CN107827694A - A kind of device and method that isooctane is produced using indirect alkylation technology - Google Patents
A kind of device and method that isooctane is produced using indirect alkylation technology Download PDFInfo
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- CN107827694A CN107827694A CN201711235599.7A CN201711235599A CN107827694A CN 107827694 A CN107827694 A CN 107827694A CN 201711235599 A CN201711235599 A CN 201711235599A CN 107827694 A CN107827694 A CN 107827694A
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- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000029936 alkylation Effects 0.000 title claims abstract description 17
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 17
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 106
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 94
- 238000006243 chemical reaction Methods 0.000 claims abstract description 93
- 239000003112 inhibitor Substances 0.000 claims abstract description 92
- 238000004821 distillation Methods 0.000 claims abstract description 84
- 238000000605 extraction Methods 0.000 claims abstract description 84
- 239000000203 mixture Substances 0.000 claims abstract description 82
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000011084 recovery Methods 0.000 claims abstract description 51
- 239000000539 dimer Substances 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 36
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims abstract description 35
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 230000004087 circulation Effects 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 127
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 61
- 238000007599 discharging Methods 0.000 claims description 55
- 238000006471 dimerization reaction Methods 0.000 claims description 40
- 239000007795 chemical reaction product Substances 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 32
- 238000012856 packing Methods 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 238000011068 loading method Methods 0.000 claims description 15
- 239000011973 solid acid Substances 0.000 claims description 15
- 230000008676 import Effects 0.000 claims description 14
- -1 Sulfonic acid cation Chemical class 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000006477 desulfuration reaction Methods 0.000 claims description 6
- 230000023556 desulfurization Effects 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 239000003456 ion exchange resin Substances 0.000 claims description 5
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 230000005764 inhibitory process Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000002184 metal Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/28—Catalytic processes with hydrides or organic compounds with ion-exchange resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of device and method that isooctane is produced using indirect alkylation technology, including fixed bed reactors I, catalytic distillation tower, extraction tower, the recovery tower being sequentially connected：Mixing carbon four, polymerization inhibitor are reacted in reactor I, and product is partly into catalytic distillation tower, another part returns after removing reaction heat by heat exchanger；After catalytic distillation, overhead product flows back after entering fixed bed reactors II reactions, and tower bottom product enters extraction tower；After extraction, the dimer of tower top enters desulfurizing tower, and the product of bottom of towe enters recovery tower；After recovered, extractant returns to extraction tower, polymerization inhibitor Returning reactor I；The hydrodesulfurization in desulfurizing tower of dimer and hydrogen, obtains isooctane, can be used as gasoline blend component.The present invention is transformed existing MTBE process units, makes production isooctane device, and the isooctane of production can use as ethanol petrol blend component, and byproduct can also continue to use as other feedstock circulations.
Description
Technical field
The present invention relates to a kind of device for producing isooctane, and in particular to one kind is produced different pungent using indirect alkylation technology
The device and method of alkane, using indirect alkylation technological transformation MTBE devices, olefin-containing is set to mix carbon four in catalyst and inhibition
Agent effect is lower to carry out dimerization reaction generation dimer, and high octane value gasoline blending component alkyl is generated after dimer hydrodesulfurization
Carburetion, the main component of alkylate oil is isooctane.
Background technology
On September 7th, 2017, China's issue and synchronization implementation GB 18351《Vehicle-use alcohol gasoline (E10)》With GB 22030
《Vehicle-use alcohol gasoline blend component oil》Two standards；Provided in two standards, in vehicle-use alcohol gasoline in addition to ethanol, other
Oxygenatedchemicals is forbidden to think to add no more than 0.5%；High-knock rating gasoline blend component master in motor petrol at present
If MTBE, but MTBE is oxygenatedchemicals；The implementation of two standards is meaned once ethanol petrol is implemented in full, and MTBE will
Gasoline blend component use can not be re-used as.On September 13rd, 2017, China's issue《On expand bio-fuel alcohol production and
The embodiment for promoting the use of vehicle-use alcohol gasoline》Notice, in northeast, Deng Duo provinces and cities promote the use of ethanol from determining 2017
Gasoline, implement all standing to the year two thousand twenty whole nation is basic；According to《Scheme》It is required that by the year two thousand twenty, MTBE products will cannot function as
Ethanol petrol blend component, MTBE devices will stop production comprehensively.《On expanding bio-fuel alcohol production and promoting the use of automobile-used
The embodiment of ethanol petrol》, cause current MTBE process units to discard, the raw material of these devices can not be used again
To produce high value-added product, and the residual carbon four that device also cannot get after the processing of MTBE devices downstream is raw material, is caused
The interruption of one industrial chain.
How these existing MTBE devices are transformed, improved device is not only continuing with, and
The product of improved device production can also continue to as gasoline blend component, makes whole industrial chain continue to continue, is current
Researcher needs to study the problem captured.
The content of the invention
The technical problems to be solved by the invention are to be directed to the deficiencies in the prior art, and are provided a kind of using indirect
Alkylation techniques produce the device and method of isooctane, and existing MTBE process units is transformed, and it is different to make production
The device of octane, and the product isooctane of device production can use as ethanol petrol blend component, and byproduct may be used also
To continue to use as other feedstock circulations, turn waste into wealth, achieve many things at one stroke.
To achieve these goals, the present invention adopts the following technical scheme that：
It is a kind of using indirect alkylation technology produce isooctane device, including be sequentially connected fixed bed reactors I, urge
Change destilling tower, extraction tower, recovery tower, it is characterised in that：
Described fixed bed reactors I, inside are filled with catalyst A, and top is provided with charging aperture I, bottom is provided with discharging opening
I：Charging aperture I is connected with that can provide the device of mixing carbon four and/or polymerization inhibitor；
Described catalytic distillation tower, top is provided with exhaust outlet I, top is provided with refluxing opening, middle part is provided with charging aperture II, bottom
Provided with discharging opening II：Charging aperture II is connected with fixed bed reactors I discharging opening I；Exhaust outlet I is connected with condenser, cold
The outlet of condenser is divided into two-way, is connected all the way by fixed bed reactors II with refluxing opening, and another way is with holding residual carbon four
Device be connected；The catalytic section of catalytic distillation tower is filled with catalyst B, and catalyst C is filled with fixed bed reactors II；
Described extraction tower, inside are filled with extractant, top is provided with discharging opening III, middle and upper part is provided with extractant import,
Middle and lower part is provided with charging aperture III, bottom is provided with mixture outlet：Charging aperture III is connected with the discharging opening II of catalytic distillation tower
Connect；Discharging opening III is connected with desulfurizing tower, and the outlet of desulfurizing tower is connected with holding the device of end-product isooctane；
Described recovery tower, top is provided with polymerization inhibitor outlet, middle and lower part is provided with mixture intake, bottom goes out provided with extractant
Mouthful：Mixture intake is connected with the mixture outlet of extraction tower；Polymerization inhibitor exports the charging aperture I phases with fixed bed reactors I
Connection；Extractant outlet is connected with the extractant import of extraction tower.
