbing material is Zr, Ti or ZrTi alloy.
2. the composite catalyst according to claim 1 for methane non oxidative aromatization synthesis benzene, which is characterized in that press According to mass percentage, Mo, M in Mo base solid catalyst1And M2Content be respectively 2%~10%, 0.1%~1.5% and The mass ratio of 0.05%~0.5%, Mo base solid catalyst and hydrogen-absorbing material is 1:(1~3).
3. the composite catalyst according to claim 1 or 2 for methane non oxidative aromatization synthesis benzene, feature exist In molecular sieve carrier ZSM-5, ZSM-11, MCM-22 or MCM-49.
4. the composite catalyst according to claim 1 or 2 for methane non oxidative aromatization synthesis benzene, feature exist In M1For Fe or Co；M2For Mg or Mn；Hydrogen storage material TiZr alloy.
5. a kind of preparation of the described in any item composite catalysts for methane non oxidative aromatization synthesis benzene of claim 1-4 Method, which comprises the steps of:
1) molecular sieve carrier roasts to 5 at 400~700 DEG C~for 24 hours；
2) by the carrier impregnation handled by step 1 to (NH4)6Mo7O24And M1And M2Nitrate aqueous solution in, stirring 8~ For 24 hours, catalyst precursor is obtained；
3) catalyst precursor for obtaining step 2 is dry, then obtains Mo base solid catalysis in 400~700 DEG C of 1~12h of roasting Agent；
4) the pre- 10~60min of carbonization treatment of the Mo base solid catalyst obtained step 3；
5) the Mo base solid catalyst for the pre- carbonization that step 4 obtains obtains to aromatisation is compound to urge with hydrogen-absorbing material physical mixed Agent.
6. preparation method according to claim 5, which is characterized in that in step 3), drying is specifically: at 90~120 DEG C Dry 4~16h.
7. preparation method according to claim 5, which is characterized in that in step 4), use CH4Pre- carbonization treatment is carried out, in advance The condition of carbonization are as follows: 550~750 DEG C of temperature, air speed is 2~15L/gh.
8. application of the composite catalyst described in claim 1 in oxygen-free aromatization reaction of methane.
9. application according to claim 8, which is characterized in that the reaction condition of methane non oxidative aromatization are as follows: air speed be 5~ 15L/gh, 600~900 DEG C of reaction temperature, reaction pressure is 0.1~3.0MPa.
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