CN103467238B - A kind of production method of xylol - Google Patents
A kind of production method of xylol Download PDFInfo
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- CN103467238B CN103467238B CN201310373250.5A CN201310373250A CN103467238B CN 103467238 B CN103467238 B CN 103467238B CN 201310373250 A CN201310373250 A CN 201310373250A CN 103467238 B CN103467238 B CN 103467238B
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- toluene
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Abstract
The present invention relates to the production method of a kind of xylol, the method includes the alkylated reaction with benzene, toluene and methanol as raw material and alkylation reaction product carries out toluene recovery and dimethylbenzene abstraction process successively, it is characterized in that: after being extracted by described dimethylbenzene, the carbon nine that left behind and above aromatic hydrocarbon substance are with after the benzene of steam dealkylation and toluene mixing raw material carry out transalkylation reaction, then carry out above-mentioned toluene recovery and dimethylbenzene abstraction process successively.The present invention is on the basis of existing technology, a part of benzene, methylbenzene raw material are generated high concentration benzene by steam dealkylation device, transalkylation reaction is utilized carbon at the bottom of benzenol hydrorefining nine and above aromatic hydrocarbons fully to be participated in reaction, promote molecular balance to carry out to the direction generating dimethylbenzene, add the concentration of xylol, improve xylol conversion per pass.The method of the present invention, can make the concentration of xylol improve 15～20%(w), the conversion ratio of benzene and toluene improves 5～10%.
Description
Technical field
The invention belongs to technical field of petrochemical industry, particularly relate to the production method of a kind of xylol.
Background technology
Xylol (PX) is one of main Organic Ingredients of petrochemical industry, has purposes widely in numerous chemical production field such as chemical fibre, synthetic resin, pesticide, medicine, plastics, is mainly used in synthesizing p-phthalic acid (PTA).Typical xylol production method is to be separated by multistage cryogenic crystallization from the mixed xylenes (C8A) of the thermodynamical equilibrium of Petroleum catalytic reforming generation or molecular sieve moving-bed adsorption separation (abbreviation adsorbing separation) technology, is separated by xylol from the isomer mixture that boiling point is the most close.Being affected by thermodynamical equilibrium, in mixed xylenes, the content of usual meta-xylene (MP) is higher, and the bigger PX content of industrial water requirement is relatively low, usually uses toluene disproportionation and the technological means such as transalkylation, C8 aromatics isomerization volume increase PX so industrial.PX product purity is up to more than 98%, but yield is the highest by only about 70%.
In recent years, along with the swift and violent increase of p-phthalic acid's production capacity, China presents the xylol situation that supply falls short of demand, price is high.The focus of people's research is become, such as Chinese patent by benzene, toluene and methanol alkylation dimethylbenzene.Toluene, methanol alkylation synthesis dimethylbenzene is a new process route of increasing yield of p-xylene, utilizes for toluene conversion and cheap methanol and provides new approach.
Summary of the invention
The purpose of the present invention is that provides a kind of brand-new method being raw material production xylol with benzene, toluene.
The technical scheme is that
A kind of production method of xylol, the method includes the alkylated reaction with benzene, toluene and methanol as raw material and alkylation reaction product carries out toluene recovery and dimethylbenzene abstraction process successively, it is characterized in that: after being extracted by described dimethylbenzene, the carbon nine that left behind and above aromatic hydrocarbon substance are with after the benzene of steam dealkylation and toluene mixing raw material carry out transalkylation reaction, then carry out above-mentioned toluene recovery and dimethylbenzene abstraction process successively.
Described alkylation reaction condition is: reactor pressure 0.05 ~ 0.8MPa, feedstock temperature 400 ~ 450 DEG C, toluene and methanol 2 ~ 6mol/mol, toluene/benzene >=1.5mol/mol, total weight of material air speed≤1.2h-1。
Described raw material toluene derives from toluene recovery operation.
Described steam dealkylation uses steam as reactant, adds a small amount of alkali and alkaline-earth metal as promoter in catalyst.
