CN105728018B - For benzene, the ZSM-5 zeolite catalyst of methanol alkylation, its preparation method and application - Google Patents
For benzene, the ZSM-5 zeolite catalyst of methanol alkylation, its preparation method and application Download PDFInfo
- Publication number
- CN105728018B CN105728018B CN201410768186.5A CN201410768186A CN105728018B CN 105728018 B CN105728018 B CN 105728018B CN 201410768186 A CN201410768186 A CN 201410768186A CN 105728018 B CN105728018 B CN 105728018B
- Authority
- CN
- China
- Prior art keywords
- benzene
- hzsm
- zsm
- molecular sieves
- zeolite catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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 present invention discloses a kind of 5 zeolite catalysts of ZSM, its preparation method and application for benzene, methanol alkylation, and the catalyst is with γ Al2O3Or η Al2O3In any one and 5 molecular sieves of multistage pore canal HZSM be carrier, load MgO is constituted；Wherein, it is in terms of 100% by total weight of carrier, 5 molecular sieves of multistage pore canal HZSM account for 50~80%, γ Al in carrier2O3Or η Al2O3In any one account for 20~50%, load MgO amount be 1~12%.The catalyst of the present invention has higher toluene, dimethylbenzene selective and stability.
Description
Technical field
The present invention relates to the catalyst in petrochemical process, more particularly to a kind of catalysis for benzene, methanol alkylation
Agent.
Background technology
Benzene is mainly derived from the by-product of catalytic reforming, the isomerization of aromatic hydrocarbons and coal tar and ethylene production technique.According to report
Road, often producing 800,000 tons of ethylene just has 150,000 tons of benzene to generate, and the increment of China's ethylene will be in 2,000,000 t/a or more, this must
It will lead to the excessive of benzene.And methanol is as a kind of excellent reagent cheap and easy to get, it has been obtained in esterification, etherificate etc.
Arrive extensive research and application, however one of the important products as coal chemical industry, with the fast development of coal chemical industry, in the market
Methanol output will increase rapidly, superfluous situation occur, and dimethylbenzene is needed as one of most important basic chemical raw materials
The amount of asking presents staggering growth situation.
From 1979, both at home and abroad for alkylation of toluene methanol reaction directly synthesize high concentration paraxylene research into
It has gone a large amount of work, modulation is carried out to the acidity and pore structure of ZSM-5 with various methods.So far, in toluene and methanol
In alkylated reaction, on how to improve para-selective catalyst and the problem of its high activity and high stability is kept not obtain yet
To solution, thus the technique is also not found in always industrial applications.And to react report with methanol alkylation few for benzene, using opposite
The downstream product such as cheap toluene, dimethylbenzene and the ethylbenzene of benzene and methanol-fueled CLC high added value, not only take full advantage of superfluous money
Source, and to meeting domestic supply and demand present situation and resisting the competitive pressure of overseas market with extremely important to domestic chemical enterprise
Realistic meaning.Benzyl alcohol alkylation is different from the reaction system of alkylation of toluene methanol, and phenyl ring is the compound of stable structure, first
The diameter of benzene and benzene molecular is also different, and benzyl alcohol alkylated reaction is difficult to alkylation of toluene methanol, needs to consider to be catalyzed
The problems such as agent structure, acidity, pore passage structure.
So far, all fewer at home and abroad in relation to benzene, the research report of methanol alkylation reaction and patent document.In
State's patent 201210025588.7 describes the technical solution using the molecular sieve carried alkaline earths of HMCM-22, thulium, will
After it is used for benzyl alcohol alkylation, the selectivity of dimethylbenzene increases.Chinese patent 200910242740.5 describe with
HMCM-56 molecular sieves are carrier, and carried metal Mo or Ni, mass content is respectively with MoO3Or NiO meter, load quality be 3~
15%, after benzyl alcohol alkylation, conversion per pass >=45% of benzene, selectivity >=89% of toluene and dimethylbenzene.China
Patent 200910075173.9 essentially describes the influence of technological design and its process conditions to benzene, methanol alkylation reaction.On
It is respectively HMCM-22, HMCM-56 to state the catalyst used in the first two patent, although selectivity all increases, is catalyzed
The stability of agent is not but fine, thus limits its industrial applications, and the patent of Shanxi Hengyang Science ＆ Technology Co., Ltd.'s application is only
Only it is to have made technological design and the change of process conditions, industrial applications value is also extremely limited.
The shortcomings of the prior art is that there are volatile when current catalyst is for the alkylated reaction of benzene and methanol
It is living, the problem that conversion ratio is low, selectivity of product is poor.How a kind of catalyst for benzene and the alkylated reaction of methanol is provided,
Higher toluene, dimethylbenzene selective and stability are made it have, those skilled in the art's urgent problem to be solved is become.
Invention content
The purpose of the present invention is to provide a kind of for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, its preparation method and answers
With, make the catalyst have higher toluene, dimethylbenzene selective and stability.
To achieve the above object, the present invention provides a kind of for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, described
Catalyst is with γ-Al2O3Or η-Al2O3In any one and multistage pore canal HZSM-5 molecular sieves be carrier, load MgO structures
At；Wherein, it is in terms of 100% by total weight of carrier, multistage pore canal HZSM-5 molecular sieves account for 50~80%, γ-Al in carrier2O3
Or η-Al2O3In any one account for 20~50%, load MgO amount be 1~12%.
Wherein, the carrier is multistage pore canal HZSM-5 molecular sieves and γ-Al2O3。
Wherein, weight ratio shared by multistage pore canal HZSM-5 molecular sieves is preferably 60~75% in the carrier.
Wherein, γ-Al in the carrier2O3Shared weight ratio is preferably 25~40%.
Wherein, weight ratio shared by MgO is loaded in the carrier be preferably 5~10%.
Wherein, the multistage pore canal HZSM-5 molecular sieves are：Using the micropore HZSM-5 molecular sieves of silica alumina ratio 180-300,
Under alkaline condition, it is modified with sodium aluminate solution, while secondary pore-forming and acid tune is carried out using ethyl orthosilicate ethanol solution
Become multistage pore canal HZSM-5 molecular sieves obtained.
