CN1358695A - Productive process for isoalkene and/or tertiary alkyl ether - Google Patents

Productive process for isoalkene and/or tertiary alkyl ether Download PDF

Info

Publication number
CN1358695A
CN1358695A CN 00134092 CN00134092A CN1358695A CN 1358695 A CN1358695 A CN 1358695A CN 00134092 CN00134092 CN 00134092 CN 00134092 A CN00134092 A CN 00134092A CN 1358695 A CN1358695 A CN 1358695A
Authority
CN
China
Prior art keywords
tert
alkyl ether
isoolefine
ether
cut
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 00134092
Other languages
Chinese (zh)
Other versions
CN1158228C (en
Inventor
周继东
韩春国
姚振卫
李学雷
张冰冰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Research Institute of Beijing Yanshan Petrochemical Corp
Original Assignee
Beijing Research Institute of Beijing Yanshan Petrochemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Research Institute of Beijing Yanshan Petrochemical Corp filed Critical Beijing Research Institute of Beijing Yanshan Petrochemical Corp
Priority to CNB001340921A priority Critical patent/CN1158228C/en
Publication of CN1358695A publication Critical patent/CN1358695A/en
Application granted granted Critical
Publication of CN1158228C publication Critical patent/CN1158228C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention discloses a dproduction process of isoolefine (tertiary olefine) and/or tertiary alkyl ether. It is characterized by that when the tertiary alkyl ether product obtained by reaction of the mixed hydrocarbon containing isoolefine and alcohol is undergone the process of separation, the high-purity tertiary alkyl ether product meeting cracking requirements can be produced from internal side line of stripping section of simple fractionating tower adopted by said ivnention, so that it can save equipment cost and reduce energy consumption. Said invention also adds the tower bottom return line or side production line of fractionating tower in second etherification reaction area so as to raise tertiary alkyl ether raw material quantity feeding into ether cracking reactor and raise isoolefine product quality. Said invention changes the water-washing tower used in existent technology into static mixer and separation tank so as to further reduce equipment cost.

Description

The production technique of isoolefine and/or tert-alkyl ether
The present invention relates to the production technique of isoolefine (tertiary olefin) and/or tert-alkyl ether, particularly the technology of hydrocarbon mixture by containing a kind of isoolefine at least and at least a pure prepared in reaction high purity tert-alkyl ether or the 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.
Tert-alkyl ether, isoolefine are the important source material of fine chemistry industry, also are the important intermediate raw material or the monomers of synthetic rubber, synthetic resins, are the raw material of preparing high-purity isoolefine as methyl tertiary butyl ether (MTBE), are again the important additives that improves fuel octane number; High-purity isobutylene is widely used in producing multiple Chemicals such as isoprene-isobutylene rubber, polyisobutene and methyl methacrylate.
When tert-alkyl ether is used for the different hydrocarbon alkene of preparing high-purity raw material, cracking technology has certain requirement to the purity of tert-alkyl ether, as the heavier content such as oligopolymer of isoolefine in the cracking stock more for a long time, can influence the activity of catalyst for cracking, simultaneously other hydrocarbon-fraction (particularly other alkene) content can influence the purity of the isoolefine that cracking obtains more for a long time in the cracking stock.With methyl tert-butyl ether cracking production high purity isoolefine is example, and its component concentration to cracking stock requires referring to table 1.
Table 1
Chemical name Be called for short ????wt％
Methyl tertiary butyl ether ????MTBE ????＞99
Methyl sec-butyl ether ????MSBE ????＜0.5
The mixed c 4 hydrocarbon ????C4 ????＜0.05
Methyl alcohol ????MeOH ????＜0.2
The trimethyl carbinol ????TBA ????＜0.5
Diisobutylene ????DIB ????＜0.1
Water ????H 2O No free-water
CN1153164A discloses the processing method of a kind of preparation chemical industry type methyl t-butyl ether (MTBE), and this invention is a kind of by mixed C 4The processing method of iso-butylene in the hydrocarbon and methyl alcohol prepared in reaction chemical industry type methyl t-butyl ether, be characterized in reacting the methyl tertiary butyl ether of generation earlier through azeotropic distillation column, the thick MTBE that comes out from component distillation Tata still is sent to the product purification tower, removing the weight component at the bottom of cat head, tower, is the high-purity methyl tertbutyl ether from the smart methyl tertiary butyl ether of rectifying section side line liquid phase extraction chemical industry type.Its shortcoming is just can obtain meeting the high-purity methyl tertbutyl ether that cracking requires after the MTBE that reactor obtains need pass through azeotropic distillation column and twice fractionation of product rectifying tower.
