CN207738670U - A kind of device producing isooctane using indirect alkylation technology - Google Patents
A kind of device producing isooctane using indirect alkylation technology Download PDFInfo
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- CN207738670U CN207738670U CN201721636640.7U CN201721636640U CN207738670U CN 207738670 U CN207738670 U CN 207738670U CN 201721636640 U CN201721636640 U CN 201721636640U CN 207738670 U CN207738670 U CN 207738670U
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Abstract
The utility model discloses a kind of devices producing isooctane using indirect alkylation technology, including sequentially connected fixed bed reactors I, catalytic distillation tower, extraction tower, recovery tower：Mixing carbon four, polymerization inhibitor are reacted in reactor I, and a product part enters 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 tower 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 utility model is transformed existing MTBE process units, makes production isooctane device, and the isooctane of production can be used as the use of ethanol petrol blend component, and byproduct can also continue to use as other feedstock circulations.
Description
Technical field
The utility model is related to a kind of devices producing isooctane, and in particular to a kind of to be produced using indirect alkylation technology
The device of isooctane makes olefin-containing mix carbon four in catalyst and polymerization inhibitor using indirect alkylation technological transformation MTBE devices
The lower dimerization reaction that carries out of effect generates dimer, generation high octane value gasoline blending component alkylation after dimer hydrodesulfurization
The main component of oil, alkylate oil is isooctane.
Background technology
On September 7th, 2017, combination with standard administration committee of National Quality Supervision Bureau General, which issues and synchronizes, implements GB 18351
《Vehicle-use alcohol gasoline (E10)》With GB 22030《Vehicle-use alcohol gasoline blend component oil》Two standards.It is provided in two standards,
In vehicle-use alcohol gasoline in addition to ethyl alcohol, other oxygenatedchemicals are not allowed to think to add no more than 0.5%.Current automobile-used vapour
High-knock rating gasoline blend component in oil is mainly MTBE, but MTBE is oxygenatedchemicals.The implementation of two standards means
Once ethanol petrol is implemented in full, MTBE cannot be re-used as gasoline blend component use.
On September 13rd, 2017, the joint publication of 15 ministries and commissions such as National Development and Reform Committee《It produces and pushes away about bio-fuel ethyl alcohol is expanded
The wide embodiment for using vehicle-use alcohol gasoline》Notice, in northeast, Deng Duo provinces and cities promote the use of ethanol vapor from determining 2017
Oil implements 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 second
Alcohol gasoline blend component, MTBE devices will stop production comprehensively.
《Embodiment about expanding the production of bio-fuel ethyl alcohol and promoting the use of vehicle-use alcohol gasoline》, cause current
MTBE process units will be discarded, and the raw material of these devices will be no longer viable for production high value-added product, and fill downstream
It sets and also cannot get MTBE devices treated that residual carbon four is raw material, cause the interruption of an industrial chain.
How these existing MTBE devices are transformed, make improved device that can not only be continuing with, and
The product of improved device production can also continue to, as gasoline blend component, entire industrial chain be made to continue to continue, and be current
Researcher needs to study the problem captured.
Invention content
Technical problem to be solved in the utility model is to be directed to the deficiencies in the prior art, and provide a kind of use
Indirect alkylation technology produces the device of isooctane, is transformed to existing MTBE process units, and it is different pungent to make production
The device of alkane, and the product isooctane of device production can be used as ethanol petrol blend component, and byproduct can be with
Continue to use as other feedstock circulations, turns waste into wealth, achieves many things at one stroke.