Wherein, steps are as follows for the multistage pore canal HZSM-5 molecular sieves preparation method：
1) under the conditions of pH value 13-13.5, according to solid-to-liquid ratio 1 in the micropore HZSM-5 molecular sieves of silica alumina ratio 180-300：
The sodium aluminate solution of 0.005~0.05mol/L is added in 10-20, and 40~60min of stirring makes molecular sieve all dissolve；
2) ice-water bath chilling operation is carried out to reactor after reaction, makes reaction all standing, filters and wash into filtrate
Property, by 3~6h of filtration cakes torrefaction, then at 500~550 DEG C of Muffle kiln roasting 5-6h, obtain white (or having slight yellowish) powder；
3) by white (or having slight yellowish) powder of gained in 65~90 DEG C of ethyl orthosilicate ethanol solution (ethyl orthosilicates
With ethyl alcohol in molar ratio 1：5-20 mixing solution) in be sufficiently stirred 90~140min of reaction；
4) to reactor carry out ice-water bath chilling operation, make reaction all standing, filter and wash to filtrate neutrality, by filter cake in
Dry 3~6h at 120 DEG C obtains HZSM-5 points of white powder multistage pore canal then at 500~550 DEG C of Muffle kiln roasting 5-6h
Son sieve.
By modified, the duct of the molecular sieve of formation is contained a certain amount of mesoporous, increases the specific surface area of catalyst.
The pore-size distribution and XRD diagram of HZSM-5 molecular sieves after being given in attached drawing of the present invention before modified, as seen from the figure catalyst
Service life greatly improves.
It is including following the present invention also provides a kind of preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation
Step：
1) micropore HZSM-5 molecular sieve of the silica alumina ratio between 180-300 is taken, under the conditions of pH value 13-13.5, described
According to solid-to-liquid ratio 1 in micropore HZSM-5 molecular sieves：The sodium aluminate solution of 0.005~0.05mol/L of 10-20 additions, stirring 40~
60min makes molecular sieve all dissolve；
2) ice-water bath chilling operation is carried out to reactor after reaction, makes reaction all standing, filters and wash into filtrate
Property, filtration cakes torrefaction is roasted, white (or having slight yellowish) powder is obtained；
3) white (or having slight yellowish) powder of gained is sufficiently stirred in 65~90 DEG C of ethyl orthosilicate ethanol solutions
React 90~140min；
4) ice-water bath chilling operation is carried out to reactor, makes reaction all standing, filter and washed to filtrate neutrality, filter cake is done
Dry, roasting obtains white powder multistage pore canal HZSM-5 molecular sieves；
5) by the multistage pore canal HZSM-5 molecular sieves and γ-Al2O3Or η-Al2O3In any one mixing, be added matter
It measures the dilute nitric acid solution that score is 1~5% and carries out kneading, extrusion, drying, roasting, obtain a carrier；
6) carrier is impregnated with magnesium acetate solution, obtained after dry, roasting it is described for benzene, methanol alkylation after
Handle ZSM-5 zeolite catalyst.
Wherein, in step 2), 3~6h of filtration cakes torrefaction is obtained white then at 500~550 DEG C of Muffle kiln roasting 5-6h
(or having slight yellowish) powder.
Wherein, in step 3), ethyl orthosilicate ethanol solution is ethyl orthosilicate and ethyl alcohol in molar ratio 1：5-20 is mixed
The solution of conjunction.
Wherein, in step 4), filter cake is dried into 3~6h at 120 DEG C, then at 500~550 DEG C of Muffle kiln roasting 5-
6h obtains white powder multistage pore canal HZSM-5 molecular sieves.
Wherein, in step 5), the multistage pore canal HZSM-5 molecular sieves and γ-Al2O3Or η-Al2O3In it is any one
It is in terms of 100% by total weight of carrier, multistage pore canal HZSM-5 molecular sieves account for 50~80%, γ-to plant mixed mixed proportion to be
Any one in Al2O3 or η-Al2O3 accounts for 20~50%.
Wherein, in step 5), the drying and roasting is that 4~12h is roasted at 450~600 DEG C.
Wherein, in step 6), the time of the dipping is 8~48h (preferably 18~36h)；It is described to be roasted in sky
With 450~600 DEG C of 4~12h of roasting in gas；Magnesium acetate solution is that analysis is pure.
Wherein, in step 6), concrete operation step is：By the measurement respective carrier weight of final required catalyst, and
Load MgO weight needed for calculating (being that the amount of MgO is loaded in terms of 100% as 1~12% by total weight of carrier), with required load
MgO selects the magnesium acetate solution of suitable concentration, weighs carrier and magnesium acetate, at ambient temperature, magnesium acetate is poured into deionization
It is completely dissolved in water, finally equi-volume impregnating is used to carry out the dip operation.
To achieve the above object, the present invention also provides a kind of above-mentioned for benzene, the ZSM-5 zeolite catalyst of methanol alkylation
Application：Above-mentioned catalyst is produced for benzene, methanol alkylation reaction in toluene, dimethylbenzene, reaction temperature 400 DEG C~500
DEG C, 0.1~1MPa of reaction pressure, 1~8h of weight space velocity-1, benzene and methanol molar ratio 0.8~1.2.
The present invention for the purity of alkylated raw material (benzene, methanol) be analyze it is pure, catalyst performance with it is active main
Evaluation index has a conversion ratio X (B) of benzene, toluene, dimethylbenzene overall selectivity S (TX) and total recovery Y (TX) and toluene choosing
The selective S (X) of selecting property S (T), dimethylbenzene.Their computational methods difference is as follows：
S (X)=Q/N × 100% (3-5)
M in formula：The molal quantity of benzene in feedstock；
N：The molal quantity of benzene homologues in product；
P：The molal quantity of toluene in product；
Q：The molal quantity of dimethylbenzene in product.
Benzyl alcohol alkylation is different from the reaction system of alkylation of toluene methanol, and phenyl ring is the compound of stable structure, first
The diameter of benzene and benzene molecular is also different, and benzyl alcohol alkylated reaction is difficult to alkylation of toluene methanol, in the knot of catalyst
The problems such as considering acidity, pore passage structure in structure design.Suitable acid amount and pore passage structure are conducive to benzyl alcohol alkylated reaction
The diffusion for generating product, prevents carbon distribution too fast, is conducive to the stability of catalyst.
