CN102942441B - Method for preparing alkyl combined paraxylene - Google Patents
Method for preparing alkyl combined paraxylene Download PDFInfo
- Publication number
- CN102942441B CN102942441B CN201210489765.7A CN201210489765A CN102942441B CN 102942441 B CN102942441 B CN 102942441B CN 201210489765 A CN201210489765 A CN 201210489765A CN 102942441 B CN102942441 B CN 102942441B
- Authority
- CN
- China
- Prior art keywords
- mcm
- reaction
- molecular sieve
- toluene
- methylcarbonate
- 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
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 title abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000002808 molecular sieve Substances 0.000 claims abstract description 20
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 36
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229920002545 silicone oil Polymers 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 230000029936 alkylation Effects 0.000 claims description 5
- 238000005804 alkylation reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000001035 methylating effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing alkyl combined paraxylene, and belongs to the field of organic synthesis. Silicon deposit modified MCM-22 molecular sieves are used as catalysts, methylbenzene and dimethyl carbonate are used as reaction raw materials, and the conversion rate of the methylbenzene is 43.1%, the selectivity of the paraxylene is 66.3% and the yield of the paraxylene is 28.6% under the reaction conditions that the reaction temperature is 380 DEG C, the molar ratio of the methylbenzene to the dimethyl carbonate is 4:1, and the mass airspeed is 1h-1. By the aid of the excellent reaction conditions, the selectivity of the paraxylene is improved without basically reducing the conversion rate of the methylbenzene, so that the yield of the paraxylene is improved.
Description
Technical field
The preparation method who the present invention relates to the synthetic p-Xylol of a kind of alkylation, belongs to organic synthesis field.
Background technology
P-Xylol is the important source material of synthetic polyester fibers.The methods such as industrial main employing xylol isomerization at present, toluene and C9 aromatic disproportion and selective disproportionation of toluene are produced p-Xylol.The equilibrium concentration of the p-Xylol that first two method obtains in three kinds of isomer of dimethylbenzene is only 24%, and because boiling point between isomer approaches, separation condition is quite harsh, the high and power consumption of equipment requirements; And in toluene selective disproportionation reaction, need to could generate more than 85% p-Xylol of one mole of purity with two moles of toluene, and toluene utilization ratio is low, and production cost is high; Toluene and methylating reagent directly the p-Xylol technique of synthetic high density are to study at present more a kind of synthesis technique, as patent CN 1224408A, CN 1721378A, CN 1234653A etc. have open report.
But how to keep high toluene conversion at the p-Xylol that obtains highly selective is problems of the prior art simultaneously.Compared with methyl alcohol, methylcarbonate is the methylating reagent that a kind of reactive behavior is higher, for example, patent ZL 200810124604.7 discloses one take methylcarbonate as methylating reagent and the synthetic p-Xylol of alkylation of toluene, selecting the MCM-22 molecular sieve that silica alumina ratio is 100 is catalyzer, take toluene and methylcarbonate as raw material, mol ratio is toluene: methylcarbonate 6:1, 360 ℃ of temperature of reaction, the transformation efficiency of toluene is 21.5%, the selectivity of p-Xylol is 76.3%, can find out, the transformation efficiency of toluene is still lower, directly cause thus the yield of p-Xylol very low.It is methylating reagent that the present invention attempts selecting the methylcarbonate that reactive behavior is high, and selecting the MCM-22 molecular sieve after modification is catalyzer, and optimizes the reaction conditions of toluene and methylcarbonate, to obtaining higher reaction yield.
Summary of the invention
The object of the invention is to the problem low for the p-Xylol yield existing in toluene and the synthetic p-Xylol of methylcarbonate alkylation and a kind of efficient preparation method who synthesizes p-Xylol is provided.
Realize the technical scheme that the object of the invention adopts as follows:
Be catalyzer by the MCM-22 molecular sieve of siliceous deposits modification, toluene and methylcarbonate are reaction raw materials, and the reaction conditions adopting is: temperature of reaction is 380 ℃, mole proportioning toluene of reaction raw materials: methylcarbonate is 4:1, and mass space velocity is 1h
-1.
