CN105367373B - The method of toluene and the benzene of alcohol production first and second - Google Patents
The method of toluene and the benzene of alcohol production first and second Download PDFInfo
- Publication number
- CN105367373B CN105367373B CN201410427966.3A CN201410427966A CN105367373B CN 105367373 B CN105367373 B CN 105367373B CN 201410427966 A CN201410427966 A CN 201410427966A CN 105367373 B CN105367373 B CN 105367373B
- Authority
- CN
- China
- Prior art keywords
- toluene
- benzene
- molecular sieve
- mcm
- molecular
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method of toluene and the benzene of alcohol production first and second, the problem of prior art has high reaction temperature, low ethanol conversion and complicated catalyst preparation is mainly solved.The present invention is by using using toluene and ethanol as reaction raw materials, in 160~240 DEG C of reaction temperature, 2.0~6.0MPa of reaction pressure, ethanol weight space velocity 0.1~1.0 hour‑1, under conditions of toluene/ethanol mol ratio 2~10, reaction raw materials contact the first and second benzene of generation with catalyst；The catalyst is in terms of parts by weight, including following component：A) 40~90 parts of micro porous molecular sieve；B) 10~60 parts of binding agent；The microporous molecular preferably solves the problem screened from the technical scheme with least one of MWW, BEA, MOR, FAU topological structure molecular sieve, in the industrial production available for toluene and the benzene of alcohol production first and second.
Description
Technical field
The present invention relates to a kind of method of toluene and the benzene of alcohol production first and second, more particularly to a kind of toluene is with ethanol in low temperature
The method of the first and second benzene of lower production.
Background technology
First and second benzene are the raw materials for producing methyl styrene, and methyl styrene is the low vaporized monomers of low toxicity, available for synthesizing
Poly- PMS, unsaturated polyester (UP), BIMS, thermoplastic elastomer (TPE), ABS resin and other binary, terpolymer, are also widely used in core
In terms of industry and polyacids reinforcing fiber and alkyl coating.But, the global production capacity of methyl styrene is relatively low, at present still
A kind of small-scale special copolymer monomer, not as a kind of polymer monomer of large-scale production.
The production of first and second benzene is in addition to small part is separated from C9 aromatic hydrocarbons is reformed, and the overwhelming majority is all by toluene and second
Alcohol catalyst in the presence of generate three isomers of the first and second benzene, typical reaction composition be containing 75% unreacted toluene,
7% methyl-ethyl benzene, 2% adjacent methyl-ethyl benzene and 2% heavy aromatics methyl-ethyl benzene, 14%.
For many years, people have made extensive and intensive studies to the catalyst for synthesizing the first and second benzene always, some companies
Constantly it is directed to producing the research of the first and second benzene new technologies by the use of molecular sieve as catalyst.Such as, Chinese patent
CN93108930.1 discloses a kind of grain size and is at least 1 micron of ZSM-5 and is steamed urging for α values no more than 80
Agent, ethyltoluene is prepared at a temperature of 370~480 DEG C by toluene ethylation, and product ethyltoluene can be dehydrogenated shape
Into polymer grade ethanol toluene.Chinese patent CN201010299104.9 by using ten-ring pore structure Hydrogen Si-Al zeolite and
The catalyst of at least one of alkaline metal oxide metal oxide composition, first is carried out at 350~440 DEG C of reaction temperature
The reaction of benzene and ethanol, solves the problem of side reactions such as disproportionated reaction and isomerization reaction are serious.Chinese patent
CN201110365524.7 discloses a kind of production method of vinyltoluene, and it is using toluene and ethanol as raw material, anhydrous three
Alumina catalyst effect the first and second benzene of lower synthesis, reaction temperature is controlled at 350~420 DEG C.Chinese patent CN94110202.5
ZSM-5 zeolite molecular sieve is used to be used for toluene and the benzene of ethanol system first and second for catalyst, catalyst is using preceding needing with containing rich lanthanum
Mischmetal is modified, the characteristics of with high shape selectivity, excellent activity stability.
Foregoing invention has carried out various modifications to catalyst, and toluene and ethanol synthesis production first and second are improved to some extent
The ethanol conversion of benzene and the first and second benzene selectives.Due to being limited in catalyst activity component by catalysis material, these methods are equal
Need the high temperature more than 300 DEG C to be reacted, be unfavorable for the energy-saving of the first and second benzene production, and there is ethanol conversion and have
The problems such as treating complicated further raising, the preparation of catalyst and cumbersome modification procedure.