To achieve the goals above, the utility model adopts the following technical solution：
It is a kind of to produce the device of isooctane using indirect alkylation technology, including sequentially connected fixed bed reactors I, urge
Change destilling tower, extraction tower, recovery tower, it is characterised in that：
The fixed bed reactors I, inside are filled with catalyst A, and top is equipped with feed inlet I, bottom is equipped with discharge port
I：Feed inlet I is connected with the device that can provide mixing carbon four and/or polymerization inhibitor；
The catalytic distillation tower, top is equipped with exhaust outlet I, top is equipped with refluxing opening, middle part is equipped with feed inlet II, bottom
Equipped with discharge port II：Feed inlet II is connected with the discharge port I of fixed bed reactors I；Exhaust outlet I is connected with condenser, condensation
The outlet of device is divided into two-way, is connected all the way with refluxing opening by fixed bed reactors II, another way and holds residual carbon four
Device is connected；The catalytic section of catalytic distillation tower is filled with catalyst B, and catalyst C is filled in fixed bed reactors II；
The extraction tower, inside are filled with extractant, top is equipped with discharge port III, middle and upper part is equipped with extractant import,
Middle and lower part is equipped with feed inlet III, bottom is equipped with mixture outlet：Feed inlet III is connected with the discharge port II of catalytic distillation tower；
Discharge port III is connected with desulfurizing tower, and the outlet of desulfurizing tower is connected with the device for holding final product isooctane；
The recovery tower, top is equipped with polymerization inhibitor outlet, middle and lower part is equipped with mixture intake, bottom goes out equipped with extractant
Mouthful：Mixture intake is connected with the mixture outlet of extraction tower；Polymerization inhibitor exports the feed inlet 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 discharge port is two-way, is connected all the way with the feed inlet II of the catalytic distillation tower
It connects, another way is connected by pumping with the import of heat exchanger, and the outlet of heat exchanger is connected with feed inlet I.
In above-mentioned technical proposal, tri- tunnels feed inlet I Fen Wei, all the way with hold the device phase for mixing carbon four and/or polymerization inhibitor
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, the desulfurizing tower, top is equipped with exhaust outlet II, middle and lower part is equipped with feed inlet IV, bottom
Equipped with discharge port IV：Exhaust outlet II is connected with flare system；Discharge port IV is connected with the device for holding final product isooctane；
IV points of feed inlet is two-way, is connected all the way with the discharge port III of the extraction tower, another way and the device phase for providing hydrogen
Connection.
In above-mentioned technical proposal, the catalytic distillation tower, the preferably internals of catalytic section are patent CN204656548U
In loading catalyst combination structured packing catalytic distillation tower, further preferably the internals of catalytic section be 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 replaced；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 matrix
With metal packing piece group；The catalyst matrix is pressed into regulation shape by the metal diamond shape expanded metals of liner same material woven wire
After shape, constituted after being packed into catalyst granules (being packed into catalyst B) spot welding sealing；The metal packing piece is by woven wire ripple
Filler or metallurgic orifice corrugated packing piece are formed by welding between being filled in catalyst matrix；Catalyst matrix and packing sheet are mutual
Every linearly equidistantly arranging along rectifying column diametric(al), with constitute catalytic distillation after the steel band beamforming of diamond shape expanded metals same material
Component module；Catalyst matrix is pressed into after using 60 mesh stainless steel cloth spot welding of stainless steel diamond shape expanded metals and same material compound
Section is two isosceles trapezoidal structures that base angle is not less than 60 °, sealing two ends；The catalyst matrix and metal packing piece group are
One or more module assembly are composed.
In above-mentioned technical proposal, the extraction tower, preferably internals are sieve tray or efficiently separate the extraction of filler
Tower, further preferably internals are sieve tray or efficiently separate the traditional extraction tower produced in MTBE devices of filler, are only needed
The internals of existing extraction tower are replaced.
In above-mentioned technical proposal, the recovery tower, preferably internals are float valve tray or efficiently separate the recycling of filler
Tower, further preferably internals are float valve tray or efficiently separate the Methanol Recovery in traditional production MTBE devices of filler
Tower, it is only necessary to be replaced 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 of the existing technology 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 sun
Ion exchange resin catalyst；The catalyst C loaded in fixed bed reactors II be solid acid catalyst, preferably macropore sulfonic acid sun from
Sub- resin catalyst；The extractant loaded in extraction tower is water.
The utility model provides a kind of method producing isooctane using indirect alkylation technology, includes the following steps：
(1) dimerization reaction：To mix carbon four and polymerization inhibitor as raw material, mixing carbon four and polymerization inhibitor are uniformly 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 detaches after carrying out catalytic distillation reaction under the action 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 the catalytic action of catalyst C
Reaction, obtained material continue catalytic distillation；Isolated recombination 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
The mixture of polymers and extractant and polymerization inhibitor：The mixture of extractant and polymerization inhibitor obtained after recycling extractant and
Polymerization inhibitor, two extractants continue extraction cycle and utilize, 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,
Isooctane is sent into flare system and is used as gasoline blend component, remaining hydrogen and hydrogen sulfide.