The MCM-22 molecular sieve of described siliceous deposits modification, its method of modifying is: get a certain amount of Powdered H type MCM-22 molecular sieve, silica alumina ratio is 50, be impregnated in massfraction and be in 10% silicone oil hexane solution, wherein the mass ratio of MCM-22 molecular sieve and silicone oil hexane solution is 1:(0.5～2), under normal temperature, stir 1～2 hour, then be placed in 90 ℃ of water-baths, evaporate to dryness hexane solution, finally the MCM-22 molecular sieve of deposition silicone oil is placed in to retort furnace, be warming up to 550 ℃, roasting 3 hours, naturally cooling and get final product.
The MCM-22 molecular sieve catalyst of siliceous deposits modification provided by the present invention by reaction conditions preferably, improves the selectivity of p-Xylol, thereby has improved the yield of p-Xylol in the situation that toluene conversion does not reduce substantially.
Embodiment
Embodiment 1
Get 10 grams of pulverous H type MCM-22 molecular sieves, silica alumina ratio is 50, be impregnated in the silicone oil hexane solution that 5 gram mass marks are 10%, under normal temperature, stir 1 hour, be then placed in 90 ℃ of water-baths, evaporate to dryness hexane solution, finally the MCM-22 molecular sieve of deposition silicone oil is placed in to retort furnace, be warming up to 550 ℃, roasting 3 hours, naturally cooling obtains required catalyzer.
Take toluene and methylcarbonate as raw material, the reaction conditions adopting is: temperature of reaction is 380 ℃, mole proportioning toluene of reaction raw materials: methylcarbonate is 4:1, and mass space velocity is 1h
-1.
Embodiment 2
Get 10 grams of pulverous H type MCM-22 molecular sieves, silica alumina ratio is 50, be impregnated in the silicone oil hexane solution that 10 gram mass marks are 10%, under normal temperature, stir 1 hour, be then placed in 90 ℃ of water-baths, evaporate to dryness hexane solution, finally the MCM-22 molecular sieve of deposition silicone oil is placed in to retort furnace, be warming up to 550 ℃, roasting 3 hours, naturally cooling obtains required catalyzer.
Take toluene and methylcarbonate as raw material, the reaction conditions adopting is: temperature of reaction is 380 ℃, mole proportioning toluene of reaction raw materials: methylcarbonate is 4:1, and mass space velocity is 1h
-1.
Embodiment 3
Get 10 grams of pulverous H type MCM-22 molecular sieves, silica alumina ratio is 50, be impregnated in the silicone oil hexane solution that 20 gram mass marks are 10%, under normal temperature, stir 1 hour, be then placed in 90 ℃ of water-baths, evaporate to dryness hexane solution, finally the MCM-22 molecular sieve of deposition silicone oil is placed in to retort furnace, be warming up to 550 ℃, roasting 3 hours, naturally cooling obtains required catalyzer.
Take toluene and methylcarbonate as raw material, the reaction conditions adopting is: temperature of reaction is 380 ℃, mole proportioning toluene of reaction raw materials: methylcarbonate is 4:1, and mass space velocity is 1h
-1.
Comparative example 1
Only change temperature of reaction, getting temperature of reaction is 360 ℃, and other conditions are with embodiment 2.
Comparative example 2
Only change temperature of reaction, getting temperature of reaction is 400 ℃, and other conditions are with embodiment 2.
Comparative example 3
Only feed change reaction mol ratio, gets a mole proportioning toluene: methylcarbonate is 2:1, and other conditions are with embodiment 2.
Comparative example 4
Only feed change reaction mol ratio, gets a mole proportioning toluene: methylcarbonate is 6:1, and other conditions are with embodiment 2.
Comparative example 5
Only change reaction mass air speed, get mass space velocity 0.5 h
-1, other conditions are with embodiment 2.
Comparative example 6
Only change reaction mass air speed, get mass space velocity 2 h
-1, other conditions are with embodiment 2.