In above-mentioned technical proposal, I points of discharging opening is two-way, is connected all the way with the charging aperture II of described catalytic distillation tower
Connect, another way is connected by pump with the import of heat exchanger, and the outlet of heat exchanger is connected with charging aperture I.
In above-mentioned technical proposal, the tunnels of charging aperture I Fen Wei tri-, the device phase of carbon four and/or polymerization inhibitor is mixed with holding all the way
Connection, is connected with the outlet of heat exchanger all the way, is connected all the way with polymerization inhibitor outlet.
In above-mentioned technical proposal, described desulfurizing tower, top is provided with exhaust outlet II, middle and lower part is provided with charging aperture IV, bottom
Provided with discharging opening IV：Exhaust outlet II is connected with flare system；Discharging opening IV is connected with holding the device of end-product isooctane
Connect；IV points of charging aperture is two-way, is connected all the way with the discharging opening III of described extraction tower, another way and the dress for providing hydrogen
Put and be connected.
In above-mentioned technical proposal, the internals of described catalytic distillation tower, preferably catalytic section are patent CN204656548U
In loading catalyst combination structured packing catalytic distillation tower, the more preferably internals of catalytic section are patent
Catalytic distillation tower in traditional production MTBE devices of the combination structured packing of loading catalyst in CN204656548U, only
The internals by the catalytic section of existing catalytic distillation tower are needed to be changed；In the combination structured packing of loading catalyst,
The catalyst of filling is catalyst B；The combination structured packing of loading catalyst in CN204656548U：Including catalyst mould
Piece and metal packing piece group；The catalyst matrix is pressed into rule by the metal rhombus expanded metals of liner phase same material woven wire
Shape after shape, formed after loading catalyst granules (loading catalyst B) spot welding sealing；The metal packing piece is by wire
Corrugated wire gauze packing or metallurgic orifice corrugated packing piece are formed by welding between being filled in catalyst matrix；Catalyst matrix and filler
Piece is spaced linearly equidistantly to arrange along rectifying column diametric(al), with structure after the steel band beamforming of material identical with rhombus expanded metals
Into catalytic distillation structure module；Catalyst matrix uses 60 mesh stainless steel cloth spot welding of stainless steel rhombus expanded metals and same material
Two isosceles trapezoidal structures that section is not less than 60 ° for base angle, sealing two ends are pressed into after compound；The catalyst matrix and
Metal packing piece group is that one or more module assembly combine.
In above-mentioned technical proposal, described extraction tower, preferably internals are sieve tray or the extraction for efficiently separating filler
Tower, more preferably internals be sieve tray or efficiently separate extraction tower in the traditional production MTBE devices of filler, only need
The internals of existing extraction tower are changed.
In above-mentioned technical proposal, described recovery tower, preferably internals are float valve tray or the recovery for efficiently separating filler
Tower, more preferably internals are the Methanol Recovery in float valve tray or the traditional production MTBE devices for efficiently separating filler
Tower, it is only necessary to changed the internals of existing recovery tower.
In above-mentioned technical proposal, fixed bed reactors I, fixed bed reactors II, desulfurizing tower, condenser, heat exchanger are
Equipment existing for prior art or commercial equipment.
In above-mentioned technical proposal, the catalyst A loaded in fixed bed reactors I is solid acid catalyst, preferably macropore
Sulfonic acid cation resin catalyst；The catalyst B loaded in catalytic distillation tower is solid acid catalyst, preferably macropore sulfonic acid
Cation resin catalyzing agent；The catalyst C loaded in fixed bed reactors II is solid acid catalyst, preferably macropore sulfonic acid
Cation resin catalyzing agent；The extractant loaded in extraction tower is water.
The present invention provides a kind of method that isooctane is produced using indirect alkylation technology, comprises the following steps：
(1) dimerization reaction：To mix carbon four and polymerization inhibitor as raw material, mixing carbon four and polymerization inhibitor are well mixed,
It is lower under the conditions of catalyst A is existing to carry out dimerization reaction, obtain reaction product；A reaction product part makes as feedstock circulation
With another part carries out catalytic distillation：
(3) catalytic distillation：Reaction product separates after carrying out catalytic distillation reaction in the presence of catalyst B, wherein：Separation
Obtained light component is carbon four after gaseous state dimerization, after carbon four is condensed after gaseous state dimerization, is continued under catalyst C catalytic action
Reaction, obtained material continue catalytic distillation；Isolated restructuring is divided into the mixture of the dimer and polymerization inhibitor of isobutene,
Carry out extraction and recovery；
(4) extraction and recovery：The dimer of isobutene and the mixture of polymerization inhibitor obtain two under the extraction of extractant
Polymers, and the mixture of extractant and polymerization inhibitor：The mixture of extractant and polymerization inhibitor obtained after recovery extractant and
Polymerization inhibitor, two extractants continue extraction cycle and utilized, and polymerization inhibitor return to step (1) recycles；It is de- that dimer carries out hydrogenation
Sulphur；
(5) hydrodesulfurization：Hydrodesulfurization reaction is carried out after dimer and hydrogen mixing, obtained isooctane and hydrogen sulfide,
Isooctane is sent into flare system and is used as gasoline blend component, remaining hydrogen and hydrogen sulfide.