The above-mentioned method for producing isooctane using indirect alkylation technology, specifically includes following steps：
(1) dimerization reaction：Mixing carbon four, polymerization inhibitor are passed into through feed inlet I in fixed bed reactors I, polymerization inhibitor with
It mixes and carries out dimerization reaction under the catalytic action of catalyst A of the carbon four in fixed bed reactors I, obtain reaction product；Reaction
A product part is recycled followed by after discharge port I, pump, heat exchanger back to feed inlet I, and reaction product is moved through heat exchanger
Except fixed bed reactors I is returned again to after reaction heat, to effectively control the temperature of fixed bed reactors I；Reaction product is another
Part enters followed by discharge port I, feed inlet II 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, cold through condenser after exhaust outlet I discharges
Solidifying to obtain residual carbon four, residual carbon four enters in fixed bed reactors II, the catalysis of catalyst C in fixed bed reactors II
It is reacted under effect, reaction product is flowed back by refluxing opening continues catalytic distillation in catalytic distillation tower；The object of bottom of tower
Material is the mixture of the dimer and polymerization inhibitor of isobutene, is entered in extraction tower followed by discharge port II, feed inlet III；
(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 tower of extraction tower obtains is the mixture of extractant and 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 recycled, the tower top of recovery tower obtains polymerization inhibitor, resistance
Poly- agent exports followed by polymerization inhibitor, after feed inlet I back to recycling in fixed bed reactors I, the bottom of tower of recovery tower obtains
To extractant, extractant exports followed by extractant, after extractant import back to recycling in extraction tower；Extraction tower
Tower top obtains dimer, is entered in hydrodesulfurization tower followed by discharge port III, feed inlet IV；
(4) hydrodesulfurization：Dimer enters desulfurizing tower, while being passed through hydrogen, dimerization to desulfurizing tower by feed inlet IV
Hydrodesulfurization reaction is carried out after object and hydrogen mixing, hydrogen, desulfurization is added to be carried out in same tower；The material that the bottom of tower of desulfurizing tower obtains
For high-octane alkylate oil --- isooctane can be used as gasoline blend component；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.
In above-mentioned technical proposal, in step (1), the group reacted in the mixing carbon four is divided into isobutene, inhibition
Agent is 0.01-1 with the molar ratio for mixing isobutene in carbon four：1, preferably 0.02-0.5：1.
In above-mentioned technical proposal, in step (1), the polymerization inhibitor is mixed alcohols polymerization inhibitor, preferably methanol, second
Arbitrary two kinds or more the mixtures mixed with arbitrary proportion in alcohol, propyl alcohol, butanol.
In above-mentioned technical proposal, in step (1), the catalyst A is solid acid catalyst, preferably macropore sulfonic acid sun
Ion exchange resin catalyst, further 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), the 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 after discharge port I, pump, heat exchanger followed by returning
Feed inlet I cycles are returned to, internal circulating load is 2~5 times of inlet amount.
In above-mentioned technical proposal, in step (2), the 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 the catalyst
B, catalyst B are solid acid catalyst, preferably macropore Sulfonic acid cation resin catalyst, further preferably patent of invention
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), the catalyst C is solid acid catalyst, preferably macropore sulfonic acid sun
Ion exchange resin catalyst, further 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
Degree is 50~70 DEG C, and 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, composition and original MTBE devices
Treated, and that residual carbon four forms is essentially identical, other than 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
Power 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, reaction
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 molar ratio are 1：2~5.
The advantages of technical solutions of the utility model, is：
(1) the utility model, to mix the isobutene in carbon four as reaction raw materials, addition polymerization inhibitor prevent trimerization and with
Upper poly reaction, to improve the conversion ratio of dimerization product；Polymerization inhibitor mainly uses our company, and (the triumphant auspicious scientific and technological share of environmental protection is limited
Company) exploitation novel mixed alcohols polymerization inhibitor, to make the isobutene in mixing carbon four carry out controllable dimerization reaction, effectively
Inhibition trimerization or more the poly- reaction of height.
(2) reactor of the utility model loads the catalyst that novel catalyst replaces production MTBE, fixed bed reaction
The catalyst loaded in device is that isobutene is made to carry out the catalyst that dimerization reaction generates isooctane, promotes isobutene to carry out dimerization anti-
It answers.
