CN106431807A - Method for alkylation reaction of isobutane and butylene and system - Google Patents
Method for alkylation reaction of isobutane and butylene and system Download PDFInfo
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- CN106431807A CN106431807A CN201610807944.9A CN201610807944A CN106431807A CN 106431807 A CN106431807 A CN 106431807A CN 201610807944 A CN201610807944 A CN 201610807944A CN 106431807 A CN106431807 A CN 106431807A
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- butane
- reactive distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/56—Addition to acyclic hydrocarbons
- C07C2/58—Catalytic processes
- C07C2/62—Catalytic processes with acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- 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
- Y02P20/10—Process efficiency
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- 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
- Y02P20/584—Recycling of catalysts
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for an alkylation reaction of isobutane and butylene and a system. The method for the alkylation reaction of the isobutane and the butylene comprises the steps of enabling a raw material containing the isobutane, n-butane and butylene to enter a reacting section in a manner of being divided into multiple feed material flows, subjecting the isobutane and the butylene to a reaction in the presence of a catalyst so as to produce C8 alkane, subjecting unreacted isobutane and butane to separation, mixing the separated isobutane and butane with the raw material, and enabling the raw material to enter a reacting section. According to the method and the system, the butylene can be thoroughly diluted in the reacting section, the possibility of polymerization of the butylene is reduced, the speed of catalyst activity lowering is lowered, meanwhile, the recycle ratio of the isobutane is lowered, and the energy consumption is lowered.
Description
Technical field
The present invention relates to a kind of alkylation production technology and device, it is catalyst in particular by solid acid, bulkhead reacts
Rectifying column is alkylated technique and the device of production.
Background technology
Isobutane and butene is alkylated reaction and can prepare high-octane alkylate oil and aviation gasoline, existing work
It is catalyst that process and equipment mainly adopts sulfuric acid or hydrofluoric acid, hydrofluoric acid and sulfuric acid is serious to equipment corrosion, spent acid processing cost
Height, production is restricted.Liquid acid catalyst is substituted using solid acid catalyst and is alkylated the corruption that can avoid equipment
Erosion and a difficult problem for spent acid process, but during solid acid catalyst alkylation, catalyst easily inactivates, and is mainly its side reaction (alkene
Polymerization) product be attached to catalyst surface, have impact on its activity, need often to regenerate.
For solving this contradiction, industrial frequently with two kinds of thinkings：
First method is to do reactor with fluid bed or moving bed, and catalyst is accomplished continuously or intermittently discharging reactor, goes
Reactor is returned again to, Chinese patent application CN103421532A discloses a kind of solid acid alkylating reaction side after regenerating unit regeneration
Method, employing is exactly this device and technique, and this process catalyst is constantly regenerating, and loss is big, high cost；
Another kind of method is to increase alkane alkene ratio, that is, increase the internal circulating load of iso-butane, reduces butylene dense in reaction system
Degree, reduces the polymerization of butylene, and usual alkane alkene ratio reaches 200:1, although this technique slow down the speed of catalyst inactivation, increase
Added the detached energy consumption of product, production cost raises, economically unreasonable it is impossible to be promoted use.
Content of the invention
For solid acid alkylating existing issue, the present invention proposes one and can reduce iso-butane internal circulating load, and profit
With alkylated reaction heat, the technique of reducing energy consumption.
The technical scheme is that：
A kind of iso-butane/butene alkylation method, the raw material containing iso-butane, normal butane and butylene is divided into multiply and enters
Material stream enters reactive distillation column conversion zone, and isobutane and butene reacts generation carbon eight alkane, unreacted under catalyst action
Iso-butane, the separated Posterior circle of butane use, be mixed into conversion zone with raw material.
Preferably, in course of reaction, iso-butane, normal butane are separated, and normal butane is sent outside as by-product.
Preferably, feed stream is 2-10 stock.This design can make butylene fully be diluted in conversion zone, reduces
The possibility of its polymerization, reduces the speed that catalyst activity reduces, and reduces iso-butane recycle ratio, reducing energy consumption simultaneously.
The present invention also provides the system realizing said method, including reactive distillation column and butane splitter, reactive distillation column
Multiple material inlets are set, and reactive distillation top of tower and butane splitter top are respectively provided with gas phase extraction mouth.