Adopt the synthetic and cracking associating preparing high-purity isoolefine of tert-alkyl ether, have the reaction preference height, do not have advantages such as pollution and corrosion.Companies such as IFP (IFP), gondola Snamprogetti all carried out research to this, and had applied for a lot of patents.US5,994,594 (1999,11,30) provide a kind of tert-alkyl ether synthetic process integration with cracking preparing high-purity isoolefine, compare this technology with traditional technology and done some improvement, but still come with some shortcomings: this invention is when the feasibility of its technology of proof, the condition of its purification part (being the purification part of embodiment) is taked the method with computed in software, what take all is the simplest, optimal situation, and practical situation are wanted the many of complexity, such as calculating for simplifying, first separation column tower bottom distillate-MTBE in this technology behind the methyltertiarvbutyl ether reactor calculates by 100%, and in fact, the tower bottom distillate of etherification reaction product behind a separation column mainly contains tert-alkyl ether, heavy components such as secondary alkyl oxide and two polyisoolefines, tert-alkyl ether in this tower bottom distillate and heavy constituent content can not satisfy the requirement of cracking technology, therefore, can not directly enter ether-splitting and separate reaction zone.Embodiment preferred of this invention adopts and increases a separation column purification tert-alkyl ether, make it satisfy the cracking requirement, but increased cost of equipment virtually, simultaneously, because tert-alkyl ether must be purified through overflash in this separation column, has increased the energy consumption of this system so greatly.In addition, use the middle and later periods at catalyzer, the low molecule ether content of the by product in the etherification reaction product increases gradually, and promptly Chun selectivity descends gradually, has influenced pure utilization ratio.In addition, this patent still adopts traditional water wash column to remove the alcohol in the material behind the etherification reaction, from improving the complicated operation degree, saves floor space, saves aspect such as cost of equipment and considers, also is further improved.
The object of the present invention is to provide a kind of production technique of improved tert-alkyl ether, adopt this technology can suppress the generation of by product, the selectivity that improves alcohol, reduction cost of equipment and energy consumption, saving floor space, simplify the operation.
Another object of the present invention is to provide a kind of improved tert-alkyl ether and isoolefine process for combination producing, adopts this technology can suppress the generation of by product, the selectivity that improves alcohol, reduction cost of equipment and energy consumption, saving floor space, simplify the operation.
For achieving the above object, when the present invention separates at the tert-alkyl ether product of hydrocarbon mixture that will contain isoolefine and alcohol reaction gained, employing meets the different tert-alkyl ether product of high purity that cracking requires in the stripping section inside cord extraction of single separation column, when preparation tert-alkyl ether and/or isoolefine, can save cost of equipment and energy consumption like this; The present invention also sets up in second etherification reaction zone return wire or side extraction line at the bottom of the fractionation Tata, enters the tert-alkyl ether material quantity that ether-splitting is separated reactor with raising, thereby increases the isoolefine product volume of this system; The present invention also can change static mixer and separating tank into by the water wash column that prior art is used, with further saving cost of equipment.The present invention also adopts isolated low-molecular-weight ether lighting end is circulated to etherification reaction zone, suppresses side reaction, especially uses the middle and later periods at catalyzer, makes alcohol keep higher selectivity, improves the utilization ratio of total system alcohol.
