CN107827694B - Device and method for producing isooctane by adopting indirect alkylation technology - Google Patents
Device and method for producing isooctane by adopting indirect alkylation technology Download PDFInfo
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- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 title claims abstract description 33
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000005516 engineering process Methods 0.000 title claims abstract description 18
- 230000029936 alkylation Effects 0.000 title claims abstract description 17
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 97
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 91
- 230000003197 catalytic effect Effects 0.000 claims abstract description 90
- 239000003112 inhibitor Substances 0.000 claims abstract description 89
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 82
- 238000000605 extraction Methods 0.000 claims abstract description 82
- 238000004821 distillation Methods 0.000 claims abstract description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000011084 recovery Methods 0.000 claims abstract description 56
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 30
- 239000000539 dimer Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 8
- 230000023556 desulfurization Effects 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 123
- 239000000203 mixture Substances 0.000 claims description 61
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 43
- 239000003795 chemical substances by application Substances 0.000 claims description 39
- 239000007795 chemical reaction product Substances 0.000 claims description 37
- 238000006471 dimerization reaction Methods 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000000945 filler Substances 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 238000004064 recycling Methods 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- 239000011973 solid acid Substances 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- 229910003460 diamond Inorganic materials 0.000 claims description 9
- 239000010432 diamond Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000003466 welding Methods 0.000 claims description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 4
- 238000007667 floating Methods 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000012856 packing Methods 0.000 description 20
- 150000001768 cations Chemical class 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- -1 carbon olefin Chemical class 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
Abstract
The invention discloses a device and a method for producing isooctane by adopting an indirect alkylation technology, wherein the device comprises a fixed bed reactor I, a catalytic distillation tower, an extraction tower and a recovery tower which are connected in sequence: mixing carbon four and polymerization inhibitor to react in a reactor I, wherein one part of the product enters a catalytic distillation tower, and the other part of the product returns after the reaction heat is removed by a heat exchanger; after catalytic distillation, the tower top product enters a fixed bed reactor II for reaction and then flows back, and the tower bottom product enters an extraction tower; after extraction, the dimer at the top of the tower enters a desulfurizing tower, and the product at the bottom of the tower enters a recovery tower; after recovery, the extractant returns to the extraction tower and the polymerization inhibitor returns to the reactor I; the dimer and hydrogen are hydrodesulfurized in a desulfurization tower to obtain isooctane which can be used as a gasoline blending component. The invention reforms the existing MTBE production device to be an isooctane production device, the produced isooctane can be used as an ethanol gasoline blending component, and the byproducts can be recycled as other raw materials.
Description
Technical Field
The invention relates to a device and a method for producing isooctane, in particular to a device and a method for producing isooctane by adopting an indirect alkylation technology, which reforms an MTBE device by adopting the indirect alkylation technology, so that olefin-containing mixed carbon four is subjected to dimerization reaction under the action of a catalyst and a polymerization inhibitor to generate a dimer, and the dimer is subjected to hydrodesulfurization to generate high-octane gasoline blending component alkylate, wherein the main component of the alkylate is isooctane.
Background
The existing MTBE production devices are to be abandoned, raw materials of the devices cannot be reused for producing products with high added value, and the downstream devices cannot obtain the residual carbon four treated by the MTBE device as raw materials, so that an industrial chain is interrupted.
How to reform the prior MTBE devices, the reformed devices can be used continuously, and products produced by the reformed devices can be used as gasoline blending components continuously, so that the whole industrial chain is continued, and the problem that researchers need to study and overcome at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a device and a method for producing isooctane by adopting an indirect alkylation technology, which reforms the prior MTBE production device to be a device for producing isooctane, and the isooctane produced by the device can be used as an ethanol gasoline blending component, and byproducts can be recycled as other raw materials, thereby changing waste into valuables and achieving multiple purposes.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the device for producing isooctane by adopting the indirect alkylation technology comprises a fixed bed reactor I, a catalytic distillation tower, an extraction tower and a recovery tower which are connected in sequence, and is characterized in that:
the fixed bed reactor I is internally filled with a catalyst A, the top of the fixed bed reactor I is provided with a feed inlet I, and the bottom of the fixed bed reactor I is provided with a discharge outlet I; the feed inlet I is connected with a device capable of providing mixed carbon four and/or polymerization inhibitor;
the catalytic distillation tower, the top be equipped with gas vent I, upper portion is equipped with the return port, the middle part is equipped with feed inlet II, the bottom is equipped with discharge gate II: the feed inlet II is connected with the discharge outlet I of the fixed bed reactor I; the exhaust port I is connected with a condenser, the outlet of the condenser is divided into two paths, one path is connected with a reflux port through a fixed bed reactor II, and the other path is connected with a device for containing the residual carbon four; the catalytic section of the catalytic distillation tower is filled with a catalyst B, and the fixed bed reactor II is filled with a catalyst C;
the extraction tower is characterized in that an extracting agent is filled in the extraction tower, a discharge port III is formed in the top of the extraction tower, an extracting agent inlet is formed in the middle upper portion of the extraction tower, a feed inlet III is formed in the middle lower portion of the extraction tower, and a mixture outlet is formed in the bottom of the extraction tower: the feed inlet III is connected with the discharge outlet II of the catalytic distillation tower; the discharge port III is connected with a desulfurizing tower, and the outlet of the desulfurizing tower is connected with a device for containing isooctane as a final product;
the top of the recovery tower is provided with a polymerization inhibitor outlet, the middle lower part of the recovery tower is provided with a mixture inlet, and the bottom of the recovery tower is provided with an extractant outlet: the mixture inlet is connected with the mixture outlet of the extraction tower; the polymerization inhibitor outlet is connected with a feed inlet I of the fixed bed reactor I; the extractant outlet is connected with the extractant inlet of the extraction tower.
In the technical scheme, the discharge port I is divided into two paths, one path is connected with the feed inlet II of the catalytic distillation tower, the other path is connected with the inlet of the heat exchanger through a pump, and the outlet of the heat exchanger is connected with the feed inlet I.
In the technical scheme, the feeding port I is divided into three paths, one path is connected with a device for containing the mixed carbon four and/or polymerization inhibitor, the other path is connected with an outlet of the heat exchanger, and the other path is connected with an outlet of the polymerization inhibitor.