Carbon is easily tied based on above-mentioned theory and catalyst existing in the prior art, catalyst is for benzene, methanol alkylation
Catalytic activity is low when reaction, the problem of selectivity of product difference, the present invention provide it is a kind of using metal oxide supported catalyst,
It has the following technical effect that：
1) present invention by using post-processing HZSM-5 zeolites as catalyst activity main body, it is metal oxide-loaded to change
Property, 400 DEG C~500 DEG C, 0.1~1MPa, 1~10h of weight space velocity-1, benzene/methanol (molar ratio) 0.6~1.2 operating condition
Under, the conversion ratio of benzene is 49.39%, and the selectivity of toluene and dimethylbenzene is 87.91%, yield 43.41%.The present invention's urges
When agent is for benzene, methanol alkylation reaction, has and be not easy coking, activity is high, the high advantage of selectivity of product.
2) catalyst of the present invention has higher toluene, dimethylbenzene selective and stability, can effectively comprehensively utilize
Benzene and the various higher chemical products of value of methanol resource production, mitigation impact environment.
3) compared with the existing technology, catalyst of the present invention has high activity and hydrothermal stability and longer use
Service life.
Below in conjunction with the drawings and specific embodiments, the present invention will be described in detail, but not as a limitation of the invention.
Description of the drawings
Fig. 1 is the BET phenograms of the embodiment of the present invention 1 and molecular sieve in embodiment 2；
Fig. 2 is the multistage pore canal HZSM-5 molecular sieve bore diameter distribution maps of the embodiment of the present invention 2；
Fig. 3 is the XRD spectra of the embodiment of the present invention 1 and 2 gained catalyst of embodiment；
Fig. 4 is the preparation method flow chart of steps of catalyst of the present invention.
Wherein, reference numeral：
1、1’：1 curve of embodiment
2、2’：2 curve of embodiment
Specific implementation mode
Technical scheme of the present invention is described in detail below in conjunction with specific embodiment, and listed illustrative embodiments are only
Make to illustrate and be used, is not intended as the limitation of the present invention.
Referring to FIG. 4, it is the preparation method flow chart of steps of catalyst of the present invention.To make catalyst that there is higher first
Benzene, dimethylbenzene selective and stability, the present invention provides a kind of ZSM-5 zeolite catalyst being used for benzene, methanol alkylation, described
Catalyst is with γ-Al2O3Or η-Al2O3In any one and multistage pore canal HZSM-5 molecular sieves be carrier, load MgO structures
At；Wherein, it is in terms of 100% by total weight of carrier, multistage pore canal HZSM-5 molecular sieves account for 50~80%, γ-Al in carrier2O3
Or η-Al2O3In any one account for 20~50%, load MgO amount be 1~12%.
Wherein, the carrier is multistage pore canal HZSM-5 molecular sieves and γ-Al2O3。
Wherein, weight ratio shared by multistage pore canal HZSM-5 molecular sieves is preferably 60~75% in the carrier.
Wherein, γ-Al in the carrier2O3Shared weight ratio is preferably 25~40%.
Wherein, weight ratio shared by MgO is loaded in the carrier be preferably 5~10%.
Wherein, the multistage pore canal HZSM-5 molecular sieves are：Using the micropore HZSM-5 molecular sieves of silica alumina ratio 180-300,
Under alkaline condition, it is modified with sodium aluminate solution, while secondary pore-forming and acid tune is carried out using ethyl orthosilicate ethanol solution
Become multistage pore canal HZSM-5 molecular sieves obtained.
Wherein, steps are as follows for the multistage pore canal HZSM-5 molecular sieves preparation method：
1) under the conditions of pH value 13-13.5, according to solid-to-liquid ratio 1 in the micropore HZSM-5 molecular sieves of silica alumina ratio 180-300：
The sodium aluminate solution of 0.005~0.05mol/L is added in 10-20, and 40~60min of stirring makes molecular sieve all dissolve；
2) ice-water bath chilling operation is carried out to reactor after reaction, makes reaction all standing, filters and wash into filtrate
Property, by 3~6h of filtration cakes torrefaction, then at 500~550 DEG C of Muffle kiln roasting 5-6h, obtain white (or having slight yellowish) powder；
3) by white (or having slight yellowish) powder of gained in 65~90 DEG C of ethyl orthosilicate ethanol solution (ethyl orthosilicates
With ethyl alcohol in molar ratio 1：5-20 mixing solution) in be sufficiently stirred 90~140min of reaction；
4) to reactor carry out ice-water bath chilling operation, make reaction all standing, filter and wash to filtrate neutrality, by filter cake in
Dry 3~6h at 120 DEG C obtains HZSM-5 points of white powder multistage pore canal then at 500~550 DEG C of Muffle kiln roasting 5-6h
Son sieve.
By modified, the duct of the molecular sieve of formation is contained a certain amount of mesoporous, increases the specific surface area of catalyst.
The pore-size distribution and XRD diagram of HZSM-5 molecular sieves after being given in attached drawing of the present invention before modified, as seen from the figure catalyst
Service life greatly improves.
It is including following the present invention also provides a kind of preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation
Step：
1) micropore HZSM-5 molecular sieve of the silica alumina ratio between 180-300 is taken, under the conditions of pH value 13-13.5, described
According to solid-to-liquid ratio 1 in micropore HZSM-5 molecular sieves：The sodium aluminate solution of 0.005~0.05mol/L of 10-20 additions, stirring 40~
60min makes molecular sieve all dissolve；
2) ice-water bath chilling operation is carried out to reactor after reaction, makes reaction all standing, filters and wash into filtrate
Property, filtration cakes torrefaction is roasted, white (or having slight yellowish) powder is obtained；
3) white (or having slight yellowish) powder of gained is sufficiently stirred in 65~90 DEG C of ethyl orthosilicate ethanol solutions
React 90~140min；
4) ice-water bath chilling operation is carried out to reactor, makes reaction all standing, filter and washed to filtrate neutrality, filter cake is done
Dry, roasting obtains white powder multistage pore canal HZSM-5 molecular sieves；
5) by the multistage pore canal HZSM-5 molecular sieves and γ-Al2O3Or η-Al2O3In any one mixing, be added matter
It measures the dilute nitric acid solution that score is 1~5% and carries out kneading, extrusion, drying, roasting, obtain a carrier；
6) carrier is impregnated with magnesium acetate solution, obtained after dry, roasting it is described for benzene, methanol alkylation after
Handle ZSM-5 zeolite catalyst.
Wherein, in step 2), 3~6h of filtration cakes torrefaction is obtained white then at 500~550 DEG C of Muffle kiln roasting 5-6h
(or having slight yellowish) powder.