Described steam dealkylation condition is: reaction temperature 590 ~ 650 DEG C, total weight of material air speed 2 ~ 4 h-1, reactor pressure 5.5 ~ 6.5MPa.
Described transalkylation reaction conditions is: pressure 2.8 ~ 3.2MPa, bed temperature 380 ~ 430 DEG C, weight space velocity 2.0 ~ 3.5h-1。
The alkylated reaction with benzene, toluene and methanol as raw material in the present invention and alkylation reaction product is carried out successively toluene recovery and dimethylbenzene abstraction process can be found in patent application " a kind of by benzene, the method and device of toluene and methanol alkylation dimethylbenzene " (application number: CN201210233169.2).
The present invention is on the basis of existing technology, a part of benzene, methylbenzene raw material are generated high concentration benzene by steam dealkylation device, transalkylation reaction is utilized carbon at the bottom of benzenol hydrorefining nine and above aromatic hydrocarbons fully to be participated in reaction, promote molecular balance to carry out to the direction generating dimethylbenzene, add the concentration of xylol, improve xylol conversion per pass.The method of the present invention, can make the concentration of xylol improve 15～20%(w), the conversion ratio of benzene and toluene improves 5～10%.
Meanwhile, in the present invention, the synthesis gas of dealkylation device top output can pass through high-pressure process synthesizing methanol, returns methanol evaporator and supplements raw material, take full advantage of carbon nine and above aromatic hydrocarbons material, it is possible to set up PSA device, purifies H2, for needing hydrogen unit hydrogen supply, add motility and the multiformity of product of device operation, there is preferable application prospect.
Accompanying drawing explanation
Fig. 1 is the technological process that xylol of the present invention produces.
Wherein, I is benzene-toluene vaporizer；II is alkylation reactor；III is methanol evaporator；IV is toluene recovery tower；V is toluene recovery tower top complete condenser；VI is benzenol hydrorefining；VII is dimethylbenzene tower top complete condenser；VIII is steam dealkylation device；Ⅸ is transalkylation reactor；Ⅹ is adsorption separation unit.
1 is aroamtic hydrocarbon raw material (benzene of arbitrary proportion and toluene.)；2 is toluene；4 is methanol steam；5 is methanol；6 is toluene recovery column overhead discharging；7 is alkylation reactor bottom discharge；8 is toluene recovery tower bottom discharging；9 is benzenol hydrorefining tower top discharging；10 is mixed xylenes；11 is xylene column bottoms discharging；12 is transalkylation reaction product；13 is benzene, methylbenzene raw material；14 is dealkylation bottom discharge；15 is synthesis gas (CO, CO2、H2)；16 is xylol.
Detailed description of the invention
The present invention is described in detail below in conjunction with the accompanying drawings.
As shown in Figure 1, the toluene 2 that aroamtic hydrocarbon raw material 1 and toluene tower top complete condenser V are extracted out together enters feed vaporizer I, mixed gaseous benzene, toluene out and together enter alkylation reactor II from methanol evaporator III methanol steam 4 out, reactor pressure 0.05～0.8MPa, inlet temperature 400～450 DEG C, toluene and methanol: 2～6mol/mol, toluene/benzene: >=1.5mol/mol, total weight of material air speed≤1.2h-1.Reactor bottom discharging 7 enters toluene recovery tower IV, and tower top is regained toluene 2 by complete condenser V and returned feed vaporizer I.Toluene recovery tower IV bottom discharge 8 enters benzenol hydrorefining VI, pressure 0.8～1.0 MPa(G), temperature 245～255 DEG C, column bottom temperature 260～290 DEG C, reflux ratio 3.5～4.5(weight ratio), tower top discharging 9, after complete condenser VII condenses, 10 enters adsorption separation unit in liquid form, obtains xylol 16.
A part of raw material 13(benzene and toluene) with steam be heated to 590 ~ 650 DEG C time, enter steam dealkylation device VIII, the rhodium with aluminium oxide as carrier is as catalyst, and a small amount of alkali and alkaline-earth metal carry out steam as promoter and take off alkyl.Total weight of material air speed 2 ~ 4 h-1, reactor pressure 5.5 ~ 6.5MPa.