Among the above-mentioned technical scheme, desulfurizing tower, the top be equipped with gas vent II, well lower part is equipped with feed inlet IV, the bottom is equipped with discharge gate IV: the exhaust port II is connected with a torch system; the discharge port IV is connected with a device for containing isooctane as a final product; the feeding port IV is divided into two paths, one path is connected with a discharging port III of the extraction tower, and the other path is connected with a device for providing hydrogen.
In the above technical solution, the catalytic distillation tower is preferably a catalytic distillation tower with catalyst-filled combined structured packing in patent CN204656548U, and more preferably a catalytic distillation tower with catalyst-filled combined structured packing in patent CN204656548U in a conventional MTBE production device, and only the internal components of the catalytic section of the existing catalytic distillation tower need to be replaced; in the combined structured packing filled with the catalyst, the filled catalyst is a catalyst B; catalyst-filled structured packing in CN 204656548U: comprises a catalyst die and a metal filler sheet group; the catalyst mold sheet is formed by pressing a metal diamond plate mesh lined with a metal mesh with the same material into a specified shape, filling catalyst particles (namely filling catalyst B) and spot-welding and sealing; the metal filler sheet is formed by welding metal wire mesh corrugated filler or metal pore plate corrugated filler sheets filled between catalyst mold sheets; the catalyst mold pieces and the filler pieces are mutually spaced and linearly and equidistantly arranged along the diameter direction of the rectifying tower, and the catalytic distillation element module is formed by using steel belt bundles with the same material as the diamond plate net; the catalyst mold sheet adopts stainless steel diamond plate mesh and 60 mesh stainless steel wire mesh which are made of the same material to be subjected to spot welding and compounding, and then is pressed into two isosceles trapezoid structures with the cross section of which the base angle is not less than 60 degrees, and two ends are sealed; the catalyst mold sheet and the metal filler sheet group are formed by assembling one or more modules.
In the above technical scheme, the extraction tower is preferably an extraction tower with internal components of a sieve tray or efficient separation packing, and is further preferably an extraction tower with internal components of a sieve tray or efficient separation packing in a traditional MTBE device, and only the internal components of the existing extraction tower are required to be replaced.
In the above technical scheme, the recovery tower is preferably a recovery tower with internal components of a floating valve tray or high-efficiency separation packing, and is further preferably a methanol recovery tower in a traditional MTBE device with internal components of a floating valve tray or high-efficiency separation packing, and only the internal components of the existing recovery tower are required to be replaced.
In the technical scheme, the fixed bed reactor I, the fixed bed reactor II, the desulfurizing tower, the condenser and the heat exchanger are all equipment existing in the prior art or commercially available equipment.
In the technical scheme, the catalyst A filled in the fixed bed reactor I is a solid acid catalyst, preferably a large Kong Huangsuan cation resin catalyst; the catalyst B filled in the catalytic distillation tower is a solid acid catalyst, preferably a large Kong Huangsuan cationic resin catalyst; the catalyst C filled in the fixed bed reactor II is a solid acid catalyst, preferably a large Kong Huangsuan cation resin catalyst; the extractant filled in the extraction tower is water.
The invention provides a method for producing isooctane by adopting an indirect alkylation technology, which comprises the following steps:
(1) Dimerization reaction: mixing the mixed carbon four and a polymerization inhibitor uniformly, and carrying out dimerization reaction in the presence of a catalyst A to obtain a reaction product; part of the reaction product is used as raw material for recycling, and the other part is subjected to catalytic distillation:
(3) Catalytic distillation: the reaction product is separated after catalytic distillation reaction under the action of a catalyst B, wherein: the separated light component is carbon four after gaseous dimerization, the carbon four after gaseous dimerization is condensed and then continuously reacts under the catalysis of a catalyst C, and the obtained material is continuously subjected to catalytic distillation; the heavy component obtained by separation is a mixture of isobutene dimer and polymerization inhibitor, and extraction and recovery are carried out;
(4) Extraction and recovery: the mixture of isobutene dimer and polymerization inhibitor is extracted by an extractant to obtain dimer, and the mixture of the extractant and the polymerization inhibitor is: recovering the mixture of the extractant and the polymerization inhibitor to obtain the extractant and the polymerization inhibitor, continuously extracting and recycling the two extractants, and returning the polymerization inhibitor to the step (1) for recycling; hydrodesulfurizing the dimer;
(5) Hydrodesulfurization: the dimer and hydrogen are mixed and then subjected to hydrodesulfurization reaction, so that the obtained isooctane and hydrogen sulfide are used as gasoline blending components, and the residual hydrogen and hydrogen sulfide are sent to a flare system for use.
The method for producing isooctane by adopting the indirect alkylation technology comprises the following steps:
(1) Dimerization reaction: introducing the mixed carbon four and a polymerization inhibitor into the fixed bed reactor I through a feed inlet I, and carrying out dimerization reaction on the polymerization inhibitor and the mixed carbon four under the catalysis of a catalyst A in the fixed bed reactor I to obtain a reaction product; part of the reaction product sequentially flows through the discharge port I, the pump and the heat exchanger and then returns to the feed port I for circulation, and the reaction product returns to the fixed bed reactor I after removing the reaction heat through the heat exchanger, so that the temperature of the fixed bed reactor I is effectively controlled; the other part of the reaction product sequentially flows through a discharge port I and a feed port II to enter a catalytic distillation tower;
(2) Catalytic distillation: after the reaction product enters a catalytic distillation tower, carrying out catalytic distillation reaction and separation under the action of a catalyst B in the catalytic distillation tower; the material at the top of the tower is carbon four after gaseous dimerization, the material is discharged from an exhaust port I and condensed by a condenser to obtain residual carbon four, the residual carbon four enters a fixed bed reactor II and reacts under the catalysis of a catalyst C in the fixed bed reactor II, and a reaction product flows back to a catalytic distillation tower through a reflux port to continue catalytic distillation; the material at the bottom of the tower is a mixture of isobutene dimer and polymerization inhibitor, and sequentially flows through a discharge port II and a feed port III to enter the extraction tower;
(3) Extraction and recovery: after the mixture of isobutene dimer and polymerization inhibitor enters an extraction tower, under the extraction of an extracting agent, the material obtained at the bottom of the extraction tower is the mixture of the extracting agent and the polymerization inhibitor, the mixture of the extracting agent and the polymerization inhibitor sequentially flows through a mixture outlet and a mixture inlet and then enters a recovery tower for recovery, the polymerization inhibitor is obtained at the top of the recovery tower, the polymerization inhibitor sequentially flows through a polymerization inhibitor outlet and a feed inlet I and then returns to a fixed bed reactor I for recycling, the extracting agent is obtained at the bottom of the recovery tower, and the extracting agent sequentially flows through an extracting agent outlet and an extracting agent inlet and then returns to the extraction tower for recycling; the dimer is obtained at the top of the extraction tower, and sequentially flows through a discharge port III and a feed port IV to enter a hydrodesulfurization tower;
(4) Hydrodesulfurization: introducing the dimer into a desulfurizing tower, introducing hydrogen into the desulfurizing tower through a feed inlet IV, mixing the dimer with the hydrogen, and then carrying out hydrodesulfurization reaction, wherein the hydrodesulfurization and the desulfurization are carried out in the same tower; the material obtained at the bottom of the desulfurizing tower is high-octane alkylate-isooctane which can be used as a gasoline blending component; the materials obtained at the top of the desulfurizing tower are the mixture of the residual hydrogen and the generated hydrogen sulfide, and can be sent to a torch system for use.