(3) reactor of the utility model is different from the reactor in MTBE devices, is fixed bed reactors, mixes carbon four
After mixing with polymerization inhibitor, into the former improved fixed bed reactors of MTBE device reactions device, dimerization reaction is carried out.This hair
Bright fixed bed reactors use the design of outer circulation+heat exchanger, and the reactor of production MTBE is transformed, increases and changes
Hot device；The partial material of reactor outlet is pressurizeed by pumping, after removing reaction heat into heat exchanger, Returning reactor import, from
And reaction heat is effectively removed, carry out controlling reaction temperature.
(4) the utility model is transformed former MTBE devices catalytic distillation tower, and the catalytic section of catalytic distillation tower is transformed
To load the catalytic section of structured packing catalyst, tower internals is changed；Structured packing catalyst is our company's patented technology
Structured packing in " ZL02233432.7 ".
(5) the utility model increases new reactor on the return path of the catalytic distillation tower of former MTBE devices,
It is fixed bed reactors, by the catalytic action of the reactor, alkene can be improved to greatest extent under the effect of no polymerization inhibitor
Conversion ratio；Catalytic distillation tower top discharge is carbon four after gaseous state dimerization, and it is further that condensed rear portion enters new reactor
As the reflux of catalytic distillation tower after reaction；Another part material is residual carbon four；The residue of residual carbon four and original MTBE devices
Carbon four forms equally, can be used as the charging of former MTBE devices downstream unit.
(6) the utility model replaces MTBE device methanol recovery systems on the basis of former MTBE devices methanol recovery system
Extraction tower tower internals and methanol distillation column tower internals, make polymerization inhibitor recovery system；New extraction tower is using water as extraction
Agent is taken, polymerization inhibitor is extracted with water, is sent into new recovery tower, recycling can be recycled.
(7) the utility model, has newly increased a hydrodesulfurization tower on the basis of former MTBE devices, and two after being extracted
Polymers enters hydrodesulfurization tower, and desulfurization operations, the high-octane alkylation of bottom of tower output are carried out while dimer is added hydrogen
Oil --- isooctane, isooctane can be used as gasoline blend component；Top of tower discharging is the mixture of hydrogen sulfide and hydrogen, can be sent into
Flare system.
(8) the utility model makes conversion ratio >=99.5% of isobutene in mixing carbon four；In product after hydrodesulfurization,
Isooctane total content >=93%, octane number >=98 can be used as gasoline blend component；Isobutene content in residual carbon four≤
0.15%, the requirement of downstream unit can be met, to after carrying out part transformation to MTBE devices, so that it may to continue entire industry
Chain.
Description of the drawings
Fig. 1：The utility model 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.
Specific implementation mode
Below to the specific implementation mode of technical solutions of the utility model be described in detail, but the utility model be not limited to
Lower description content：
The utility model provides a kind of device producing isooctane using indirect alkylation technology, including sequentially connected solid
Fixed bed reactor I 1, catalytic distillation tower 2, extraction tower 3, recovery tower 4, as shown in Figure 1：
The fixed bed reactors I, inside are filled with catalyst A, and top is equipped with feed inlet I, bottom is equipped with discharge port
I：Feed inlet I is connected with the device that can provide mixing carbon four and/or polymerization inhibitor；
The catalytic distillation tower, top is equipped with exhaust outlet I, top is equipped with refluxing opening, middle part is equipped with feed inlet II, bottom
Equipped with discharge port II：Feed inlet II is connected with the discharge port I of fixed bed reactors I；Exhaust outlet I is connected with condenser 7, condensation
The outlet of device is divided into two-way, is connected all the way with refluxing opening by fixed bed reactors II 5, another way and holds residual carbon four
Device be connected；The catalytic section of catalytic distillation tower is filled with catalyst B, and catalyst C is filled in fixed bed reactors II；
The extraction tower 3, inside are filled with extractant, top is equipped with discharge port III, middle and upper part be equipped with extractant into
Mouth, middle and lower part are equipped with feed inlet III, bottom is equipped with mixture outlet：Feed inlet III is connected with the discharge port II of catalytic distillation tower
It connects；Discharge port III is connected with desulfurizing tower 6；
The desulfurizing tower 6, top is equipped with exhaust outlet II, middle and lower part is equipped with feed inlet IV, bottom is equipped with discharge port IV：Row
Gas port II is connected with flare system；Discharge port IV is connected with the device for holding final product isooctane；It is two that feed inlet IV, which is divided to,
Road is connected with the discharge port III of the extraction tower all the way, and another way is connected with the device for providing hydrogen；
The recovery tower 4, top is equipped with polymerization inhibitor outlet, middle and lower part is equipped with mixture intake, bottom is equipped with extractant
Outlet：Mixture intake is connected with the mixture outlet of extraction tower；Polymerization inhibitor exports the feed inlet I with fixed bed reactors I
It is connected；Extractant outlet is connected with the extractant import of extraction tower；
Discharge port I points are two-way, are connected all the way with the feed inlet II of the catalytic distillation tower, another way by pump with
The import of heat exchanger 8 is connected, and the outlet of heat exchanger is connected with feed inlet I；
Tri- tunnels feed inlet I Fen Wei, all the way with hold mixing carbon four and/or the device of polymerization inhibitor is connected, all the way with heat exchange
The outlet of device is connected, and is connected all the way with polymerization inhibitor outlet.