The content of the invention
It is high that the technical problems to be solved by the invention are that prior art has a reaction temperature, and ethanol conversion is low and catalyst
There is provided a kind of method of new toluene and the benzene of alcohol production first and second for the problem of preparing complicated.This method has reaction temperature low, second
The characteristics of alcohol conversion height and simple catalyst preparation.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of toluene and the benzene of alcohol production first and second
Method, using toluene and ethanol as reaction raw materials, in 160~240 DEG C of reaction temperature, 2.0~6.0MPa of reaction pressure, ethanol weight
Measure air speed 0.1~1.0 hour-1, under conditions of toluene/ethanol mol ratio 2~10, reaction raw materials contact generation first and second with catalyst
Benzene；The catalyst is in terms of parts by weight, including following component：A) 40~90 parts of micro porous molecular sieve；B) 10~60 parts viscous
Tie agent；
Wherein, the microporous molecular is screened from at least one in MWW, BEA, MOR or FAU topological structure molecular sieve
Kind.
In above-mentioned technical proposal, it is preferable that the microporous molecular screened from MCM-22 molecular sieves, MCM-49 molecular sieves,
At least one of MCM-56 molecular sieves, mercerising molecular sieve, Beta molecular sieves or Y type molecular sieve.It is highly preferred that the micropore point
Son is screened from MCM-22 molecular sieves, MCM-49 molecular sieves, MCM-56 molecular sieves, mercerising molecular sieve, Beta molecular sieves or Y type molecules
At least two in sieve.Most preferably, the microporous molecular is screened from MCM-22 molecular sieves, MCM-49 molecular sieves or MCM-56 points
At least two in son sieve.
In above-mentioned technical proposal, it is preferable that the SiO of the micro porous molecular sieve2/Al2O3Mol ratio is 5~100.More preferably
Ground, the SiO of the micro porous molecular sieve2/Al2O3Mol ratio is 10~80.Most preferably, the SiO of the micro porous molecular sieve2/Al2O3
Mol ratio is 15~75.
In above-mentioned technical proposal, it is preferable that in terms of parts by weight, the consumption of micro porous molecular sieve is 50~80 parts, binding agent
Consumption be 20~50 parts.
In above-mentioned technical proposal, it is preferable that the binding agent is selected from aluminum oxide or silica.
In above-mentioned technical proposal, it is preferable that reaction temperature is 180~220 DEG C, reaction pressure is 3.0~5.0MPa, ethanol
Weight space velocity is 0.2~1.0 hour-1, toluene/ethanol mol ratio is 3~8.
In the inventive method, the micro porous molecular sieve is exchanged using known ammonium, dried and roasted before being molded with binding agent
Burning technology processing.For example, ammonium exchange using weight concentration 1~20% ammonium salt solution, under the conditions of 0~100 DEG C handle 0.5~
24 hours.The ammonium salt is selected from least one of ammonium nitrate, ammonium chloride, ammonium oxalate, ammonium sulfate or ammonium citrate.It is described to exchange
Typically also include filtering, water-washing step.Drying steps are to be handled 1~10 hour at 100~140 DEG C.Calcination stepses are 500
Handled 1~10 hour at~550 DEG C.
The molecular sieve with MWW, BEA, MOR or FAU topological structure that the inventive method is used as catalyst work
Property component, with prior art generally using ten-ring ZSM-5 equimoleculars sieve compared with, these topological structure molecular sieves contain 12
Membered ring channel, at low temperature reactant molecule can just be reacted into duct on activated centre, twelve-ring duct is also
It is easy to the diffusion of reaction product, is effectively reduced side reaction or the generation of secondary response.Point especially with MWW topological structures
Son sieve has half supercage of twelve-ring in outer surface, it is easier to react and product diffusion.Meanwhile, by using lower sial
The molecular sieve of ratio, can provide more active sites, improve the conversion ratio of ethanol.Using the inventive method, reaction temperature can be reduced
To 170~220 DEG C, ethanol conversion can improve 1.3~3.7 percentage points, and the preparation process of catalyst is simple, need not change
Property processing, achieve preferable technique effect.
Below by embodiment further instruction is given to the present invention.
Embodiment
【Comparative example 1】
The ZSM-5 molecular sieve that 100 grams have ten-ring is exchanged 5 hours with the ammonium nitrate solution of 4000 gram 10% (wt),
Gained molecular sieve then through 550 DEG C of steam treatments 5 hours, then carries mischmetal lanthanum and cerium through 120 DEG C of drying, 550 DEG C of roastings
Amount be 1.0%, product silicon amount be 3.0%, gained sample is weighed 70 grams, with 30 grams of aluminum oxide mediate extruded moulding, drying,
The first and second benzene catalyst W1 are made in roasting, and its active constituent Rare Earth Lanthanum, the weight content of cerium modification ZSM-5 molecular sieve are 70%.