In the above technical scheme, in the step (1), the component in the mixed carbon four which is reacted is isobutene, and the molar ratio of the polymerization inhibitor to isobutene in the mixed carbon four is 0.01-1:1, preferably 0.02-0.5:1.
in the above technical scheme, in the step (1), the polymerization inhibitor is a mixed alcohol polymerization inhibitor, preferably a mixture of any two or more of methanol, ethanol, propanol and butanol in any proportion.
In the above technical scheme, in the step (1), the catalyst a is a solid acid catalyst, preferably a large Kong Huangsuan cationic resin catalyst, and further preferably an invention patent CN103447089a (a low carbon olefin polymerization catalyst and a preparation method thereof, kei chemical company, inc.).
In the technical scheme, in the step (1), the dimerization reaction has a space velocity of 0.5-1 h -1 The reaction temperature is 35-70 ℃, and the reaction pressure is 0.8-1.2 Mpa; wherein the temperature is preferably 35-50 ℃, and the reaction pressure is preferably 1.0-1.2 Mpa.
In the technical scheme, in the step (1), part of the reaction product sequentially flows through the discharge port I, the pump and the heat exchanger and then returns to the feed port I for circulation, and the circulation amount is 2-5 times of the feed amount.
In the above technical scheme, in the step (2), the catalytic distillation tower is filled with the catalyst-filled combined structured packing in CN204656548U at the catalytic section, the catalyst filled in the catalyst-filled combined structured packing is the catalyst B, and the catalyst B is a solid acid catalyst, preferably a Kong Huangsuan cation resin catalyst, and further preferably an invention patent CN103447089a (a low carbon olefin polymerization catalyst and a preparation method thereof, kei chemical company).
In the above technical scheme, in the step (2), the catalyst C is a solid acid catalyst, preferably a large Kong Huangsuan cationic resin catalyst, and further preferably an invention patent CN103447089a (a low carbon olefin polymerization catalyst and a preparation method thereof, kei chemical company, inc.).
In the above technical scheme, in the step (2), the reaction conditions of the catalytic distillation reaction are as follows: airspeed of 1-3 h -1 The reaction temperature is 50-70 ℃, and the reaction pressure is 0.5-0.7 Mpa.
In the above technical scheme, in the step (2), the reaction conditions in the fixed bed reactor II (5) are as follows: airspeed of 0.5 to 1h -1 The reaction temperature is 35-70 ℃, and the reaction pressure is 0.8-1.2 Mpa; wherein the temperature is preferably 35-50 ℃, and the reaction pressure is preferably 1.0-1.2 Mpa.
In the above technical scheme, in the step (2), the composition of the residual carbon four is basically the same as that of the residual carbon four processed by the original MTBE device after condensing by a condenser, and the residual carbon four can be conveyed to a device for containing the residual carbon four as a raw material of a downstream device besides being introduced into a fixed bed reactor II for reaction.
In the above technical scheme, in the step (3), the extractant in the extraction tower (3) is water.
In the technical scheme, in the step (3), the reaction conditions of the extraction tower (3) are as follows: the reaction temperature is 38-42 ℃ and the reaction pressure is 0.5-1MPa.
In the technical scheme, in the step (3), the reaction conditions of the recovery tower (4) are as follows: temperature: 80-130 ℃ and 0-0.5Mpa.
In the above technical scheme, in the step (4), in the desulfurizing tower, the reaction conditions of the hydrodesulfurization reaction are as follows: the reaction temperature is 200-300 ℃ and the reaction pressure is 0.8-1.2 Mpa.
In the above technical scheme, in step (4), the molar ratio of dimer to hydrogen is 1:2 to 5.
The technical scheme of the invention has the advantages that:
(1) According to the invention, isobutene in the mixed carbon four is used as a reaction raw material, and a polymerization inhibitor is added to prevent trimerization and polymerization reaction, so that the conversion rate of a dimerization product is improved; the polymerization inhibitor mainly adopts a novel mixed alcohol polymerization inhibitor developed by the company (Kai Rui environmental protection technology Co., ltd.) so as to enable isobutene in mixed carbon four to carry out controllable dimerization reaction and effectively inhibit trimerization and higher polymerization reaction.
(2) According to the reactor disclosed by the invention, a novel catalyst is filled to replace a catalyst for producing MTBE, and the catalyst filled in the fixed bed reactor is a catalyst for enabling isobutene to carry out dimerization reaction to generate isooctane, so that isobutene is promoted to carry out dimerization reaction.
(3) The reactor is different from the reactor in the MTBE device, is a fixed bed reactor, and after being uniformly mixed with the mixed carbon four and the polymerization inhibitor, the mixed carbon four and the polymerization inhibitor enter the fixed bed reactor after the original MTBE device reactor is modified to carry out dimerization reaction. The fixed bed reactor adopts the conception of external circulation and heat exchangers, the reactor for producing MTBE is modified, and the heat exchangers are added; part of materials at the outlet of the reactor are pressurized by a pump, enter a heat exchanger to remove the reaction heat, and then return to the inlet of the reactor, so that the reaction heat is effectively removed to control the reaction temperature.
(4) The invention reforms the catalytic distillation tower of the original MTBE device, reforms the catalytic section of the catalytic distillation tower into the catalytic section filled with the structured packing catalyst, and changes the internal parts of the tower; the structured packing catalyst is structured packing in the patent technology ZL02233432.7 of the company.