Wherein, in step 3), ethyl orthosilicate ethanol solution is ethyl orthosilicate and ethyl alcohol in molar ratio 1：5-20 is mixed
The solution of conjunction.
Wherein, in step 4), filter cake is dried into 3~6h at 120 DEG C, then at 500~550 DEG C of Muffle kiln roasting 5-
6h obtains white powder multistage pore canal HZSM-5 molecular sieves.
Wherein, in step 5), the multistage pore canal HZSM-5 molecular sieves and γ-Al2O3Or η-Al2O3In it is any one
It is in terms of 100% by total weight of carrier, multistage pore canal HZSM-5 molecular sieves account for 50~80%, γ-to plant mixed mixed proportion to be
Any one in Al2O3 or η-Al2O3 accounts for 20~50%.
Wherein, in step 5), the drying and roasting is that 4~12h is roasted at 450~600 DEG C.
Wherein, in step 6), the time of the dipping is 8~48h (preferably 18~36h)；It is described to be roasted in sky
With 450~600 DEG C of 4~12h of roasting in gas；Magnesium acetate solution is that analysis is pure.
Wherein, in step 6), concrete operation step is：By the measurement respective carrier weight of final required catalyst, and
Load MgO weight needed for calculating (being that the amount of MgO is loaded in terms of 100% as 1~12% by total weight of carrier), with required load
MgO selects the magnesium acetate solution of suitable concentration, weighs carrier and magnesium acetate, at ambient temperature, magnesium acetate is poured into deionization
It is completely dissolved in water, finally equi-volume impregnating is used to carry out the dip operation.
The present invention also provides a kind of above-mentioned applications for benzene, the ZSM-5 zeolite catalyst of methanol alkylation：It is urged above-mentioned
Agent is produced for benzene, methanol alkylation reaction in toluene, dimethylbenzene, 400 DEG C~500 DEG C of reaction temperature, and reaction pressure 0.1~
1MPa, 1~8h of weight space velocity-1, benzene and methanol molar ratio 0.8~1.2.
Embodiment a
It is including following the present embodiment provides a kind of preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation
Step：
1) micropore HZSM-5 molecular sieve of the silica alumina ratio 180 is taken, under the conditions of pH value 13, in the micropore HZSM-5 molecules
According to solid-to-liquid ratio 1 in sieve：10 are added the sodium aluminate solution of 0.005mol/L, and stirring 40min makes molecular sieve all dissolve；
2) ice-water bath chilling operation is carried out to reactor after reaction, makes reaction all standing, filters and wash into filtrate
Property, dry 3h at 120 DEG C of filter cake is obtained into white (or having slight yellowish) powder then at 500 DEG C of Muffle kiln roasting 5h；
3) by white (or having slight yellowish) powder of gained in 65 DEG C of ethyl orthosilicate ethanol solutions (ethyl orthosilicate and second
Alcohol in molar ratio 1：5 mixing solution) in be sufficiently stirred reaction 90min；
4) to reactor carry out ice-water bath chilling operation, make reaction all standing, filter and wash to filtrate neutrality, by filter cake in
Dry 3h obtains white powder multistage pore canal HZSM-5 molecular sieves then at 500 DEG C of Muffle kiln roasting 5h at 120 DEG C；
5) by the multistage pore canal HZSM-5 molecular sieves and γ-Al2O3(mixed proportion is to be with total weight of carrier for mixing
100% meter, multistage pore canal HZSM-5 molecular sieves account for 50%, γ-Al2O3 and account for 20%), and the dust technology that mass fraction is 1% is added
Solution carries out kneading, extrusion, drying, roasts 4h at 450 DEG C, obtains a carrier；
6) carrier magnesium acetate solution being impregnated into 8h, guarantee final load MgO weight is vehicle weight 1%, dry,
It is described for benzene, the post-processing ZSM-5 zeolite catalyst of methanol alkylation to be obtained after 450 DEG C of roasting 4h in air.
The present embodiment provides a kind of for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, and the catalyst is with γ-
Al2O3It is carrier with multistage pore canal HZSM-5 molecular sieves, load MgO is constituted；Wherein, it is to be carried in terms of 100% by total weight of carrier
Multistage pore canal HZSM-5 molecular sieves account for 50%, γ-Al in body2O320% is accounted for, the amount for loading MgO is 1%.
The present embodiment also provides a kind of above-mentioned application for benzene, the ZSM-5 zeolite catalyst of methanol alkylation：It will be above-mentioned
Catalyst is produced for benzene, methanol alkylation reaction in toluene, dimethylbenzene, 400 DEG C of reaction temperature, reaction pressure 0.1MPa, again
Measure air speed 1h-1, benzene and methanol molar ratio 0.8.
Embodiment b
It is including following the present embodiment provides a kind of preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation
Step：
1) micropore HZSM-5 molecular sieve of the silica alumina ratio 300 is taken, under the conditions of pH value 13.5, at the micropore HZSM-5 points
According to solid-to-liquid ratio 1 in son sieve：20 are added the sodium aluminate solution of 0.05mol/L, and stirring 60min makes molecular sieve all dissolve；
2) ice-water bath chilling operation is carried out to reactor after reaction, makes reaction all standing, filters and wash into filtrate
Property, dry 6h at 120 DEG C of filter cake is obtained into white (or having slight yellowish) powder then at 550 DEG C of Muffle kiln roasting 6h；
3) by white (or having slight yellowish) powder of gained in 90 DEG C of ethyl orthosilicate ethanol solutions (ethyl orthosilicate and second
Alcohol in molar ratio 1：20 mixing solution) in be sufficiently stirred reaction 140min；
4) to reactor carry out ice-water bath chilling operation, make reaction all standing, filter and wash to filtrate neutrality, by filter cake in
Dry 6h obtains white powder multistage pore canal HZSM-5 molecular sieves then at 550 DEG C of Muffle kiln roasting 6h at 120 DEG C；
5) by the multistage pore canal HZSM-5 molecular sieves and γ-Al2O3(mixed proportion is to be with total weight of carrier for mixing
100% meter, multistage pore canal HZSM-5 molecular sieves account for 80%, γ-Al2O3 and account for 50%), and the dust technology that mass fraction is 5% is added
Solution carries out kneading, extrusion, drying, roasts 12h at 600 DEG C, obtains a carrier；
6) carrier magnesium acetate solution is impregnated into 48h, guarantee final load MgO weight is vehicle weight 12%, is done
It is dry, described for benzene, the post-processing ZSM-5 zeolite catalyst of methanol alkylation to be obtained after 600 DEG C of roasting 12h in air.
