CN107540502A - The method that oxygen-containing compound material is catalytically conveted to ethene, propylene and aromatic hydrocarbons - Google Patents

The method that oxygen-containing compound material is catalytically conveted to ethene, propylene and aromatic hydrocarbons Download PDF

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Publication number
CN107540502A
CN107540502A CN201610498406.6A CN201610498406A CN107540502A CN 107540502 A CN107540502 A CN 107540502A CN 201610498406 A CN201610498406 A CN 201610498406A CN 107540502 A CN107540502 A CN 107540502A
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propylene
ethene
oxygen
aromatic hydrocarbons
catalyst
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李晓红
齐国祯
王艳学
王菊
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/40Ethylene production

Abstract

The present invention relates to a kind of method that oxygen-containing compound material is converted into ethene, propylene and aromatic hydrocarbons, mainly solves the problems, such as to be difficult to obtain higher diene and aromatics yield when ethene, propylene and aromatic hydrocarbons coproduction in the prior art.Carbon content of the invention by controlling catalyst in fluidized-bed reactor, and complex reaction condition adjusts, obtain ethene and propylene one way carbon base absorption rate is more than 20%, aromatic hydrocarbons one way carbon base absorption rate is more than 48% technical scheme, preferably solves the problem, available in ethene, propylene and arene industrial production.

Description

The method that oxygen-containing compound material is catalytically conveted to ethene, propylene and aromatic hydrocarbons
Technical field
The present invention relates to a kind of method that oxygen-containing compound material is catalytically conveted to ethene, propylene and aromatic hydrocarbons.
Background technology
Ethene, propylene and aromatic hydrocarbons (especially triphen, benzene Benzene, toluene Toluene, dimethylbenzene Xylene, i.e. BTX) It is important basic organic synthesis raw material.Driven by downstream derivative thing demand, the market demand of ethene, propylene and aromatic hydrocarbons continues Increase.
It is ethene, propylene and virtue with the steam cracking process that liquid hydrocarbon (such as naphtha, diesel oil, secondary operation oil) is raw material The main production of hydrocarbon.The technique belongs to petroleum path production technology, in recent years, due to the limited supply of petroleum resources and Higher price, cost of material are continuously increased.By factor, alternative materials prepare ethene, propylene and aromatic hydrocarbons technology cause it is more next More widely pay close attention to.Wherein, for coal-based methanol, dimethyl ether raw material, due to China's coal aboundresources, it is increasingly becoming one kind Important Chemical Manufacture raw material, turn into the important supplement of petroleum.Accordingly, it is considered to using methanol and/or dimethyl ether as raw material system Standby ethene, propylene and aromatic hydrocarbons.
In various existing methanol, dimethyl ether catalysis transformation technology, the product of methanol/dimethyl ether conversion aromatic hydrocarbons is simultaneously Including ethene, propylene and aromatic hydrocarbons.The technology initially sees Chang of Mobil companies in 1977 et al. (Journal of Catalysis, 1977,47,249) report methanol and its oxygenatedchemicals conversion preparation virtue on ZSM-5 molecular sieve catalyst The method of the hydrocarbons such as hydrocarbon.1985, Mobil companies disclosed first in its United States Patent (USP) applied US1590321 The result of study of methanol, dimethyl ether conversion aromatic hydrocarbons, it is catalysis that the research, which uses the phosphorous ZSM-5 molecular sieve for 2.7 weight %, Agent, reaction temperature are 400~450 DEG C, methanol, dimethyl ether air speed 1.3 hours -1.
The relevant report and patent in the field are more, but the purpose product of most of technologies is aromatic hydrocarbons, ethene, propylene category It is low in accessory substance, yield.Such as the patent in terms of methanol arenes catalytic agent:Chinese patent CN102372535, CN102371176、CN102371177、CN102372550、CN102372536、CN102371178、CN102416342、 CN101550051, United States Patent (USP) US4615995, US2002/0099249A1 etc..Such as in terms of methanol aromatics process Patent:United States Patent (USP) US4686312, Chinese patent ZL101244969, ZL1880288, CN101602646, CN101823929, CN101671226, CN102199069, CN102199446, CN1880288 etc..
In addition, while technology path disclosed in some patents is methanol aromatic hydrocarbons co-producing light olefins, gasoline etc. other Product, such as patent CN102775261, CN102146010, CN102531821, CN102190546, CN102372537.
Wherein, Multi-function methanol processing method disclosed in patent CN102775261 and device utilize methanol production low-carbon alkene Hydrocarbon, gasoline, aromatic hydrocarbons.This method uses two-step method production technology, and first step methanol feedstock produces low under the effect of special-purpose catalyst 1 Carbon olefin, second step by the reaction gas containing low-carbon alkene after heat exchange, chilling, carrying out washing treatment, in the presence of special-purpose catalyst 2 Synthesize aromatic hydrocarbons and/or gasoline.The reactor of two courses of reaction can be fixed bed or fluid bed.This method uses two kinds of catalyst, Technological process is complicated.
Patent CN102146010 discloses the work that low-carbon alkene and arene parallel cogeneration gasoline are produced using methanol as raw material Skill.Low-carbon alkene and aromatic hydrocarbons are produced using methanol as raw material and using molecular sieve catalyst through methanol alkylation reaction and aromatization Co-production gasoline.The reactor of methanol alkylation reaction and aromatization is various types of fixed bed reactors.
Patent CN102531821 discloses methanol and the method for the co-feeding production low-carbon alkene of naphtha and/or aromatic hydrocarbons, Using load 2.2~6.0 weight %La and 1.0~2.8 weight %P ZSM-5 catalyst, fixed bed reactors or stream can be used Fluidized bed reactor.Reaction temperature is 550~670 DEG C, air speed 1.0~5 hours -1.Methanol and naphtha are co-feeding in this method, Using a reactor.
The method that patent CN102372537 and CN102190546 disclose preparing propylene by methanol transformation and aromatic hydrocarbons.This two specially Profit is developed on the basis of preparing propylene by methanol transformation technology, and propylene is main purpose product, and aromatics yield is relatively low.
Technological process complexity, ethene, the problem of propylene and aromatics yield are low in above-mentioned patented technology all be present.Pin of the present invention Technical scheme is proposed to property, solves above mentioned problem.
The content of the invention
The technical problems to be solved by the invention are difficult to obtain higher when being ethene, propylene and aromatic hydrocarbons coproduction in the prior art The technical problem of diene and aromatics yield, there is provided a kind of oxygen-containing compound material is catalytically conveted to the side of ethene, propylene and aromatic hydrocarbons Method.This method has the advantages of diene and high aromatics yield.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:A kind of oxygen-containing compound material catalysis turns The method for turning to ethene, propylene and aromatic hydrocarbons, oxygen-containing compound material enter fluidized-bed reactor and including aluminosilicate molecular sieves Catalyst reaction, be more than the condition that 20%, aromatic hydrocarbons one way carbon base absorption rate is more than 48% in ethene and propylene one way carbon base absorption rate Under, reaction obtains the product rich in ethene, propylene and aromatic hydrocarbons, it is characterised in that the carbon in fluidized-bed reactor on catalyst, with The mass percent meter of catalyst, content are 0.2~1.5%.
In above-mentioned technical proposal, the carbon in fluidized-bed reactor on catalyst, in terms of the mass percent of catalyst, content For 0.5~1.1%.
In above-mentioned technical proposal, it is preferred that reaction temperature is 460~520 DEG C, and catalyst in reactor bed density is 200~450 kilograms per cubic meter, the mass space velocity of oxygen-containing compound material is 0.3~3 hour-1, reaction pressure is calculated as 0 with gauge pressure ~0.3 MPa.
In above-mentioned technical proposal, ethene and propylene one way carbon base absorption rate are more than 22%, and aromatic hydrocarbons one way carbon base absorption rate is more than 50%.
In above-mentioned technical proposal, fluidized-bed reactor interior reaction temperature is 480~510 DEG C, catalyst in reactor bed Density is 280~400 kilograms per cubic meter, and the mass space velocity of oxygen-containing compound material is 0.5~2 hour -1, and reaction pressure is with table Pressure is calculated as 0~0.25 MPa.
In above-mentioned technical proposal, oxygen-containing compound material include at least one selection methanol, ethanol, normal propyl alcohol, isopropanol, C4~C20Alcohol, ethyl methyl ether, dimethyl ether, diethyl ether, Di Iso Propyl Ether, formaldehyde, dimethyl carbonate, acetone, the compound of acetic acid, it is excellent Select methanol, ethanol, dimethyl ether.
In above-mentioned technical proposal, the weight/mass percentage composition of oxygenatedchemicals is at least 10% in oxygen-containing compound material, excellent Choosing at least 30%.
In above-mentioned technical proposal, catalyst activity component ZSM-5, ZSM-23, ZSM-11, beta-molecular sieve, Y molecular sieve or The composite molecular screen formed each other, preferably ZSM-5;Carrier is kaolin, aluminum oxide, silica;Active component and carrier Mass ratio be 10~50: 50~90, preferably 20~40: 60~80.
In above-mentioned technical proposal, catalyst is loaded with one or more elements or oxidation in Zn, Ag, P, Ga, Cu, Mn, Mg Thing, preferably Zn, P;In terms of the mass percent of catalyst, the content of the element of load on a catalyst is 0.01~15 weight Measure %, preferably 0.02~8 weight %.
In above-mentioned technical proposal, the active component of catalyst is selected from ZSM-5 molecular sieve, with the percentage by weight of catalyst Count, 0.01~5 weight % Zn elements or oxide, 0.1~8 weight % P element or oxide are loaded on catalyst.
Oxygenatedchemicals aromatization process, oxygenatedchemicals are first dehydrated generation lower carbon number hydrocarbons, and lower carbon number hydrocarbons continues that aromatisation occurs Reaction.Result of study shows that the catalyst activity and reaction condition that two-step reaction needs differ.It is active using low catalyst, Short residence time can effectively suppress second step reaction, lower carbon number hydrocarbons is retained, while improve the selectivity of ethene, propylene. Therefore can be by regulating and controlling coke content on catalyst, and complex reaction condition adjusts, it is possible to achieve ethene and propylene one way carbon Base yield is more than 20%, and aromatic hydrocarbons one way carbon base absorption rate is more than 48%.Now, the carbon in fluidized-bed reactor on catalyst, to urge The mass percent meter of agent, content are 0.2~1.5%, and each point temperature is 450~520 DEG C, and catalyst in reactor bed is close Spend for 200~450 kilograms per cubic meter, the mass space velocity of oxygen-containing compound material is 0.1~4 hour-1, reaction pressure is with gauge pressure It is calculated as 0~0.5 MPa.
Using technical scheme, oxygen-containing compound material is methanol;The reaction temperature of fluidized-bed reactor is 490 DEG C, catalyst in reactor bed density is 350 kilograms per cubic meter, and the mass space velocity of methanol is 1 hour -1, reaction pressure with Gauge pressure is calculated as 0.1 MPa;Carbon on catalyst in reactor, in terms of the mass percent of catalyst, content 0.5%;Using Modified ZSM-5 catalyst;Ethene and propylene carbon base absorption rate are 23.1 weight %, and aromatic hydrocarbons carbon base absorption rate is 57.5 weight %.
Embodiment
【Embodiment 1】
Oxygen-containing compound material is methanol.Each point temperature is 460 DEG C in fluidized-bed reactor, and beds density is 450 kilograms per cubic meter, the mass space velocity of methanol is 0.3 hour-1, reaction pressure is calculated as 0 MPa with gauge pressure.It is catalyzed in reactor Carbon in agent, in terms of the mass percent of catalyst, content 0.2%.Using Ag-ZSM-5 catalyst, Ag constituent contents are 1.3%, the mass ratio of ZSM-5 molecular sieve and matrix is 4:6, the silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 25.Reaction result is shown in Table 1。
【Embodiment 2】
Oxygen-containing compound material is dimethyl ether.Each point temperature is 520 DEG C in fluidized-bed reactor, and beds density is 200 kilograms per cubic meter, the mass space velocity of methanol is 3 hours-1, reaction pressure is calculated as 0.3 MPa with gauge pressure.It is catalyzed in reactor Carbon in agent, in terms of the mass percent of catalyst, content 1.5%.Using Mn-ZSM-11 catalyst, ZSM-11 molecular sieves Mass ratio with matrix is 3:7;The silicoaluminophosphate molecular ratio of ZSM-11 molecular sieves is 50;Matrix is the mixed of kaolin and alundum (Al2O3) Compound, both mass ratioes are 7:3, Mn constituent contents are 9.09%.Reaction result is shown in Table 1.
【Embodiment 3】
Oxygen-containing compound material is ethanol.Each point temperature is 500 DEG C in fluidized-bed reactor, and beds density is 250 kilograms per cubic meter, the mass space velocity of methanol is 0.8 hour-1, reaction pressure is calculated as 0.05 MPa with gauge pressure.Urged in reactor Carbon in agent, in terms of the mass percent of catalyst, content 0.6%.Using La-ZSM-5- beta catalysts, ZSM-5 and β divide Son sieve and the mass ratio of matrix are 3.5: 6.5.The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 38;The silicoaluminophosphate molecular ratio of beta-molecular sieve is 20;The mass ratio of ZSM-5 and beta-molecular sieve is 9:1.La constituent contents are 5.4%.Reaction result is shown in Table 1.
【Embodiment 4】
Oxygen-containing compound material is methanol.Each point temperature is 480 DEG C in fluidized-bed reactor, and beds density is 280 kilograms per cubic meter, the mass space velocity of methanol is 0.5 hour-1, reaction pressure is calculated as 0 MPa with gauge pressure.It is catalyzed in reactor Carbon in agent, in terms of the mass percent of catalyst, content 0.8%.Using Zn-P-ZSM-5 catalyst, ZSM-5 molecular sieve Mass ratio with matrix is 3.5:6.5;The silicoaluminophosphate molecular ratio of ZSM-5 molecular sieve is 25;Matrix is kaolin and alundum (Al2O3) Mixture, both mass ratioes be 7:3, Zn constituent contents are 2.87%, and P element content is 1.48%.Reaction result is shown in Table 1。
【Embodiment 5】
Using the raw material and catalyst of embodiment 4.Each point temperature is 490 DEG C in fluidized-bed reactor, and beds are close Spend for 320 kilograms per cubic meter, the mass space velocity of methanol is 1.5 hours-1, reaction pressure is calculated as 0.1 MPa with gauge pressure.Reactor Carbon on interior catalyst, in terms of the mass percent of catalyst, content 0.5%.Reaction result is shown in Table 1.
【Embodiment 6】
Using the raw material and catalyst of embodiment 4.Each point temperature is 510 DEG C in fluidized-bed reactor, and beds are close Spend for 400 kilograms per cubic meter, the mass space velocity of methanol is 2.5 hours-1, reaction pressure is calculated as 0.25 MPa with gauge pressure.Reactor Carbon on interior catalyst, in terms of the mass percent of catalyst, content 1.1%.Reaction result is shown in Table 1.
【Comparative example 1】
Using the raw material and catalyst of embodiment 4.Each point temperature is 540 DEG C in fluidized-bed reactor, and beds are close Spend for 180 kilograms per cubic meter, the mass space velocity of methanol is 3.5 hours-1, reaction pressure is calculated as 0.4 MPa with gauge pressure.Reactor Carbon on interior catalyst, in terms of the mass percent of catalyst, content 1.7%.Reaction result is shown in Table 1.
【Comparative example 2】
Using the raw material and catalyst of embodiment 4.Each point temperature is 430 DEG C in fluidized-bed reactor, and beds are close Spend for 480 kilograms per cubic meter, the mass space velocity of methanol is 0.2 hour-1, reaction pressure is calculated as 0 MPa with gauge pressure.In reactor Carbon on catalyst, in terms of the mass percent of catalyst, content 0.1%.Reaction result is shown in Table 1.
【Comparative example 3】
Using the raw material, catalyst and reaction condition of embodiment 5.Carbon on catalyst in reactor, with the matter of catalyst Measure percentages, content 1.0%.Reaction result is shown in Table 1.
Table 1

Claims (10)

1. a kind of method that oxygen-containing compound material is catalytically conveted to ethene, propylene and aromatic hydrocarbons, oxygen-containing compound material enters to become a mandarin Fluidized bed reactor and the catalyst reaction including aluminosilicate molecular sieves, be more than 20% in ethene and propylene one way carbon base absorption rate, Aromatic hydrocarbons one way carbon base absorption rate is more than under conditions of 48%, and reaction obtains the product rich in ethene, propylene and aromatic hydrocarbons, it is characterised in that Carbon in fluidized-bed reactor on catalyst, in terms of the mass percent of catalyst, content is 0.2~1.5%.
2. the method that oxygen-containing compound material according to claim 1 is catalytically conveted to ethene, propylene and aromatic hydrocarbons, its feature It is that ethene and propylene one way carbon base absorption rate are more than 22%, aromatic hydrocarbons one way carbon base absorption rate and are more than 50%.
3. the method that oxygen-containing compound material according to claim 1 is catalytically conveted to ethene, propylene and aromatic hydrocarbons, its feature The carbon being in fluidized-bed reactor on catalyst, in terms of the mass percent of catalyst, content is 0.5~1.1%.
4. the method that oxygen-containing compound material according to claim 1 is catalytically conveted to ethene, propylene and aromatic hydrocarbons, its feature It is 460~520 DEG C to be reaction temperature, and catalyst in reactor bed density is 200~450 kilograms per cubic meter, oxygen-containing chemical combination The mass space velocity of raw material is 0.3~3 hour-1, reaction pressure is calculated as 0~0.3 MPa with gauge pressure.
5. the method that oxygen-containing compound material according to claim 4 is catalytically conveted to ethene, propylene and aromatic hydrocarbons, its feature It is 480~510 DEG C to be reaction temperature, and catalyst in reactor bed density is 280~400 kilograms per cubic meter, oxygen-containing chemical combination The mass space velocity of raw material is 0.5~2 hour-1, reaction pressure is calculated as 0~0.25 MPa with gauge pressure.
6. the method that oxygen-containing compound material according to claim 1 is catalytically conveted to ethene, propylene and aromatic hydrocarbons, its feature It is that oxygen-containing compound material includes at least one selection methanol, ethanol, normal propyl alcohol, isopropanol, C4~C20Alcohol, ethyl methyl ether, two Methyl ether, diethyl ether, Di Iso Propyl Ether, formaldehyde, dimethyl carbonate, acetone, the compound of acetic acid.
7. the method that oxygen-containing compound material according to claim 5 is catalytically conveted to ethene, propylene and aromatic hydrocarbons, its feature In oxygen-containing compound material the weight/mass percentage composition of oxygenatedchemicals be at least 10%.
8. the method that oxygen-containing compound material according to claim 1 is catalytically conveted to ethene, propylene and aromatic hydrocarbons, its feature The active component for being catalyst is ZSM-5, ZSM-23, ZSM-11, β, Y or the composite molecular screen formed each other;Carrier is Kaolin, aluminum oxide, silica.
9. the method that oxygen-containing compound material according to claim 8 is catalytically conveted to ethene, propylene and aromatic hydrocarbons, its feature The mass ratio for being active component and carrier is 10~50: 50~90.
10. the method that oxygen-containing compound material according to claim 8 is catalytically conveted to ethene, propylene and aromatic hydrocarbons, it is special Sign is being loaded with one or more elements or oxide in Zn, Ag, P, Ga, Cu, Mn, Mg in catalyst, with the quality of catalyst Percentages, its content are 0.01~15%.
CN201610498406.6A 2016-06-29 2016-06-29 The method that oxygen-containing compound material is catalytically conveted to ethene, propylene and aromatic hydrocarbons Pending CN107540502A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108786914A (en) * 2018-05-29 2018-11-13 河南师范大学 A kind of preparation method of ZSM-11/5 composite molecular screens
CN110872524A (en) * 2018-09-04 2020-03-10 中国科学院大连化学物理研究所 Method for preparing aromatic hydrocarbon by converting ABE fermentation liquor
CN112920011A (en) * 2019-12-05 2021-06-08 中国科学院大连化学物理研究所 Method for preparing aromatic hydrocarbon compound from methanol

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CN101844089A (en) * 2010-05-25 2010-09-29 兆威兴业有限公司 Method for partially regenerating catalyst for preparing low-carbon alkenes from methanol or dimethyl ether
CN104549072A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Fluidized bed reaction system and method for preparing ethylene, propylene and aromatic hydrocarbon by converting methanol and/or dimethyl ether
JP2017088595A (en) * 2015-11-04 2017-05-25 鶴壁宝発能源科技股▲ふん▼有限公司 System and process for co-producing mixed olefin, aromatic hydrocarbon and liquefied gas from crude dimethyl ether

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101844089A (en) * 2010-05-25 2010-09-29 兆威兴业有限公司 Method for partially regenerating catalyst for preparing low-carbon alkenes from methanol or dimethyl ether
CN104549072A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Fluidized bed reaction system and method for preparing ethylene, propylene and aromatic hydrocarbon by converting methanol and/or dimethyl ether
JP2017088595A (en) * 2015-11-04 2017-05-25 鶴壁宝発能源科技股▲ふん▼有限公司 System and process for co-producing mixed olefin, aromatic hydrocarbon and liquefied gas from crude dimethyl ether

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108786914A (en) * 2018-05-29 2018-11-13 河南师范大学 A kind of preparation method of ZSM-11/5 composite molecular screens
CN110872524A (en) * 2018-09-04 2020-03-10 中国科学院大连化学物理研究所 Method for preparing aromatic hydrocarbon by converting ABE fermentation liquor
CN110872524B (en) * 2018-09-04 2021-12-17 中国科学院大连化学物理研究所 Method for preparing aromatic hydrocarbon by converting ABE fermentation liquor
CN112920011A (en) * 2019-12-05 2021-06-08 中国科学院大连化学物理研究所 Method for preparing aromatic hydrocarbon compound from methanol

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