The above-mentioned method that isooctane is produced using indirect alkylation technology, specifically includes following steps：
(1) dimerization reaction：Mixing carbon four, polymerization inhibitor are passed into fixed bed reactors I through charging aperture I, polymerization inhibitor with
Mix and carry out dimerization reaction under catalyst A of the carbon four in fixed bed reactors I catalytic action, obtain reaction product；Reaction
A product part flows through successively to be returned to charging aperture I after discharging opening I, pump, heat exchanger and is circulated, and reaction product is through heat exchanger
Fixed bed reactors I is returned again to after removing reaction heat, so as to effectively control fixed bed reactors I temperature；Reaction product is another
A part flows through discharging opening I successively, charging aperture II is entered in catalytic distillation tower；
(2) catalytic distillation：After reaction product enters catalytic distillation tower, the effect of the catalyst B in catalytic distillation tower
Lower progress catalytic distillation reaction and separation；The material of tower top is carbon four after gaseous state dimerization, through condenser after exhaust outlet I discharges
Condensation obtains residual carbon four, and residual carbon four is entered in fixed bed reactors II, the catalyst C in fixed bed reactors II
Reacted under catalytic action, reaction product is back in catalytic distillation tower by refluxing opening continues catalytic distillation；Bottom of towe
Material for isobutene dimer and polymerization inhibitor mixture, flow through discharging opening II successively, charging aperture III enters extraction
In tower；
(3) extraction and recovery：After the dimer of isobutene and the mixture of polymerization inhibitor enter extraction tower, in the extraction of extractant
Remove, the material that the bottom of towe of extraction tower obtains is extractant and the mixture of polymerization inhibitor, the mixture of extractant and polymerization inhibitor according to
It is secondary flow through to enter in recovery tower after mixture outlet, mixture intake reclaimed, the tower top of recovery tower obtains polymerization inhibitor,
Polymerization inhibitor flows through polymerization inhibitor outlet successively, returns in fixed bed reactors I after charging aperture I and recycles, the bottom of towe of recovery tower
Obtain extractant, extractant is flowed through to return in extraction tower after extractant outlet, extractant import successively and recycled；Extraction
The tower top of tower obtains dimer, flows through discharging opening III successively, charging aperture IV is entered in hydrodesulfurization tower；
(4) hydrodesulfurization：Dimer enters desulfurizing tower, while is passed through hydrogen, dimerization to desulfurizing tower by charging aperture IV
Hydrodesulfurization reaction is carried out after thing and hydrogen mixing, hydrogenation, desulfurization are carried out in same tower；The thing that the bottom of towe of desulfurizing tower obtains
Expect for high-octane alkylate oil --- isooctane, gasoline blend component can be used as；The material that the tower top of desulfurizing tower obtains is
The mixture of remaining hydrogen and the hydrogen sulfide of generation, can be sent into flare system and be used.
In above-mentioned technical proposal, in step (1), the component reacted in described mixing carbon four is isobutene, inhibition
Agent is 0.01-1 with the mol ratio for mixing isobutene in carbon four：1, preferably 0.02-0.5：1.
In above-mentioned technical proposal, in step (1), described polymerization inhibitor is mixed alcohols polymerization inhibitor, preferably methanol, second
The mixture that any two kinds in alcohol, propyl alcohol, butanol and the above are mixed with arbitrary proportion.
In above-mentioned technical proposal, in step (1), described catalyst A is solid acid catalyst, preferably macropore sulfonic acid sun
Ion exchange resin catalyst, more preferably patent of invention CN103447089A (a kind of polymerization of low-carbon olefin catalyst and its system
Preparation Method, Kairui Chemical Co., Ltd.).
In above-mentioned technical proposal, in step (1), described dimerization reaction, air speed is 0.5~1h-1, reaction temperature be 35~
70 DEG C, reaction pressure is 0.8~1.2Mpa；Wherein, temperature is preferably 35~50 DEG C, and reaction pressure is preferably 1.0~
1.2Mpa。
In above-mentioned technical proposal, in step (1), a reaction product part is returned after flowing through discharging opening I, pump, heat exchanger successively
Charging aperture I circulations are returned to, internal circulating load is 2~5 times of inlet amount.
In above-mentioned technical proposal, in step (2), described catalytic distillation tower, catalytic section is loaded in CN204656548U
The combination structured packing of loading catalyst, the catalyst loaded in the combination structured packing of loading catalyst are described catalysis
Agent B, catalyst B are solid acid catalyst, preferably macropore Sulfonic acid cation resin catalyst, and more preferably invention is special
Sharp CN103447089A (a kind of polymerization of low-carbon olefin catalyst and preparation method thereof, Kairui Chemical Co., Ltd.).
In above-mentioned technical proposal, in step (2), described catalyst C is solid acid catalyst, preferably macropore sulfonic acid sun
Ion exchange resin catalyst, more preferably patent of invention CN103447089A (a kind of polymerization of low-carbon olefin catalyst and its system
Preparation Method, Kairui Chemical Co., Ltd.).
In above-mentioned technical proposal, in step (2), the reaction condition of catalytic distillation reaction is：Air speed is 1~3h-1, reaction temperature
Spend for 50~70 DEG C, reaction pressure is 0.5~0.7Mpa.
In above-mentioned technical proposal, in step (2), the condition reacted in fixed bed reactors II (5) is：Air speed is
0.5~1h-1, reaction temperature is 35~70 DEG C, and reaction pressure is 0.8~1.2Mpa；Wherein, temperature is preferably 35~50 DEG C, instead
It is preferably 1.0~1.2Mpa to answer pressure.
In above-mentioned technical proposal, in step (2), condensed device condenses to obtain residual carbon four, and it is formed and former MTBE devices
Residual carbon four after processing forms essentially identical, in addition to being passed through and being reacted in fixed bed reactors II, can also be delivered to
In the device for holding residual carbon four, the raw material as downstream unit.
In above-mentioned technical proposal, in step (3), the extractant in extraction tower (3) is water.
In above-mentioned technical proposal, in step (3), the reaction condition of extraction tower (3) is：38-42 DEG C of reaction temperature, reaction
Pressure 0.5-1MPa.
In above-mentioned technical proposal, in step (3), the reaction condition of recovery tower (4) is reaction：Temperature：80-130 DEG C, it is anti-
Answer pressure 0-0.5Mpa.
In above-mentioned technical proposal, in step (4), in desulfurizing tower, the reaction condition of hydrodesulfurization reaction is：Reaction temperature
200~300 DEG C, 0.8~1.2Mpa of reaction pressure.
In above-mentioned technical proposal, in step (4), dimer and hydrogen mol ratio are 1：2~5.
The advantages of technical solution of the present invention, is：
(1) it is of the invention, prevent that trimerization and the above are more as reaction raw materials, addition polymerization inhibitor to mix the isobutene in carbon four
Poly- reaction, to improve the conversion ratio of dimerization product；Polymerization inhibitor mainly employs our company's (limited public affairs of the triumphant auspicious scientific and technological share of environmental protection
Department) exploitation new mixed alcohols polymerization inhibitor so that the isobutene in mixing carbon four carries out controllable dimerization reaction, effectively
The poly- reaction of the height for suppressing trimerization and the above.
(2) reactor of the invention, loads the catalyst that new catalyst replaces production MTBE, in fixed bed reactors
The catalyst of filling is the catalyst for making isobutene carry out dimerization reaction generation isooctane, promotes isobutene to carry out dimerization reaction.
(3) reactor of the invention is different from the reactor in MTBE devices, is fixed bed reactors, mixes carbon four and resistance
After poly- agent is well mixed, into the former improved fixed bed reactors of MTBE device reactions device, dimerization reaction is carried out.The present invention
Fixed bed reactors employ the design of outer circulation+heat exchanger, production MTBE reactor is transformed, adds and changes
Hot device；The partial material of reactor outlet is pressurizeed by pump, after removing reaction heat into heat exchanger, Returning reactor import, from
And reaction heat is effectively removed, carry out controlling reaction temperature.