【Comparative example 2】
The ZSM-5 molecular sieve that 100 grams have ten-ring is exchanged 5 hours with the ammonium nitrate solution of 4000 gram 10% (wt),
Gained molecular sieve through 120 DEG C of drying, 550 DEG C of roastings, then with 7.5% magnesium nitrate solution modification 10 hours, drying,
After roasting, gained sample is weighed 80 grams, the aluminum oxide with 20 grams mediates extruded moulding, drying, the obtained first and second benzene catalysis of roasting
Agent W2, the weight content for the ZSM-5 molecular sieve that its active constituent alkaline metal oxide is modified is 80%, and the content of magnesium is
0.32%.
【Embodiment 1】
By 100 grams of ammonium nitrate solutions with 4000 gram 10% (wt) of MCM-22 molecular sieves with MWW topological structures in 40
Handled 20 hours at DEG C, 50 grams are weighed after gained molecular sieve drying, roasting, the aluminum oxide with 50 grams mediates extruded moulding, baking
The first and second benzene catalyst A are made in dry, roasting, and the weight content of its active constituent MCM-22 molecular sieves is 50%.
【Embodiment 2】
By 100 grams of the Beta molecular sieves with BEA topological structures and the MCM-22 molecular sieves 100 with MWW topological structures
The ammonium nitrate solution with 4000 gram 10% (wt) at 40 DEG C in handling 20 hours gram respectively, after gained molecular sieve drying, roasting
35 grams are respectively weighed, the aluminum oxide with 30 grams mediates extruded moulding, drying, the obtained first and second benzene catalyst B of roasting, its active constituent
The gross weight content of Beta molecular sieves and MCM-22 molecular sieves is 70%.
【Embodiment 3】
By 100 grams of ammonium nitrate solutions with 4000 gram 10% (wt) of Y type molecular sieve with FAU topological structures at 40 DEG C
Processing 20 hours, 60 grams are weighed after gained molecular sieve drying, roasting, and the aluminum oxide with 40 grams mediates extruded moulding, drying, roasting
The first and second benzene catalyst C are fired to obtain, the weight content of its active constituent Y type molecular sieve is 60%.
【Embodiment 4】
By 100 grams of ammonium nitrate solutions with 4000 gram 10% (wt) of MCM-22 molecular sieves with MWW topological structures in 80
Handled 10 hours at DEG C, 60 grams are weighed after gained molecular sieve drying, roasting, the aluminum oxide with 30 grams mediates extruded moulding, baking
The first and second benzene catalyst D are made in dry, roasting, and the weight content of its active constituent MCM-22 molecular sieves is 60%.
【Embodiment 5】
By 100 grams of ammonium nitrate solutions with 4000 gram 10% (wt) of Beta molecular sieves with BEA topological structures in 80 DEG C
Lower processing 10 hours, 60 grams are weighed after gained molecular sieve drying, roasting, with 40 grams of aluminum oxide mediate extruded moulding, drying,
The first and second benzene catalyst E are made in roasting, and the weight content of its active constituent Beta molecular sieves is 60%.
【Embodiment 6】
By 100 grams of 100 grams of MCM-22 molecular sieves and MCM-56 molecular sieves with MWW topological structures respectively with 4000 grams
10% (wt) ammonium nitrate solution at 80 DEG C handle 10 hours, gained molecular sieve drying, roasting after weigh respectively 50 grams and
30 grams, the silica with 20 grams mediates extruded moulding, drying, the obtained first and second benzene catalyst F of roasting, MCM-22 points of its active constituent
The weight content of son sieve and MCM-56 molecular sieves is 80%.
【Embodiment 7】
By 100 grams of ammonium nitrate solutions with 4000 gram 10% (wt) of mercerising molecular sieve with MOR topological structures in 80 DEG C
Lower processing 10 hours, 50 grams are weighed after gained molecular sieve drying, roasting, with 50 grams of silica mediate extruded moulding, drying,
The first and second benzene catalyst G are made in roasting, and the weight content of its active constituent mercerising molecular sieve is 50%.
【Embodiment 8】
By 100 grams of Y type molecular sieve and 100 grams of difference of MCM-56 molecular sieves of MWW topological structures with FAU topological structures
Ammonium nitrate solution with 4000 gram 10% (wt) claims respectively in being handled 10 hours at 80 DEG C after gained molecular sieve drying, roasting
45 grams and 30 grams are taken, the silica with 25 grams mediates extruded moulding, drying, the obtained first and second benzene catalyst H of roasting, its active constituent
The weight content of Y type molecular sieve and MCM-56 molecular sieves is 75%.
