CN103772097A - Alkylate treatment method - Google Patents
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- CN103772097A CN103772097A CN201210412553.9A CN201210412553A CN103772097A CN 103772097 A CN103772097 A CN 103772097A CN 201210412553 A CN201210412553 A CN 201210412553A CN 103772097 A CN103772097 A CN 103772097A
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Abstract
The invention relates to an alkylate treatment method, and mainly solves the problem that in the prior art, organic acid in alkylate can corrode follow-up equipment. Through the adoption of the technical scheme that the alkylate treatment method sequentially comprises the following steps: feeding an alkylation reaction product into an adsorption bed with an absorbent to obtain a deacidified gas phase reaction product, wherein the absorbent is a solid alkali absorbent, cooling the gas phase reaction product, feeding into an oil-water separator for separation to obtain an oil phase product and a water phase product after cooling the gas phase reaction product, feeding the oil phase product into a follow-up fractionating system, and feeding the water phase product into a follow-up sewage treatment system, the technical problem is well solved, and the purification method can be applied to industrial production process of alkylation.
Description
Technical field
The present invention relates to a kind of alkylate treatment process, especially for the alkylate treatment process in the allied processes such as Benzylation, toluene methylation, styroyl.
Background technology
Dimethylbenzene is a kind of important Organic Chemicals, mainly comprises ethylbenzene, p-Xylol, o-Xylol and m-xylene.Source with toluene in industry triphen is the most sufficient, but its industrial use can not show a candle to benzene and dimethylbenzene, therefore causes toluene relative surplus; And p-Xylol all has purposes extremely widely in fields such as trevira, medicine, agricultural chemicals, dye well solvents, but this product only accounts for 4.2 % in pyrolysis gasoline, is 7.5 % in reformate, is 22～26% in C8 BTX aromatics, output wretched insufficiency.Therefore, toluene is changed into greatest extent the market requirement vigorous, the p-Xylol of high added value is an important research direction in petrochemical technology always.
Toluene methylation is novel dimethylbenzene synthetic route, it is to have utilized alkylating reagent with the difference of toluene disproportionation technology in the past, and has therefore improved the utilization ratio of benzene, toluene, has saved petroleum resources.External report the earliest comes from the seventies in last century, investigator carries out the alkylated reaction of toluene and methyl alcohol on the Y zeolite catalyzer of various cationic exchange, find that its products distribution presents certain para-selectivity, in dimethylbenzene, para-isomeride content can reach 45～50%, obviously exceeded equilibrium composition the concentration of due 24-25%.Because p-Xylol is the xylene isomer of usage quantity maximum, therefore above-mentioned para-selectivity ground is found to make this technology receive many concerns.But studies have found that toluene methylation reaction product water presents slightly acidic, and wherein contain the Determination of Organic Acids such as formic acid, acetic acid, follow-up separation system is caused to corrosion.
Chinese patent CN100378199C has invented a kind of catalytic deacidification method of hydrocarbon raw material, comprise described hydrocarbon feed 100～300 ℃ and deacidifying catalyst contact reacts, described deacidifying catalyst comprises calcium oxide and calcium sulfate, and wherein the mass ratio of calcium oxide and calcium sulfate is 0.1～2.0.The method can effective elimination crude oil or distillate in naphthenic acid.
Chinese patent CN102186559A invention provides a kind of mixed air to remove acid method, and the method is in absorptive unit, contacts mixed air with absorption agent, and absorption agent contains mutual unmixed organic phase and carries a phase; Organic phase absorbs acid gas, acid gas is converted into absorbed acid gas, thereby absorption agent is converted into rich acid gas absorption agent, gas mixture is converted into the mixed air being purified; Absorbed acid gas is transferred to and carries phase, thereby in rich acid gas absorption agent, forms the first poor acid gas phase and rich acid gas phase, rich acid gas absorption agent is offered to separating unit, thereby the first poor acid gas phase and rich acid gas are separated; The first poor acid gas of every separation is looped back to absorptive unit mutually; Separated rich acid gas is offered to regeneration unit mutually, thereby obtain acid gas and the second poor acid gas phase; And the second poor acid gas is looped back to absorptive unit mutually.