(4) it is of the invention, former MTBE devices catalytic distillation tower is transformed, transform the catalytic section of catalytic distillation tower as dress
The catalytic section of structured packing catalyst is filled out, changes tower internals；Structured packing catalyst is our company's patented technology
Structured packing in " ZL02233432.7 ".
(5) it is of the invention, add new reactor, Ye Shigu on the return path of the catalytic distillation tower of former MTBE devices
Fixed bed reactor, by the catalytic action of the reactor, turning for alkene can be improved to greatest extent under the effect of no polymerization inhibitor
Rate；Catalytic distillation tower top discharge is carbon four after gaseous state dimerization, and condensed rear portion is further reacted into new reactor
Backflow as catalytic distillation tower afterwards；Another part material is residual carbon four；The residual carbon four of residual carbon four and former MTBE devices
Composition is the same, can be as the charging of former MTBE devices downstream unit.
(6) it is of the invention, on the basis of former MTBE devices methanol recovery system, change MTBE device methanol recovery systems
Extraction tower tower internals and methanol distillation column tower internals, make polymerization inhibitor recovery system；New extraction tower is used as extraction using water
Agent, polymerization inhibitor is extracted with water, be sent into new recovery tower, recovery can be recycled.
(7) it is of the invention, a hydrodesulfurization tower, the dimer after being extracted have been newly increased on the basis of former MTBE devices
Into hydrodesulfurization tower, desulfurization operations are carried out while dimer is hydrogenated with, the high-octane alkylate oil of bottom of towe output ---
Isooctane, isooctane can be used as gasoline blend component；Top of tower discharging is hydrogen sulfide and the mixture of hydrogen, can be sent into torch
System.
(8) it is of the invention, make conversion ratio >=99.5% of isobutene in mixing carbon four；It is different pungent in product after hydrodesulfurization
Alkane total content >=93%, octane number >=98 can be as gasoline blend component；Isobutene content≤0.15% in residual carbon four, can
Meet the requirement of downstream unit, so as to after part transformation is carried out to MTBE devices, it is possible to continue whole industrial chain.
Brief description of the drawings
Fig. 1：The present invention produces the flow chart of the method for isooctane using indirect alkylation technology；
Fig. 2：The present invention produces the overall structure diagram of the device of isooctane using indirect alkylation technology；
Wherein：1 is fixed bed reactors I；2 be catalytic distillation tower；3 be extraction tower；4 be recovery tower；5 be fixed bed reaction
Device II；6 be desulfurizing tower；7 be condenser；8 be heat exchanger.
Embodiment
The embodiment of technical solution of the present invention is described in detail below, but the present invention is not limited in following description
Hold：
The present invention provides a kind of device that isooctane is produced using indirect alkylation technology, including the fixed bed being sequentially connected
Reactor I 1, catalytic distillation tower 2, extraction tower 3, recovery tower 4, as shown in Figure 2：
Described fixed bed reactors I, inside are filled with catalyst A, and top is provided with charging aperture I, bottom is provided with discharging opening
I：Charging aperture I is connected with that can provide the device of mixing carbon four and/or polymerization inhibitor；
Described catalytic distillation tower, top is provided with exhaust outlet I, top is provided with refluxing opening, middle part is provided with charging aperture II, bottom
Provided with discharging opening II：Charging aperture II is connected with fixed bed reactors I discharging opening I；Exhaust outlet I is connected with condenser 7, cold
The outlet of condenser is divided into two-way, is connected all the way by fixed bed reactors II 5 with refluxing opening, and another way is with holding residual carbon
Four device is connected；The catalytic section of catalytic distillation tower is filled with catalyst B, and catalyst C is filled with fixed bed reactors II；
Described extraction tower 3, inside are filled with extractant, and top is provided with discharging opening III, middle and upper part is entered provided with extractant
Mouth, middle and lower part are provided with charging aperture III, bottom is provided with mixture outlet：Charging aperture III and catalytic distillation tower discharging opening II phases
Connection；Discharging opening III is connected with desulfurizing tower 6；
Described desulfurizing tower 6, top is provided with exhaust outlet II, middle and lower part is provided with charging aperture IV, bottom is provided with discharging opening IV：Row
Gas port II is connected with flare system；Discharging opening IV is connected with holding the device of end-product isooctane；Charging aperture IV is divided to for two
Road, it is connected all the way with the discharging opening III of described extraction tower, another way is connected with providing the device of hydrogen；
Described recovery tower 4, top is provided with polymerization inhibitor outlet, middle and lower part is provided with mixture intake, bottom is provided with extractant
Outlet：Mixture intake is connected with the mixture outlet of extraction tower；Polymerization inhibitor exports the charging aperture I with fixed bed reactors I
It is connected；Extractant outlet is connected with the extractant import of extraction tower；
Discharging opening I points be two-way, are connected all the way with the charging aperture II of described catalytic distillation tower, another way by pump and
The import of heat exchanger 8 is connected, and the outlet of heat exchanger is connected with charging aperture I；
The tunnels of charging aperture I Fen Wei tri-, be connected all the way with holding mixing carbon four and/or the device of polymerization inhibitor, all the way with heat exchange
The outlet of device is connected, and is connected all the way with polymerization inhibitor outlet.
Further, described catalytic distillation tower 2, internals are preferably the combination structured packing (patent of loading catalyst
CN204656548U), the internals of the catalytic distillation tower in traditional production MTBE devices are changed；Loading catalyst
Combination structured packing in, the catalyst of filling is catalyst B.The combination of loading catalyst in CN204656548U is regular
Filler：Including catalyst matrix and metal packing piece group；The catalyst matrix by liner phase same material woven wire metal
After rhombus expanded metals is pressed into regulation shape, formed after loading catalyst granules (loading catalyst B) spot welding sealing；The gold
Category packing sheet is filled between catalyst matrix by corrugated wire gauze packing or metallurgic orifice corrugated packing piece to be formed by welding；
Catalyst matrix and packing sheet is spaced is linearly equidistantly arranged along rectifying column diametric(al), with material identical with rhombus expanded metals
Catalytic distillation structure module is formed after the steel band beamforming of matter；Catalyst matrix uses the 60 of stainless steel rhombus expanded metals and same material
Two isosceles trapezoidal structures that section is not less than 60 ° for base angle, sealing two ends are pressed into after mesh stainless steel cloth spot welding is compound；
Catalyst matrix and metal packing the piece group is that one or more module assembly combine.
Further, described extraction tower, internals are preferably sieve tray or efficiently separate filler, by traditional production
The internals of extraction tower in MTBE devices are changed.
Further, described recovery tower, internals are preferably float valve tray or efficiently separate filler, by traditional production
The internals of recovery tower in MTBE devices are changed.
