CN1239444C - Isoalkene producing process - Google Patents
Isoalkene producing process Download PDFInfo
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- CN1239444C CN1239444C CN 03142602 CN03142602A CN1239444C CN 1239444 C CN1239444 C CN 1239444C CN 03142602 CN03142602 CN 03142602 CN 03142602 A CN03142602 A CN 03142602A CN 1239444 C CN1239444 C CN 1239444C
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Abstract
The present invention discloses a technology for producing isoolefine. The technology comprises: hydrocarbon mixture containing isoolefine and alcohol are led in an etherification reactor (R1), obtained products (P1) mainly containing tertiary alkyl ether are separated by a first fractionating tower (C1) and a second fractionating tower (C2) and then led in an ether cracking reactor (R2) after being heated by a heater (E1), products (P2) mainly containing unreacted tertiary alkyl ether, isoolefine and alcohol are obtained, heavy fractions of the obtained products are removed by a third fractionating tower (C3), isoolefine is obtained, or high-purity products of tertiary alkyl ether are directly led in the ether cracking reactor after being heated and vaporized, and isoolefine is obtained through the elimination of heavy fractions by the third fractionating tower (C3). The present invention is characterized in that materials on the top of the second fractionating tower (C2) are extracted in a gas phase mode. In this way, the amounts of circulating water and vapour can be reduced, and the consumption of devices can be lowered. The present invention can directly load gas phase reaction products of an outlet of the ether cracking reactor (R2) in the third fractionating tower (C3). In this way, the amount of vapour and the total amount of circulating water can be reduced, and the consumption of devices can be lowered further.
Description
Technical field
The present invention relates to the production technique of isoolefine (tertiary olefin), particularly hydrocarbon mixture by containing a kind of isoolefine at least and at least a pure prepared in reaction high purity tert-alkyl ether, prepare the technology of isoolefine by the cracking tert-alkyl ether again or directly prepare the technology of isoolefine by the cracking tert-alkyl ether.
Background technology
Isoolefine, tert-alkyl ether are the important source material of fine chemistry industry, also be the important intermediate raw material or the monomer of synthetic rubber, synthetic resins, be widely used in producing multiple Chemicals such as isoprene-isobutylene rubber, polyisobutene and methyl methacrylate as high-purity isobutylene; Methyl tertiary butyl ether (MTBE) is the raw material of preparing high-purity isoolefine, is again the important additives that improves fuel octane number.
Adopt the synthetic and cracking associating preparing high-purity isoolefine of tert-alkyl ether cracking and tert-alkyl ether, have the reaction preference height, do not have advantages such as pollution and corrosion.Domestic industrialized tert-alkyl ether is synthetic as follows with cracking preparing high-purity tert-alkyl ether and high purity isoolefine general technology at present: the hydrocarbon mixture and the alcohol that will contain isoolefine are sent into the methyltertiarvbutyl ether reactor that catalyst for etherification is housed, the product that is mainly contained tert-alkyl ether, after two separation columns separate, the high purity tert-alkyl ether cut that obtains is cooled to liquid phase and enters the product jar; High purity tert-alkyl ether heater via heating vaporization from the product jar, and its temperature risen to send into ether-splitting behind the cracking temperature and separate reactor, the product that is mainly contained unreacted tert-alkyl ether and isoolefine and alcohol, this cracking product obtains the high purity isoolefine after taking off heavily, taking off light and extracting and separating.The shortcoming of this technology is that the high purity tert-alkyl ether product that will obtain is sent into ether-splitting after with liquid form extraction and heater via heating vaporization to separate the reactor energy consumption higher; In addition, ether-splitting being separated the product that obtains after the reaction sends into separation column to carry out isolating energy consumption also higher after heat exchange is cooled to liquid-phase product.
Summary of the invention
The object of the present invention is to provide a kind of improved tert-alkyl ether to synthesize and unite the production technique of making isoolefine, adopt this technology can reduce the water coolant of device and the consumption of heating steam, promptly reduce the energy consumption of whole device with cracking.
Another object of the present invention is to provide a kind of production technique of improved isoolefine.Adopt this technology can reduce the water coolant of device and the consumption of heating steam, promptly reduce the energy consumption of whole device.
For achieving the above object, the after-fractionating column overhead product of the present invention's synthesis stage in combined process flow is with the extraction of gas phase form, again through being heated to after ether-splitting separates temperature of reaction, directly enter ether-splitting and separate reactor, like this, when the preparation isoolefine, can reduce the energy consumption of device; The present invention also separates ether-splitting the gas-phase reaction product of reactor outlet and directly sends into the 3rd separation column, removes a large amount of pure and mild unreacted tert-alkyl ethers, like this, can reduce the heating load of separation column, further reduces the energy consumption of device.
In isoolefine production technique of the present invention, ether-splitting is separated the gas-phase reaction product of reactor outlet and directly sent into the 3rd separation column, remove a large amount of pure and mild unreacted tert-alkyl ethers, like this, can reduce the heating load of separation column, reduce the energy consumption of device.
The invention provides a kind of production technique of isoolefine, comprise following operation:
(1) hydrocarbon mixture and at least a alcohol that will contain a kind of isoolefine is at least sent into the methyltertiarvbutyl ether reactor R1 that catalyst for etherification is housed, to make the product P 1 that contains a kind of tert-alkyl ether at least.
(2) product P 1 that operation (1) is obtained is sent into the first separation column C1, with the fraction B 1 that obtains mainly to contain the organic fraction O1 of unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent and mainly contain tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent.
(3) fraction B 1 that mainly contains tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent that operation (2) is obtained is sent into after-fractionating tower C2, obtains high purity tert-alkyl ether cut O2 and the fraction B 2 that contains alkyl oxide, secondary alkyl oxide and low polyisoolefines heavy constituent.
(4) the high purity tert-alkyl ether cut O2 that operation (3) is obtained sends into ether-splitting and separates reactor R2, is mainly contained unreacted tert-alkyl ether and isoolefine and corresponding pure P2.After further separating, obtain isoolefine again;
Wherein the high purity tert-alkyl ether cut O2 of operation (3) gained enters ether-splitting with the gas phase form and separates reactor R2.
After the high purity tert-alkyl ether with obtaining gas phase in the operation (3) that all adopts on the industrialized unit at present cooled off, part was returned this after-fractionating tower C2, to keep the normal running of this tower; Part enters the product jar with the liquid form extraction, again with the vaporization of this liquid-phase product and be heated to scission reaction and send into cracking reactor after temperature required.And the present invention returns this separation column after the after-fractionating tower C2 overhead fraction partial condensation in operation (3), to keep the normal running of this tower; The direct gas phase extraction of the high-purity tert-alkyl ether cut of another part O2, and gaseous products O2 is heated to scission reaction sends into cracking reactor after temperature required.Like this, can reduce the recirculated water consumption of after-fractionating tower C2 and the steam consumption of well heater E1, thereby reduce the energy consumption of complete assembly.