Summary of the invention
Technical problem to be solved by this invention is for containing the etching problem of organic dialkylaminobenzoic acid product to follow-up equipment, and a kind of new alkylate treatment process is provided, and it is short that this treatment process has flow process, low equipment investment, operation is simple and reliable, and energy consumption is low, the advantage that industrializing implementation is strong.
For solving the problems of the technologies described above, technical scheme provided by the invention is as follows: a kind of alkylate treatment process, comprises the following steps successively:
A) alkylation reaction product is sent into the adsorption bed that is filled with sorbent material, obtains the gas-phase reaction product after depickling; Wherein said sorbent material is solid alkali sorbent material;
B) gas-phase reaction product is sent into water-and-oil separator after cooling, separates and obtains oil-phase product and water-phase product;
C) oil-phase product is sent into follow-up fractionating system, and water-phase product is sent into follow-up Sewage treatment systems.
In technique scheme, preferred technical scheme, alkylate is at least one in the alkylation reaction of arene products such as Benzylation, toluene methylation, styroyl; The alkylating reagent of alkylated reaction at least comprises the one in methyl alcohol, ethanol, propyl alcohol; A kind of organic acid in the formic acid that at least contains in alkylate, acetic acid, propionic acid, organic acid weight content preferable range is 1 ~ 5000ppm; Adsorption bed service temperature is equal to or less than the temperature out of alkylation reactor, and alkylation reactor outlet logistics can directly be sent into adsorption bed under gas phase state, and this temperature preferable range is 200 ~ 800 ℃, and working pressure preferable range is 0.1 ~ 1.0MPa; Sorbent material is solid alkali sorbent material, the oxide compound that comprises at least one metal in basic metal or alkaline-earth metal or oxyhydroxide and aluminum oxide composition.Preferred technical scheme, the oxide compound that sorbent material comprises at least one metal in basic metal or alkaline-earth metal and oxyhydroxide and aluminum oxide composition.Adsorption bed service temperature preferable range is at 300 ~ 600 ℃, and working pressure preferable range is at 0.2 ~ 1.0MPa.Preferred technical scheme, alkylate is cooled to 100 ~ 200 ℃ by cooling system.Preferred technical scheme, is characterized in that adsorption bed connects with alkylation reactor.Preferred technical scheme, sorbent material and catalysts tandem fill in same reactor.Preferred technical scheme, solid alkali sorbent material is the solid alkali sorbent material that the micro porous molecular sieves such as X-type, Y type, L-type or MCM-41, SBA-15 mesopore molecular sieve obtain through alkali modification.
Adopt the technical program of the present invention, alkylate is directly used to the method for sorbent material high-temperature catalytic depickling, this adsorption bed both can with reactors in series, also can directly sorbent material and catalysts tandem be filled in same reactor, solve the corrosion of organic acid to upstream device from source, therefore whole treating processes flow process is short, low equipment investment, operation is simple and reliable, and energy consumption is low, obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of a kind of alkylate treatment process of the present invention.
Fig. 2 is the full scale plant schematic flow sheet of a kind of alkylate treatment process of the present invention.
In Fig. 1, I is high temperature deacidification system, and II is reaction product cooling system, and III is water-and-oil separator.1 is gas-phase reaction product, and 2 is reaction product after high temperature depickling, and 3 is liquid-phase reaction product, and 4 is oil phase, and 5 is water.