【Embodiment 9】
By 100 grams of 100 grams of MCM-49 molecular sieves and MCM-56 molecular sieves with MWW topological structures respectively with 4000 grams
10% (wt) ammonium nitrate solution at 80 DEG C handle 10 hours, gained molecular sieve drying, roasting after weigh respectively 40 grams and
20 grams, the silica with 20 grams mediates extruded moulding, drying, the obtained first and second benzene catalyst I of roasting, MCM-49 points of its active constituent
The gross weight content of son sieve and MCM-56 molecular sieves is 60%.
【Embodiment 10】
The first and second benzene catalyst A~I that the present invention is provided and comparative example catalyst W1, W2 reacts in toluene and ethanol alkylation
Middle contrast effect, reaction pressure is 4.0MPa, and the mol ratio of toluene/ethanol is 5, and ethanol weight space velocity is 0.4 hour -1, catalysis
The loadings of agent are 6.0, and specific reaction result is shown in Table 1.
The response data of the toluene of table 1 and the benzene of ethanol alkylation system first and second
| First and second benzene catalyst | Reaction temperature (DEG C) | Ethanol conversion (%) |
| A | 180 | 98.2 |
| B | 180 | 98.8 |
| C | 190 | 97.9 |
| D | 190 | 98.4 |
| E | 200 | 97.8 |
| F | 210 | 99.0 |
| G | 210 | 97.6 |
| H | 220 | 98.5 |
| I | 220 | 99.1 |
| W1 | 400 | 96.3 |
| W2 | 390 | 95.4 |
Claims (10)
1. a kind of method of toluene and the benzene of alcohol production first and second, using toluene and ethanol as reaction raw materials, reaction temperature 160~
200 DEG C, 2.0~6.0MPa of reaction pressure, ethanol weight space velocity 0.1~1.0 hour-1, the bar of toluene/ethanol mol ratio 2~10
Under part, reaction raw materials contact the first and second benzene of generation with catalyst；The catalyst is in terms of parts by weight, including following component：a)40
~90 parts of micro porous molecular sieve；B) 10~60 parts of binding agent；
Wherein, the microporous molecular is screened from at least one of MWW, BEA, MOR or FAU topological structure molecular sieve.
2. the method for toluene and the benzene of alcohol production first and second according to claim 1, it is characterised in that the microporous molecular screening
From in MCM-22 molecular sieves, MCM-49 molecular sieves, MCM-56 molecular sieves, mercerising molecular sieve, Beta molecular sieves or Y type molecular sieve
It is at least one.
3. the method for toluene and the benzene of alcohol production first and second according to claim 2, it is characterised in that the microporous molecular screening
From in MCM-22 molecular sieves, MCM-49 molecular sieves, MCM-56 molecular sieves, mercerising molecular sieve, Beta molecular sieves or Y type molecular sieve
At least two.
4. the method for toluene and the benzene of alcohol production first and second according to claim 3, it is characterised in that the microporous molecular screening
At least two from MCM-22 molecular sieves, MCM-49 molecular sieves or MCM-56 molecular sieves.
5. the method for toluene and the benzene of alcohol production first and second according to claim 1, it is characterised in that the micro porous molecular sieve
SiO2/Al2O3Mol ratio is 5~100.
6. the method for toluene and the benzene of alcohol production first and second according to claim 5, it is characterised in that the micro porous molecular sieve
SiO2/Al2O3Mol ratio is 10~80.
7. the method for toluene and the benzene of alcohol production first and second according to claim 6, it is characterised in that the micro porous molecular sieve
SiO2/Al2O3Mol ratio is 15~75.
8. the method for toluene and the benzene of alcohol production first and second according to claim 1, it is characterised in that in terms of parts by weight, micropore
The consumption of molecular sieve is 50~80 parts, and the consumption of binding agent is 20~50 parts.
9. the method for toluene and the benzene of alcohol production first and second according to claim 1, it is characterised in that the binding agent is selected from oxygen
Change aluminium or silica.