When adopting method of the present invention from after-fractionating tower C2, directly to send into cracking reactor R2 after extraction gas phase high purity tert-alkyl ether and the heating, the working pressure of requirement after-fractionating tower C2 is separated the working pressure of reactor R2 greater than ether-splitting, after-fractionating tower C2 and cracking reactor R2 pressure reduction are enough to overcome the resistance drop of gas when two equipment rooms flow, and separate reactor R2 thereby make gas phase high purity tert-alkyl ether successfully enter ether-splitting from after-fractionating tower C2.
The production technique of isoolefine of the present invention, can also comprise operation (5), the product P 2 that in operation (5) operation (4) is obtained is sent into the 3rd separation column C3, with the fraction B 3 that obtains mainly to contain the light constituent cut O3 of isoolefine, a small amount of alcohol, a small amount of lower molecular weight ether and mainly contain alcohol, unreacted tert-alkyl ether.The product P 2 that operation (4) obtains is sent into the 3rd separation column C3 with liquid form or with the gas phase form.When product P 2 is sent into the 3rd separation column C3 with liquid form, after being cooled to liquid state, the product P 2 (for gaseous state) that needs elder generation that operation (4) is obtained sends into the 3rd separation column C3 again; When product P 2 is sent into the 3rd separation column C3 with the gas phase form, require ether-splitting to separate the working pressure of the working pressure of reactor R2 greater than the 3rd separation column C3, cracking reactor R2 and the 3rd separation column C3 pressure reduction are enough to overcome the resistance drop of gas when two equipment rooms flow, thereby the product P 2 that the tert-alkyl ether cracking is obtained can successfully be separated reactor R2 from ether-splitting and entered the 3rd separation column C3.Consider that from energy-conservation angle preferential back one scheme that adopts can reduce steam consumption and total recirculated water consumption, thereby further reduce plant energy consumption.
The production technique of isoolefine of the present invention, can also comprise operation (6), at least a portion cut O3 that in operation (6) the 3rd separation column C3 of operation (5) is obtained sends into water wash column T1, to obtain mainly moisture, pure aqueous phase B 4 and mainly to contain the organic phase O4 of isoolefine, a small amount of lower molecular weight ether light constituent.
The production technique of isoolefine of the present invention can also comprise operation (7), and at least a portion that in operation (7) operation (6) is obtained contains the aqueous phase B 4 of alcohol and sends into the 4th separation column C4, with aqueous distillate B3 and the rich pure cut O5 that obtains poor alcohol.Also the pure cut O5 of the described richness of at least a portion of gained can be circulated to the methyltertiarvbutyl ether reactor R1 of operation (1); The described aqueous distillate B3 of at least a portion of gained is circulated to the water wash column T1 of operation (7), to recycle alcohol and water.
The production technique of isoolefine of the present invention can also comprise operation (8), and the organic phase O4 that in operation (8) operation (6) is obtained sends into the 5th separation column C5, to obtain mainly to contain the light constituent cut O6 and the high purity isoolefine fraction B 6 of lower molecular weight ether.Also the described light constituent cut of at least a portion of gained O6 can be circulated to the methyltertiarvbutyl ether reactor R1 of operation (1),, improve the selectivity of alcohol to suppress the generation of the by products such as lower molecular weight ether among the methyltertiarvbutyl ether reactor R1.
The present invention also provides a kind of production technique of isoolefine, comprises following operation:
Operation (4): high purity liquid phase tert-alkyl ether O2 sends into ether-splitting and separates reactor R2 after the heating vaporization, mainly contained the product P 2 of unreacted tert-alkyl ether and isoolefine and alcohol.
Operation (5): the product P 2 that operation (4) obtains is sent into the 3rd separation column C3, with the fraction B 3 that obtains mainly to contain the light constituent cut O3 of isoolefine, a small amount of alcohol, a small amount of lower molecular weight ether and mainly contain alcohol, unreacted tert-alkyl ether.
Wherein the product P 2 of operation (4) gained enters the 3rd separation column C3 with the gas phase form.
The product P 2 that operation (4) obtains is gaseous product, sends into the 3rd separation column C3 again after the product P 2 (for gaseous state) that all adopts elder generation that operation (4) is obtained at present on the full scale plant is cooled to liquid state, and its shortcoming is that plant energy consumption is higher relatively.And the present invention's employing is sent into the 3rd separation column C3 with the product P 2 of gained with the gas phase form, can reduce steam consumption and total recirculated water consumption like this, thereby reduces plant energy consumption.
When adopting method of the present invention that the product P 2 of gained is sent into the 3rd separation column C3 with the gas phase form, require ether-splitting to separate the working pressure of the working pressure of reactor R2 greater than the 3rd separation column C3, cracking reactor R2 and the 3rd separation column C3 pressure reduction are enough to overcome the resistance drop of gas when two equipment rooms flow, thereby the product P 2 that the tert-alkyl ether cracking is obtained can successfully be separated reactor R2 from ether-splitting and entered the 3rd separation column C3.
The production technique of isoolefine of the present invention, can also comprise operation (6), at least a portion cut O3 that in operation (6) the 3rd separation column C3 of operation (5) is obtained sends into water wash column T1, to obtain mainly moisture, pure aqueous phase B 4 and mainly to contain the organic phase O4 of isoolefine, a small amount of lower molecular weight ether light constituent.
The production technique of isoolefine of the present invention can also comprise operation (7), and at least a portion that in operation (7) operation (6) is obtained contains the aqueous phase B 4 of alcohol and sends into the 4th separation column C4, with aqueous distillate B5 and the rich pure cut O5 that obtains poor alcohol.The described aqueous distillate B5 of at least a portion can be circulated to the water wash column T1 of operation (6), with recycle water.
The production technique of isoolefine of the present invention can also comprise operation (8), and the organic phase O4 that in operation (8) operation (6) is obtained sends into the 5th separation column C5, to obtain mainly to contain the light constituent cut O6 and the high purity isoolefine fraction B 6 of lower molecular weight ether.
Hydrocarbon material of the present invention contains at least a isoolefine (tertiary olefin), also contains component such as other saturated or unsaturated hydrocarbons, as the C from oil refining or petrochemical complex
3And/or C
4Material, C
3And/or C
4Steam cracking material (being generally the material of extraction behind the diene), all can be used as hydrocarbon material of the present invention from the material after isomerized catalytic pyrolysis material (hydrogenation isomerization and skeletal isomerization) and the paraffin dehydrogenation; Alcohol of the present invention mainly is the alcohol of 1-4 carbon atom, particular methanol and ethanol.The tert-alkyl ether of available prepared of the present invention is mainly methyl tertiary butyl ether (MTBE), Ethyl Tertisry Butyl Ether (ETBE), ethyl pentyl group ether (ETAE), tertiary amyl-methyl ether (TAME), sec.-propyl tertbutyl ether etc., the tertbutyl ether cracking obtains iso-butylene, the isoolefine that other tert-alkyl ether cracking obtains is a mixture, and cracking obtains 2-methyl-2-butene and 2-methyl-1-butene alkene mixture as TAME.The pure isoolefine that makes with the synthetic and cracking process integration of tert-alkyl ether of the present invention on one of them double key carbon with the compound of branched-chain alkyl (methyl), these compounds are generally the isoolefine that contains 4-8 carbon atom, the isoolefine that preferably contains 4-6 carbon atom is as iso-butylene and isopentene, dissident's alkene, isooctene, isodecyl alkene etc.