Dealkylation bottom discharge 14(high concentration benzene) with benzenol hydrorefining VI bottom discharge 11(carbon nine and above aromatic hydrocarbon substance) react in transalkylation reactor Ⅸ, weight space velocity 2.0～3.5 h-1, pressure 2.8～3.2 MPa(G), bed temperature 380～430 DEG C, transalkylation reaction product 12 returns toluene recovery tower IV, proceeds to separate, finally gives xylol 16.
Steam dealkylation device VIII top gas 15 can be actually needed entrance methanol synthesizer or hydrogen purification device in combination according to device.
Claims (3)
1. the production method of an xylol, the method includes the alkylated reaction with benzene, toluene and methanol as raw material and alkylation reaction product carries out toluene recovery and dimethylbenzene abstraction process successively, it is characterized in that: after being extracted by described dimethylbenzene, the carbon nine that left behind and above aromatic hydrocarbons are with after the benzene of steam dealkylation and toluene mixing raw material carry out transalkylation reaction, then carry out above-mentioned toluene recovery and dimethylbenzene abstraction process successively；
Described steam dealkylation is to use steam as reactant, and the rhodium with aluminium oxide as carrier is as catalyst, and a small amount of alkali and alkaline-earth metal carry out steam as promoter and take off alkyl, reaction temperature 590 ~ 650 DEG C, total weight of material air speed 2 ~ 4 h-1, reactor pressure 5.5 ~ 6.5MPa；
Described transalkylation reaction conditions is: pressure 2.8 ~ 3.2MPa, bed temperature 380 ~ 430 DEG C, weight space velocity 2.0 ~ 3.5h-1。
2. according to the production method of the xylol described in claim 1, it is characterized in that described alkylation reaction condition is: reactor pressure 0.05 ~ 0.8MPa, feedstock temperature 400 ~ 450 DEG C, toluene and methanol 2 ~ 6mol/mol, toluene/benzene >=1.5mol/mol, total weight of material air speed≤1.2h-1。
3. according to the production method of the xylol described in claim 1 or 2, it is characterised in that described raw material toluene derives from toluene recovery operation.
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| CN201310373250.5A CN103467238B (en) | 2013-08-23 | 2013-08-23 | A kind of production method of xylol |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5942651A (en) * | 1997-06-13 | 1999-08-24 | Mobile Oil Corporation | Process for converting C9 + aromatic hydrocarbons to lighter aromatic products by transalkylation in the prescence of two zeolite-containing catalysts |
| CN1340489A (en) * | 2000-08-29 | 2002-03-20 | 中国石油化工集团公司 | Process for preparing p-xylene |
| CN102746099A (en) * | 2012-07-06 | 2012-10-24 | 宁夏宝塔石化集团有限公司 | Method and device for preparing dimethylbenzene by alkylating benzene, methylbenzene and methanol |
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2013
- 2013-08-23 CN CN201310373250.5A patent/CN103467238B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5942651A (en) * | 1997-06-13 | 1999-08-24 | Mobile Oil Corporation | Process for converting C9 + aromatic hydrocarbons to lighter aromatic products by transalkylation in the prescence of two zeolite-containing catalysts |
| CN1340489A (en) * | 2000-08-29 | 2002-03-20 | 中国石油化工集团公司 | Process for preparing p-xylene |
| CN102746099A (en) * | 2012-07-06 | 2012-10-24 | 宁夏宝塔石化集团有限公司 | Method and device for preparing dimethylbenzene by alkylating benzene, methylbenzene and methanol |
Non-Patent Citations (2)
| Title |
|---|
| 对二甲苯增产技术发展趋向;陈庆龄等;《石油化工》;20041231;第33卷(第10期);909-915 * |
| 烷基芳烃催化脱烷基;秦永宁等;《精细石油化工》;19891231(第1期);40-45转31 * |
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