Further, the 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 replaced；Loading catalyst
Combination structured packing in, the catalyst of filling is catalyst B.The combination of loading catalyst in CN204656548U is regular to fill out
Material：Including catalyst matrix and metal packing piece group；The catalyst matrix by liner same material woven wire metal water chestnut
After shape expanded metals is pressed into regulation shape, constituted after being packed into catalyst granules (being packed into catalyst B) spot welding sealing；The metal is filled out
Tablet is filled between catalyst matrix by corrugated wire gauze packing or metallurgic orifice corrugated packing piece and is formed by welding；Catalyst
Matrix and packing sheet is spaced linearly equidistantly arranges along rectifying column diametric(al), with the steel band with diamond shape expanded metals same material
Catalytic distillation structure module is constituted after beamforming；Catalyst matrix uses 60 mesh stainless steel wires of stainless steel diamond shape expanded metals and same material
Site weld it is compound after to be pressed into section be that base angle is not less than 60 ° of two isosceles trapezoidal structures, sealing two ends；The catalyst mould
Piece and metal packing piece group are that one or more module assembly are composed.
Further, the extraction tower, internals are preferably sieve tray or efficiently separate filler, by traditional production
The internals of extraction tower in MTBE devices are replaced.
Further, the recovery tower, internals are preferably float valve tray or efficiently separate filler, by traditional production
The internals of recovery tower in MTBE devices are replaced.
Further, the fixed bed reactors I, fixed bed reactors II, desulfurizing tower, condenser, heat exchanger are
Equipment of the existing technology or commercial equipment.
Further, the catalyst A loaded in the fixed bed reactors I is solid acid catalyst, preferably macropore
Sulfonic acid cation resin catalyst；The catalyst B loaded in the catalytic distillation tower is solid acid catalyst, preferably macropore
Sulfonic acid cation resin catalyst；The catalyst C loaded in the fixed bed reactors II is solid acid catalyst, preferably
Macropore Sulfonic acid cation resin catalyst；The extractant loaded in the extraction tower is water.
The utility model also provides a kind of method producing isooctane using indirect alkylation technology：
(1) dimerization reaction：Mixing carbon four, polymerization inhibitor are passed into through feed inlet I in fixed bed reactors I 1, polymerization inhibitor
Dimerization reaction is carried out under the catalytic action for mixing catalyst A of the carbon four in fixed bed reactors I, obtains reaction product；Instead
A product part is answered followed by being recycled back to feed inlet I after discharge port I, pump, heat exchanger 8, reaction product is through heat exchange
Device returns again to fixed bed reactors I after removing reaction heat, to effectively control the temperature of fixed bed reactors I；Reaction product
Another part enters followed by discharge port I, feed inlet II 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 enters in fixed bed reactors II 5, the catalyst C in fixed bed reactors II
It is reacted under catalytic action, reaction product is flowed back by refluxing opening continues catalytic distillation in catalytic distillation tower；Bottom of tower
Material be isobutene dimer and polymerization inhibitor mixture, enter extraction tower followed by discharge port II, feed inlet III
In；
(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 tower of extraction tower obtains is the mixture of extractant and polymerization inhibitor, the mixture of extractant and polymerization inhibitor
It is recycled followed by being entered in recovery tower 4 after mixture outlet, mixture intake, the tower top of recovery tower is inhibited
Agent, polymerization inhibitor exports followed by polymerization inhibitor, after feed inlet I back to recycling in fixed bed reactors I, the tower of recovery tower
Bottom obtains extractant, extractant exports followed by extractant, after extractant import back to recycling in extraction tower；Extraction
The tower top of tower obtains dimer, is entered in hydrodesulfurization tower 6 followed by discharge port III, feed inlet IV；
(4) hydrodesulfurization：Dimer enters desulfurizing tower 6, while being passed through hydrogen, dimerization to desulfurizing tower by feed inlet IV