Description of drawings
Fig. 1-2 is the schematic flow sheet of the synthetic and cracking process integration system isoolefine of tert-alkyl ether of the present invention
Fig. 3 is the schema of isoolefine production technique of the present invention
The operation that dotted line representative in the accompanying drawing may exist, containing of the main code name in the accompanying drawing means:
R1-methyltertiarvbutyl ether reactor C1-first separation column
C2-after-fractionating tower E1-well heater
R2-ether-splitting is separated reactor E2-interchanger
C3-the 3rd separation column T1-water wash column
C4-the 4th separation column C5-the 5th separation column
Below in conjunction with accompanying drawing 1-3 the production technique of isoolefine of the present invention is further described.
The synthetic production technique (referring to accompanying drawing 1) for preparing isoolefine with cracking of tert-alkyl ether of the present invention comprises operation 1, operation 2, operation 3 and operation 4, in operation 1, at least the hydrocarbon mixture and at least a alcohol that contain a kind of isoolefine are sent into the methyltertiarvbutyl ether reactor R1 that catalyst for etherification is housed through pipeline 1,2 and 3 respectively, contained a kind of product P 1 of tert-alkyl ether at least.In operation 2, to obtain at least a portion etherification product P1 by operation 1 and send into the first separation column C1 through pipeline 4, cat head is mainly contained the organic fraction O1 of unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent, organic fraction O1 can be used as Organic Chemicals, or is used as liquefied fuel gas etc. after removing alcohol; Mainly contained the fraction B 1 of tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent at the bottom of the tower, tower bottom distillate B1 can be used as fuel dope, also can further separate through the after-fractionating tower C2 that pipeline 6 is sent in the operation 3.In operation 3, the tower bottom distillate B1 that the first separation column C1 in the operation 2 is obtained sends into after-fractionating tower C2 fractionation, obtain containing the fraction B 2 of tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent at the bottom of the after-fractionating tower C2 tower, tower bottom distillate B2 can be used as fuel dope; After-fractionating tower C2 overhead product gas phase extraction high purity tert-alkyl ether O2 sends into operation 4; In operation 4, the high purity tert-alkyl ether O2 that operation 3 obtains gas phase sends into well heater E1 (as steam heater etc.) when being heated to the desired temperature of scission reaction through pipeline 7, send into through pipeline 7a again and ether-splitting is housed separates the ether-splitting of catalyzer and separate reactor R2, obtain containing the product P 2 of at least a alcohol of at least a isoolefine, after further separating, obtain isoolefine again.In the distil process of routine (when not doing specified otherwise), distillation tower cat head gas phase enters a return tank after condenser condenses is liquid phase, and a part is sent the branch distillation tower back to and refluxed, a part of extraction.The present invention adopts the extraction of a part of cut gas phase directly to enter operation 4 in after-fractionating tower C2 technological operation, and another part gas phase fraction is condensed, to guarantee the backflow of this separation column.Like this, can reduce the heat exchange load of the condenser of this separation column.
Tert-alkyl ether of the present invention is synthetic to prepare the production technique of isoolefine in operation 1 with cracking, 2,3 and 4 also comprise operation 5 (referring to accompanying drawing 2) when existing, in operation 5, ether-splitting in the operation 4 is separated the product P 2 that contains at least a alcohol of at least a isoolefine that reactor R2 obtains directly to be sent into the 3rd separation column C3 or product P 2 is sent into through pipeline 9a with the gas phase form interchanger E2 is cooled to liquid phase after pipeline 9b sends into the 3rd separation column C3 through pipeline 9 with the gas phase form, mainly contained isoolefine, the cut O3 of pure and mild lower molecular weight ether light constituent and contain alcohol, the fraction B 3 of unreacted tert-alkyl ether, consider that from energy-conservation angle the present invention preferably directly sends into the 3rd separation column C3 with product P 2 with the gas phase form.The fraction B 3 that at least a portion mainly contains pure and mild unreacted tert-alkyl ether at the bottom of the 3rd separation column C3 tower can be back to methyltertiarvbutyl ether reactor R1 through pipeline 11,11a and 3, and another part cut can be discharged through pipeline 11 and 11b; The cut O3 that mainly contains isoolefine, pure and mild lower molecular weight ether light constituent can be used as industrial chemicals or is used for further separation to obtain highly purified isoolefine product.
For the isoolefine of ether-splitting being separated the technology gained separates with alcohol, the production technique of isoolefine of the present invention is in operation 1,2,3,4 and 5 also comprise operation 6 (referring to accompanying drawing 2) when existing, in operation 6, will be from the overhead fraction O3 of the 3rd separation column C3 of operation 5 through pipeline 10,14 send into water wash column T1, fresh water W1 is sent into water wash column T1 through pipeline 12, obtain mainly moisture, alcohol pure aqueous phase B 4 and mainly contain isoolefine, the organic phase O4 of a small amount of lower molecular weight ether light constituent mainly contains isoolefine, the organic phase O4 of a small amount of lower molecular weight ether light constituent can be used as Organic Chemicals or liquefied gas etc., also can further separate to obtain highly purified isoolefine.
For the alcohol in the alcohol aqueous phase B 4 at the bottom of the further recovery water wash column T1 tower, the production technique of isoolefine of the present invention also comprises operation 7 (referring to accompanying drawing 2) when water wash column T1 exists, in operation 7, to send into the 4th separation column C4 through pipeline 13 from containing of operation 6 of pure aqueous phase B 4, with aqueous distillate B5 and the rich pure cut O5 that obtains poor alcohol.The rich pure cut O5 of at least a portion that cat head obtains (preferred most of) returns to methyltertiarvbutyl ether reactor R1 through pipeline 16,16a, 3, at least a portion at the bottom of the tower of the 4th separation column C4 (preferred most of) aqueous distillate B5 through manage 17,17a, 14 returns to water wash column T1, can water at the bottom of the tower of a spot of the 4th separation column C4 through pipeline 17,17b discharge.The water that enters water wash column T1 can be reuse water (recirculated water) at the bottom of pipeline 17,17a, 14 the 4th separation column C4 towers that add, also can be by the fresh water W1 of pipeline 12 addings.