The present embodiment provides a kind of for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, and the catalyst is with γ-
Al2O3It is carrier with multistage pore canal HZSM-5 molecular sieves, load MgO is constituted；Wherein, it is to be carried in terms of 100% by total weight of carrier
Multistage pore canal HZSM-5 molecular sieves account for 80%, γ-Al in body2O350% is accounted for, the amount for loading MgO is 12%.
The present embodiment also provides a kind of above-mentioned application for benzene, the ZSM-5 zeolite catalyst of methanol alkylation：It will be above-mentioned
Catalyst is produced for benzene, methanol alkylation reaction in toluene, dimethylbenzene, 500 DEG C of reaction temperature, reaction pressure 1MPa, weight
Air speed 8h-1, benzene and methanol molar ratio 1.2.
Embodiment c
It is including following the present embodiment provides a kind of preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation
Step：
1) micropore HZSM-5 molecular sieve of the silica alumina ratio 200 is taken, under the conditions of pH value 13.2, at the micropore HZSM-5 points
According to solid-to-liquid ratio 1 in son sieve：15 are added the sodium aluminate solution of 0.01mol/L, and stirring 50min makes molecular sieve all dissolve；
2) ice-water bath chilling operation is carried out to reactor after reaction, makes reaction all standing, filters and wash into filtrate
Property, dry 4h at 120 DEG C of filter cake is obtained into white (or having slight yellowish) powder then at 520 DEG C of Muffle kiln roasting 5.2h；
3) by white (or having slight yellowish) powder of gained in 70 DEG C of ethyl orthosilicate ethanol solutions (ethyl orthosilicate and second
Alcohol in molar ratio 1：10 mixing solution) in be sufficiently stirred reaction 100min；
4) to reactor carry out ice-water bath chilling operation, make reaction all standing, filter and wash to filtrate neutrality, by filter cake in
Dry 4h obtains white powder multistage pore canal HZSM-5 molecular sieves then at 520 DEG C of Muffle kiln roasting 5.2h at 120 DEG C；
5) by the multistage pore canal HZSM-5 molecular sieves and γ-Al2O3(mixed proportion is to be with total weight of carrier for mixing
100% meter, multistage pore canal HZSM-5 molecular sieves account for 60%, γ-Al2O3 and account for 25%), and the dust technology that mass fraction is 2% is added
Solution carries out kneading, extrusion, drying, roasts 8h at 500 DEG C, obtains a carrier；
6) carrier magnesium acetate solution is impregnated into 18h, guarantee final load MgO weight is vehicle weight 5%, is done
It is dry, described for benzene, the post-processing ZSM-5 zeolite catalyst of methanol alkylation to be obtained after 500 DEG C of roasting 8h in air.
The present embodiment provides a kind of for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, and the catalyst is with γ-
Al2O3It is carrier with multistage pore canal HZSM-5 molecular sieves, load MgO is constituted；Wherein, it is to be carried in terms of 100% by total weight of carrier
Multistage pore canal HZSM-5 molecular sieves account for 60%, γ-Al in body2O325% is accounted for, the amount for loading MgO is 5%.
The present embodiment also provides a kind of above-mentioned application for benzene, the ZSM-5 zeolite catalyst of methanol alkylation：It will be above-mentioned
Catalyst is produced for benzene, methanol alkylation reaction in toluene, dimethylbenzene, 450 DEG C of reaction temperature, reaction pressure 0.5MPa, again
Measure air speed 3h-1, benzene and methanol molar ratio 0.9.
Embodiment d
It is including following the present embodiment provides a kind of preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation
Step：
1) micropore HZSM-5 molecular sieve of the silica alumina ratio 250 is taken, under the conditions of pH value 13.4, at the micropore HZSM-5 points
According to solid-to-liquid ratio 1 in son sieve：17 are added the sodium aluminate solution of 0.03mol/L, and stirring 55min makes molecular sieve all dissolve；
2) ice-water bath chilling operation is carried out to reactor after reaction, makes reaction all standing, filters and wash into filtrate
Property, dry 5h at 120 DEG C of filter cake is obtained into white (or having slight yellowish) powder then at 540 DEG C of Muffle kiln roasting 5.4h；
3) by white (or having slight yellowish) powder of gained in 80 DEG C of ethyl orthosilicate ethanol solutions (ethyl orthosilicate and second
Alcohol in molar ratio 1：15 mixing solution) in be sufficiently stirred reaction 120min；
4) to reactor carry out ice-water bath chilling operation, make reaction all standing, filter and wash to filtrate neutrality, by filter cake in
Dry 5h obtains white powder multistage pore canal HZSM-5 molecular sieves then at 540 DEG C of Muffle kiln roasting 5.4h at 120 DEG C；
5) by the multistage pore canal HZSM-5 molecular sieves and γ-Al2O3(mixed proportion is to be with total weight of carrier for mixing
100% meter, multistage pore canal HZSM-5 molecular sieves account for 75%, γ-Al2O3 and account for 40%), and the dust technology that mass fraction is 4% is added
Solution carries out kneading, extrusion, drying, roasts 10h at 550 DEG C, obtains a carrier；
6) carrier magnesium acetate solution is impregnated into 36h, guarantee final load MgO weight is vehicle weight 10%, is done
It is dry, described for benzene, the post-processing ZSM-5 zeolite catalyst of methanol alkylation to be obtained after 550 DEG C of roasting 10h in air.
The present embodiment provides a kind of for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, and the catalyst is with γ-
Al2O3It is carrier with multistage pore canal HZSM-5 molecular sieves, load MgO is constituted；Wherein, it is to be carried in terms of 100% by total weight of carrier
Multistage pore canal HZSM-5 molecular sieves account for 75%, γ-Al in body2O340% is accounted for, the amount for loading MgO is 10%.
The present embodiment also provides a kind of above-mentioned application for benzene, the ZSM-5 zeolite catalyst of methanol alkylation：It will be above-mentioned
Catalyst is produced for benzene, methanol alkylation reaction in toluene, dimethylbenzene, 470 DEG C of reaction temperature, reaction pressure 0.7MPa, again
Measure air speed 5h-1, benzene and methanol molar ratio 1.0.