Further, described fixed bed reactors I, fixed bed reactors II, desulfurizing tower, condenser, heat exchanger are
Equipment existing for prior art or commercial equipment.
Further, the catalyst A loaded in described fixed bed reactors I is solid acid catalyst, preferably macropore
Sulfonic acid cation resin catalyst；The catalyst B loaded in described catalytic distillation tower is solid acid catalyst, is preferably big
Hole Sulfonic acid cation resin catalyst；The catalyst C loaded in described fixed bed reactors II is solid acid catalyst, excellent
Elect macropore Sulfonic acid cation resin catalyst as；The extractant loaded in described extraction tower is water.
The present invention also provides a kind of method that isooctane is produced using indirect alkylation technology, and flow chart is as shown in Figure 1：
(1) dimerization reaction：Mixing carbon four, polymerization inhibitor are passed into fixed bed reactors I 1 through charging aperture I, polymerization inhibitor
With carrying out dimerization reaction under mixing catalyst A of the carbon four in fixed bed reactors I catalytic action, reaction product is obtained；Instead
Answer a product part to flow through successively to return to charging aperture I after discharging opening I, pump, heat exchanger 8 and circulated, reaction product is through heat exchange
Device returns again to fixed bed reactors I after removing reaction heat, so as to effectively control fixed bed reactors I temperature；Reaction product
Another part flows through discharging opening I successively, charging aperture II is entered in catalytic distillation tower 2；
(2) catalytic distillation：After reaction product enters catalytic distillation tower 2, the effect of the catalyst B in catalytic distillation tower
Lower progress catalytic distillation reaction and separation；The material of tower top is carbon four after gaseous state dimerization, through condenser 7 after exhaust outlet I discharges
Condensation obtains residual carbon four, and residual carbon four is entered in fixed bed reactors II 5, the catalyst C in fixed bed reactors II
Catalytic action under reacted, reaction product is back in catalytic distillation tower by refluxing opening continues catalytic distillation；Tower
The material at bottom is the dimer of isobutene and the mixture of polymerization inhibitor, flows through discharging opening II successively, charging aperture III enters extraction
Take in tower；
(3) extraction and recovery：After the dimer of isobutene and the mixture of polymerization inhibitor enter extraction tower 3, in extractant
Under extraction, the material that the bottom of towe of extraction tower obtains is the mixture of extractant and the mixture of polymerization inhibitor, extractant and polymerization inhibitor
Flow through to enter in recovery tower 4 after mixture outlet, mixture intake successively and reclaimed, the tower top of recovery tower is inhibited
Agent, polymerization inhibitor flows through polymerization inhibitor outlet successively, returns in fixed bed reactors I after charging aperture I and recycles, recovery tower
Bottom of towe obtains extractant, and extractant is flowed through to return in extraction tower after extractant outlet, extractant import successively and recycled；
The tower top of extraction tower obtains dimer, flows through discharging opening III successively, charging aperture IV is entered in hydrodesulfurization tower 6；
(4) hydrodesulfurization：Dimer enters desulfurizing tower 6, while is passed through hydrogen, dimerization to desulfurizing tower by charging aperture IV
Hydrodesulfurization reaction is carried out after thing and hydrogen mixing, hydrogenation, desulfurization are carried out in same tower；The material that the bottom of towe of desulfurizing tower obtains
For high-octane alkylate oil --- isooctane, gasoline blend component can be used as；The material that the tower top of desulfurizing tower obtains is residue
Hydrogen and generation hydrogen sulfide mixture, flare system can be sent into and be used.
The inventive method and device are illustrated with reference to specific embodiment：
Embodiment 1：
A kind of method that isooctane is produced using indirect alkylation technology, specifically includes following steps：
(1) dimerization reaction：Mixing carbon four, polymerization inhibitor are passed into fixed bed reactors I through charging aperture I, polymerization inhibitor with
Mix and carry out dimerization reaction under catalyst A of the carbon four in fixed bed reactors I catalytic action, obtain reaction product；Reaction
A product part flows through successively to be returned to charging aperture I after discharging opening I, pump, heat exchanger and is circulated, and reaction product is through heat exchanger
Fixed bed reactors I is returned again to after removing reaction heat, so as to effectively control fixed bed reactors I temperature；Reaction product is another
A part flows through discharging opening I successively, charging aperture II is entered in catalytic distillation tower；
The component reacted in described mixing carbon four is isobutene；Described polymerization inhibitor is the mixing of ethanol and methanol
Thing (mass ratio 1:1)；Described catalyst A is macropore sulfonic acid ion exchange resin catalyst (embodiment in CN103447089A
KR01 in 1)；
Described polymerization inhibitor is 0.05 with the mol ratio for mixing isobutene in carbon four：1；
The condition of described dimerization reaction is：Air speed is 0.9h-1, reaction temperature be 35~50 DEG C, reaction pressure be 1.0~
1.2Mpa；
A reaction product part flows through charging aperture I circulations are returned to after discharging opening I, pump, heat exchanger successively, internal circulating load be into
4 times of doses.
(2) catalytic distillation：After reaction product enters catalytic distillation tower, the effect of the catalyst B in catalytic distillation tower
Lower progress catalytic distillation reaction and separation；The material of tower top is carbon four after gaseous state dimerization, through condenser after exhaust outlet I discharges
Condensation obtains residual carbon four, and residual carbon four is entered in fixed bed reactors II, the catalyst C in fixed bed reactors II
Reacted under catalytic action, reaction product is back in catalytic distillation tower by refluxing opening continues catalytic distillation；Bottom of towe
Material for isobutene dimer and polymerization inhibitor mixture, flow through discharging opening II successively, charging aperture III enters extraction
In tower；
Described catalyst B is macropore Sulfonic acid cation resin catalyst (in CN103447089A in embodiment 1
KR01)；Described catalyst C is macropore Sulfonic acid cation resin catalyst (in CN103447089A in embodiment 1
KR01)；
The condition of described catalytic distillation reaction is：Air speed is 2h-1, reaction temperature is 50~70 DEG C, and reaction pressure is
0.5~0.7Mpa；
The condition reacted in fixed bed reactors II is：Air speed is 0.9h-1, reaction temperature is 35~50 DEG C, instead
It is 1.0~1.2Mpa to answer pressure；
Condensed device condenses to obtain residual carbon four, and it is formed forms basic phase with the residual carbon four after the processing of former MTBE devices
Together, in addition to being passed through and being reacted in fixed bed reactors II, also it is delivered in the device for holding residual carbon four, as downstream
The raw material of device.