For further light constituent among the organic phase O4 being separated with isoolefine, to obtain the high purity isoolefine, the production technique of isoolefine of the present invention also comprises operation 8 (referring to accompanying drawing 2) when water wash column T1 exists, in operation 8, the organic phase O4 that will mainly be contained isoolefine, a small amount of lower molecular weight ether light constituent from water wash column sends into the 5th separation column C5 of operation 8 through pipeline 15, is mainly contained low molecule ether light constituent cut O6 and high purity isoolefine fraction B 6.High purity isoolefine B6 discharges through pipeline 19, can be used as polymer raw.Mainly containing low molecule ether light constituent cut O6 can discharge through pipeline 18,18b, also at least a portion overhead fraction O6 can be returned methyltertiarvbutyl ether reactor R1 through pipeline 18,18a, the by products such as lower molecular weight ether that can suppress among the methyltertiarvbutyl ether reactor R1 generate, and improve the selectivity of alcohol.
The present invention also provides a kind of production technique of isoolefine, comprise operation 4 and operation 5 (referring to accompanying drawing 3), in operation 4, with high purity liquid phase tert-alkyl ether O2 through being heated to cracking temperature after pipeline 7a sends into and ether-splitting is housed separates the ether-splitting of catalyzer and separate reactor R2, obtain containing the product P 2 of isoolefine and alcohol.In operation 5, ether-splitting in the operation 4 is separated the product P 2 that contains isoolefine and alcohol that reactor R2 obtains directly send into the 3rd separation column C3 through pipeline 9, mainly contained the cut O3 of isoolefine, pure and mild lower molecular weight ether light constituent and contain the fraction B 3 of alcohol, unreacted tert-alkyl ether with the gas phase form.The fraction B 3 that mainly contains pure and mild unreacted tert-alkyl ether at the bottom of the 3rd separation column C3 tower can be discharged through pipeline 11, is used to reclaim tert-alkyl ether and alcohol; The cut O3 that mainly contains isoolefine, pure and mild lower molecular weight ether light constituent can be used as industrial chemicals or is used for further refining isoolefine.The present invention adopts the product P 2 of gained is sent into the 3rd separation column C3 with the gas phase form, can reduce the recirculated water consumption of the steam consumption of this separation column like this, promptly reduces the energy consumption of this equipment.
For the isoolefine of ether-splitting being separated the technology gained separates with alcohol, the production technique of isoolefine of the present invention is in operation 4,5 also comprise operation 6 (referring to accompanying drawing 3) when existing, in operation 6, will be from the overhead fraction O3 of the 3rd separation column C3 of operation 5 through pipeline 10,14 send into water wash column T1, fresh water W1 is sent into water wash column T1 through pipeline 12, obtain mainly moisture, alcohol pure aqueous phase B 4 and mainly contain isoolefine, the organic phase O4 of a small amount of lower molecular weight ether light constituent mainly contains isoolefine, the organic phase O4 of a small amount of lower molecular weight ether light constituent can be used as Organic Chemicals or liquefied gas etc., also can further separate to obtain highly purified isoolefine product.
For the alcohol in the alcohol aqueous phase B 4 at the bottom of the further recovery water wash column T1 tower, the production technique of isoolefine of the present invention also comprises operation 7 (referring to accompanying drawing 3) when water wash column T1 exists, in operation 7, to send into the 4th separation column C4 through pipeline 13 from containing of operation 6 of pure aqueous phase B 4, with aqueous distillate B3 and the rich pure cut O5 that obtains poor alcohol.The rich pure cut O6 of at least a portion that cat head obtains discharges through pipeline 16, and this richness alcohol cut can be used to prepare tert-alkyl ether or other Chemicals.At least a portion at the bottom of the tower of the 4th separation column C4 (preferred most of) aqueous distillate B5 returns to water wash column T1 through pipeline 17,17a, 14, water at the bottom of the tower of a spot of the 4th separation column C4 can be discharged through pipeline 17,17b.The water that enters water wash column T1 can be reuse water (recirculated water) at the bottom of pipeline 17,17a, 14 the 4th separation column C4 towers that add, also can be by the fresh water W1 of pipeline 12 addings.
For further light constituent among the organic phase O4 being separated with isoolefine, to obtain the high purity isoolefine, isoolefine production technique of the present invention also comprises operation 8 (referring to accompanying drawing 3) when water wash column T1 exists, in operation 8, the organic phase O4 that will mainly be contained isoolefine, a small amount of lower molecular weight ether light constituent from water wash column T1 sends into the 5th separation column C5 of operation 8 through pipeline 15, is mainly contained low molecule ether light constituent cut O6 and high purity isoolefine fraction B 6.High purity isoolefine B6 discharges through pipeline 19, can be used as polymer raw; Mainly containing low molecule ether light constituent cut O6 can discharge through pipeline 18.
The operational condition of each operation is as described below in the production technique of preparation isoolefine of the present invention: in operation 1, the reaction raw materials that contains a kind of hydrocarbon mixture of isoolefine at least and contain a kind of alcohol at least enters methyltertiarvbutyl ether reactor R1.The methyltertiarvbutyl ether reactor that prior art is announced all can be used for the present invention, as can be simple catalyticreactor, also can be the catalytic distillation reactor.Catalyst for etherification can be disclosed any catalyzer that can be used for the isoolefine etherificate in the prior art, as an acidic catalyst (being generally the solid acid catalyst that forms by organic acid acetic) and mineral acid ester catalyst, the present invention preferentially selects solid acid resin catalyst such as Amberlyst 15 or 35 (this catalyzer can be bought from the market) for use, the range of reaction temperature of methyltertiarvbutyl ether reactor R1 is 30 ℃～100 ℃, preferable range is 40 ℃～90 ℃, pressure range is 0.1～4.0MPa, preferred pressure range is 0.5～2.5MPa, and the air speed scope of methyltertiarvbutyl ether reactor is 0.01～50hr
-1, preferable range is 0.1～10hr
-1The alcohol that enters this methyltertiarvbutyl ether reactor can be the reuse alcohol from pure recovery tower C4, can be fresh alcohol also, and the alcohol that enters this methyltertiarvbutyl ether reactor is 0.3～5.0 with the scope that contains the hydrocarbon mixture weight ratio of isoolefine, and preferable range is 0.5～3.0.
The operational condition of the first separation column C1 in the operation 2 is as follows: the working pressure scope of the first separation column C1 is at 0.2～2.0MPa, and preferable range is 0.5～1.5MPa, and the number of theoretical plate of this tower is between 3～80, and preferable range is between 10～50.
The operational condition of after-fractionating tower C2 in the operation 3 is as follows: the working pressure scope of after-fractionating tower C2 is at 0.4～2.5MPa, and preferable range is 0.6～1.5MPa, and the number of theoretical plate of this tower is between 3～80, and preferable range is between 10～50.