The present invention for the purity of alkylated raw material (benzene, methanol) be analyze it is pure, catalyst performance with it is active main
Evaluation index has a conversion ratio X (B) of benzene, toluene, dimethylbenzene overall selectivity S (TX) and total recovery Y (TX) and toluene choosing
The selective S (X) of selecting property S (T), dimethylbenzene.Their computational methods difference is as follows：
S (X)=Q/N × 100% (3-5)
M in formula：The molal quantity of benzene in feedstock；
N：The molal quantity of benzene homologues in product；
P：The molal quantity of toluene in product；
Q：The molal quantity of dimethylbenzene in product.
Benzyl alcohol alkylation is different from the reaction system of alkylation of toluene methanol, and phenyl ring is the compound of stable structure, first
The diameter of benzene and benzene molecular is also different, and benzyl alcohol alkylated reaction is difficult to alkylation of toluene methanol, in the knot of catalyst
The problems such as considering acidity, pore passage structure in structure design.Suitable acid amount and pore passage structure are conducive to benzyl alcohol alkylated reaction
The diffusion for generating product, prevents carbon distribution too fast, is conducive to the stability of catalyst.
Carbon is easily tied based on above-mentioned theory and catalyst existing in the prior art, catalyst is for benzene, methanol alkylation
Catalytic activity is low when reaction, the problem of selectivity of product difference, the present invention provide it is a kind of using metal oxide supported catalyst,
It has the following technical effect that：
1) present invention by using post-processing HZSM-5 zeolites as catalyst activity main body, it is metal oxide-loaded to change
Property, 400 DEG C~500 DEG C, 0.1~1MPa, 1~10h of weight space velocity-1, benzene/methanol (molar ratio) 0.6~1.2 operating condition
Under, the conversion ratio of benzene is 49.39%, and the selectivity of toluene and dimethylbenzene is 87.91%, yield 43.41%.The present invention's urges
When agent is for benzene, methanol alkylation reaction, has and be not easy coking, activity is high, the high advantage of selectivity of product.
2) catalyst of the present invention has higher toluene, dimethylbenzene selective and stability, can effectively comprehensively utilize
Benzene and the various higher chemical products of value of methanol resource production, mitigation impact environment.
3) compared with the existing technology, catalyst of the present invention has high activity and hydrothermal stability and longer use
Service life.
Below by under different technology conditions embodiment and its experimental data the invention will be further described, with clear
Show its technique effect.
Embodiment 1
The micropore HZSM-5 molecular sieve 7g bought from southization catalyst plant are weighed, γ-Al are added2O33g, after mixing,
4% dust technology is added and carries out kneading, extruded moulding is put into thermostatic drying chamber under conditions of 120 DEG C after dry 12h, and roasting is simultaneously
Strip catalyst is crushed to the particle of 20~40 mesh, and catalyst A is obtained after finally fired again.
Embodiment 2
A certain amount of micropore HZSM-5 molecular sieves (southization catalyst plant) are weighed, (sodium hydroxide can be used in pH value 13.3
Adjust) under the conditions of, HZSM-5 molecular sieves are modified with the sodium aluminate solution of 0.005mol/L, solid-to-liquid ratio 1：10, stirring
40min, and washing to filtrate neutrality, by filtration cakes torrefaction 6h, then at 500~550 DEG C of Muffle kiln roasting 6h, obtaining white (or has
Slight yellowish) powder；Gained powder is sufficiently stirred to reaction 100min in 90 DEG C of ethyl orthosilicate ethanol solutions, to reactor
Ice-water bath chilling operation is carried out, reaction all standing is made, filter and is washed to filtrate neutrality, filter cake is dried into 6h at 120 DEG C, then at
500~550 DEG C of Muffle kiln roasting 6h, suction filtration obtain multistage pore canal HZSM-5 molecular sieves；Weigh this treated multistage pore canal
γ-Al are added in HZSM-5 molecular sieve 7g2O33g is added 4% dust technology and carries out kneading, extruded moulding is put into perseverance after mixing
Warm drying box after dry 12h, roasts the particle that simultaneously strip catalyst powder is broken to 20~40 mesh, finally again under conditions of 120 DEG C
Catalyst B is obtained after fired.
Embodiment 3
A certain amount of micropore HZSM-5 molecular sieves (southization catalyst plant) are weighed, (sodium hydroxide can be used in pH value 13.5
Adjust) under the conditions of, HZSM-5 molecular sieves are modified with the sodium aluminate solution of 0.05mol/L, solid-to-liquid ratio 1：20, stirring
60min, and washing to filtrate neutrality, by filtration cakes torrefaction 6h, then at 500~550 DEG C of Muffle kiln roasting 6h, obtaining white (or has
Slight yellowish) powder；Gained powder is sufficiently stirred to reaction 120min in 75 DEG C of ethyl orthosilicate ethanol solutions, to reactor
Ice-water bath chilling operation is carried out, reaction all standing is made, filter and is washed to filtrate neutrality, filter cake is dried into 6h at 120 DEG C, then at
500~550 DEG C of Muffle kiln roasting 6h, suction filtration obtain multistage pore canal HZSM-5 molecular sieves；Weigh this treated multistage pore canal
γ-Al are added in HZSM-5 molecular sieve 7g2O33g is added 4% dust technology and carries out kneading, extruded moulding is put into perseverance after mixing
Warm drying box after dry 12h, roasts the particle that simultaneously strip catalyst powder is broken to 20~40 mesh, finally again under conditions of 120 DEG C
Catalyst C is obtained after fired.
It please refers to Fig.1 to Fig. 3, which show the catalyst performance parameters of the embodiment of the present invention 1 to embodiment 3.
Fig. 1 is the molecular sieve BET phenograms of embodiment 1, embodiment 2, and abscissa is relative pressure (Relative
Pressure), ordinate is adsorbance (Quantity absorbed).Include four curves, two, top curve 2 altogether in Fig. 1
For the adsorption curve and desorption curve of the multistage pore canal HZSM-5 molecular sieves obtained by embodiment 2, the curve 1 of lower part two is to implement
The adsorption curve and desorption curve of the common HZSM-5 molecular sieves of example 1 (two curves are to overlap).In addition, Fig. 2 is embodiment 2
Aperture (Pore size) distribution map of middle multistage pore canal HZSM-5 molecular sieves.