(5) According to the invention, a new reactor, also a fixed bed reactor, is added on the reflux route of the catalytic distillation tower of the original MTBE device, and the conversion rate of olefin can be improved to the maximum extent under the action of no polymerization inhibitor through the catalytic action of the reactor; the top discharge of the catalytic distillation tower is carbon four after gaseous dimerization, and part of the condensed material enters a new reactor to further react and is used as reflux of the catalytic distillation tower; the other part of the materials are the rest carbon four; the remaining carbon four is the same as the remaining carbon four of the original MTBE device, and can be used as the feed of the downstream device of the original MTBE device.
(6) According to the invention, on the basis of an original MTBE device methanol recovery system, the inner part of the extraction tower of the MTBE device methanol recovery system and the inner part of the methanol recovery tower are replaced to form a polymerization inhibitor recovery system; the new extraction tower uses water as extractant, uses water to extract polymerization inhibitor, and sends the polymerization inhibitor into the new recovery tower for recycling.
(7) According to the invention, a hydrodesulfurization tower is additionally arranged on the basis of an original MTBE device, the extracted dimer enters the hydrodesulfurization tower, desulfurization operation is carried out while the dimer is hydrogenated, and high-octane alkylate, i.e. isooctane, is produced at the bottom of the tower and can be used as a gasoline blending component; the top discharge of the tower is a mixture of hydrogen sulfide and hydrogen, and can be sent to a torch system.
(8) The conversion rate of isobutene in the mixed carbon four is more than or equal to 99.5 percent; in the product after hydrodesulfurization, the total content of isooctane is more than or equal to 93 percent, and the octane number is more than or equal to 98 percent, and can be used as a gasoline blending component; the isobutene content in the residual carbon number IV is less than or equal to 0.15%, and the requirement of a downstream device can be met, so that the whole industrial chain can be continued after the MTBE device is partially modified.
Drawings
Fig. 1: the invention adopts a flow chart of a method for producing isooctane by indirect alkylation technology;
fig. 2: the invention adopts the indirect alkylation technology to produce the overall structure schematic diagram of the device of isooctane;
wherein: 1 is a fixed bed reactor I;2 is a catalytic distillation tower; 3 is an extraction tower; 4 is a recovery tower; 5 is a fixed bed reactor II;6 is a desulfurizing tower; 7 is a condenser; 8 is a heat exchanger.
Detailed Description
The following detailed description of the technical scheme of the present invention is provided, but the present invention is not limited to the following descriptions:
the invention provides a device for producing isooctane by adopting an indirect alkylation technology, which comprises a fixed bed reactor I1, a catalytic distillation tower 2, an extraction tower 3 and a recovery tower 4 which are connected in sequence, as shown in figure 2:
the fixed bed reactor I, inside catalyst A of packing, the top is equipped with feed inlet I, the bottom is equipped with discharge gate I: the feed inlet I is connected with a device capable of providing mixed carbon four and/or polymerization inhibitor;
the catalytic distillation tower, the top be equipped with gas vent I, upper portion is equipped with the return port, the middle part is equipped with feed inlet II, the bottom is equipped with discharge gate II: the feed inlet II is connected with the discharge outlet I of the fixed bed reactor I; the exhaust port I is connected with a condenser 7, the outlet of the condenser is divided into two paths, one path is connected with a reflux port through a fixed bed reactor II5, and the other path is connected with a device for containing the residual carbon four; the catalytic section of the catalytic distillation tower is filled with a catalyst B, and the fixed bed reactor II is filled with a catalyst C;
the extraction tower 3, inside packing has the extractant, and the top is equipped with discharge gate III, well upper portion is equipped with the extractant import, well lower part is equipped with feed inlet III, the bottom is equipped with the mixture export: the feed inlet III is connected with the discharge outlet II of the catalytic distillation tower; the discharge port III is connected with a desulfurizing tower 6;
desulfurizing tower 6, the top be equipped with gas vent II, well lower part is equipped with feed inlet IV, the bottom is equipped with discharge gate IV: the exhaust port II is connected with a torch system; the discharge port IV is connected with a device for containing isooctane as a final product; the feeding port IV is divided into two paths, one path is connected with a discharging port III of the extraction tower, and the other path is connected with a device for providing hydrogen;
the recovery tower 4 is provided with a polymerization inhibitor outlet at the top, a mixture inlet at the middle lower part and an extractant outlet at the bottom: the mixture inlet is connected with the mixture outlet of the extraction tower; the polymerization inhibitor outlet is connected with a feed inlet I of the fixed bed reactor I; the extractant outlet is connected with the extractant inlet of the extraction tower;
the discharge port I is divided into two paths, one path is connected with the feed port II of the catalytic distillation tower, the other path is connected with the inlet of the heat exchanger 8 through a pump, and the outlet of the heat exchanger is connected with the feed port I;
the feeding port I is divided into three paths, one path is connected with a device for containing mixed carbon four and/or polymerization inhibitor, the other path is connected with an outlet of the heat exchanger, and the other path is connected with an outlet of the polymerization inhibitor.
Further, the internal parts of the catalytic distillation tower 2 are preferably combined structured packing filled with catalyst (patent CN 204656548U), and the internal parts of the catalytic distillation tower in the traditional MTBE production device can be replaced; in the combined structured packing filled with the catalyst, the filled catalyst is catalyst B. Catalyst-filled structured packing in CN 204656548U: comprises a catalyst die and a metal filler sheet group; the catalyst mold sheet is formed by pressing a metal diamond plate mesh lined with a metal mesh with the same material into a specified shape, filling catalyst particles (namely filling catalyst B) and spot-welding and sealing; the metal filler sheet is formed by welding metal wire mesh corrugated filler or metal pore plate corrugated filler sheets filled between catalyst mold sheets; the catalyst mold pieces and the filler pieces are mutually spaced and linearly and equidistantly arranged along the diameter direction of the rectifying tower, and the catalytic distillation element module is formed by using steel belt bundles with the same material as the diamond plate net; the catalyst mold sheet adopts stainless steel diamond plate mesh and 60 mesh stainless steel wire mesh which are made of the same material to be subjected to spot welding and compounding, and then is pressed into two isosceles trapezoid structures with the cross section of which the base angle is not less than 60 degrees, and two ends are sealed; the catalyst mold sheet and the metal filler sheet group are formed by assembling one or more modules.