The condition that ether-splitting in the operation 4 is separated reactor is as follows: the methyltertiarvbutyl ether reactor that prior art is announced all can be used for the present invention.Catalyst for etherification can be disclosed any ether cracked catalyzer that can be used in the prior art, preferably select solid acid catalyst for use, the present invention preferentially selects loading type inorganic acid salt catalyzer for use, this catalyzer is to adopt the described method of GB1173128 patent to make, its acid quality generally is controlled at 20%～30%, the reaction pressure that this ether-splitting is separated reactor is controlled between 0.3～1.5MPa, preferable range is between 0.4～1.0MPa, temperature of reaction is between 50 ℃～300 ℃, preferable range is between 100 ℃～250 ℃, and this ether-splitting is separated the air speed of reactor at 0.5～50h
-1Between, preferable range is at 1～10h
-1Between.
When adopting method of the present invention from after-fractionating tower C2, directly to send into cracking reactor R2 after extraction gas phase high purity tert-alkyl ether and the heating, the working pressure of requirement after-fractionating tower C2 is separated the working pressure of reactor R2 greater than ether-splitting, after-fractionating tower C2 and cracking reactor R2 pressure reduction are enough to overcome the resistance drop of gas when two equipment rooms flow, and enter ether-splitting from after-fractionating tower C2 smoothly and separate reactor R2 thereby make.
The operational condition of the 3rd separation column C3 in the operation 5 is as follows: the working pressure scope is at 0.2～1.2MPa, and preferable range is 0.3～0.8MPa, and the number of theoretical plate of this tower is between 3～80, and preferable range is between 10～50.
Adopt method of the present invention when ether-splitting is separated the direct extraction gaseous products of reactor R2 P2 and sent into the 3rd separation column C3, require ether-splitting to separate the working pressure of the working pressure of reactor R2 greater than the 3rd separation column C3, cracking reactor R2 and the 3rd separation column C3 pressure reduction are enough to overcome the resistance drop of gas when two equipment rooms flow, and enter the 3rd separation column C3 thereby make gaseous products P2 separate reactor R2 from ether-splitting smoothly.
The operational condition of water wash column T1 in the operation 6 is as follows: containing pure cut is 0.005～20 with the water weight ratio that enters this water wash column, and preferable range is between 0.01～5.The working pressure of this washing disengaging zone is between 0.1～2.0MPa, and preferable range is between 0.1～1.5MPa, and service temperature is 10 ℃～60 ℃.
The operational condition of the 4th separation column C4 in the operation 7 is as follows: the working pressure of this separation column is between 0.1～1.2MPa, and preferable range is between 0.1～0.8MPa, and number of theoretical plate is between 3～80, and preferable range is between 10～50.
The operational condition of C5 in the operation 8 is as follows: the working pressure of this separation column is between 0.1～1.5MPa, and preferable range is between 0.3～1.0MPa, and number of theoretical plate is between 3～80, and preferable range is between 5～50.
Embodiment
Further specify the present invention below in conjunction with embodiment, but do not limit to its scope.
Embodiments of the invention with methyl tertiary butyl ether synthetic with cracking process preparing high-purity iso-butylene (IB) and high-purity methyl tertbutyl ether (MTBE) cracking preparing high-purity iso-butylene be that example illustrates production technique of the present invention.Wherein to separate the catalyzer of reactor charge be solid acid catalyst to ether-splitting, is to adopt the described method preparation of GB1173128 patent, and concrete preparation method is as follows: flood γ-Al with aluminum sulfate aqueous solution
2O
3, its after drying also was prepared from 450 ℃ of roastings in 3 hours, and the content of sulfate radical is 20% (weight percent) on the catalyzer.When not specializing, be liquid phase from the material of separation column extraction.
The mixed c 4 hydrocarbon that contains iso-butylene (removes the cracking c_4 raw material behind the diene, down with) and methyl alcohol enter methyltertiarvbutyl ether reactor R1 through pipeline 1,2 and 3 respectively, the content of iso-butylene is about 20.1% (weight) in the mixed c 4 hydrocarbon, the material quantity that enters methyltertiarvbutyl ether reactor is 100kg/h, and Amberlyst 15 solid acid resin catalyst (ROHM ﹠amp are housed among the methyltertiarvbutyl ether reactor R1; HAAS produces), 60 ℃ of the temperature of reaction of methyltertiarvbutyl ether reactor R1, reaction pressure are 1.2MPa, the air speed 6hr of methyltertiarvbutyl ether reactor
-1Entering the methyl alcohol of this methyltertiarvbutyl ether reactor and the weight ratio of iso-butylene is 0.6.Etherification product P1 enters the first separation column C1 through pipeline 4, the working pressure of the first separation column C1 is 0.9MPa, the number of theoretical plate of this tower is 35, the fraction B 1 that mainly contains methyl tertiary butyl ether is by sending into after-fractionating tower C2 through pipeline 6 at the bottom of the tower, the working pressure of after-fractionating tower C2 is 0.8MPa, the number of theoretical plate of this tower is 30, the cut O2 of cat head gas phase extraction high-purity methyl tertbutyl ether, when being heated to 200 ℃, steam heater E1 sends into ether-splitting reactor R2, the reaction pressure that this ether-splitting is separated reactor is 0.55MPa, temperature of reaction is 200 ℃, and reaction velocity is 2h
-1, technical process is adopted technology of the present invention referring to Fig. 1, and the steam consumption of the feed heater that the cooling water and steam consumption of after-fractionating tower C2 and ether-splitting are separated reactor sees Table 1.
Comparative Examples 1
Contain the mixed c 4 hydrocarbon of iso-butylene and methyl alcohol (MeOH) respectively through pipeline 1,2 and 3 enter methyltertiarvbutyl ether reactor R1, the content of iso-butylene is 20.1% (weight) in the mixed c 4 hydrocarbon, the material quantity that enters methyltertiarvbutyl ether reactor is 100kg/h, etherification product P1 enters the first separation column C1 through pipeline 4, the fraction B 1 that mainly contains methyl tertiary butyl ether is by sending into after-fractionating tower C2 through pipeline 6 at the bottom of the tower, cat head extraction liquid phase high-purity methyl tertbutyl ether from after-fractionating tower C2, after steam heater E1 is heated to 200 ℃, send into ether-splitting reactor R2, the operation of equipment condition is all with embodiment 1, adopt this technology, the steam consumption of the feed heater that the cooling water and steam consumption of after-fractionating tower C2 and ether-splitting are separated reactor sees Table 1.
Table 1
| | Comparative Examples 1 | |||
| C2 tower condenser | Steam heater E1 | C2 tower condenser | Steam heater E1 | |
| Steam consumption (kg/kgIB product) | 0.088 | 0.324 | ||
| Cooling water amount (kg/kgIB product) | 14.9 | 27.4 | ||
As can be seen from Table 1, the overhead fraction O2 of after-fractionating tower C2 directly enters ether-splitting with the gas phase form and separates reactor R2, can reduce the energy consumption of relevant device.