The experimental result of above-described embodiment 1～3 and comparative example 1～6 is as shown in the table.
| ? | Reaction conditions: temperature of reaction, mole proportioning toluene: methylcarbonate, mass space velocity | Toluene conversion, % | Selectivity for paraxylene, % | P-Xylol yield, % |
| Embodiment 1 | 380℃，4：1，1h -1 | 43.5 | 53.8 | 23.4 |
| Embodiment 2 | 380℃，4：1，1h -1 | 43.1 | 66.3 | 28.6 |
| Embodiment 3 | 380℃，4：1，1h -1 | 41.8 | 67.2 | 28.1 |
| Comparative example 1 | 360℃，4：1，1h -1 | 35.7 | 48.6 | 17.3 |
| Comparative example 2 | 400℃，4：1，1h -1 | 44.4 | 52.5 | 23.3 |
| Comparative example 3 | 380℃，2：1，1h -1 | 28.5 | 32.4 | 9.2 |
| Comparative example 4 | 380℃，6：1，1h -1 | 38.9 | 63.5 | 24.7 |
| Comparative example 5 | 380℃，4：1，0.5h -1 | 43.8 | 33.8 | 14.8 |
| Comparative example 6 | 380℃，4：1，2h -1 | 40.2 | 66.5 | 26.7 |
As can be seen from the table, the present invention is in the preparation process that catalyzes and synthesizes p-Xylol, and the variation of catalytic reaction condition plays a part very important to the yield of p-Xylol, wherein, when 380 ℃ of temperature of reaction, mole proportioning toluene: methylcarbonate is 4:1, mass space velocity is 1h
-1, the transformation efficiency of toluene is 43.1%, and the selectivity of p-Xylol is 66.3%, and the yield of p-Xylol reaches 28.6%.
Claims (1)
1. the preparation method of the synthetic p-Xylol of alkylation, be catalyzer by the MCM-22 molecular sieve of siliceous deposits modification, toluene and methylcarbonate are reaction raw materials, the reaction conditions adopting is: temperature of reaction is 380 ℃, mole proportioning toluene of reaction raw materials: methylcarbonate is 4:1, mass space velocity is 1h
-1it is characterized in that: the MCM-22 molecular sieve of described siliceous deposits modification, its method of modifying is: get a certain amount of Powdered H type MCM-22 molecular sieve, silica alumina ratio is 50, being impregnated in massfraction is in 10% silicone oil hexane solution, wherein the mass ratio of MCM-22 molecular sieve and silicone oil hexane solution is 1:(0.5～2), under normal temperature, stir 1～2 hour, then be placed in 90 ℃ of water-baths, evaporate to dryness hexane solution, is finally placed in retort furnace by the MCM-22 molecular sieve of deposition silicone oil, is warming up to 550 ℃, roasting 3 hours, naturally cooling and get final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210489765.7A CN102942441B (en) | 2012-11-27 | 2012-11-27 | Method for preparing alkyl combined paraxylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210489765.7A CN102942441B (en) | 2012-11-27 | 2012-11-27 | Method for preparing alkyl combined paraxylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102942441A CN102942441A (en) | 2013-02-27 |
| CN102942441B true CN102942441B (en) | 2014-06-04 |
Family
ID=47725462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210489765.7A Active CN102942441B (en) | 2012-11-27 | 2012-11-27 | Method for preparing alkyl combined paraxylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102942441B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103272632B (en) * | 2013-06-08 | 2015-01-28 | 张宇 | Porous silica/ZSM-5 molecule sieve catalyst preparation method |
| CN103263946B (en) * | 2013-06-08 | 2015-02-25 | 张宇 | Preparation method of porous nanometer silicon dioxide/MCM (Multi Chip Module)-22 molecular sieve catalyst |
| CN108484889A (en) * | 2018-01-23 | 2018-09-04 | 浙江省现代纺织工业研究院 | A kind of preparation method of differential paraxylene |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3965210A (en) * | 1975-01-06 | 1976-06-22 | Mobil Oil Corporation | Selective production of para-xylene and catalyst therefor |
| US4090981A (en) * | 1976-09-23 | 1978-05-23 | Mobile Oil Corporation | Catalyst for selective production of para dialkyl substituted benzenes |
| US4491678A (en) * | 1982-10-19 | 1985-01-01 | Idemitsu Kosan Company Limited | Process for the production of para-xylene |
| US5488194A (en) * | 1994-05-16 | 1996-01-30 | Mobil Oil Corp. | Selective production of para-dialkyl substituted benzenes and catalyst therefor |
| CN100443176C (en) * | 2005-08-15 | 2008-12-17 | 中国石油化工股份有限公司 | Catalyst for alkylation of toluene methanol |
| CN101306974B (en) * | 2008-06-12 | 2011-03-30 | 江苏工业学院 | Process for catalytically synthesizing p-xylene |
-
2012