Hydrodesulfurization reaction is carried out after object and hydrogen mixing, hydrogen, desulfurization is added to be carried out in same tower；The material that the bottom of tower of desulfurizing tower obtains
For high-octane alkylate oil --- isooctane can be used as gasoline blend component；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 utility model method and apparatus are illustrated with reference to specific embodiment：
Embodiment 1：
A method of isooctane is produced using indirect alkylation technology, specifically includes following steps：
(1) dimerization reaction：Mixing carbon four, polymerization inhibitor are passed into through feed inlet I in fixed bed reactors I, polymerization inhibitor with
It mixes and carries out dimerization reaction under the catalytic action of catalyst A of the carbon four in fixed bed reactors I, obtain reaction product；Reaction
A product part is recycled followed by after discharge port I, pump, heat exchanger back to feed inlet I, and reaction product is moved through heat exchanger
Except fixed bed reactors I is returned again to after reaction heat, to effectively control the temperature of fixed bed reactors I；Reaction product is another
Part enters followed by discharge port I, feed inlet II in catalytic distillation tower；
The group reacted in the mixing carbon four is divided into isobutene；The polymerization inhibitor is the mixing of ethyl alcohol and methanol
Object (mass ratio 1:1)；The catalyst A is macropore sulfonic acid ion exchange resin catalyst (embodiment 1 in CN103447089A
In KR01)；
The polymerization inhibitor is 0.05 with the molar ratio for mixing isobutene in carbon four：1；
The condition of the 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 followed by returning to feed inlet I cycle after discharge port I, pump, heat exchanger, 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, cold through condenser after exhaust outlet I discharges
Solidifying to obtain residual carbon four, residual carbon four enters in fixed bed reactors II, the catalysis of catalyst C in fixed bed reactors II
It is reacted under effect, reaction product is flowed back by refluxing opening continues catalytic distillation in catalytic distillation tower；The object of bottom of tower
Material is the mixture of the dimer and polymerization inhibitor of isobutene, is entered in extraction tower followed by discharge port II, feed inlet III；
The catalyst B is macropore Sulfonic acid cation resin catalyst (in CN103447089A in embodiment 1
KR01)；The catalyst C is macropore Sulfonic acid cation resin catalyst (KR01 in CN103447089A in embodiment 1)；
The condition of the described catalytic distillation reaction is：Air speed is 2h-1, reaction temperature is 50~70 DEG C, reaction pressure 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 treated that residual carbon four forms basic phase for composition and original MTBE devices
Together, it other than being passed through and being reacted in fixed bed reactors II, is also delivered in the device for holding residual carbon four, is filled as downstream
The raw material set.
(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 tower of extraction tower obtains is the mixture of extractant and 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 recycled, the tower top of recovery tower obtains polymerization inhibitor, resistance
Poly- agent exports followed by polymerization inhibitor, after feed inlet I back to recycling in fixed bed reactors I, the bottom of tower of recovery tower obtains
To extractant, extractant exports followed by extractant, after extractant import back to recycling in extraction tower；Extraction tower
Tower top obtains dimer, is entered in hydrodesulfurization tower followed by discharge port III, feed inlet IV；Extractant in extraction tower
For 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 being passed through hydrogen, dimerization to desulfurizing tower by feed inlet IV
Hydrodesulfurization reaction is carried out after object and hydrogen mixing, hydrogen, desulfurization is added to be carried out in same tower；The material that the bottom of tower of desulfurizing tower obtains
For high-octane alkylate oil --- isooctane can be used as gasoline blend component；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 reaction condition of hydrodesulfurization reaction is：Reaction temperature is 200~300 DEG C, and reaction pressure is 0.8~1.2Mpa；
Dimer and the molar 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 used as gasoline blend component；Isobutene content≤0.15% in residual carbon four, can
Meet the requirement of downstream unit, to after carrying out part transformation to MTBE devices, so that it may to continue entire industrial chain.