The mixed c 4 hydrocarbon and the methyl alcohol that contain iso-butylene enter methyltertiarvbutyl ether reactor R1 through pipeline 1,2 and 3 respectively, the content of iso-butylene is 20.1% (weight) in the mixed c 4 hydrocarbon, the material quantity that enters methyltertiarvbutyl ether reactor is 100kg/h, and Amberlyst 15 solid acid resin catalyst (ROHM ﹠amp are housed among the methyltertiarvbutyl ether reactor R1; HAAS produces), 60 ℃ of the temperature of reaction of methyltertiarvbutyl ether reactor R1, reaction pressure are 1.2MPa, the air speed 6hr of methyltertiarvbutyl ether reactor
-1Entering the methyl alcohol of this methyltertiarvbutyl ether reactor and the weight ratio of iso-butylene is 0.6.Etherification product P1 enters the first separation column C1 through pipeline 4, the working pressure of the first separation column C1 is 0.9MPa, the number of theoretical plate of this tower is 35, the fraction B 1 that mainly contains methyl tertiary butyl ether is by sending into after-fractionating tower C2 through pipeline 6 at the bottom of the tower, the working pressure of after-fractionating tower C2 is 0.8MPa, the number of theoretical plate of this tower is 30, the cut O2 of cat head gas phase extraction high-purity methyl tertbutyl ether, enter ether-splitting reactor R2, it is solid acid catalyst that the ether-splitting that is equipped with among the reactor R2 is separated catalyzer, and its sulfate radical content is 20%, and the reaction pressure that this ether-splitting is separated reactor is 0.55MPa, temperature of reaction is 200 ℃, and reaction velocity is 2h
-1Separate product P 2 that reactor obtains after interchanger E2 cooling from ether-splitting, enter the 3rd separation column C3, the working pressure of the 3rd separation column C3 is 0.6MPa, number of theoretical plate is 25, the overhead fraction O3 of the 3rd separation column C3 enters water wash column T1 through pipeline 10 and 14, the working pressure of water wash column T1 is 0.6Mpa, service temperature is 40 ℃, fresh water W1 enters water wash column through pipeline 12 by cat head, the weight ratio of fresh water W1 and organic fraction O3 is 0.4, sends into the 4th separation column C4 from the isolated organic phase O4 of water wash column cat head through pipeline 15, and the working pressure of separation column C5 is 0.7MPa, number of theoretical plate is 35, obtain purity at the bottom of the 4th separation column C4 tower and be 99.95% iso-butylene, this product can be used as the monomer of polymerization product, and its technical process (is not used the dotted line 16 among the figure referring to Fig. 2,16a; 18,18a; 11,11a; Pipeline 9 and the 4th separation column C4), table 2～table 4 has provided the mass flow and the composition of each equipment of turnover in this technical process.
Table 2
| The R1 cut (kg/h) that enters the mouth | R1 exports cut P1 (kg/h) | C1 overhead fraction O1 (kg/h) | B1 cut (kg/h) at the bottom of the C1 tower | C2 cat head O2 cut (kg/h) | |
| H 2O | 0.035 | 0.052 | 0.052 | ||
| IB | 20.100 | 3.000 | 3.00 | ||
| All the other C4 | 68.365 | 68.365 | 68.358 | 0.007 | 0.007 |
| MeOH | 11.500 | 1.800 | 1.800 | ||
| MTBE | 26.276 | 0.050 | 26.226 | 25.495 | |
| MSBE * | 0.008 | 0.008 | 0.008 | ||
| DME * | 0.100 | 0.100 | |||
| TBA * | 0.099 | 0.099 | 0.098 | ||
| DIB * | 0.300 | 0.300 | 0.003 | ||
| Add up to | 100.000 | 100.000 | 73.360 | 26.640 | 25.611 |
*On behalf of the trimethyl carbinol, DIB, MSBE represent methylidene sec-butyl ether, TBA represent Diisobutylene, DME to represent dme.
Table 3
| C2 tower bottom distillate B2 (kg/h) | R2 exports cut P2 (kg/h) | C3 tower bottom distillate B3 (kg/h) | C3 overhead fraction O3 (kg/h) | T1 import wash water W1 (kg/h) | |
| H 2O | 0.076 | 0.076 | 6.000 | ||
| IB | 14.498 | 14.498 | |||
| All the other C4 | 0.007 | 0.007 | |||
| MeOH | 8.198 | 7.721 | 0.477 | ||
| MTBE | 0.731 | 2.595 | 2.595 | ||
| MSBE | 0.016 | 0.016 | |||
| DME | 0.128 | 0.128 | |||
| TBA | 0.001 | 0.022 | 0.022 | ||
| DIB | 0.297 | 0.071 | 0.071 | ||
| Add up to | 1.029 | 25.611 | 10.501 | 15.110 | 6.000 |
Table 4
| Aqueous phase B 4 (kg/h) at the bottom of the T1 tower | T1 cat head organic phase O4 (kg/h) | C4 overhead fraction O4 (kg/h) | C4 tower bottom distillate B4 (kg/h) | |
| H 2O | 5.990 | 0.010 | 0.010 | |
| IB | 14.498 | 0.213 | 14.285 | |
| All the other C4 | 0.007 | 0.007 | ||
| MeOH | 0.477 | |||
| MTBE | ||||
| MSBE | ||||
| DME | 0.064 | 0.064 | 0.064 | |
| TBA | ||||
| DIB | ||||
| Add up to | 6.531 | 14.579 | 0.287 | 14.292 |
MTBE raw material O2 (commercially available) enters ether-splitting reactor R2 through pipeline 7a, it is solid acid catalyst that the ether-splitting that is equipped with among the reactor R2 is separated catalyzer, its sulfate radical content is 20%, the material quantity that enters cracking reactor is 100kg/h, the reaction pressure that this ether-splitting is separated reactor is 0.65MPa, temperature of reaction is at 200 ℃, reaction velocity 2h
-1Between, separate the product P 2 that reactor obtains from ether-splitting, enter the 3rd separation column C3 with the gas phase form, the working pressure of the 3rd separation column C3 is 0.45MPa, number of theoretical plate is 25, the overhead fraction O3 of the 3rd separation column C3 enters water wash column T1 through pipeline 10 and 14, the working pressure of water wash column T1 is 0.6Mpa, service temperature is 40 ℃, fresh water W1 enters water wash column T1 by cat head through pipeline 12, the weight ratio of fresh water W1 and organic fraction O3 is 0.4, send into the 4th separation column C4 from the isolated organic phase O4 of water wash column cat head through pipeline 15, the working pressure of separation column C5 is 0.7MPa, and number of theoretical plate is 35, obtains purity at the bottom of the 4th separation column C4 tower and be 99.95% iso-butylene, this product can be used as the monomer of polymerization product, its technical process is referring to Fig. 3, and (not using dotted line and the 4th separation column C4 among the figure), table 5 has provided embodiment 2 and has implemented steam consumption and the recirculated water consumption of separation column C3 and interchanger E2 in 3; Table 6～table 8 has provided the mass flow and the composition of each equipment of turnover in this technical process simultaneously.
Table 5
| | | |||||||
| C3 tower condenser | C3 tower reboiler | Interchanger E2 | Add up to | C3 tower condenser | C3 tower reboiler | Interchanger E2 | Add up to | |
| Steam consumption (kg/kgIB product) | 0.365 | 0.365 | 0.055 | 0.055 | ||||
| Recirculated water consumption (kg/kgIB product) | 14.73 | 37.14 | 51.87 | 36.34 | — | 36.34 | ||
From the result of table 5, separate the product P 2 that reactor obtains from ether-splitting among the embodiment 3, enter the 3rd separation column C3 with the gas phase form, can reduce steam consumption and total recirculated water consumption.
Table 6
| The R2 cut (kg/h) that enters the mouth | R2 exports cut P1 (kg/h) | C3 overhead fraction O3 (kg/h) | B3 cut (kg/h) at the bottom of the C3 tower | |
| H 2O | 0.297 | 0.297 | ||
| IB | 56.610 | 56.610 | ||
| All the other C4 | 0.027 | 0.027 | 0.027 | |
| MeOH | 31.955 | 1.969 | 29.986 | |
| MTBE | 99.547 | 10.187 | 10.187 | |
| MSBE | 0.031 | 0.062 | 0.062 | |
| DME | 0.500 | 0.500 | ||
| TBA | 0.383 | 0.086 | 0.086 | |
| DIB | 0.012 | 0.276 | 0.276 | |
| Add up to | 100.000 | 100.000 | 59.106 | 40.894 |
Table 7
| T1 import wash water W1 (kg/h) | Aqueous phase B 4 (kg/h) at the bottom of the T1 tower | T1 cat head organic phase O4 (kg/h) | C4 overhead fraction O4 (kg/h) | C4 tower bottom distillate B4 (kg/h) | |
| H 2O | 24.000 | 23.960 | 0.040 | 0.040 | |
| IB | 56.610 | 0.832 | 55.778 | ||
| All the other C4 | 0.027 | O.027 | |||
| MeOH | 1.969 | ||||
| MTBE | |||||
| MSBE | |||||
| DME | 0.250 | 0.250 | 0.250 | ||
| TBA | |||||
| DIB | |||||
| Add up to | 24.000 | 26.179 | 56.927 | 1.122 | 55.805 |
In a word, by embodiment 1 and Comparative Examples 1 employing technology of the present invention can be described, the cat head material that is after-fractionating tower C2 is with the extraction of gas phase form, and be heated to the temperature of scission reaction requirement through steam heater after, send into ether-splitting and separate reactor R2, like this, with traditional iso-butylene preparation technology comparison, reduce the cooling load of condenser of after-fractionating tower C2 and the heating load of steam heater E1, reduced the energy consumption of device.The comparing result of equipment component energy consumption from embodiment 2 and embodiment 3 is separated the product P 2 that reactor obtains from ether-splitting, directly enters the 3rd separation column C3 with the gas phase form, has further reduced the energy consumption of device.By embodiment 2 and 3 all as can be seen, adopt technology of the present invention, can obtain purity greater than 99.5% polymerization-grade isoolefine product.
Claims (35)
1. the production technique of an isoolefine comprises following operation:
(1) hydrocarbon mixture and at least a alcohol that will contain a kind of isoolefine is at least sent into the methyltertiarvbutyl ether reactor (R1) that catalyst for etherification is housed, to make the product (P1) that contains a kind of tert-alkyl ether at least;
(2) product (P1) that operation (1) is obtained is sent into first separation column (C1), with the cut (B1) that obtains mainly to contain the organic fraction (O1) of unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent and mainly contain tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent;
(3) cut (B1) that mainly contains tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent that operation (2) is obtained is sent into after-fractionating tower (C2), obtains high purity tert-alkyl ether cut (O2) and contains the cut (B2) of tert-alkyl ether, secondary alkyl oxide and low polyisoolefines heavy constituent;
(4) send into ether-splitting after high purity tert-alkyl ether cut (O2) heater via (E1) heating that operation (3) is obtained and separate reactor (R2), mainly contained the product (P2) of unreacted tert-alkyl ether and isoolefine and alcohol; After further separating, obtain isoolefine again;
The high purity tert-alkyl ether cut (O2) that it is characterized in that operation (3) gained enters ether-splitting with the gas phase form and separates reactor (R2), and the working pressure of after-fractionating tower (C2) is separated the working pressure of reactor (R2) greater than ether-splitting.
2. the production technique of isoolefine according to claim 1, it is characterized in that also comprising operation (5), the product (P2) that in operation (5) operation (4) is obtained is sent into the 3rd separation column (C3), with the cut (B3) that obtains mainly to contain the light constituent cut (O3) of isoolefine, a small amount of alcohol, a small amount of lower molecular weight ether and mainly contain alcohol, unreacted tert-alkyl ether.
3. the production technique of isoolefine according to claim 2 is characterized in that the product (P2) that operation (4) obtains sends into the 3rd separation column (C3) with liquid form.
4. the production technique of isoolefine according to claim 2 is characterized in that the product (P2) that operation (4) obtains sends into the 3rd separation column (C3) with the gas phase form.
5. the production technique of isoolefine according to claim 4 is characterized in that ether-splitting separates the working pressure of the working pressure of reactor (R2) greater than the 3rd separation column (C3).
6. according to the production technique of each described isoolefine of claim 3-5, it is characterized in that also comprising operation (6), the cut (O3) that in operation (6) the 3rd separation column (C3) of operation (5) is obtained is sent into water wash column (T1), to obtain mainly moisture, pure water (B4) and mainly to contain the organic phase (O4) of isoolefine, a small amount of lower molecular weight ether light constituent.
7. the production technique of isoolefine according to claim 6, it is characterized in that also comprising operation (7), the water (B4) that in operation (7) operation (6) is obtained is sent into the 4th separation column (C4), with aqueous distillate (B5) and the rich pure cut (O5) that obtains poor alcohol.
8. the production technique of isoolefine according to claim 7 is characterized in that the pure cut of the described richness of at least a portion (O5) is circulated to the methyltertiarvbutyl ether reactor (R1) of operation (1).
9. the production technique of isoolefine according to claim 7 is characterized in that the described aqueous distillate of at least a portion (B5) is circulated to the water wash column (T1) of operation (7).