Preferably, reactive distillation column and butane splitter are a rectifying tower with bulkhead, and rectifying tower with bulkhead is separated by dividing plate
Become reactive distillation column and butane splitter；Rectifying tower with bulkhead side is reactive distillation column, arranges multiple conversion zones in the middle part of it, reaction
The gas phase extraction mouth at rectifying column top produces mouth, reactive distillation tower bottom setting carbon eight alkane extraction mouth for butane；Bulkhead rectifying
Tower opposite side is butane splitter, and the gas phase extraction mouth at butane splitter top produces mouth, butane splitter bottom for iso-butane
Setting normal butane extraction mouth；Gas phase produces the material inlet that mouth is connected to reactive distillation top of tower；In the middle part of reactive distillation column
The gas phase interface being connected with butane splitter is set.Design using rectifying tower with bulkhead can be by the use of alkylated reaction heat as product
Thing separates and the detached thermal source of butane, decreases energy consumption.
Preferably, reactive distillation column and butane splitter adopt a tower reactor, arrange multiple anti-in the middle part of reactive distillation column
Answer section, reactive distillation top of tower setting iso-butane extraction mouth, iso-butane extraction mouth connects to enter to the raw material of reactive distillation top of tower
Material mouth；Butane splitter top setting normal butane extraction mouth, normal butane produces as by-product；Tower reactor setting carbon eight alkane extraction
Mouthful.
Preferably, multiple conversion zones are set in the middle part of reactive distillation column, and reactive distillation top of tower setting iso-butane produces mouth,
Iso-butane extraction mouth connects to the material inlet of reactive distillation top of tower；The extraction of reactive distillation column tower reactor introduces butane and separates
Tower, butane splitter top setting normal butane extraction mouth, normal butane produces as by-product, and butane splitter tower reactor arranges carbon eight alkane
Hydrocarbon produces mouth.
Preferably, in order that the catalyst of inactivation is regenerated, conversion zone is moving bed or recirculating fluidized bed, also may be used
To adopt fixed bed, and regular regeneration.
Preferably, catalyst is set in conversion zone.
Preferably, return again to use by after catalyst removal reactive distillation column regeneration.
Brief description
Fig. 1 is the structural representation of the embodiment of the present invention 1；
Fig. 2 is the structural representation of the embodiment of the present invention 2；
Fig. 3 is the structural representation of the embodiment of the present invention 3.
Wherein：
1- reactive distillation column；2- butane splitter；3- conversion zone；4- raw material；5- carbon eight alkane；6- normal butane；7- isobutyl
Alkane；8- unreacted butylene；9- gas phase interface；10- butane splitter tower top iso-butane directly returns reactive distillation column pipeline.
Specific embodiment
Embodiment 1：
The rectifying tower with bulkhead that assembly of the invention is formed by a reactive distillation column 1 and a butane splitter 2, reaction
Rectifying column 1 arranges multiple conversion zones 3, arranges multiple material inlets, such as arranges 2-10 conversion zone it might even be possible to more than 10；
From battery limit (BL) containing iso-butane, normal butane, the raw material 4 of alkene and the unreacted butane 8 from reactive distillation column overhead extraction and
After iso-butane 7 mixing of butane splitter overhead extraction, it is divided into the conversion zone 3 that reactive distillation column 1 middle part is entered in multiply logistics,
Isobutane and butene reacts generation carbon eight alkane (octane) in the presence of catalyst, separates through rectifying, in reactive distillation column 1
Tower reactor obtains carbon eight alkane 5；Set butane splitter gas phase import 9 in the middle part of reactive distillation column, divide extraction portion from reactive distillation column
Dividing not sending out answers butylene gas phase to enter butane splitter, and in butane splitter, normal butane is separated with iso-butane, butane splitter
Tower reactor produces as normal butane 6, send battery limit (BL) as by-product, and overhead extraction returns reaction essence for iso-butane 7 after mixing with feedstock
Evaporate tower, iso-butane overhead extraction can also separate and partly directly return to reactive distillation column 1 top.