Furthermore, the internal parts of the extraction tower are preferably sieve tray trays or high-efficiency separation packing, and the internal parts of the extraction tower in the traditional MTBE production device can be replaced.
Furthermore, the internal parts of the recovery tower are preferably floating valve trays or high-efficiency separation packing, and the internal parts of the recovery tower in the traditional MTBE production device can be replaced.
Furthermore, the fixed bed reactor I, the fixed bed reactor II, the desulfurizing tower, the condenser and the heat exchanger are all equipment existing in the prior art or commercially available equipment.
Further, the catalyst A filled in the fixed bed reactor I is a solid acid catalyst, preferably a large Kong Huangsuan cation resin catalyst; the catalyst B filled in the catalytic distillation tower is a solid acid catalyst, preferably a large Kong Huangsuan cationic resin catalyst; the catalyst C filled in the fixed bed reactor II is a solid acid catalyst, preferably a large Kong Huangsuan cation resin catalyst; the extractant filled in the extraction tower is water.
The invention also provides a method for producing isooctane by adopting an indirect alkylation technology, and the flow chart is shown in figure 1:
(1) Dimerization reaction: introducing the mixed carbon four and a polymerization inhibitor into a fixed bed reactor I1 through a feed inlet I, and carrying out dimerization reaction on the polymerization inhibitor and the mixed carbon four under the catalysis of a catalyst A in the fixed bed reactor I to obtain a reaction product; part of the reaction product sequentially flows through the discharge port I, the pump and the heat exchanger 8 and then returns to the feed port I for circulation, and the reaction product returns to the fixed bed reactor I after removing the reaction heat through the heat exchanger, so that the temperature of the fixed bed reactor I is effectively controlled; the other part of the reaction product sequentially flows through a discharge port I and a feed port II to enter a catalytic distillation tower 2;
(2) Catalytic distillation: after the reaction product enters the catalytic distillation tower 2, carrying out catalytic distillation reaction and separation under the action of a catalyst B in the catalytic distillation tower; the material at the top of the tower is carbon four after gaseous dimerization, the material is discharged from an exhaust port I and condensed by a condenser 7 to obtain residual carbon four, the residual carbon four enters a fixed bed reactor II5 and reacts under the catalysis of a catalyst C in the fixed bed reactor II, and a reaction product flows back to a catalytic distillation tower through a reflux port to continue catalytic distillation; the material at the bottom of the tower is a mixture of isobutene dimer and polymerization inhibitor, and sequentially flows through a discharge port II and a feed port III to enter the extraction tower;
(3) Extraction and recovery: after the mixture of isobutene dimer and polymerization inhibitor enters an extraction tower 3, under the extraction of an extracting agent, the material obtained at the bottom of the extraction tower is the mixture of the extracting agent and the polymerization inhibitor, the mixture of the extracting agent and the polymerization inhibitor sequentially flows through a mixture outlet and a mixture inlet and then enters a recovery tower 4 for recovery, the polymerization inhibitor is obtained at the top of the recovery tower, the polymerization inhibitor sequentially flows through a polymerization inhibitor outlet and a feed inlet I and then returns to a fixed bed reactor I for recycling, the extracting agent is obtained at the bottom of the recovery tower, and the extracting agent sequentially flows through an extracting agent outlet and an extracting agent inlet and then returns to the extraction tower for recycling; the dimer obtained at the top of the extraction tower sequentially flows through a discharge port III and a feed port IV to enter a hydrodesulfurization tower 6;
(4) Hydrodesulfurization: introducing the dimer into a desulfurization tower 6, introducing hydrogen into the desulfurization tower through a feed port IV, mixing the dimer with the hydrogen, and then performing hydrodesulfurization reaction, wherein the hydrodesulfurization is performed in the same tower; the material obtained at the bottom of the desulfurizing tower is high-octane alkylate-isooctane which can be used as a gasoline blending component; the materials obtained at the top of the desulfurizing tower are the mixture of the residual hydrogen and the generated hydrogen sulfide, and can be sent to a torch system for use.
The method and apparatus of the present invention will now be described with reference to specific examples:
example 1:
a method for producing isooctane by adopting indirect alkylation technology specifically comprises the following steps:
(1) Dimerization reaction: introducing the mixed carbon four and a polymerization inhibitor into the fixed bed reactor I through a feed inlet I, and carrying out dimerization reaction on the polymerization inhibitor and the mixed carbon four under the catalysis of a catalyst A in the fixed bed reactor I to obtain a reaction product; part of the reaction product sequentially flows through the discharge port I, the pump and the heat exchanger and then returns to the feed port I for circulation, and the reaction product returns to the fixed bed reactor I after removing the reaction heat through the heat exchanger, so that the temperature of the fixed bed reactor I is effectively controlled; the other part of the reaction product sequentially flows through a discharge port I and a feed port II to enter a catalytic distillation tower;
the component for reaction in the mixed carbon four is isobutene; the polymerization inhibitor is a mixture of ethanol and methanol (mass ratio is 1:1); the catalyst A is macroporous sulfonic acid ion exchange resin catalyst (KR 01 in example 1 in CN 103447089A);
the mole ratio of the polymerization inhibitor to the isobutene in the mixed carbon four is 0.05:1, a step of;
the dimerization reaction conditions are as follows: space velocity of 0.9h -1 The reaction temperature is 35-50 ℃, and the reaction pressure is 1.0-1.2 Mpa;
and part of the reaction product sequentially flows through the discharge port I, the pump and the heat exchanger and then returns to the feed port I for circulation, wherein the circulation amount is 4 times of the feed amount.