Embodiment 2：
A method of isooctane is produced using indirect alkylation technology, specifically includes following steps：
(1) dimerization reaction：Mixing carbon four, polymerization inhibitor are passed into through feed inlet I in fixed bed reactors I, polymerization inhibitor with
It mixes and carries out dimerization reaction under the catalytic action of catalyst A of the carbon four in fixed bed reactors I, obtain reaction product；Reaction
A product part is recycled followed by after discharge port I, pump, heat exchanger back to feed inlet I, and reaction product is moved through heat exchanger
Except fixed bed reactors I is returned again to after reaction heat, to effectively control the temperature of fixed bed reactors I；Reaction product is another
Part enters followed by discharge port I, feed inlet II in catalytic distillation tower；
The group reacted in the mixing carbon four is divided into isobutene；The polymerization inhibitor is ethyl alcohol, propyl alcohol and butanol
Mixture (mass ratio 1:2:1)；The catalyst A is macropore sulfonic acid ion exchange resin catalyst (CN103447089A
KR07 in middle embodiment 1)；
The polymerization inhibitor is 0.07 with the molar ratio for mixing isobutene in carbon four：1；
The condition of the 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 followed by returning to feed inlet I cycle after discharge port I, pump, heat exchanger, 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, cold through condenser after exhaust outlet I discharges
Solidifying to obtain residual carbon four, residual carbon four enters in fixed bed reactors II, the catalysis of catalyst C in fixed bed reactors II
It is reacted under effect, reaction product is flowed back by refluxing opening continues catalytic distillation in catalytic distillation tower；The object of bottom of tower
Material is the mixture of the dimer and polymerization inhibitor of isobutene, is entered in extraction tower followed by discharge port II, feed inlet III；
The catalyst B is macropore Sulfonic acid cation resin catalyst (in CN103447089A in embodiment 7
KR07)；The catalyst C is macropore Sulfonic acid cation resin catalyst (KR07 in CN103447089A in embodiment 7)；
The condition of the 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 condenses to obtain residual carbon four, and treated that residual carbon four forms basic phase for composition and original MTBE devices
Together, it other than being passed through and being reacted in fixed bed reactors II, is also delivered in the device for holding residual carbon four, is filled as downstream
The raw material set.
(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 tower of extraction tower obtains is the mixture of extractant and 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 recycled, the tower top of recovery tower obtains polymerization inhibitor, resistance
Poly- agent exports followed by polymerization inhibitor, after feed inlet I back to recycling in fixed bed reactors I, the bottom of tower of recovery tower obtains
To extractant, extractant exports followed by extractant, after extractant import back to recycling in extraction tower；Extraction tower
Tower top obtains dimer, is entered in hydrodesulfurization tower followed by discharge port III, feed inlet IV；Extractant in extraction tower
For 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 being passed through hydrogen, dimerization to desulfurizing tower by feed inlet IV
Hydrodesulfurization reaction is carried out after object and hydrogen mixing, hydrogen, desulfurization is added to be carried out in same tower；The material that the bottom of tower of desulfurizing tower obtains
For high-octane alkylate oil --- isooctane can be used as gasoline blend component；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 reaction condition of hydrodesulfurization reaction is：Reaction temperature is 200~300 DEG C, and reaction pressure is 0.8~1.2Mpa；
Dimer and the molar ratio of hydrogen are 1：4.
The present invention makes conversion ratio >=99.5% of isobutene in mixing carbon four；In product after hydrodesulfurization, isooctane is total
Content >=93%, octane number >=98 can be used as gasoline blend component；Isobutene content≤0.15% in residual carbon four can meet
The requirement of downstream unit, to after carrying out part transformation to MTBE devices, so that it may to continue entire industrial chain.
Examples detailed above is to illustrate the technical concept and technical characterstic of the utility model, can not limit this reality with this
With novel protection domain.The equivalent transformation or modification that all essence according to the present utility model is done, should all cover in this reality
Within novel protection domain.