The invention provides the production technique of a kind of isoolefine and/or tert-alkyl ether, comprise following operation:
(1) hydrocarbon mixture and at least a alcohol that will contain a kind of isoolefine is at least sent into the etherification reaction zone R1 that catalyst for etherification is housed, to make the product P 1 that contains a kind of tert-alkyl ether at least;
(2) at least a portion product P 1 that operation 1 is obtained is sent into separation column C1, with the organic fraction B1 of the organic fraction O1 that obtains mainly to contain unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent, high purity tert-alkyl ether with mainly contain the fraction B 2 of secondary alkyl oxide, low polyisoolefines heavy constituent;
Wherein the high purity tert-alkyl ether fraction B 1 of operation 2 gained is from the side line extraction of the first separation column C1, and this side line extraction mouth is located in the stripping section of this tower, and side line extraction mouth is at least one, and preferred side line extraction mouth is located at the position of the 1/3-2/3 of this tower stripping section; The organic fraction O1 that mainly contains unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent discharges from cat head; And the fraction B 2 that mainly contains secondary alkyl oxide, low polyisoolefines heavy constituent is discharged at the bottom of this Tata.
The present invention also provides the production technique of a kind of isoolefine and/or tert-alkyl ether, comprises following operation:
(1) hydrocarbon mixture and at least a alcohol that will contain a kind of isoolefine is at least sent into the etherification reaction zone R1 that catalyst for etherification is housed, to make the product P 1 that contains a kind of tert-alkyl ether at least;
(2) at least a portion product P 1 that operation 1 is obtained is sent into separation column C1, with the organic fraction B1 of the organic fraction O1 that obtains mainly to contain unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent, high purity tert-alkyl ether with mainly contain the fraction B 2 of secondary alkyl oxide, low polyisoolefines heavy constituent;
The side stream B1 of at least a portion high purity tert-alkyl ether that (3) operation 2 is obtained sends into and ether-splitting is housed separates the ether-splitting of catalyzer and separate reaction zone R3, to make the product P 3 that contains at least a alcohol of at least a isoolefine;
(4) product P 3 that operation 3 is obtained is sent into separation column C4, with the cut O6 that obtains mainly to contain operation 3 resulting most of isoolefine, a small amount of alcohol, a small amount of lower molecular weight ether light constituent with mainly contain alcohol, the fraction B 6 of cracking tert-alkyl ether not.
Wherein the high purity tert-alkyl ether fraction B 1 of operation 2 gained is from the side line extraction of the first separation column C1, and this side line extraction mouth is located in the stripping section of this tower, and side line extraction mouth is at least one, and preferred side line extraction mouth is located at the position of the 1/3-2/3 of this tower stripping section; The organic fraction O1 that mainly contains unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent discharges from cat head; And the fraction B 2 that mainly contains secondary alkyl oxide, low polyisoolefines heavy constituent is discharged at the bottom of this Tata.
The present invention also provides a kind of production technique for preparing isoolefine and/or tert-alkyl ether, comprises following operation:
(1) hydrocarbon mixture and at least a alcohol that will contain a kind of isoolefine is at least sent into the etherification reaction zone R1 that catalyst for etherification is housed, to make the product P 1 that contains a kind of tert-alkyl ether at least;
(2) at least a portion product P 1 that operation 1 is obtained is sent into separation column C1, with the organic fraction B1 of the organic fraction O1 that obtains mainly to contain unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent, high purity tert-alkyl ether with mainly contain the fraction B 2 of secondary alkyl oxide, low polyisoolefines heavy constituent;
The side stream B1 of at least a portion high purity tert-alkyl ether that (3) operation 2 is obtained sends into and ether-splitting is housed separates the ether-splitting of catalyzer and separate reaction zone R3, to make the product P 3 that contains at least a isoolefine and at least a alcohol, carries out operation 7 afterwards;
(7) product P 3 that operation 3 is obtained is sent into alcohol washing disengaging zone L2, to obtain mainly moisture, pure aqueous phase B 7 and mainly to contain isoolefine, the organic phase O8a of cracking tert-alkyl ether, a small amount of lower molecular weight ether light constituent not, carries out operation 4 afterwards;
(4) operation 7 is obtained at least a portion organic phase O8a and send into separation column C4, with the cut O6 that obtains mainly to contain operation 3 resulting most of isoolefine, a small amount of lower molecular weight ether light constituent and the fraction B 6a of cracking tert-alkyl ether not.