In Fig. 2, E1 is reaction input and output material interchanger, and A1 is air cooler, and C1 is water cooler, and R1 is reactor, and D1 is adsorption bed, and D3 is gun barrel.1 is raw material, and 2 is the raw material after heating, and 3 is vapor-phase alkylation product, 4 is the alkylation reaction product gas after depickling, and 5 is through the cooled reaction product of heat exchange, and 6 is through the cooled reaction product of air cooler, 7 is through the cooled reaction product of water cooler, and 8 is oil-phase product, and 9 is that water is to product.
In the technical process of a kind of alkylate treatment process shown in Fig. 1, first gas-phase reaction product 1 enters high temperature deacidification system I and removes organic acid, reaction product 2 after depickling is sent into reaction product cooling system II and is cooled to liquid phase, after liquid-phase reaction product 3, send into water-and-oil separator III, the oil phase 4 separating in water-and-oil separator III is sent into follow-up separation system, and the water 5 of separation is sent into follow-up Sewage treatment systems.
The full scale plant flow process of a kind of alkylate treatment process shown in Fig. 2, raw material 1 first with after 4 heat exchange of reaction product gas is sent into reactive system, the alkylate 3 obtaining contains formic acid, the impurity such as acetic acid, alkylate 3 is introduced into adsorption bed D1 (independently adsorption bed of this adsorption bed, also can filled with adsorbent in reactor), after high-temperature catalytic reaction depickling, deliver to follow-up cooling system, through input and output material interchanger E1, air cooler A1, water cooler C1 enters gun barrel D2 after being cooled to 60 ℃, the isolated oil phase 8 of gun barrel D2 is sent into follow-up aromatic hydrocarbons separation system, the water 9 that gun barrel D2 separates is sent into follow-up Sewage treatment systems.
Below by specific embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
Concrete embodiment device flow process as depicted in figs. 1 and 2.Raw material 1 first with after 4 heat exchange of reaction product gas is sent into reactive system, the alkylate 3 obtaining contains formic acid, the impurity such as acetic acid, alkylate 3 is introduced into adsorption bed D1 (independently adsorption bed of this adsorption bed, also can filled with adsorbent in reactor), after high-temperature catalytic reaction depickling, deliver to follow-up cooling system, through input and output material interchanger E1, air cooler A1, water cooler C1 enters gun barrel D2 after being cooled to 60 ℃, the isolated oil phase 8 of gun barrel D2 is sent into follow-up aromatic hydrocarbons separation system, the water 9 that gun barrel D2 separates is sent into follow-up Sewage treatment systems.
Table 1 is the composition of alkylate.Table 2 is the feed conditions of alkylate.Table 3 is the operational condition of equipment.Table 4 is final oil-phase product composition.
[embodiment 2]
Concrete embodiment device flow process as depicted in figs. 1 and 2.
In the technical process of a kind of alkylate treatment process shown in Fig. 1, first gas-phase reaction product 1 enters high temperature deacidification system I and removes organic acid, reaction product 2 after depickling is sent into reaction product cooling system II and is cooled to liquid phase, after liquid-phase reaction product 3, send into water-and-oil separator III, the oil phase 4 separating in water-and-oil separator III is sent into follow-up separation system, and the water 5 of separation is sent into follow-up Sewage treatment systems.
The full scale plant flow process of a kind of alkylate treatment process shown in Fig. 2, raw material 1 first with after 4 heat exchange of reaction product gas is sent into reactive system, the alkylate 3 obtaining contains formic acid, the impurity such as acetic acid, alkylate 3 is introduced into adsorption bed D1 (independently adsorption bed of this adsorption bed, also can filled with adsorbent in reactor), after high-temperature catalytic reaction depickling, deliver to follow-up cooling system, through input and output material interchanger E1, air cooler A1, water cooler C1 enters gun barrel D2 after being cooled to 60 ℃, the isolated oil phase 8 of gun barrel D2 is sent into follow-up aromatic hydrocarbons separation system, the water 9 that gun barrel D2 separates is sent into follow-up Sewage treatment systems.