The reactive distillation column number of plates is 40, and reflux ratio is 9, and feed entrance point is the 20th block of column plate.Tower top pressure is 1.5MPa,
Temperature is 85 DEG C, and reaction fragment position is 10 to 30 blocks of column plates, conversion zone temperature 86-88 DEG C.Iso-butane 55% in raw material, butylene
35%, normal butane 10%, feeding temperature is 30, and tower top pressure is 1.5MPa.The butane splitter tower number of plates is 60, and reflux ratio is
4, feed entrance point is the 30th block of column plate.Tower top pressure is 1.5MPa, and temperature is 86 DEG C.Using selectively 3 bursts of logistics chargings, different pungent
Alkane selectivity ratios sub-thread logistics charging is high by 10%.Common rectifying tower energy consumption is adopted to drop 30% using rectifying tower with bulkhead observable index.
Embodiment 2：
Assembly of the invention is reactive distillation column 1 and butane splitter 2 adopts a tower reactor, sets in the middle part of reactive distillation column 1
Put multiple conversion zones, reactive distillation column 1 top setting iso-butane 7 extraction mouth, iso-butane 7 extraction mouth connects to reactive distillation column 1
The material inlet at top；Butane splitter 2 top setting normal butane 6 extraction mouth, normal butane 6 produces as by-product；Tower reactor sets
Put carbon eight alkane 5 extraction mouth.
Embodiment 3：
Reactive distillation column 1 middle part of the present invention arranges multiple conversion zones, and reactive distillation column 1 top setting iso-butane 7 produces
Mouthful, iso-butane 7 produces mouth and connects to the material inlet at reactive distillation column 1 middle part；The extraction of reactive distillation column 1 tower reactor introduces butane
Knockout tower 2, butane separates 2 top setting normal butane 6 extraction mouths, and normal butane 6 produces as by-product, and butane splitter 2 tower reactor sets
Put carbon eight alkane 5 extraction mouth.
Claims (10)
1. a kind of method of iso-butane/butene alkylation it is characterised in that：Will be former containing iso-butane, normal butane and butylene
Material is divided into multiply charging logistics and enters reactive distillation column conversion zone, and isobutane and butene reacts generation carbon eight under catalyst action
Alkane, the separated Posterior circle of unreacted iso-butane, normal butane uses, and is mixed into conversion zone with raw material.
2. as claimed in claim 1 a kind of method of iso-butane/butene alkylation it is characterised in that：In course of reaction, different
Butane, normal butane are separated, and normal butane is sent outside as by-product.
3. as claimed in claim 1 a kind of method of iso-butane/butene alkylation it is characterised in that：Feed stream is 2-
10 strands.
4. realize methods described as arbitrary in claim 1-3 system it is characterised in that：Separate with butane including reactive distillation column
Tower, reactive distillation column arranges multiple material inlets, and reactive distillation top of tower and butane splitter top are respectively provided with gas phase and adopt
Outlet.
5. system as claimed in claim 4 it is characterised in that：Reactive distillation column and butane splitter are a rectifying tower with bulkhead,
Rectifying tower with bulkhead is separated into reactive distillation column and butane splitter by dividing plate；Rectifying tower with bulkhead side is reactive distillation column, its
Middle part arranges multiple conversion zones, and the gas phase extraction mouth of reactive distillation top of tower produces mouth for butane, and reactive distillation tower bottom is arranged
Carbon eight alkane produces mouth；Rectifying tower with bulkhead opposite side is butane splitter, and the gas phase extraction mouth at butane splitter top is isobutyl
Alkane produces mouth, butane splitter bottom setting normal butane extraction mouth；Gas phase extraction mouth is connected to the former of reactive distillation top of tower
Material charging aperture；The gas phase interface being connected with butane splitter is set in the middle part of reactive distillation column.
6. system as claimed in claim 4 it is characterised in that：Reactive distillation column and butane splitter adopt a tower reactor, instead
Answer and multiple conversion zones be set in the middle part of rectifying column, reactive distillation top of tower setting iso-butane extraction mouth, iso-butane extraction mouth connect to
Material inlet in the middle part of reactive distillation column；Butane splitter top setting normal butane extraction mouth, normal butane produces as by-product；
Tower reactor setting carbon eight alkane extraction mouth.
7. system as claimed in claim 4 it is characterised in that：Multiple conversion zones, reactive distillation are set in the middle part of reactive distillation column
Top of tower setting iso-butane extraction mouth, iso-butane extraction mouth connects the material inlet in the middle part of reactive distillation column；Reactive distillation
The extraction of tower tower reactor introduces butane splitter, butane splitter top setting normal butane extraction mouth, and normal butane produces as by-product, fourth
Alkane knockout tower tower reactor setting carbon eight alkane extraction mouth.
8. described system as arbitrary in claim 5-7 it is characterised in that：Conversion zone is fixed bed, moving bed or recycle stream
Change bed.
9. described system as arbitrary in claim 5-7 it is characterised in that：Catalyst is set in conversion zone.
10. system as claimed in claim 7 it is characterised in that：Return again to make by after catalyst removal reactive distillation column regeneration
With.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610293811 | 2016-05-06 | ||
| CN2016102938114 | 2016-05-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106431807A true CN106431807A (en) | 2017-02-22 |
| CN106431807B CN106431807B (en) | 2019-06-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610807944.9A Expired - Fee Related CN106431807B (en) | 2016-05-06 | 2016-09-07 | A kind of method and system of iso-butane/butene alkylation |
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| CN (1) | CN106431807B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786671A (en) * | 2017-04-27 | 2018-11-13 | 中国科学院大连化学物理研究所 | The fluidized bed plant and method of methanol and/or dimethyl ether and benzene paraxylene co-producing light olefins |
| CN111589407A (en) * | 2020-05-20 | 2020-08-28 | 中石化南京工程有限公司 | Sulfuric acid alkylation system and method for producing isooctane by using same |
| CN114829550A (en) * | 2019-12-19 | 2022-07-29 | 凯洛格·布朗及鲁特有限公司 | Divided wall column for reactor recycle and product separation in alkylation process |
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| CN1834074A (en) * | 2005-03-15 | 2006-09-20 | 中国石油化工股份有限公司 | Solid acid alkylating process of isomerized alkane and olefin |
| US20070299292A1 (en) * | 2006-06-23 | 2007-12-27 | Catalytic Distillation Technologies | Paraffin alkylation |
| CN102614916A (en) * | 2012-02-28 | 2012-08-01 | 同济大学 | Preparation method of high-acidity fluorination resin catalyst used for alkylating of isobutane and butene |
| CN103421532A (en) * | 2012-05-15 | 2013-12-04 | 中国石油化工股份有限公司 | Solid acid alkylation reaction method |
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2016
- 2016-09-07 CN CN201610807944.9A patent/CN106431807B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1834074A (en) * | 2005-03-15 | 2006-09-20 | 中国石油化工股份有限公司 | Solid acid alkylating process of isomerized alkane and olefin |
| US20070299292A1 (en) * | 2006-06-23 | 2007-12-27 | Catalytic Distillation Technologies | Paraffin alkylation |
| CN102614916A (en) * | 2012-02-28 | 2012-08-01 | 同济大学 | Preparation method of high-acidity fluorination resin catalyst used for alkylating of isobutane and butene |
| CN103421532A (en) * | 2012-05-15 | 2013-12-04 | 中国石油化工股份有限公司 | Solid acid alkylation reaction method |
Non-Patent Citations (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786671A (en) * | 2017-04-27 | 2018-11-13 | 中国科学院大连化学物理研究所 | The fluidized bed plant and method of methanol and/or dimethyl ether and benzene paraxylene co-producing light olefins |
| US11161085B2 (en) | 2017-04-27 | 2021-11-02 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Fluidized bed device and method for preparing para-xylene and co-producing light olefins from methanol and/or dimethyl ether and benzene |
| CN114829550A (en) * | 2019-12-19 | 2022-07-29 | 凯洛格·布朗及鲁特有限公司 | Divided wall column for reactor recycle and product separation in alkylation process |
| CN111589407A (en) * | 2020-05-20 | 2020-08-28 | 中石化南京工程有限公司 | Sulfuric acid alkylation system and method for producing isooctane by using same |
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| CN106431807B (en) | 2019-06-18 |
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