- 2012-11-27 CN CN201210489765.7A patent/CN102942441B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102942441A (en) | 2013-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101121624B (en) | Method for preparing ethylene by ethanol dehydration | |
| KR102326358B1 (en) | In situ production method and reaction process of catalyst for producing at least one of toluene, P-xylene and light olefins | |
| CN104557376B (en) | Synthesising gas systeming carbinol methylates with aromatic hydrocarbons the reaction method connected | |
| CN101767038A (en) | Catalyst for preparing paraxylene by methyl alcohol conversion, preparation method thereof and application | |
| CN102942441B (en) | Method for preparing alkyl combined paraxylene | |
| CN104096589A (en) | Toluene and methanol shape-selective alkylation catalyst and method thereof | |
| CN103263946B (en) | Preparation method of porous nanometer silicon dioxide/MCM (Multi Chip Module)-22 molecular sieve catalyst | |
| CN103588612A (en) | Production method of p-xylene | |
| CN108794288B (en) | Method for preparing low-carbon olefin and co-producing p-xylene | |
| CN103342629A (en) | Fluidization catalytic method for producing m-cresol and p-cresol through isomerization of o-cresol | |
| JP2017518995A (en) | A method for producing p-xylene with high selectivity and co-producing propylene | |
| CN102304011B (en) | Method for producing 1,2,4-trimethylbenzene by C9 aromatic hydrocarbon isomerization | |
| CN107774298B (en) | Porous metal/molecular sieve composite catalyst, preparation method thereof and application thereof in preparation of low-carbon olefin from synthesis gas | |
| CN102464566B (en) | Method for producing isopropylbenzene by using benzene and propylene | |
| CN102464565B (en) | Method for producing isopropylbenzene by using benzene and propylene | |
| JP7038820B2 (en) | Molecular sieve catalyst reformer and method | |
| CN108794290B (en) | In-situ and on-line preparation method of catalyst for preparing p-xylene by toluene and methanol alkylation | |
| CN104549432B (en) | The synthetic method of aromatic hydrocarbons methylation catalyst and dimethylbenzene | |
| CN103272632B (en) | Porous silica/ZSM-5 molecule sieve catalyst preparation method | |
| CN102557858B (en) | Method for producing p-tert-Butyltoluene by using mordenite for catalyzing toluene and tertiary butanol | |
| CN111187133B (en) | Method for preparing p-xylene and co-producing ethylbenzene and propylene from methanol and/or dimethyl ether and benzene | |
| CN108786905B (en) | In-situ preparation method of catalyst for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol | |
| CN108786904B (en) | In-situ preparation method of catalyst for preparing low-carbon olefin and co-producing p-xylene | |
| CN113333014A (en) | Solid catalyst for preparing diethylbenzene by ethyl benzene ethanol/ethylene alkylation and preparation method thereof | |
| CN102464563B (en) | Method for producing isopropylbenzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 223100 Dongfeng Road, Hongze, Jiangsu, China, No. 17, No. Patentee after: CHANGSHU RESEARCH INSTITUTE CO LTD OF NANJING University OF SCIENCE AND TECHNOLOGY Address before: The Science Park Research Institute of Jiangsu province Suzhou City Road 215513, Changshou City economic and Technological Development Zone No. 5 Patentee before: CHANGSHU RESEARCH INSTITUTE CO LTD OF NANJING University OF SCIENCE AND TECHNOLOGY |
|
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: The Science Park Research Institute of Jiangsu province Suzhou City Road 215513, Changshou City economic and Technological Development Zone No. 5 Patentee after: CHANGSHU RESEARCH INSTITUTE CO LTD OF NANJING University OF SCIENCE AND TECHNOLOGY Address before: 223100 Dongfeng Road, Hongze, Jiangsu, China, No. 17, No. Patentee before: CHANGSHU RESEARCH INSTITUTE CO LTD OF NANJING University OF SCIENCE AND TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240204 Address after: No. 88 Tonggang Road, Changshu Economic Development Zone, Suzhou City, Jiangsu Province, 215517 Patentee after: Changshu Economic Development Zone High tech Venture Capital Co.,Ltd. Country or region after: China Address before: 215513 No.5, research institute road, kechuangyuan, Changshu Economic and Technological Development Zone, Suzhou City, Jiangsu Province Patentee before: CHANGSHU RESEARCH INSTITUTE CO LTD OF NANJING University OF SCIENCE AND TECHNOLOGY Country or region before: China |