Raw material 1 first with after 4 heat exchange of reaction product gas is sent into reactive system, the alkylate 3 obtaining contains formic acid, the impurity such as acetic acid, alkylate 3 is introduced into adsorption bed D1 (independently adsorption bed of this adsorption bed, also can filled with adsorbent in reactor), after high-temperature catalytic reaction depickling, deliver to follow-up cooling system, through input and output material interchanger E1, air cooler A1, water cooler C1 enters gun barrel D2 after being cooled to 60 ℃, the isolated oil phase 8 of gun barrel D2 is sent into follow-up aromatic hydrocarbons separation system, the water 9 that gun barrel D2 separates is sent into follow-up Sewage treatment systems.
Table 5 is the composition of alkylate.Table 6 is the feed conditions of alkylate.Table 7 is the operational condition of equipment.Table 8 is final oil-phase product composition.
Table 1
| Component | Weight content (wt%) |
| Toluene | 49.01 |
| Water | 21.01 |
| Benzene | 1.77 |
| Dimethylbenzene | 19.96 |
| C9 aromatic | 5.41 |
| C10 aromartic | 2.13 |
| Lighter hydrocarbons | 0.67 |
| Formic acid | 4.8(mg/L) |
| Acetic acid | 206.4(mg/L) |
| PH value | 3 |
Table 2
| Title | Inlet amount (t/h) | Pressure (MPa) | Temperature (℃) |
| Alkylate 3 | 100 | 0.46 | 300 |
Table 3
Table 4
| Component | Weight content (wt%) |
| Toluene | 49.01 |
| Water | 21.01 |
| Benzene | 1.77 |
| Dimethylbenzene | 19.96 |
| C9 aromatic | 5.41 |
| C10 aromartic | 2.13 |
| Lighter hydrocarbons | 0.67 |
| Formic acid | 0(mg/L) |
| Acetic acid | 2.4 (mg/L) |
| PH value | 7.1 |
Table 5
| Component | Weight content (wt%) |
| Toluene | 49.01 |
| Water | 21.01 |
| Benzene | 1.77 |
| Dimethylbenzene | 19.96 |
| C9 aromatic | 5.41 |
| C10 aromartic | 2.13 |
| Lighter hydrocarbons | 0.67 |
| Formic acid | 4.8(mg/L) |
| Acetic acid | 206.4(mg/L) |
| PH value | 4 |
Table 6
| Title | Inlet amount (t/h) | Pressure (MPa) | Temperature (℃) |
| Alkylate 3 | 100 | 0.46 | 500 |
Table 7
| Device name | Working pressure (MPa) | Service temperature (℃) | Major dimension |
| Adsorption bed D1 | 0.46 | 400 | Φ 2800 × 6000, the Y zeolite catalyzed by solid base sorbent material of in-built 10t potassium modification. |
| Water-and-oil separator D2 | 0.20 | 60 | Φ3400×11000 |
Table 8
| Component | Weight content (wt%) |
| Toluene | 49.01 |
| Water | 21.01 |
| Benzene | 1.77 |
| Dimethylbenzene | 19.96 |
| C9 aromatic | 5.41 |
| C10 aromartic | 2.13 |
| Lighter hydrocarbons | 0.67 |
| Formic acid | 0(mg/L) |
| Acetic acid | 2.4 (mg/L) |
| PH value | 8.1 |
Claims (10)
1. an alkylate treatment process, comprises the following steps successively:
A) alkylation reaction product is sent into the adsorption bed that is filled with sorbent material, obtains the gas-phase reaction product after depickling; Wherein said sorbent material is solid alkali sorbent material;
B) gas-phase reaction product is sent into water-and-oil separator after cooling, separates and obtains oil-phase product and water-phase product;
C) oil-phase product is sent into follow-up fractionating system, and water-phase product is sent into follow-up Sewage treatment systems.
2. alkylate treatment process according to claim 1, is characterized in that alkylate is at least one in the alkylation reaction of arene products such as Benzylation, toluene methylation, styroyl; The alkylating reagent of described alkylated reaction comprises at least one in methyl alcohol, ethanol, propyl alcohol.
3. alkylate treatment process according to claim 1, at least one organic acid in the formic acid that it is characterized in that containing in alkylate, acetic acid, propionic acid, organic acid weight content is 1 ~ 5000ppm.
4. alkylate treatment process according to claim 1, it is characterized in that adsorption bed service temperature is equal to or less than the temperature out of alkylation reactor, adsorption bed is directly sent in alkylation reactor outlet logistics under gas phase state, adsorption bed operating temperature range is 200 ~ 800 ℃, and working pressure is at 0.1 ~ 2.0MPa.
5. alkylate treatment process according to claim 1, is characterized in that oxide compound, oxyhydroxide and aluminum oxide composition that sorbent material comprises at least one metal in basic metal or alkaline-earth metal.
6. alkylate treatment process according to claim 4, is characterized in that adsorption bed service temperature is at 300 ~ 600 ℃, and working pressure is at 0.2 ~ 1.0MPa.
7. alkylate treatment process according to claim 1, is characterized in that alkylate is cooled to 100 ~ 200 ℃ by cooling system.
8. alkylate treatment process according to claim 1, is characterized in that adsorption bed connects with alkylation reactor.
9. alkylate treatment process according to claim 1, is characterized in that sorbent material and catalysts tandem fill in same reactor.
10. alkylate treatment process according to claim 1, is characterized in that solid alkali sorbent material is the solid alkali sorbent material that the micro porous molecular sieves such as X-type, Y type, L-type or MCM-41, SBA-15 mesopore molecular sieve obtain through alkali modification.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107899603A (en) * | 2017-11-15 | 2018-04-13 | 宁波科邦华诚技术转移服务有限公司 | A kind of preparation method of aerogel type methanol paraxylene catalyst |
| CN110538674A (en) * | 2018-05-28 | 2019-12-06 | 中国石油化工股份有限公司 | Catalyst containing Y-type molecular sieve and preparation method thereof |
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| GB1426924A (en) * | 1972-06-06 | 1976-03-03 | Sun Research Dev Co | Preocess for separating strucurally similar hydrocarbons |
| WO2009080342A1 (en) * | 2007-12-20 | 2009-07-02 | Borealis Technology Oy | Purification of cumene |
| CN102617314A (en) * | 2012-02-22 | 2012-08-01 | 吉林化工学院 | Application of inorganic alkaline and fixed-bed adsorption technique to deacidification and purification of diisobutyl ketone |
| CN102731243A (en) * | 2012-07-06 | 2012-10-17 | 宁夏宝塔石化集团有限公司 | Method for separating benzene/toluene and methanol-alkylated reaction product |
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2012
- 2012-10-25 CN CN201210412553.9A patent/CN103772097B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1426924A (en) * | 1972-06-06 | 1976-03-03 | Sun Research Dev Co | Preocess for separating strucurally similar hydrocarbons |
| WO2009080342A1 (en) * | 2007-12-20 | 2009-07-02 | Borealis Technology Oy | Purification of cumene |
| CN102617314A (en) * | 2012-02-22 | 2012-08-01 | 吉林化工学院 | Application of inorganic alkaline and fixed-bed adsorption technique to deacidification and purification of diisobutyl ketone |
| CN102731243A (en) * | 2012-07-06 | 2012-10-17 | 宁夏宝塔石化集团有限公司 | Method for separating benzene/toluene and methanol-alkylated reaction product |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107899603A (en) * | 2017-11-15 | 2018-04-13 | 宁波科邦华诚技术转移服务有限公司 | A kind of preparation method of aerogel type methanol paraxylene catalyst |
| CN110538674A (en) * | 2018-05-28 | 2019-12-06 | 中国石油化工股份有限公司 | Catalyst containing Y-type molecular sieve and preparation method thereof |
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