(3) extraction and recovery：After the dimer of isobutene and the mixture of polymerization inhibitor enter extraction tower, in the extraction of extractant
Remove, the material that the bottom of towe of extraction tower obtains is extractant and the mixture of polymerization inhibitor, the mixture of extractant and polymerization inhibitor according to
It is secondary flow through to enter in recovery tower after mixture outlet, mixture intake reclaimed, the tower top of recovery tower obtains polymerization inhibitor,
Polymerization inhibitor flows through polymerization inhibitor outlet successively, returns in fixed bed reactors I after charging aperture I and recycles, the bottom of towe of recovery tower
Obtain extractant, extractant is flowed through to return in extraction tower after extractant outlet, extractant import successively and recycled；Extraction
The tower top of tower obtains dimer, flows through discharging opening III successively, charging aperture IV is entered in hydrodesulfurization tower；
Extractant in extraction tower is water；
The operating condition of extraction tower is：Operation temperature is 40 DEG C, tower top pressure 0.6Mpa, tower bottom pressure 0.8MPa；
The operating condition of recovery tower is that tower top temperature is 82 DEG C, tower top pressure 0.1MPa.
(4) hydrodesulfurization：Dimer enters desulfurizing tower, while is passed through hydrogen, dimerization to desulfurizing tower by charging aperture IV
Hydrodesulfurization reaction is carried out after thing and hydrogen mixing, hydrogenation, desulfurization are carried out in same tower；The thing that the bottom of towe of desulfurizing tower obtains
Expect for high-octane alkylate oil --- isooctane, gasoline blend component can be used as；The material that the tower top of desulfurizing tower obtains is
The mixture of remaining hydrogen and the hydrogen sulfide of generation, can be sent into flare system and be used；
The reaction condition of hydrodesulfurization reaction is：Reaction temperature is 200~300 DEG C, and reaction pressure is 0.8~1.2Mpa；
Dimer and the mol ratio of hydrogen are 1：3.5.
In the present embodiment, make conversion ratio >=99.5% of isobutene in mixing carbon four；It is different pungent in product after hydrodesulfurization
Alkane total content >=93%, octane number >=98 can be as gasoline blend component；Isobutene content≤0.15% in residual carbon four, can
Meet the requirement of downstream unit, so as to after part transformation is carried out to MTBE devices, it is possible to continue whole industrial chain.
Embodiment 2：
A kind of method that isooctane is produced using indirect alkylation technology, specifically includes following steps：
(1) dimerization reaction：Mixing carbon four, polymerization inhibitor are passed into fixed bed reactors I through charging aperture I, polymerization inhibitor with
Mix and carry out dimerization reaction under catalyst A of the carbon four in fixed bed reactors I catalytic action, obtain reaction product；Reaction
A product part flows through successively to be returned to charging aperture I after discharging opening I, pump, heat exchanger and is circulated, and reaction product is through heat exchanger
Fixed bed reactors I is returned again to after removing reaction heat, so as to effectively control fixed bed reactors I temperature；Reaction product is another
A part flows through discharging opening I successively, charging aperture II is entered in catalytic distillation tower；
The component reacted in described mixing carbon four is isobutene；Described polymerization inhibitor is ethanol, propyl alcohol and butanol
Mixture (mass ratio 1:2:1)；Described catalyst A is macropore sulfonic acid ion exchange resin catalyst (CN103447089A
KR07 in middle embodiment 7)；
Described polymerization inhibitor is 0.07 with the mol ratio for mixing isobutene in carbon four：1；
The condition of described dimerization reaction is：Air speed is 0.8h-1, reaction temperature be 35~50 DEG C, reaction pressure be 1.0~
1.2Mpa；
A reaction product part flows through charging aperture I circulations are returned to after discharging opening I, pump, heat exchanger successively, internal circulating load be into
4 times of doses.
(2) catalytic distillation：After reaction product enters catalytic distillation tower, the effect of the catalyst B in catalytic distillation tower
Lower progress catalytic distillation reaction and separation；The material of tower top is carbon four after gaseous state dimerization, through condenser after exhaust outlet I discharges
Condensation obtains residual carbon four, and residual carbon four is entered in fixed bed reactors II, the catalyst C in fixed bed reactors II
Reacted under catalytic action, reaction product is back in catalytic distillation tower by refluxing opening continues catalytic distillation；Bottom of towe
Material for isobutene dimer and polymerization inhibitor mixture, flow through discharging opening II successively, charging aperture III enters extraction
In tower；
Described catalyst B is macropore Sulfonic acid cation resin catalyst (in CN103447089A in embodiment 7
KR07)；Described catalyst C is macropore Sulfonic acid cation resin catalyst (in CN103447089A in embodiment 7
KR07)；
The condition of described catalytic distillation reaction is：Air speed is 1.5h-1, reaction temperature is 50~70 DEG C, and reaction pressure is
0.5~0.7Mpa；
The condition reacted in fixed bed reactors II is：Air speed is 0.7h-1, reaction temperature is 35~50 DEG C, instead
It is 1.0~1.2Mpa to answer pressure；
Condensed device (7) condensation obtains residual carbon four, and it is formed forms base with the residual carbon four after the processing of former MTBE devices
This is identical, in addition to being passed through and being reacted in fixed bed reactors II, is also delivered in the device for holding residual carbon four, as
The raw material of downstream unit.
(3) extraction and recovery：After the dimer of isobutene and the mixture of polymerization inhibitor enter extraction tower, in the extraction of extractant
Remove, the material that the bottom of towe of extraction tower obtains is extractant and the mixture of polymerization inhibitor, the mixture of extractant and polymerization inhibitor according to
It is secondary flow through to enter in recovery tower after mixture outlet, mixture intake reclaimed, the tower top of recovery tower obtains polymerization inhibitor,
Polymerization inhibitor flows through polymerization inhibitor outlet successively, returns in fixed bed reactors I after charging aperture I and recycles, the bottom of towe of recovery tower
Obtain extractant, extractant is flowed through to return in extraction tower after extractant outlet, extractant import successively and recycled；Extraction
The tower top of tower obtains dimer, flows through discharging opening III successively, charging aperture IV is entered in hydrodesulfurization tower；
Extractant in extraction tower is water；
The operating condition of extraction tower is：Operation temperature is 40 DEG C, tower top pressure 0.6Mpa, tower bottom pressure 0.8MPa；
The operating condition of recovery tower is that tower top temperature is 82 DEG C, tower top pressure 0.1MPa.
(4) hydrodesulfurization：Dimer enters desulfurizing tower, while is passed through hydrogen, dimerization to desulfurizing tower by charging aperture IV
Hydrodesulfurization reaction is carried out after thing and hydrogen mixing, hydrogenation, desulfurization are carried out in same tower；The thing that the bottom of towe of desulfurizing tower obtains
Expect for high-octane alkylate oil --- isooctane, gasoline blend component can be used as；The material that the tower top of desulfurizing tower obtains is
The mixture of remaining hydrogen and the hydrogen sulfide of generation, can be sent into flare system and be used；
The reaction condition of hydrodesulfurization reaction is：Reaction temperature is 200~300 DEG C, and reaction pressure is 0.8~1.2Mpa；
Dimer and the mol ratio of hydrogen are 1：4.