10. the production technique of isoolefine according to claim 6, it is characterized in that also comprising operation (8), the organic phase (O4) that in operation (8) operation (6) is obtained is sent into the 5th separation column (C5), to obtain mainly to contain the light constituent cut (O6) and the high purity isoolefine cut (B6) of lower molecular weight ether.
11. the production technique of isoolefine according to claim 7, it is characterized in that also comprising operation (8), the organic phase (O4) that in operation (8) operation (6) is obtained is sent into the 5th separation column (C5), to obtain mainly to contain the light constituent cut (O6) and the high purity isoolefine cut (B6) of lower molecular weight ether.
12. the production technique of isoolefine according to claim 8, it is characterized in that also comprising operation (8), the organic phase (O4) that in operation (8) operation (6) is obtained is sent into the 5th separation column (C5), to obtain mainly to contain the light constituent cut (O6) and the high purity isoolefine cut (B6) of lower molecular weight ether.
13. the production technique of isoolefine according to claim 9, it is characterized in that also comprising operation (8), the organic phase (O4) that in operation (8) operation (6) is obtained is sent into the 5th separation column (C5), to obtain mainly to contain the light constituent cut (O6) and the high purity isoolefine cut (B6) of lower molecular weight ether.
14. the production technique of isoolefine according to claim 10 is characterized in that the described light constituent cut of at least a portion (O6) is circulated to the methyltertiarvbutyl ether reactor (R1) of operation (1).
15. the production technique of isoolefine according to claim 11 is characterized in that the described light constituent cut of at least a portion (O6) is circulated to the methyltertiarvbutyl ether reactor (R1) of operation (1).
16. the production technique of isoolefine according to claim 12 is characterized in that the described light constituent cut of at least a portion (O6) is circulated to the methyltertiarvbutyl ether reactor (R1) of operation (1).
17. the production technique of isoolefine according to claim 13 is characterized in that the described light constituent cut of at least a portion (O6) is circulated to the methyltertiarvbutyl ether reactor (R1) of operation (1).
18., it is characterized in that at least a portion cut (B3) is sent into reactor (R1) according to the production technique of each described isoolefine of claim 2-5.
19. the production technique of isoolefine according to claim 6 is characterized in that at least a portion cut (B3) is sent into reactor (R1).
20. the production technique of isoolefine according to claim 7 is characterized in that at least a portion cut (B3) is sent into reactor (R1).
21. the production technique of isoolefine according to claim 8 is characterized in that at least a portion cut (B3) is sent into reactor (R1).
22. the production technique of isoolefine according to claim 9 is characterized in that at least a portion cut (B3) is sent into reactor (R1).
23. the production technique of isoolefine according to claim 10 is characterized in that at least a portion cut (B3) is sent into reactor (R1).
24. the production technique of isoolefine according to claim 11 is characterized in that at least a portion cut (B3) is sent into reactor (R1).
25. the production technique of isoolefine according to claim 12 is characterized in that at least a portion cut (B3) is sent into reactor (R1).
26. the production technique of isoolefine according to claim 13 is characterized in that at least a portion cut (B3) is sent into reactor (R1).
27. the production technique of isoolefine according to claim 14 is characterized in that at least a portion cut (B3) is sent into reactor (R1).
28. the production technique of isoolefine according to claim 15 is characterized in that at least a portion cut (B3) is sent into reactor (R1).
29. the production technique of isoolefine according to claim 16 is characterized in that at least a portion cut (B3) is sent into reactor (R1).
30. the production technique of isoolefine according to claim 17 is characterized in that at least a portion cut (B3) is sent into reactor (R1).
31. the production technique of an isoolefine comprises following operation:
Operation (4): high purity liquid phase tert-alkyl ether (O2) is sent into ether-splitting and is separated reactor (R2) after the heating vaporization, mainly contained the product (P2) of unreacted tert-alkyl ether and isoolefine and alcohol;
Operation (5): the product (P2) that operation (4) obtains is sent into the 3rd separation column (C3), with the cut (B3) that obtains mainly to contain the light constituent cut (O3) of isoolefine, a small amount of alcohol, a small amount of lower molecular weight ether and mainly contain alcohol, unreacted tert-alkyl ether
The product (P2) that it is characterized in that operation (4) gained enters the 3rd separation column (C3) with the gas phase form, and ether-splitting is separated the working pressure of the working pressure of reactor (R2) greater than the 3rd separation column (C3).
32. the production technique of isoolefine according to claim 31, it is characterized in that also comprising operation (6), at least a portion cut (O3) that in operation (6) the 3rd separation column (C3) of operation (5) is obtained is sent into water wash column (T1), to obtain mainly moisture, pure water (B4) and mainly to contain the organic phase (O4) of isoolefine, a small amount of lower molecular weight ether light constituent.
33. the production technique of isoolefine according to claim 32, it is characterized in that also comprising operation (7), at least a portion water (B4) that in operation (7) operation (6) is obtained is sent into the 4th separation column (C4), with aqueous distillate (B5) and the rich pure cut (O5) that obtains poor alcohol.
34. the production technique of isoolefine according to claim 32 is characterized in that the described aqueous distillate of at least a portion (B5) is circulated to the water wash column (T1) of operation (6).
35. production technique according to claim 33 or 34 described isoolefine, it is characterized in that also comprising operation (8), the organic phase (O4) that in operation (8) operation (6) is obtained is sent into the 5th separation column (C5), to obtain mainly to contain the light constituent cut (O6) and the high purity isoolefine cut (B6) of lower molecular weight ether.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4056549A1 (en) | 2021-03-08 | 2022-09-14 | Basf Se | Process for obtaining isobutene from a c4-hydrocarbon mixture |
| WO2022189218A1 (en) | 2021-03-08 | 2022-09-15 | Basf Se | Process for obtaining isobutene from a c4-hydrocarbon mixture |
| WO2023217810A1 (en) | 2022-05-13 | 2023-11-16 | Basf Se | Process for purifying a raw c4-hydrocarbon mixture |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102050690B (en) * | 2009-10-30 | 2014-04-02 | 中国石油化工股份有限公司 | Isoolefine production method |
| CN103172487B (en) * | 2011-12-23 | 2015-05-13 | 中国石油化工股份有限公司 | Production process of high-purity isoolefine (tert-olefin) |
| CN103172483B (en) * | 2011-12-23 | 2015-05-13 | 中国石油化工股份有限公司 | Production process of high-purity isoolefine (tert-olefin) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4056549A1 (en) | 2021-03-08 | 2022-09-14 | Basf Se | Process for obtaining isobutene from a c4-hydrocarbon mixture |
| WO2022189218A1 (en) | 2021-03-08 | 2022-09-15 | Basf Se | Process for obtaining isobutene from a c4-hydrocarbon mixture |
| WO2023217810A1 (en) | 2022-05-13 | 2023-11-16 | Basf Se | Process for purifying a raw c4-hydrocarbon mixture |
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