Molecular sieve is characterized using N2 physical absorptions, obtained the pore volume of molecular sieve, pore-size distribution and compares table
The performances such as area, to judge the pore passage structure of synthesis of molecular sieve.By Fig. 1,2 are carried it is found that according to international purely chemistry and application
The classification of chemical combined meeting (IUPAC), multistage pore canal HZSM-5 molecular sieves are in relative pressure P/P0Have one between=0.6~1.0
A obviously hysteresis loop (belonging to H2 types hysteretic loop), this hysteresis loop are existing since capillary condensation occurring in meso-hole structure
Pictograph at, illustrate synthesis HZSM-5 molecular sieves there are a certain amount of mesoporous.
Fig. 3 is the XRD spectra of embodiment 1 and 2 gained catalyst of embodiment.Curve 1 ' is embodiment 1, and curve 2 ' is to implement
Example 2.As seen from the figure, compared with common HZSM-5 molecular sieves, multistage pore canal HZSM-5 molecular sieves are special at 2 θ=22~25 °
The width of sign diffraction maximum increased, this shows that sample has nano-scale.
In addition, catalyst A, B, C for being prepared in Example 1~3 are loaded in tubular reactor respectively, and it is anti-in fixed window
It answers and investigation evaluation is carried out to the alkylation catalytic performance of its benzene, methanol on valuator device.The loadings of catalyst are 2.5g,
Benzene/methanol=1mol/1mol, mass space velocity 2.0h-1, N2Under conditions of flow is 50ml/min, three kinds of differences is investigated and have urged
Influence of the agent to benzene, methanol alkylation reaction, reaction result are listed in table 1.
Table 1
From the point of view of data by table 1, by the HZSM-5 molecular sieves bought by southization catalyst plant it is post-treated after, benzene-
The catalytic performance of methanol alkylation reaction is greatly improved, and the conversion ratio of benzene improves nearly 9 percentage points, toluene, two
The overall selectivity of toluene also improves 2 percentage points, wherein most it is worth mentioning that the selectivity of dimethylbenzene improves nearly 8
Percentage point further improves the economic benefit and social benefit of benzene-methanol alkylation reaction, there is relatively good industrialization to answer
Use foreground.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding change and deformations, but these corresponding change and deformations can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. a kind of preparation method for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, which is characterized in that by following steps
Composition：
1) micropore HZSM-5 molecular sieve of the silica alumina ratio between 180-300 is taken, under the conditions of pH value 13-13.5, in the micropore
According to solid-to-liquid ratio 1 in HZSM-5 molecular sieves：The sodium aluminate solution of 0.005~0.05mol/L is added in 10-20, stirs 40~60min
Molecular sieve is set all to dissolve；
2) ice-water bath chilling operation is carried out to reactor after reaction, makes reaction all standing, filter and washed to filtrate neutrality, it will
Filtration cakes torrefaction roasts, and obtains white powder；
3) gained white powder is sufficiently stirred 90~140min of reaction in 65~90 DEG C of ethyl orthosilicate ethanol solutions；
4) ice-water bath chilling operation is carried out to reactor, makes reaction all standing, filter and washed to filtrate neutrality, by filtration cakes torrefaction,
Roasting, obtains white powder multistage pore canal HZSM-5 molecular sieves；
5) by the multistage pore canal HZSM-5 molecular sieves and γ-Al2O3Or η-Al2O3In any one mixing, quality point is added
Number carries out kneading, extrusion, drying, roasting for 1~5% dilute nitric acid solution, obtains a carrier；
6) carrier is impregnated with magnesium acetate solution, is obtained after dry, roasting described for benzene, the ZSM-5 of methanol alkylation
Zeolite catalyst；
Wherein, the ZSM-5 zeolite catalyst for benzene, methanol alkylation is with γ-Al2O3Or η-Al2O3In it is any one
Kind and multistage pore canal HZSM-5 molecular sieves are carrier, and load MgO is constituted；It is multistage in carrier in terms of 100% by total weight of carrier
Duct HZSM-5 molecular sieves account for 50~80%, γ-Al2O3Or η-Al2O3In any one account for 20~50%, load the amount of MgO
It is 1~12%.
2. the preparation method according to claim 1 for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, feature
It is, in step 3), ethyl orthosilicate ethanol solution is ethyl orthosilicate and ethyl alcohol in molar ratio 1：The solution of 5-20 mixing.
3. the preparation method according to claim 1 for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, feature
It is, in step 5), the multistage pore canal HZSM-5 molecular sieves and γ-Al2O3Or η-Al2O3In any one mixing
Mixed proportion is, is in terms of 100% by total weight of carrier, multistage pore canal HZSM-5 molecular sieves account for 50~80%, γ-Al2O3Or η-
Al2O3In any one account for 20~50%.
4. the preparation method according to claim 1 for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, feature
It is, in step 6), the time of the dipping is 8~48h；It is described be roasted in air with 450~600 DEG C roasting 4~
12h。
5. a kind of for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, which is characterized in that it is any via claim 1-4
Method described in is made.
6. according to claim 5 for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, which is characterized in that the load
Body is multistage pore canal HZSM-5 molecular sieves and γ-Al2O3。
7. according to claim 5 for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, which is characterized in that the load
Weight ratio shared by multistage pore canal HZSM-5 molecular sieves is 60~75% in body.
8. according to claim 5 for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, which is characterized in that the load
γ-Al in body2O3Shared weight ratio is 25~40%.
9. according to claim 5 for benzene, the ZSM-5 zeolite catalyst of methanol alkylation, which is characterized in that load
Weight ratio shared by MgO is 5~10%.