Claims (9)
1. a kind of device producing isooctane using indirect alkylation technology, including sequentially connected fixed bed reactors I (1),
Catalytic distillation tower (2), extraction tower (3), recovery tower (4), it is characterised in that：
The fixed bed reactors I (1), inside are filled with catalyst A, and top is equipped with feed inlet I, bottom is equipped with discharge port I：
Feed inlet I is connected with the device that can provide mixing carbon four and/or polymerization inhibitor；
The catalytic distillation tower (2), top is equipped with exhaust outlet I, top is equipped with refluxing opening, middle part is equipped with feed inlet II, bottom
Equipped with discharge port II：Feed inlet II is connected with the discharge port I of fixed bed reactors I；Exhaust outlet I is connected with condenser (7), cold
The outlet of condenser is divided into two-way, is connected all the way with refluxing opening by fixed bed reactors II (5), another way and holds residual carbon
Four device is connected；The catalytic section of catalytic distillation tower is filled with catalyst B, and catalyst C is filled in fixed bed reactors II；
The extraction tower (3), inside are filled with extractant, top is equipped with discharge port III, middle and upper part is equipped with extractant import,
Middle and lower part is equipped with feed inlet III, bottom is equipped with mixture outlet：Feed inlet III is connected with the discharge port II of catalytic distillation tower；
Discharge port III is connected with desulfurizing tower (6), and the outlet of desulfurizing tower is connected with the device for holding final product isooctane；
The recovery tower (4), top is equipped with polymerization inhibitor outlet, middle and lower part is equipped with mixture intake, bottom goes out equipped with extractant
Mouthful：Mixture intake is connected with the mixture outlet of extraction tower；Polymerization inhibitor exports the feed inlet I phases with fixed bed reactors I
Connection；Extractant outlet is connected with the extractant import of extraction tower.
2. the apparatus according to claim 1, it is characterised in that：Discharge port I points are two-way, all the way with the catalytic distillation
The feed inlet II of tower is connected, and another way is connected by pumping with the import of heat exchanger (8), outlet and the feed inlet I of heat exchanger
It is connected.
3. device according to claim 1 or 2, it is characterised in that：Tri- tunnels feed inlet I Fen Wei mix carbon with holding all the way
Four and/or the device of polymerization inhibitor be connected, be connected all the way with the outlet of heat exchanger, be connected all the way with polymerization inhibitor outlet.
4. the apparatus according to claim 1, it is characterised in that：The desulfurizing tower (6), top be equipped with exhaust outlet II, in
Lower part is equipped with feed inlet IV, bottom is equipped with discharge port IV：Exhaust outlet II is connected with flare system；Discharge port IV and hold whole production
The device of object isooctane is connected；IV points of feed inlet is two-way, is connected all the way with the discharge port III of the extraction tower, separately
It is connected all the way with the device for providing hydrogen.
5. the apparatus according to claim 1, it is characterised in that：The catalytic distillation tower (2), the internals of catalytic section include
Catalyst matrix and metal packing piece group；The catalyst matrix by liner same material woven wire metal diamond shape expanded metals pressure
After regulation shape is made, constituted after being packed into catalyst granules spot welding sealing；The metal packing piece is by corrugated wire gauze packing
Or metallurgic orifice corrugated packing piece be filled in catalyst matrix between be formed by welding；Catalyst matrix and the spaced edge of packing sheet
Rectifying column diametric(al) is linearly equidistantly arranged, with constitute catalytic distillation structure after the steel band beamforming of diamond shape expanded metals same material
Module；Catalyst matrix is pressed into section after using 60 mesh stainless steel cloth spot welding of stainless steel diamond shape expanded metals and same material compound
It is not less than 60 ° of two isosceles trapezoidal structures, sealing two ends for base angle；The catalyst matrix and metal packing piece group are one
Or multiple module assembly are composed；Catalyst granules is the catalyst B.
6. the apparatus according to claim 1, it is characterised in that：The extraction tower (3), internals are for sieve tray or efficiently
Detach filler.
7. the apparatus according to claim 1, it is characterised in that：The recovery tower (4), recovery tower (4) internals are float valve
Tower tray efficiently separates filler.
8. the apparatus according to claim 1, it is characterised in that：The catalyst A is solid acid catalyst, and described urges
Agent B is solid acid catalyst, and the catalyst C is solid acid catalyst.
9. device according to claim 8, it is characterised in that：The solid acid catalyst is macropore Sulfonic acid cation tree
Fat catalyst.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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2017
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109354567B (en) * | 2018-12-13 | 2023-11-10 | 丹东明珠特种树脂有限公司 | Superposition process method of isobutene superposition system device reconstructed by methyl tertiary butyl ether device |
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