10. the method for toluene and the benzene of alcohol production first and second according to claim 1, it is characterised in that reaction temperature is 180~
200 DEG C, reaction pressure is 3.0~5.0MPa, and ethanol weight space velocity is 0.2~1.0 hour-1, toluene/ethanol mol ratio be 3~
8。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410427966.3A CN105367373B (en) | 2014-08-27 | 2014-08-27 | The method of toluene and the benzene of alcohol production first and second |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410427966.3A CN105367373B (en) | 2014-08-27 | 2014-08-27 | The method of toluene and the benzene of alcohol production first and second |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105367373A CN105367373A (en) | 2016-03-02 |
| CN105367373B true CN105367373B (en) | 2017-09-15 |
Family
ID=55370074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410427966.3A Active CN105367373B (en) | 2014-08-27 | 2014-08-27 | The method of toluene and the benzene of alcohol production first and second |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105367373B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102599A (en) * | 1985-04-01 | 1986-09-17 | 大连工学院 | Hydrogen zeolite catalyst |
| CN101618335A (en) * | 2009-08-06 | 2010-01-06 | 上海卓悦化工科技有限公司 | Method for preparing catalyst for compounding p-diethylbenzene by alkylation reaction of ethylbenzene and ethane or alcohol |
| CN102276411A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Method for synthesizing ethylbenzene from ethanol and benzene |
| CN102276413A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Method for preparing ethyl benzene through gas phase alkylation of ethanol and benzene |
| CN103664474A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for synthesizing p-diethylbenzene employing ethylbenzene-ethanol alkylation reaction |
| CN103664483A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for producing ethylbenzene by reaction of benzene and ethanol |
-
2014
- 2014-08-27 CN CN201410427966.3A patent/CN105367373B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102599A (en) * | 1985-04-01 | 1986-09-17 | 大连工学院 | Hydrogen zeolite catalyst |
| CN101618335A (en) * | 2009-08-06 | 2010-01-06 | 上海卓悦化工科技有限公司 | Method for preparing catalyst for compounding p-diethylbenzene by alkylation reaction of ethylbenzene and ethane or alcohol |
| CN102276411A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Method for synthesizing ethylbenzene from ethanol and benzene |
| CN102276413A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Method for preparing ethyl benzene through gas phase alkylation of ethanol and benzene |
| CN103664474A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for synthesizing p-diethylbenzene employing ethylbenzene-ethanol alkylation reaction |
| CN103664483A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for producing ethylbenzene by reaction of benzene and ethanol |
Non-Patent Citations (1)
| Title |
|---|
| 甲苯与乙醇选择性烷基化生成对甲乙苯;刘上垣等;《石油化工》;19871231;第16卷;第556页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105367373A (en) | 2016-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105536863B (en) | A kind of molecular sieve catalyst and its preparation method and purposes for methanol conversion for preparing arene | |
| CN103539152B (en) | Core-shell molecular sieve of Si modification and preparation method thereof | |
| CN104549479A (en) | Catalyst for preparing aromatics by use of methanol and preparation method of catalyst | |
| CN102040459A (en) | Toluene methanol methylation reaction method | |
| WO2018010360A1 (en) | Preparation and application of high-performance toluene side-chain alkylation catalyst | |
| CN103785464B (en) | A kind of high activity alkylation of toluene methanol catalyst and its preparation method and application | |
| CN101352690B (en) | Preparation method and use of molecular sieve catalyst for producing phenylethane from alkylation of benzene with dilute ethylene | |
| CN110026234A (en) | A kind of alkylation catalyst and its preparation method and application | |
| CN102746096A (en) | Method for liquid phase transalkylation of polyethylbenzene and benzene | |
| CN103028430B (en) | A kind of MWW type molecular sieve carrier catalyst and its preparation method and application | |
| CN103418425B (en) | Catalyst of preparing propylene by methanol transformation and preparation method thereof | |
| CN103028435A (en) | Catalyst for preparing propylene through conversion of methanol and preparation method of catalyst | |
| CN104148108B (en) | A kind of alkylated reaction catalyst and its preparation method and application | |
| CN102039150A (en) | Preparation method of binderless Y zeolite catalyst | |
| CN105367373B (en) | The method of toluene and the benzene of alcohol production first and second | |
| CN110871105B (en) | ZSM-5 molecular sieve catalyst and preparation method and application thereof | |
| CN105272797B (en) | Benzene and methanol alkylation reaction method | |
| CN107759433A (en) | Paraxylene and ethylbenzene selective disproportionation method | |
| CN100368356C (en) | Method for producing propylene through catalytic cracking C4 olefin | |
| CN104276924B (en) | Toluene and ethylbenzene selective disproportionation method | |
| CN105749961B (en) | A kind of shape-selective catalyst for preparing paraxylene and its preparation and application | |
| CN102875315B (en) | The method of ethanol and benzene producing ethyl benzene through alkylation in gas phase | |
| CN103785463B (en) | Alkylation of toluene methanol catalyst and its preparation method and application | |
| CN114433220B (en) | Preparation method of benzene and synthesis gas alkylation catalyst | |
| CN103041845B (en) | Catalyst composition containing modified ZSM-11 zeolite and application of catalyst composition |
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 |