10. the application for benzene, the ZSM-5 zeolite catalyst of methanol alkylation described in a kind of claim 5, feature exist
In, the catalyst is reacted for benzene, methanol alkylation and is produced in toluene, dimethylbenzene, 400 DEG C~500 DEG C of reaction temperature, instead
Answer 0.1~1MPa of pressure, 1~8h of weight space velocity-1, benzene and methanol molar ratio 0.8~1.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410768186.5A CN105728018B (en) | 2014-12-11 | 2014-12-11 | For benzene, the ZSM-5 zeolite catalyst of methanol alkylation, its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410768186.5A CN105728018B (en) | 2014-12-11 | 2014-12-11 | For benzene, the ZSM-5 zeolite catalyst of methanol alkylation, its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105728018A CN105728018A (en) | 2016-07-06 |
| CN105728018B true CN105728018B (en) | 2018-10-16 |
Family
ID=56241464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410768186.5A Active CN105728018B (en) | 2014-12-11 | 2014-12-11 | For benzene, the ZSM-5 zeolite catalyst of methanol alkylation, its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105728018B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669791B (en) * | 2017-01-20 | 2019-08-27 | 河北玺尧新能源科技有限公司 | A kind of ZSM-5 Type Zeolites agent and its preparation method and application |
| CN107777700B (en) * | 2017-10-16 | 2019-07-09 | 中国石油天然气股份有限公司 | A kind of step hole HZSM-5 molecular sieve and preparation method thereof |
| CN108187728B (en) * | 2018-01-11 | 2019-12-03 | 阳泉煤业（集团）有限责任公司 | A kind of preparation method and applications forming ZSM-5 molecular sieve catalyst |
| CN108970636B (en) * | 2018-06-27 | 2021-01-05 | 大连理工大学 | Preparation method of benzene alkylation catalyst |
| CN109603903B (en) * | 2018-12-17 | 2022-02-22 | 兰州理工大学 | Catalyst for benzene and methanol alkylation reaction and preparation method and application thereof |
| CN109847794B (en) * | 2018-12-17 | 2022-02-22 | 兰州理工大学 | Catalyst for preparing toluene from benzene and methanol, and preparation method and application thereof |
| CN111518584A (en) * | 2020-05-15 | 2020-08-11 | 浙江工业大学 | Method for producing high-octane aromatic gasoline by alkylating benzene and methanol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101818A (en) * | 2009-12-16 | 2011-06-22 | 中国石油天然气股份有限公司 | Method for synthesizing dimethylbenzene by alkylation of benzene and methanol |
| CN102674392A (en) * | 2012-05-16 | 2012-09-19 | 上海师范大学 | Hollow capsule nano ZSM-5 molecular sieve and preparation method thereof |
| CN102688771A (en) * | 2011-03-23 | 2012-09-26 | 中国石油天然气股份有限公司 | Catalyst for alkylation of benzene and methanol, and preparation and application thereof |
| CN102962090A (en) * | 2012-11-30 | 2013-03-13 | 哈尔滨工业大学 | Preparation method of high-activity environment-friendly low-cost Friedel-Crafts alkylation catalyst |
-
2014
- 2014-12-11 CN CN201410768186.5A patent/CN105728018B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101818A (en) * | 2009-12-16 | 2011-06-22 | 中国石油天然气股份有限公司 | Method for synthesizing dimethylbenzene by alkylation of benzene and methanol |
| CN102688771A (en) * | 2011-03-23 | 2012-09-26 | 中国石油天然气股份有限公司 | Catalyst for alkylation of benzene and methanol, and preparation and application thereof |
| CN102674392A (en) * | 2012-05-16 | 2012-09-19 | 上海师范大学 | Hollow capsule nano ZSM-5 molecular sieve and preparation method thereof |
| CN102962090A (en) * | 2012-11-30 | 2013-03-13 | 哈尔滨工业大学 | Preparation method of high-activity environment-friendly low-cost Friedel-Crafts alkylation catalyst |
Non-Patent Citations (2)
| Title |
|---|
| "Interdependence between porosity, acidity, and catalytic performance in hierarchical ZSM-5 zeolites prepared by post-synthetic modification";Maria Milina等;《Journal of Catalysis》;20130917;第308卷;第398-407页 * |
| "ZSM-5分子筛催化苯、甲醇烷基化反应的研究";陆璐;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20120715;B014-321 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105728018A (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105728018B (en) | For benzene, the ZSM-5 zeolite catalyst of methanol alkylation, its preparation method and application | |
| CN101468318B (en) | Modified rare-earth-containing molecular sieve catalyst as well as preparation method and use thereof | |
| CN102302934B (en) | Novel auxiliary-modified catalyst for preparing methanol by catalytic hydrogenation of carbon dioxide and preparation method of catalyst | |
| CN104056652B (en) | A kind of hud typed ZSM-5 molecular sieve pellet catalyst | |
| CN105502433B (en) | A kind of preparing gasoline by methanol catalyst nano Zn ZSM 5 preparation method | |
| AU2015258645B2 (en) | Catalyst suitable for production of aviation kerosene from biomass Fischer-Tropsch synthesis oil and preparation method therefor | |
| CN104043477A (en) | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof | |
| RU2015114322A (en) | METHOD FOR PRODUCING HYDROCRACKING CATALYST | |
| CN102633279A (en) | Aluminum silicophosphate molecular sieve with macro-porous structure and preparation method thereof | |
| CN105597815A (en) | ZSM-5/ZnVPI-8 composite structure molecular sieve catalyst | |
| CN104525246A (en) | Preparation method and application of no-template-agent small-grain Zn-ZSM-5 catalyst | |
| CN109046444A (en) | A kind of bifunctional catalyst and preparation method thereof of C8 aromatics isomerization | |
| CN106607079A (en) | Methanol-to-aromatic hydrocarbon catalyst and uses tehreof | |
| CN109621968B (en) | High-pressure low-sulfur-resistant shift catalyst and preparation method thereof | |
| CN104399514B (en) | Preparation method for boric-acid-modified microporous molecular sieve shape-selective catalyst | |
| CN104096571B (en) | Synthesis gas liquification catalyst and catalyzing method thereof, beds and preparation method | |
| CN101992123B (en) | Adhesive-free mordenite/MCM-22 intergrowth molecular sieve catalyst and preparation method thereof | |
| CN102949997A (en) | Catalyst-absorbent complex for absorbing and strengthening low-carbon hydrocarbon steam reforming hydrogen and preparing method of complex | |
| CN103285915B (en) | A kind of preparation method being carried on the palladium catalyst of SAPO-11 molecular sieve carrier | |
| CN102259014A (en) | ZSM-5 molecular sieve for synthesizing propylene by utilizing methanol, as well as preparation method and application thereof | |
| CN102039172B (en) | Binderless beta zeolite/MCM-22 symbiotic molecular sieve catalyst and preparation method thereof | |
| CN105621439B (en) | A kind of synthetic method of Beta zeolites | |
| CN109529911B (en) | Platinum-tin-based mesoporous catalyst for propane anaerobic dehydrogenation and preparation and application thereof | |
| CN105540605B (en) | A kind of method of synthesizing aluminum-enriched Beta zeolites | |
| CN103058209B (en) | Method for synthesizing small-grain PZSM-5 molecular sieve catalyst through two-step hydrothermal method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |