CN101607864A - The method of a kind of methyl alcohol/dimethyl ether conversion produced in high yields p-Xylol - Google Patents
The method of a kind of methyl alcohol/dimethyl ether conversion produced in high yields p-Xylol Download PDFInfo
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- CN101607864A CN101607864A CNA2009100900042A CN200910090004A CN101607864A CN 101607864 A CN101607864 A CN 101607864A CN A2009100900042 A CNA2009100900042 A CN A2009100900042A CN 200910090004 A CN200910090004 A CN 200910090004A CN 101607864 A CN101607864 A CN 101607864A
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- xylol
- methyl alcohol
- dimethyl ether
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- 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 method of a kind of methyl alcohol/dimethyl ether conversion produced in high yields p-Xylol is at the molecular sieve catalyst of metal and silanization modification, by add the yield that aromatic hydrocarbons improves p-Xylol in methyl alcohol/dimethyl ether conversion product in raw material.Aromatic hydrocarbons source is divided or all is recycled to reactive system through separate rear part for benzene that methyl alcohol/dimethyl ether conversion reaction generates and/or toluene, or in reaction raw materials extra toluene and/or the benzene of adding.Adopt that aromaticity content can reach more than the 50wt% in this method methyl alcohol/dimethyl ether conversion reaction product, wherein in the aromatic hydrocarbons p-Xylol content greater than 80wt%, p-Xylol in xylene isomer selectivity greater than 99wt%.
Description
Technical field
The present invention relates to the technology of a kind of methyl alcohol/dimethyl ether conversion produced in high yields p-Xylol, relate to particularly by in raw material, adding the yield that aromatic hydrocarbons improves p-Xylol in methyl alcohol/dimethyl ether conversion product.
Background technology
P-Xylol is the basic raw material of synthesizing polyester (PET).At present, toluene, C are mainly adopted in p-Xylol production
9Aromatic hydrocarbons and xylol are raw material, produce by disproportionation, isomerization, fractionation by adsorption or low temperature separation process.Because the p-Xylol content in its product is subjected to thermodynamic control, p-Xylol is at C
8Only account in the BTX aromatics about 20%, material circular treatment amount is big in the technological process, and equipment is huge, the process cost height.Particularly the boiling point of three isomer of dimethylbenzene differs very little, adopts common distillation technique can not obtain the high purity p-Xylol, and must adopt expensive adsorptive separation technology.In recent years, domestic and international many patent disclosures the p-Xylol new way of producing, the p-Xylol that toluene methylation can the production highly selective wherein, but this process still depends on petroleum resources-toluene.
Methyl alcohol/dimethyl ether production aromatic hydrocarbons technology is the new way that is prepared aromatic hydrocarbons by coal or Sweet natural gas, prepares aromatic hydrocarbons by methyl alcohol/dme direct aromizing on metal and molecular sieve composite catalyst.The ZSM-5 molecular sieve is that aromatic hydrocarbons has unique effect to methanol conversion, and in preparing gasoline by methanol (MTG) reaction, the hydrocarbons that ZSM-5 can become to have the gasoline boiling range with methanol conversion effectively contains the aromatic hydrocarbons about 60% in the synthetic gasoline.On acidic molecular sieve, methyl alcohol can be converted into alkane, alkene and aromatic hydrocarbons etc., and molecular sieve type difference, proportion of products are distinguished to some extent, is the effective ways that improve aromatics yield with alkane, alkene dehydroaromatizationof.Therefore the normal at present catalyzer that adopts the metal-modified method of acidic molecular sieve to prepare methyl alcohol system aromatic hydrocarbons.
1977, the people such as Chang of Mobil company (Journal of Catalysis, 1977,47,249) reported that on ZSM-5 molecular sieve catalyst methyl alcohol and oxygenate thereof prepare the method for hydrocarbon polymers such as aromatic hydrocarbons.Studies show that under the metal component effect, alkane, alkene can be converted into aromatic hydrocarbons under certain condition.Therefore, ZSM-5 is carried out the metal component modification, thereby in the methanol conversion process, generate more aromatic hydrocarbons, become the main direction of present research.At present the study on the modification to ZSM-5 mainly concentrates on Zn, Ga modification, and other metal such as Ag, Cu etc. are metal-modified also report.People such as Ono (J.Chem.Soc., Faraday Trans.1,1988,84 (4), 1091 of Japan; Microporous Materials, 1995,4,379) utilize ion exchange method that Zn and Ag are incorporated in the ZSM-5 molecular sieve, investigated the catalytic performance of methyl alcohol system aromatic hydrocarbons (MTA).After the Zn introducing, the content of aromatic hydrocarbons increases in the product, can reach about 67.4% (C%), and aromatics yield can reach about 80% behind the introducing Ag.
Chinese patent CN 101244969 discloses a kind of C
1-C
2The fluidizer of hydro carbons or aromatization of methanol and catalyst regeneration utilizes this device and catalyzer, can regulate the coking state of the catalyzer in the aromatization reactor at any time, transforms C thereby reach continuous high-efficient
1-C
2Hydro carbons or methyl alcohol and highly selective generate the purpose of aromatic hydrocarbons.Chinese patent CN 1880288 discloses a kind of process of methanol conversion for preparing arene, and on the modified zsm-5 zeolite catalyzer, methyl alcohol is catalytically conveted to the product based on aromatic hydrocarbons, has aromatic hydrocarbons overall selectivity height, the flexible process operation advantage.U.S. Pat 4615995 discloses a kind of ZSM-5 molecular sieve catalyst that has supported Zn and Mn, is used for methanol conversion and prepares alkene and aromatic hydrocarbons, can change the ratio of low-carbon alkene/aromatic hydroxy compound in the product by the content of Zn in the regulating catalyst and Mn.
Above-mentioned methanol conversion prepares the aromatic hydrocarbons that obtains in aromatic hydrocarbons technology and the method and is BTX aromatics, the product complexity, and marketable value is low.Handle by silanization the HZSM-5 zeolite molecular sieve, can realize methyl alcohol/dimethyl ether conversion highly-selective preparation p-Xylol, but, since zeolite molecular sieve through acidity behind the silylation modification a little less than, aromaticity content is lower in methyl alcohol/dimethyl ether conversion product, so keeping under the highly-selective preparation p-Xylol condition, how to improve further that aromatics yield will be the key of methyl alcohol/dimethyl ether conversion produced in high yields p-Xylol in the product.
Summary of the invention
The object of the present invention is to provide the method for a kind of methyl alcohol/dimethyl ether conversion produced in high yields p-Xylol.Aromaticity content can be brought up to more than the 50wt% in methyl alcohol/dimethyl ether conversion product, wherein in the aromatic hydrocarbons p-Xylol content greater than 80wt%, p-Xylol in xylene isomer selectivity greater than 99wt%.
For achieving the above object, the present invention is by adding the yield that aromatic hydrocarbons improves p-Xylol in methyl alcohol/dimethyl ether conversion product in raw material.Aromatic hydrocarbons source is divided or all is recycled to reactive system through separate rear part for benzene that methyl alcohol/dimethyl ether conversion reaction generates and/or toluene, or in reaction raw materials extra toluene and/or the benzene of adding.
For achieving the above object, the present invention adopts metal and the combined modified zeolite [molecular sieve of silanization, this catalyzer carries out the former powder of zeolite molecular sieve metal-modified earlier, again through compound-modified surface acidity of siloxanes and pore structure, thereby obtain methyl alcohol/dimethyl ether conversion highly-selective preparation p-Xylol catalyzer.
The catalyzer that the present invention uses, wherein zeolite molecular sieve is the silico-aluminate with crystallization skeleton structure, structure type is MFI or MEL.
The catalyzer that the present invention uses, wherein silico-aluminate is that ZSM-5 is or/and ZSM-11 zeolite molecular sieve, preferably ZSM-5.
The present invention uses the Preparation of catalysts method, and wherein metal is Mn, Co, Ni, Cu, Zn, Mo, Ga oxide compound or its soluble salt, preferred Mn, Zn, Mo oxide compound or its soluble salt.
The present invention uses the Preparation of catalysts method, and wherein metal content is the 0.1-8wt% of total catalyst weight;
The present invention uses the Preparation of catalysts method, and wherein the siloxanes compound is shown below:
R wherein
1, R
2, R
3And R
4It is the alkyl of 1-10 carbon atom.
The present invention uses the Preparation of catalysts method, and wherein, the siloxanes compound is a tetraethyl silicate.
Method of the present invention, wherein, reaction mass is that methyl alcohol is or/and dme.
The method of methyl alcohol of the present invention/dimethyl ether conversion produced in high yields p-Xylol, reactive mode can adopt any form of fixed bed or fluidized-bed.Reaction conditions is: temperature of reaction is 350-550 ℃, is preferably 400-500 ℃; Reaction pressure is 0-2MPa, is preferably 0-1MPa; Methyl alcohol/dme feed weight air speed is 0.1-20h
-1, be preferably 1-10h
-1When toluene or benzene content were not more than 10wt% in methyl alcohol/dme raw material, aromaticity content can reach more than the 50wt% in the reaction product, wherein in the aromatic hydrocarbons p-Xylol content greater than 80wt%, p-Xylol in xylene isomer selectivity greater than 99wt%.
Embodiment
Adopting methyl alcohol or dme and the mixture of the two is raw material, and wherein methyl alcohol can be aqueous methanol, and methanol quality concentration is 50-100%.By in raw material, adding the yield that aromatic hydrocarbons improves p-Xylol in methyl alcohol/dimethyl ether conversion product.Aromatic hydrocarbons source is divided or all is recycled to reactive system through separate rear part for benzene that methyl alcohol/dimethyl ether conversion reaction generates and/or toluene, or in reaction raw materials extra toluene and/or the benzene of adding.Adopt metal and the combined modified zeolite [molecular sieve of silanization, under 400-500 ℃ of condition, will contain and feed after the methyl alcohol of toluene or benzene or the dme feed vaporization in the reactor and the catalyzer contact reacts, product after being incubated by the gas-chromatography on-line analysis.
The catalyzer that the present invention uses is to be active ingredient with the silico-aluminate with crystallization skeleton structure MFI or MEL structure type, after adjusting and reforming property of metal, by silicone agent its outer surface acidity and duct are modified and be prepared into methyl alcohol/dimethyl ether conversion and prepare the p-Xylol catalyzer, its preparation process is as follows:
1, with the former powder of zeolite molecular sieve through NH
4 +Ion-exchange, roasting are prepared into acidic zeolite.
2, use metal soluble salt solution that acidic zeolite is flooded modification, obtain metal-modified zeolite molecular sieve.
3, use siloxanes reagent that metal-modified zeolite molecular sieve is carried out finishing, regulating catalyst outer surface acidity and pore structure obtain metal and silanization combined modified catalyst.
4, will use behind step 3 preparation modified catalyst compressing tablet or the spray drying forming.
The catalyzer that the present invention uses is the Si-Al zeolite molecular sieve of MFI or MEL structure type, can select ZSM-5, ZSM-11 zeolite molecular sieve for use.
The catalyst modification metal that the present invention uses is Mn, Co, Ni, Cu, Zn, Mo, Ga oxide compound or its soluble salt, preferred Mn, Zn, Mo oxide compound or its soluble salt.
In the catalyzer that the present invention uses, metal content 0.1-8wt%.
The present invention uses the Preparation of catalysts method, and wherein the siloxanes compound is shown below:
R wherein
1, R
2, R
3And R
4It is the alkyl of 1-10 carbon atom.
The present invention uses the Preparation of catalysts method, and wherein the siloxanes compound is a tetraethyl silicate.
Reactive mode of the present invention is reaction mass and catalyzer contact reacts, and temperature of reaction is 350-550 ℃, is preferably 400-500 ℃; Reaction pressure is 0-2MPa, is preferably 0-1MPa; Methyl alcohol/dme feed weight air speed is 0.1-20h
-1, be preferably 1-10h
-1When toluene or benzene content were not more than 10wt% in methyl alcohol/dme raw material, aromaticity content can reach more than the 50wt% in the reaction product, wherein in the aromatic hydrocarbons p-Xylol content greater than 80wt%, p-Xylol in xylene isomer selectivity greater than 99wt%.
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to following examples.
The preparation of embodiment 1 fixed bed catalyst
1) with the former powder of 500g ZSM-5 zeolite molecular sieve (Catalyst Factory, Nankai Univ) (SiO
2/ Al
2O
3=50) remove template 550 ℃ of following roastings, the ammonium nitrate solution with 0.5 molar equivalent in 80 ℃ of water-baths exchanges 4 times, and exchange is then dried in 120 ℃ of air, and 550 ℃ of following roastings 3 hours obtain the HZSM-5 zeolite molecular sieve.
2) getting the HZSM-5 zeolite molecular sieve 20g compression molding that step 1) prepares, obtain 40-60 order sample behind crushing and screening, is 9% volume zinc nitrate [Zn (NO with mass concentration
3)
2] solution normal temperature dipping 4 hours, roasting is 6 hours in 120 ℃ of back 550 ℃ of air of oven dry; HZSM-5 zeolite molecular sieve behind employing tetraethoxy (TEOS) the normal temperature dipping zinc modification 24 hours, incline and behind the supernatant liquid that roasting obtained zinc and the combined modified HZSM-5 catalyzer of silanization in 6 hours in 120 ℃ of oven dry, the 550 ℃ of air, Zn content is about 3wt% in the catalyzer, catalyzer called after MTA-06.
The preparation of embodiment 2 fixed bed catalysts
Getting the HZSM-5 zeolite molecular sieve 20g compression molding of step 1) preparation among the embodiment 1, obtain 40-60 order sample behind crushing and screening, is 11.1% nitric acid molybdenum [Mo (NO with mass concentration
3)
3] solution normal temperature dipping HZSM-5 molecular sieve 4 hours, roasting is 6 hours in 120 ℃ of back 550 ℃ of air of oven dry; HZSM-5 zeolite molecular sieve after the modification of employing tetraethoxy (TEOS) normal temperature dipping molybdenum 24 hours, incline and behind the supernatant liquid that roasting obtained molybdenum and the combined modified HZSM-5 catalyzer of silanization in 6 hours in 120 ℃ of oven dry, the 550 ℃ of air, Mo content is about 3wt% in the catalyzer, catalyzer called after MTA-07.
The preparation of embodiment 3 fluid catalysts.
1) gets the HZSM-5 zeolite molecular sieve 200g that step 1) prepares among the embodiment 1, with the manganous nitrate [Mn (NO that with mass concentration is 9.8%
3)
2] solution normal temperature dipping 4 hours, roasting obtained Mn modified HZSM-5 zeolite molecular sieve in 6 hours in 120 ℃ of back 550 ℃ of air of oven dry, and Mn content is about 3wt% in the molecular sieve.
2) HZSM-5 sample and kaolin, silicon sol, aluminium colloidal sol and the deionized water with above-mentioned Mn modification is mixed into slurry, and the butt mass ratio of molecular sieve and kaolin, silicon sol, aluminium colloidal sol is 30: 35: 25: 10, and solid content of slurry is about 35wt%.Slurry obtains the microspherical catalyst that particle diameter is 20-100 μ m at aged at room temperature 5h and by spray shaping behind the colloidal mill glued membrane.
3) microspherical catalyst of the above-mentioned preparation of use tetraethoxy (TEOS) normal temperature dipping is 24 hours, incline and behind the supernatant liquid that roasting obtained manganese and the combined modified HZSM-5 microspherical catalyst of silanization, catalyzer called after MTA-08 in 6 hours in 120 ℃ of oven dry, the 550 ℃ of air.
Comparative Examples 1 fixed bed reaction evaluation
,, in 550 ℃ of air atmospheres, handled 1 hour as catalysts with the catalyzer MTA-06 of preparation among the embodiment 1, under nitrogen atmosphere, cool to 450 ℃ of temperature of reaction the 5g catalyzer fixed-bed reactor of packing into.By fresh feed pump methyl alcohol is pumped into reactor and catalyzer contact reacts.Material benzenemethanol feed weight air speed is 2h
-1, reaction product adopts the on-line analysis of Varian3800 gas-chromatography.Reaction result is as shown in table 1, and aromaticity content is 35.86wt% in the product (remove and generate water), and p-Xylol content is 82.91wt% in the aromatic hydrocarbons, and p-Xylol selectivity in xylene isomer is 99.37wt%.
Table 1
| Catalyzer | ??MTA-06 |
| Temperature of reaction | ??450 |
| Methanol conversion (wt%) | ??86.76 |
| Aromatics yield in the hydrocarbon product (wt%) | ??35.86 |
| P-Xylol is selectivity (wt%) in aromatic hydrocarbons | ??82.91 |
| P-Xylol is selectivity (wt%) in dimethylbenzene | ??99.37 |
Embodiment 4 fixed bed reaction evaluations
,, handled 1 hour in 550 ℃ of air atmospheres the 5g catalyzer fixed-bed reactor of packing into as catalysts with the MTA-06 catalyzer of preparation among the embodiment 1, cool to 450 ℃ of temperature of reaction, 500 ℃ respectively under nitrogen atmosphere, pressure is 0.1MPa.The methanol feedstock that will contain 2wt% toluene by fresh feed pump pumps into reactor and catalyzer contact reacts.Material benzenemethanol feed weight air speed is 2h
-1, reaction product adopts the on-line analysis of Varian3800 gas-chromatography.Reaction result is as shown in table 2, aromaticity content is respectively 52.23wt%, 53.28% in the product (remove and generate water), p-Xylol content is 88.39wt%, 87.99% in the aromatic hydrocarbons, and p-Xylol selectivity in xylene isomer is 99.95wt%, 99.86%.
Table 2
Embodiment 5 fixed bed reaction evaluations
,, handled 1 hour in 550 ℃ of air atmospheres the 5g catalyzer fixed-bed reactor of packing into as catalysts with the MTA-07 catalyzer of preparation among the embodiment 2, cool to 400 ℃ of temperature of reaction, 450 ℃ respectively down at nitrogen atmosphere, pressure is 0.15MPa.The methanol feedstock that will contain 7wt% benzene by fresh feed pump pumps into reactor and catalyzer contact reacts.Material benzenemethanol feed weight air speed is 2h
-1, reaction product adopts the on-line analysis of Varian3800 gas-chromatography.Reaction result is as shown in table 3, in the product (remove generate water) aromaticity content be respectively 64.19%, 64.91wt%, in the aromatic hydrocarbons p-Xylol content be respectively 81.56%, 82.56wt%, p-Xylol selectivity in xylene isomer is respectively 99.58%, 99.36wt%.
Table 3
| Catalyzer | ??MTA-07???MTA-07 |
| Temperature of reaction | ??400??????450 |
| Methanol conversion (wt%) | ??87.39????88.95 |
| Aromatics yield in the hydrocarbon product (wt%) | ??64.19????64.91 |
| P-Xylol is selectivity (wt%) in aromatic hydrocarbons | ??81.56????82.56 |
| P-Xylol is selectivity (wt%) in dimethylbenzene | ??99.58????99.36 |
Embodiment 6 fluidized-bed reaction evaluations
,, in 550 ℃ of air atmospheres, handled 1 hour as catalysts with the MTA-08 catalyzer of preparation among the embodiment 3, under nitrogen atmosphere, cool to 450 ℃ of temperature of reaction the 10g catalyzer fixed fluidized-bed reactor of packing into.The methanol feedstock that will contain 5wt% toluene by fresh feed pump imports preheater, enters fixed fluidized-bed reactor after raw material is vaporized and contact with catalyzer in 280 ℃ of preheaters, and the feed weight air speed of material benzenemethanol is 2h
-1, reaction product adopts the on-line analysis of Varian3800 gas-chromatography.Reaction result is as shown in table 4, and aromaticity content is 65.21wt% in the product (remove and generate water), and p-Xylol content is 87.81wt% in the aromatic hydrocarbons, and p-Xylol selectivity in xylene isomer is 99.54wt%.
Table 3
| Catalyzer | ??MTA-08 |
| Temperature of reaction | ??450 |
| Methanol conversion (wt%) | ??84.47 |
| Aromatics yield in the hydrocarbon product (wt%) | ??65.21 |
| P-Xylol is selectivity (wt%) in aromatic hydrocarbons | ??87.81 |
| P-Xylol is selectivity (wt%) in dimethylbenzene | ??99.54 |
Claims (5)
1, the method for a kind of methyl alcohol/dimethyl ether conversion produced in high yields p-Xylol, the molecular sieve catalyst of employing metal and silanization modification by add aromatic hydrocarbons in methyl alcohol/dme raw material, improves the yield of p-Xylol in methyl alcohol/dimethyl ether conversion product; Aromaticity content can reach more than the 50wt% in the product, wherein in the aromatic hydrocarbons p-Xylol content greater than 80wt%, p-Xylol in xylene isomer selectivity greater than 99wt%.
2, the method for methyl alcohol as claimed in claim 1/dimethyl ether conversion produced in high yields p-Xylol, it is characterized in that: the aromatic hydrocarbons of adding is meant toluene and/or benzene, and benzene that its source generates for the reaction of methyl alcohol/dimethyl ether conversion and/or toluene divide or all are recycled to reactive system through separate rear part.
3, the method for methyl alcohol as claimed in claim 1/dimethyl ether conversion produced in high yields p-Xylol is characterized in that: extra toluene and/or the benzene of adding in the reaction raw materials, its add-on is not more than 10wt% in methyl alcohol/dme raw material.
4, the method for methyl alcohol as claimed in claim 1/dimethyl ether conversion produced in high yields p-Xylol, it is characterized in that: reaction conditions is: temperature of reaction is 350-550 ℃, is preferably 400-500 ℃; Reaction pressure is 0-2MPa, is preferably 0-1MPa; Methyl alcohol/dme feed weight air speed is 0.1-20h
-1, be preferably 1-10h
-1
5, the method for methyl alcohol as claimed in claim 1/dimethyl ether conversion produced in high yields p-Xylol is characterized in that: reactive mode is any form of fixed bed or fluidized-bed.
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| US10196325B2 (en) | 2015-01-15 | 2019-02-05 | Exxonmobil Chemical Patents Inc. | Process for converting syngas to aromatics and catalyst system suitable therefor |
| WO2016160081A1 (en) | 2015-03-31 | 2016-10-06 | Exxonmobil Chemical Patents Inc. | Oxygenated hydrocarbon conversion zoned method |
| US10059638B2 (en) | 2015-03-31 | 2018-08-28 | Exxonmobil Chemical Patents Inc. | Oxygenated hydrocarbon conversion zoned method |
| CN108794290A (en) * | 2017-04-27 | 2018-11-13 | 中国科学院大连化学物理研究所 | A kind of original position of the catalyst of alkylation of toluene methanol paraxylene and online preparation method |
| CN109603898A (en) * | 2017-10-17 | 2019-04-12 | 苏州大学 | A kind of catalyst for dehydrogenation of low-carbon paraffin and the method for preparing low-carbon alkene |
| CN109603898B (en) * | 2017-10-17 | 2021-12-21 | 苏州大学 | Low-carbon alkane dehydrogenation catalyst and method for preparing low-carbon olefin |
| CN111187133A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing p-xylene and co-producing ethylbenzene and propylene from methanol and/or dimethyl ether and benzene |
| CN111187132A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing gasoline and co-producing p-xylene from methanol and/or dimethyl ether |
| CN111187134A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing paraxylene and co-produced gasoline from methanol and/or dimethyl ether |
| WO2020098002A1 (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing p-xylene co-produced gasoline from methanol and/or dimethyl ether |
| CN111187141A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing paraxylene and co-produced gasoline from methanol and/or dimethyl ether |
| CN109395674A (en) * | 2018-12-20 | 2019-03-01 | 清华大学 | Alcohol/ether/C3-C5 hydrocarbon directly prepares paraxylene reactor and method |
| CN113121297A (en) * | 2020-01-15 | 2021-07-16 | 中国石油天然气股份有限公司 | Method for producing aromatic hydrocarbon by using methanol |
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