The present invention, make conversion ratio >=99.5% of isobutene in mixing carbon four；In product after hydrodesulfurization, isooctane is total
Content >=93%, octane number >=98 can be as gasoline blend component；Isobutene content≤0.15% in residual carbon four, it can meet
The requirement of downstream unit, so as to after part transformation is carried out to MTBE devices, it is possible to continue whole industrial chain.
Examples detailed above is technical concept and technical characterstic to illustrate the invention, can not limit the present invention's with this
Protection domain.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (10)
- A kind of 1. method that isooctane is produced using indirect alkylation technology, it is characterised in that comprise the following steps：(1) dimerization reaction：To mix carbon four and polymerization inhibitor as raw material, mixing carbon four and polymerization inhibitor are well mixed, are being catalyzed It is lower under the conditions of agent A is existing to carry out dimerization reaction, obtain reaction product；A reaction product part uses as feedstock circulation, separately A part carries out catalytic distillation：(3) catalytic distillation：Reaction product separates after carrying out catalytic distillation reaction in the presence of catalyst B, wherein：It is isolated Light component be carbon four after gaseous state dimerization, after carbon four is condensed after gaseous state dimerization, continue under catalyst C catalytic action anti- Should, obtained material continues catalytic distillation；Isolated restructuring is divided into the mixture of the dimer and polymerization inhibitor of isobutene, enters Row extraction and recovery；(4) extraction and recovery：The dimer of isobutene and the mixture of polymerization inhibitor obtain dimer under the extraction of extractant, And the mixture of extractant and polymerization inhibitor：The mixture of extractant and polymerization inhibitor obtains extractant and inhibition after recovery Agent, two extractants continue extraction cycle and utilized, and polymerization inhibitor return to step (1) recycles；Dimer carries out hydrodesulfurization；(5) hydrodesulfurization：Hydrodesulfurization reaction is carried out after dimer and hydrogen mixing, obtained isooctane and hydrogen sulfide is different pungent Alkane is sent into flare system and is used as gasoline blend component, remaining hydrogen and hydrogen sulfide.
- 2. according to the method for claim 1, it is characterised in that specifically include following steps：(1) dimerization reaction：Mixing carbon four, polymerization inhibitor are passed into fixed bed reactors I (1) through charging aperture I, and polymerization inhibitor is with mixing Close and carry out dimerization reaction under catalyst A of the carbon four in fixed bed reactors I catalytic action, obtain reaction product；Reaction production A thing part flows through successively to be returned to charging aperture I after discharging opening I, pump, heat exchanger (8) and is circulated, and reaction product is through heat exchanger Fixed bed reactors I is returned again to after removing reaction heat, so as to effectively control fixed bed reactors I temperature；Reaction product is another A part flows through discharging opening I successively, charging aperture II is entered in catalytic distillation tower (2)；The component reacted in described mixing carbon four is isobutene；Described polymerization inhibitor is mixed alcohols polymerization inhibitor；It is described Catalyst A be solid acid catalyst；Described polymerization inhibitor is 0.01-1 with the mol ratio for mixing isobutene in carbon four：1；The condition of described dimerization reaction is：Air speed is 0.5~1h-1, reaction temperature be 35~70 DEG C, reaction pressure be 0.8~ 1.2Mpa；(2) catalytic distillation：After reaction product enters catalytic distillation tower (2), in the presence of the catalyst B in catalytic distillation tower Carry out catalytic distillation reaction and separation；The material of tower top is carbon four after gaseous state dimerization, through condenser (7) after exhaust outlet I discharges Condensation obtains residual carbon four, and residual carbon four is entered in fixed bed reactors II (5), the catalyst C in fixed bed reactors II Catalytic action under reacted, reaction product is back in catalytic distillation tower by refluxing opening continues catalytic distillation；Tower The material at bottom is the dimer of isobutene and the mixture of polymerization inhibitor, flows through discharging opening II successively, charging aperture III enters extraction In tower；Described catalyst B is solid acid catalyst；Described catalyst C is solid acid catalyst；The condition of described catalytic distillation reaction is：Air speed is 1~3h-1, reaction temperature is 50~70 DEG C, reaction pressure 0.5 ~0.7Mpa；The condition reacted in fixed bed reactors II (5) is：Air speed is 0.5~1h-1, reaction temperature is 35~70 DEG C, Reaction pressure is 0.8~1.2Mpa；(3) extraction and recovery：After the dimer of isobutene and the mixture of polymerization inhibitor enter extraction tower, in the extraction of extractant Under, material that the bottom of towe of extraction tower obtains is extractant and the mixture of polymerization inhibitor, and the mixture of extractant and polymerization inhibitor is successively Flowing through to enter in recovery tower (4) after mixture outlet, mixture intake and reclaimed, the tower top of recovery tower obtains polymerization inhibitor, Polymerization inhibitor flows through polymerization inhibitor outlet successively, returns in fixed bed reactors I after charging aperture I and recycles, the bottom of towe of recovery tower Obtain extractant, extractant is flowed through to return in extraction tower after extractant outlet, extractant import successively and recycled；Extraction tower Tower top obtain dimer, flow through discharging opening III successively, charging aperture IV is entered in hydrodesulfurization tower；Extractant in extraction tower (3) is water；The reaction condition of extraction tower (3) is：38-42 DEG C of reaction temperature, reaction pressure 0.5-1MPa；The reaction condition of recovery tower (4) is：Reaction temperature：80-130 DEG C, reaction pressure 0-0.5Mpa；(4) hydrodesulfurization：Dimer enters desulfurizing tower, while is passed through hydrogen to desulfurizing tower by charging aperture IV, dimer and Hydrodesulfurization reaction is carried out after hydrogen mixing, hydrogenation, desulfurization are carried out in same tower；The material that the bottom of towe of desulfurizing tower obtains is height The alkylate oil of octane number --- isooctane, gasoline blend component can be used as；The material that the tower top of desulfurizing tower obtains is remaining hydrogen The mixture of gas and the hydrogen sulfide of generation, can be sent into flare system and be used；The reaction condition of hydrodesulfurization reaction is：Reaction temperature is 200~300 DEG C, and reaction pressure is 0.8~1.2Mpa；The molar ratio of dimer and hydrogen is 1：2-5.
- 3. according to the method for claim 2, it is characterised in that in step (1), described mixed alcohols polymerization inhibitor is first The mixture that any two kinds in alcohol, ethanol, propyl alcohol, butanol and the above are mixed with arbitrary proportion；Described catalyst A is Macropore Sulfonic acid cation resin catalyst.