(2) Catalytic distillation: after the reaction product enters a catalytic distillation tower, carrying out catalytic distillation reaction and separation under the action of a catalyst B in the catalytic distillation tower; the material at the top of the tower is carbon four after gaseous dimerization, the material is discharged from an exhaust port I and condensed by a condenser to obtain residual carbon four, the residual carbon four enters a fixed bed reactor II and reacts under the catalysis of a catalyst C in the fixed bed reactor II, and a reaction product flows back to a catalytic distillation tower through a reflux port to continue catalytic distillation; the material at the bottom of the tower is a mixture of isobutene dimer and polymerization inhibitor, and sequentially flows through a discharge port II and a feed port III to enter the extraction tower;
catalyst B was a large Kong Huangsuan cationic resin catalyst (KR 01 from example 1 in CN 103447089A);
catalyst C was a large Kong Huangsuan cationic resin catalyst (KR 01 from example 1 in CN 103447089A);
the conditions of the catalytic distillation reaction are as follows: the airspeed is 2h < -1 >, the reaction temperature is 50-70 ℃, and the reaction pressure is 0.5-0.7 Mpa;
in a fixed bed reactor IIThe conditions for the reaction were: space velocity of 0.9h -1 The reaction temperature is 35-50 ℃, and the reaction pressure is 1.0-1.2 Mpa;
condensing by a condenser to obtain the residual carbon four, wherein the composition of the residual carbon four is basically the same as that of the residual carbon four processed by the original MTBE device, and the residual carbon four is conveyed to a device for containing the residual carbon four as a raw material of a downstream device besides being introduced into a fixed bed reactor II for reaction.
(3) Extraction and recovery: after the mixture of isobutene dimer and polymerization inhibitor enters an extraction tower, under the extraction of an extracting agent, the material obtained at the bottom of the extraction tower is the mixture of the extracting agent and the polymerization inhibitor, the mixture of the extracting agent and the polymerization inhibitor sequentially flows through a mixture outlet and a mixture inlet and then enters a recovery tower for recovery, the polymerization inhibitor is obtained at the top of the recovery tower, the polymerization inhibitor sequentially flows through a polymerization inhibitor outlet and a feed inlet I and then returns to a fixed bed reactor I for recycling, the extracting agent is obtained at the bottom of the recovery tower, and the extracting agent sequentially flows through an extracting agent outlet and an extracting agent inlet and then returns to the extraction tower for recycling; the dimer is obtained at the top of the extraction tower, and sequentially flows through a discharge port III and a feed port IV to enter a hydrodesulfurization tower;
the extractant in the extraction tower is water;
the operating conditions of the extraction column were: the operation temperature is 40 ℃, the tower top pressure is 0.6Mpa, and the tower bottom pressure is 0.8Mpa;
(4) Hydrodesulfurization: introducing the dimer into a desulfurizing tower, introducing hydrogen into the desulfurizing tower through a feed inlet IV, mixing the dimer with the hydrogen, and then carrying out hydrodesulfurization reaction, wherein the hydrodesulfurization and the desulfurization are carried out in the same tower; the material obtained at the bottom of the desulfurizing tower is high-octane alkylate-isooctane which can be used as a gasoline blending component; the materials obtained from the top of the desulfurizing tower are the mixture of the residual hydrogen and the generated hydrogen sulfide, and can be sent to a torch system for utilization;
the reaction conditions of the hydrodesulfurization reaction are as follows: the reaction temperature is 200-300 ℃, and the reaction pressure is 0.8-1.2 Mpa;
the molar ratio of dimer to hydrogen was 1:3.5.
in the embodiment, the conversion rate of isobutene in the mixed carbon four is more than or equal to 99.5 percent; in the product after hydrodesulfurization, the total content of isooctane is more than or equal to 93 percent, and the octane number is more than or equal to 98 percent, and can be used as a gasoline blending component; the isobutene content in the residual carbon number IV is less than or equal to 0.15%, and the requirement of a downstream device can be met, so that the whole industrial chain can be continued after the MTBE device is partially modified.
Example 2:
a method for producing isooctane by adopting indirect alkylation technology specifically comprises the following steps:
(1) Dimerization reaction: introducing the mixed carbon four and a polymerization inhibitor into the fixed bed reactor I through a feed inlet I, and carrying out dimerization reaction on the polymerization inhibitor and the mixed carbon four under the catalysis of a catalyst A in the fixed bed reactor I to obtain a reaction product; part of the reaction product sequentially flows through the discharge port I, the pump and the heat exchanger and then returns to the feed port I for circulation, and the reaction product returns to the fixed bed reactor I after removing the reaction heat through the heat exchanger, so that the temperature of the fixed bed reactor I is effectively controlled; the other part of the reaction product sequentially flows through a discharge port I and a feed port II to enter a catalytic distillation tower;
the component for reaction in the mixed carbon four is isobutene; the polymerization inhibitor is a mixture of ethanol, propanol and butanol (mass ratio of 1:2:1); the catalyst A is macroporous sulfonic acid ion exchange resin catalyst (KR 07 in example 7 in CN 103447089A);
the mole ratio of the polymerization inhibitor to the isobutene in the mixed carbon four is 0.07:1, a step of;
the dimerization reaction conditions are as follows: space velocity of 0.8h -1 The reaction temperature is 35-50 ℃, and the reaction pressure is 1.0-1.2 Mpa;
and part of the reaction product sequentially flows through the discharge port I, the pump and the heat exchanger and then returns to the feed port I for circulation, wherein the circulation amount is 4 times of the feed amount.
(2) Catalytic distillation: after the reaction product enters a catalytic distillation tower, carrying out catalytic distillation reaction and separation under the action of a catalyst B in the catalytic distillation tower; the material at the top of the tower is carbon four after gaseous dimerization, the material is discharged from an exhaust port I and condensed by a condenser to obtain residual carbon four, the residual carbon four enters a fixed bed reactor II and reacts under the catalysis of a catalyst C in the fixed bed reactor II, and a reaction product flows back to a catalytic distillation tower through a reflux port to continue catalytic distillation; the material at the bottom of the tower is a mixture of isobutene dimer and polymerization inhibitor, and sequentially flows through a discharge port II and a feed port III to enter the extraction tower;
catalyst B was a large Kong Huangsuan cationic resin catalyst (KR 07 in example 7 in CN103447089 a);
catalyst C was a large Kong Huangsuan cationic resin catalyst (KR 07 in example 7 in CN 103447089A);
the conditions of the catalytic distillation reaction are as follows: space velocity of 1.5h -1 The reaction temperature is 50-70 ℃, and the reaction pressure is 0.5-0.7 Mpa;
the conditions for carrying out the reaction in the fixed bed reactor II are: space velocity of 0.7h -1 The reaction temperature is 35-50 ℃, and the reaction pressure is 1.0-1.2 Mpa;
the residual carbon four is obtained by condensation of a condenser (7), the composition of the residual carbon four is basically the same as that of the residual carbon four processed by the original MTBE device, and the residual carbon four is conveyed to a device for containing the residual carbon four as a raw material of a downstream device besides being introduced into a fixed bed reactor II for reaction.
(3) Extraction and recovery: after the mixture of isobutene dimer and polymerization inhibitor enters an extraction tower, under the extraction of an extracting agent, the material obtained at the bottom of the extraction tower is the mixture of the extracting agent and the polymerization inhibitor, the mixture of the extracting agent and the polymerization inhibitor sequentially flows through a mixture outlet and a mixture inlet and then enters a recovery tower for recovery, the polymerization inhibitor is obtained at the top of the recovery tower, the polymerization inhibitor sequentially flows through a polymerization inhibitor outlet and a feed inlet I and then returns to a fixed bed reactor I for recycling, the extracting agent is obtained at the bottom of the recovery tower, and the extracting agent sequentially flows through an extracting agent outlet and an extracting agent inlet and then returns to the extraction tower for recycling; the dimer is obtained at the top of the extraction tower, and sequentially flows through a discharge port III and a feed port IV to enter a hydrodesulfurization tower;
the extractant in the extraction tower is water;
the operating conditions of the extraction column were: the operation temperature is 40 ℃, the tower top pressure is 0.6Mpa, and the tower bottom pressure is 0.8Mpa;
the recovery column was operated at a column top temperature of 82℃and a column top pressure of 0.1MPa.
(4) Hydrodesulfurization: introducing the dimer into a desulfurizing tower, introducing hydrogen into the desulfurizing tower through a feed inlet IV, mixing the dimer with the hydrogen, and then carrying out hydrodesulfurization reaction, wherein the hydrodesulfurization and the desulfurization are carried out in the same tower; the material obtained at the bottom of the desulfurizing tower is high-octane alkylate-isooctane which can be used as a gasoline blending component; the materials obtained from the top of the desulfurizing tower are the mixture of the residual hydrogen and the generated hydrogen sulfide, and can be sent to a torch system for utilization;
the reaction conditions of the hydrodesulfurization reaction are as follows: the reaction temperature is 200-300 ℃, and the reaction pressure is 0.8-1.2 Mpa;
the molar ratio of dimer to hydrogen was 1:4.
the conversion rate of isobutene in the mixed carbon four is more than or equal to 99.5 percent; in the product after hydrodesulfurization, the total content of isooctane is more than or equal to 93 percent, and the octane number is more than or equal to 98 percent, and can be used as a gasoline blending component; the isobutene content in the residual carbon number IV is less than or equal to 0.15%, and the requirement of a downstream device can be met, so that the whole industrial chain can be continued after the MTBE device is partially modified.
The foregoing examples are merely illustrative of the technical concept and technical features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the essence of the present invention should be included in the scope of the present invention.
Claims (5)
1. A method for producing isooctane by adopting an indirect alkylation technology, which is characterized by comprising the following steps:
(1) Dimerization reaction: introducing the mixed carbon IV and a polymerization inhibitor into a fixed bed reactor I (1) through a feed inlet I, and carrying out dimerization reaction on the polymerization inhibitor and the mixed carbon IV under the catalysis of a catalyst A in the fixed bed reactor I to obtain a reaction product; part of the reaction product sequentially flows through a discharge port I, a pump and a heat exchanger (8) and then returns to the feed port I for circulation, and the reaction product returns to the fixed bed reactor I after the heat of reaction is removed by the heat exchanger, so that the temperature of the fixed bed reactor I is effectively controlled; the other part of the reaction product sequentially flows through a discharge port I and a feed port II to enter a catalytic distillation tower (2);
the component for reaction in the mixed carbon four is isobutene; the polymerization inhibitor is a mixed alcohol polymerization inhibitor, in particular a mixture formed by mixing any two or more of methanol, ethanol, propanol and butanol according to any proportion; the catalyst A is a large Kong Huangsuan cationic resin catalyst;
the mole ratio of the polymerization inhibitor to the isobutene in the mixed carbon four is 0.02-0.5:1, a step of;
the dimerization reaction conditions are as follows: the airspeed is 0.5-1 h < -1 >, the reaction temperature is 35-70 ℃, and the reaction pressure is 0.8-1.2 Mpa;
(2) Catalytic distillation: after the reaction product enters a catalytic distillation tower (2), carrying out catalytic distillation reaction and separation under the action of a catalyst B in the catalytic distillation tower; the material at the top of the tower is carbon four after gaseous dimerization, the material is discharged from an exhaust port I and condensed by a condenser (7) to obtain residual carbon four, the residual carbon four enters a fixed bed reactor II (5), the reaction is carried out under the catalysis of a catalyst C in the fixed bed reactor II, and the reaction product flows back to a catalytic distillation tower through a reflux port to continue catalytic distillation; the material at the bottom of the tower is a mixture of isobutene dimer and polymerization inhibitor, and sequentially flows through a discharge port II and a feed port III to enter the extraction tower;
the catalyst B is a large Kong Huangsuan cationic resin catalyst, and the catalyst C is a large Kong Huangsuan cationic resin catalyst;
the conditions of the catalytic distillation reaction are as follows: airspeed of 1-3 h -1 The reaction temperature is 50-70 ℃, and the reaction pressure is 0.5-0.7 Mpa;
the conditions for carrying out the reaction in the fixed bed reactor II (5) are: airspeed of 0.5 to 1h -1 The reaction temperature is 35-70 ℃, and the reaction pressure is 0.8-1.2 Mpa;
(3) Extraction and recovery: after the mixture of isobutene dimer and polymerization inhibitor enters an extraction tower, under the extraction of an extracting agent, the material obtained at the bottom of the extraction tower is the mixture of the extracting agent and the polymerization inhibitor, the mixture of the extracting agent and the polymerization inhibitor sequentially flows through a mixture outlet and a mixture inlet and then enters a recovery tower (4) for recovery, the polymerization inhibitor is obtained at the top of the recovery tower, the polymerization inhibitor sequentially flows through a polymerization inhibitor outlet and a feed inlet I and then returns to a fixed bed reactor I for recycling, the extracting agent is obtained at the bottom of the recovery tower, and the extracting agent sequentially flows through an extracting agent outlet and an extracting agent inlet and then returns to the extraction tower for recycling; the dimer is obtained at the top of the extraction tower, and sequentially flows through a discharge port III and a feed port IV to enter a hydrodesulfurization tower;
the extractant in the extraction tower (3) is water;
the reaction conditions of the extraction tower (3) are as follows: the reaction temperature is 38-42 ℃ and the reaction pressure is 0.5-1MPa;
the reaction conditions of the recovery tower (4) are as follows: reaction temperature: 80-130 ℃ and 0-0.5Mpa of reaction pressure;
(4) Hydrodesulfurization: introducing the dimer into a desulfurizing tower, introducing hydrogen into the desulfurizing tower through a feed inlet IV, mixing the dimer with the hydrogen, and then carrying out hydrodesulfurization reaction, wherein the hydrodesulfurization and the desulfurization are carried out in the same tower; the material obtained at the bottom of the desulfurizing tower is high-octane alkylate-isooctane which can be used as a gasoline blending component; the materials obtained from the top of the desulfurizing tower are the mixture of the residual hydrogen and the generated hydrogen sulfide, and can be sent to a torch system for utilization;
the reaction conditions of the hydrodesulfurization reaction are as follows: the reaction temperature is 200-300 ℃, and the reaction pressure is 0.8-1.2 Mpa;
the molar ratio of dimer to hydrogen was 1:2-5.
2. The method according to claim 1, wherein in the step (1), a part of the reaction product sequentially flows through the discharge port I, the pump and the heat exchanger (8) and then returns to the feed port I for circulation, and the circulation amount is 2-5 times of the feed amount.
3. The process according to claim 1, wherein in step (2) the remaining carbon four is obtained by condensation in a condenser (7) and has a composition substantially identical to the composition of the remaining carbon four after the treatment in the original MTBE plant, and is fed to the plant containing the remaining carbon four as a feed to a downstream plant in addition to the reaction in the fixed bed reactor II (5).
4. The utility model provides an adopt indirect alkylation technology to produce device of isooctane, includes fixed bed reactor I (1), catalytic distillation tower (2), extraction tower (3), recovery tower (4) that connect gradually, its characterized in that:
the fixed bed reactor I (1) is internally filled with a catalyst A, the top is provided with a feed inlet I, and the bottom is provided with a discharge outlet I: the feed inlet I is connected with a device capable of providing mixed carbon four and/or polymerization inhibitor;
the catalytic distillation tower (2), the top be equipped with gas vent I, upper portion is equipped with the return port, the middle part is equipped with feed inlet II, the bottom is equipped with discharge gate II: the feed inlet II is connected with the discharge outlet I of the fixed bed reactor I; the exhaust port I is connected with a condenser (7), the outlet of the condenser is divided into two paths, one path is connected with a reflux port through a fixed bed reactor II (5), and the other path is connected with a device for containing the residual carbon four; the catalytic section of the catalytic distillation tower is filled with a catalyst B, and the fixed bed reactor II is filled with a catalyst C;
the extraction tower (3) is internally filled with an extracting agent, the top is provided with a discharge hole III, the middle upper part is provided with an extracting agent inlet, the middle lower part is provided with a feed inlet III, and the bottom is provided with a mixture outlet: the feed inlet III is connected with the discharge outlet II of the catalytic distillation tower; the discharge hole III is connected with a desulfurizing tower (6);
desulfurizing tower (6), the top be equipped with gas vent II, well lower part is equipped with feed inlet IV, the bottom is equipped with discharge gate IV: the exhaust port II is connected with a torch system; the discharge port IV is connected with a device for containing isooctane as a final product; the feeding port IV is divided into two paths, one path is connected with a discharging port III of the extraction tower, and the other path is connected with a device for providing hydrogen;
the recovery tower (4) is characterized in that a polymerization inhibitor outlet is formed in the top, a mixture inlet is formed in the middle lower portion of the recovery tower, and an extractant outlet is formed in the bottom of the recovery tower: the mixture inlet is connected with the mixture outlet of the extraction tower; the polymerization inhibitor outlet is connected with a feed inlet I of the fixed bed reactor I; the extractant outlet is connected with the extractant inlet of the extraction tower;
the discharge port I is divided into two paths, one path is connected with the feed port II of the catalytic distillation tower, the other path is connected with the inlet of the heat exchanger (8) through a pump, and the outlet of the heat exchanger is connected with the feed port I;
the feeding port I is divided into three paths, one path is connected with a device for containing mixed carbon four and/or polymerization inhibitor, one path is connected with a polymerization inhibitor outlet, and the other path is connected with an outlet of the heat exchanger.
5. The apparatus according to claim 4, wherein: the catalytic distillation tower (2) is characterized in that the internal parts of the catalytic section comprise catalyst mold pieces and metal filler sheet groups; the catalyst mold sheet is formed by pressing a metal diamond plate mesh lined with a metal mesh with the same material into a specified shape, and then filling catalyst particles for spot welding and sealing; the metal filler sheet is formed by welding metal wire mesh corrugated filler or metal pore plate corrugated filler sheets filled between catalyst mold sheets; the catalyst mold pieces and the filler pieces are mutually spaced and linearly and equidistantly arranged along the diameter direction of the rectifying tower, and the catalytic distillation element module is formed by using steel belt bundles with the same material as the diamond plate net; the catalyst mold sheet adopts stainless steel diamond plate mesh and 60 mesh stainless steel wire mesh which are made of the same material to be subjected to spot welding and compounding, and then is pressed into two isosceles trapezoid structures with the cross section of which the base angle is not less than 60 degrees, and two ends are sealed; the catalyst mold sheet and the metal filler sheet group are formed by assembling one or more modules;
the extraction tower (3) is characterized in that the internal parts are sieve tray trays or high-efficiency separation fillers; the recovery tower (4) is characterized in that the internal parts are floating valve trays or high-efficiency separation fillers; the catalyst A filled in the fixed bed reactor I (1) is a solid acid catalyst, the catalyst B filled in the catalytic distillation tower (2) is a solid acid catalyst, and the catalyst C filled in the fixed bed reactor II (5) is a solid acid catalyst; the extractant filled in the extraction tower (3) is water.
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| CN111217661B (en) * | 2018-11-27 | 2022-11-18 | 中国石油化工股份有限公司 | Method for preparing isooctane by isobutene superposition-hydrogenation |
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| 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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| CN104876785A (en) * | 2015-06-10 | 2015-09-02 | 中国海洋石油总公司 | Process and device for producing MTBE (methyl tert-butyl ether)/butene-1 from remaining C4 |
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| CN107473917A (en) * | 2016-06-07 | 2017-12-15 | 中国石油化工股份有限公司 | Mix the technique that carbon four produces diisobutylene |
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