- 4. according to the method for claim 2, it is characterised in that in step (1), a reaction product part flows through discharging successively Charging aperture I circulations are returned to after mouth I, pump, heat exchanger (8), internal circulating load is 2~5 times of inlet amount.
- 5. according to the method for claim 2, it is characterised in that in step (2), condensed device (7) condensation obtains residual carbon Four, its form and former MTBE devices processing after residual carbon four form it is essentially identical, except being passed through in fixed bed reactors II (5) Outside being reacted, also it is delivered in the device for holding residual carbon four, the raw material as downstream unit.
- 6. according to the method for claim 2, it is characterised in that in step (2), described catalyst B is macropore sulfonic acid sun Ion exchange resin catalyst, described catalyst C are macropore Sulfonic acid cation resin catalyst.
- 7. it is a kind of using indirect alkylation technology produce isooctane device, including be sequentially connected fixed bed reactors I (1), Catalytic distillation tower (2), extraction tower (3), recovery tower (4), it is characterised in that：Described fixed bed reactors I (1), inside are filled with catalyst A, and top is provided with charging aperture I, bottom is provided with discharging opening I： Charging aperture I is connected with that can provide the device of mixing carbon four and/or polymerization inhibitor；Described catalytic distillation tower (2), top is provided with exhaust outlet I, top is provided with refluxing opening, middle part is provided with charging aperture II, bottom Provided with discharging opening II：Charging aperture II is connected with fixed bed reactors I discharging opening I；Exhaust outlet I is connected with condenser (7), cold The outlet of condenser is divided into two-way, is connected all the way by fixed bed reactors II (5) with refluxing opening, and another way is with holding residual carbon Four device is connected；The catalytic section of catalytic distillation tower is filled with catalyst B, and catalyst C is filled with fixed bed reactors II；Described extraction tower (3), inside are filled with extractant, top is provided with discharging opening III, middle and upper part is provided with extractant import, Middle and lower part is provided with charging aperture III, bottom is provided with mixture outlet：Charging aperture III is connected with the discharging opening II of catalytic distillation tower； Discharging opening III is connected with desulfurizing tower (6)；Described desulfurizing tower (6), top is provided with exhaust outlet II, middle and lower part is provided with charging aperture IV, bottom is provided with discharging opening IV：Exhaust Mouth II is connected with flare system；Discharging opening IV is connected with holding the device of end-product isooctane；IV points of charging aperture is two-way, It is connected all the way with the discharging opening III of described extraction tower, another way is connected with providing the device of hydrogen；Described recovery tower (4), top is provided with polymerization inhibitor outlet, middle and lower part is provided with mixture intake, bottom goes out provided with extractant Mouthful：Mixture intake is connected with the mixture outlet of extraction tower；Polymerization inhibitor exports the charging aperture I phases with fixed bed reactors I Connection；Extractant outlet is connected with the extractant import of extraction tower.
- 8. device according to claim 7, it is characterised in that：Discharging opening I points are two-way, all the way with described catalytic distillation The charging aperture II of tower is connected, and another way is connected by pump with the import of heat exchanger (8), outlet and the charging aperture I of heat exchanger It is connected；The tunnels of charging aperture I Fen Wei tri-, it is connected all the way with holding the device of mixing carbon four and/or polymerization inhibitor, goes out all the way with polymerization inhibitor Mouth is connected, and another way is connected with the outlet of heat exchanger.
- 9. device according to claim 7, it is characterised in that：Described catalytic distillation tower (2), the internals of catalytic section are special The combination structured packing of loading catalyst in sharp CN204656548U, that is loaded in the combination structured packing of loading catalyst urges Agent is catalyst B；Described extraction tower (3), internals are sieve tray or efficiently separate filler；Described recovery tower (4), it is interior Part is float valve tray or efficiently separates filler.
- 10. the device according to claim 7 or 9, it is characterised in that：The catalyst A of filling in fixed bed reactors I (1) For solid acid catalyst；The catalyst B of filling is solid acid catalyst in catalytic distillation tower (2)；In fixed bed reactors II (5) The catalyst C of filling is solid acid catalyst；The extractant of filling is water in extraction tower (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711235599.7A CN107827694B (en) | 2017-11-30 | 2017-11-30 | Device and method for producing isooctane by adopting indirect alkylation technology |
Applications Claiming Priority (1)
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| CN108658763A (en) * | 2018-06-21 | 2018-10-16 | 岳阳富和科技有限公司 | A kind of to generate isooctene using acetic acid mixing C4, repeated hydrogenation produces the manufacturing method of high pure isooctane |
| CN109354567A (en) * | 2018-12-13 | 2019-02-19 | 丹东明珠特种树脂有限公司 | The isobutene lamination system device and coincidence process method converted by methyl tertiary butyl ether(MTBE) plant modification |
| CN110452083A (en) * | 2019-08-05 | 2019-11-15 | 中国石油天然气集团有限公司 | The production method and device of diisobutylene |
| CN110452082A (en) * | 2019-08-05 | 2019-11-15 | 中国石油天然气集团有限公司 | It is the method and device that raw material produces diisobutylene to mix carbon four |
| CN110526796A (en) * | 2019-08-30 | 2019-12-03 | 凯瑞环保科技股份有限公司 | It is a kind of to provide the device and method of four raw material of carbon for MTBE downstream unit |
| CN111217662A (en) * | 2018-11-27 | 2020-06-02 | 中国石油化工股份有限公司 | Method for preparing isooctane by isobutene superposition-hydrogenation |
| CN111217661A (en) * | 2018-11-27 | 2020-06-02 | 中国石油化工股份有限公司 | Method for preparing isooctane by isobutene superposition-hydrogenation |
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| CN108658763A (en) * | 2018-06-21 | 2018-10-16 | 岳阳富和科技有限公司 | A kind of to generate isooctene using acetic acid mixing C4, repeated hydrogenation produces the manufacturing method of high pure isooctane |
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| CN109354567A (en) * | 2018-12-13 | 2019-02-19 | 丹东明珠特种树脂有限公司 | The isobutene lamination system device and coincidence process method converted by methyl tertiary butyl ether(MTBE) plant modification |
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| CN110452083B (en) * | 2019-08-05 | 2021-11-30 | 中国石油天然气集团有限公司 | Method and device for producing diisobutylene |
| CN110526796A (en) * | 2019-08-30 | 2019-12-03 | 凯瑞环保科技股份有限公司 | It is a kind of to provide the device and method of four raw material of carbon for MTBE downstream unit |
| CN110526796B (en) * | 2019-08-30 | 2024-02-06 | 凯瑞环保科技股份有限公司 | Device and method capable of providing four-carbon raw materials for MTBE downstream device |
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