Wherein the high purity tert-alkyl ether fraction B 1 of operation 2 gained is from the side line extraction of the first separation column C1, and this side line extraction mouth is located in the stripping section of this tower, and side line extraction mouth is at least one, and preferred side line extraction mouth is located at the position of the 1/3-2/3 of this tower stripping section; The organic fraction O1 that mainly contains unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent discharges from cat head; And the fraction B 2 that mainly contains secondary alkyl oxide, low polyisoolefines heavy constituent is discharged at the bottom of this Tata.
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 4And/or C 5Material, C 1And/or C 5Steam 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 two key 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.
When the present invention separates at the tert-alkyl ether product of hydrocarbon mixture that will contain isoolefine and alcohol reaction gained, adopt stripping section inside cord extraction to meet the high purity tert-alkyl ether product that cracking requires at single separation column; And prepare the high purity tert-alkyl ether that meets the cracking requirement with prior art, and need with at least two separation columns, when preparation tert-alkyl ether and/or isoolefine, can save cost of equipment and energy consumption like this; Adopt technology of the present invention in addition, heavy constituent can be discharged at the bottom of the tower of tert-alkyl ether separation column, has exhausting impurity function, can prevent the accumulation of heavy constituent, after long-time running, can also keep iso-butylene that very high yield is arranged with the synthetic and cracking machinery that guarantees tert-alkyl ether at the tert-alkyl ether cracking zone.
When prior art removes pure in the organic fraction, adopt water wash column, and the present invention adopts static mixer and separating tank, can further save cost of equipment.
The present invention also adopts the low-molecular-weight ether lighting end of isolated part is circulated to etherification reaction zone, to suppress the generation of by product lower molecular weight ether, improves the selectivity (especially when catalyzer turns round for a long time) of alcohol.
Production technique below in conjunction with 1～16 pair of isoolefine of the present invention of accompanying drawing and/or tert-alkyl ether is further described.
Accompanying drawing 1～16th, the schematic flow sheet of isoolefine of the present invention and/or tert-alkyl ether production technique.The operation that dotted line representative in the accompanying drawing may exist, containing of the main code name in the accompanying drawing means:
R1-etherification reaction zone R2-etherification reaction zone
C1-separation column C2-separation column
Mn-static mixer Vn-separating tank
C3-separation column L1 alcohol washing disengaging zone
The R3-ether-splitting is separated reaction C4-separation column
L2 alcohol washing disengaging zone
Mm-static mixer Vm-separating tank
C5-separation column C6-separation column
The production technology of isoalkene of the present invention and/or tert-alkyl ether comprises operation 1 and operation 2 (referring to accompanying drawing 1), in operation 1, at least the hydrocarbon mixture and at least a alcohol that contain a kind of isoalkene are sent into the etherification reaction zone R1 that catalyst for etherification is housed through pipeline 1,2 and 3 respectively, contained at least a kind of product P 1 of tert-alkyl ether. In operation 2, to obtain at least a portion etherification product P1 by operation 1 and send into fractionating column C1 through pipeline 4, mainly be contained the organic fraction O1 of unreacted hydrocarbon mixture, unreacting alcohol, a small amount of low-molecular-weight ether light component, by the high-purity tert-alkyl ether fraction B 1 of this tower side line extraction, by the fraction B 2 that mainly contains secondary alkyl ether, low polyisoolefines restructuring minute of discharging at the bottom of the tower. Organic fraction O1 can be used as Organic Chemicals or liquefied gas etc., also can further separate, can also partly send back to etherification reaction zone R1 and/or return to etherification reaction zone R2 through pipeline 5,5a, 18e, 18d and 8 through pipeline 5,5a and 18f and (can suppress the accessory substance generations such as low-molecular-weight ether, improve the selective of alcohol, referring to accompanying drawing 4), preferably further separate; High-purity tert-alkyl ether fraction B 1 can be used as fuel additive, industrial chemicals or is used for further cracking isoalkene; Fraction B 2 can be used as fuel additive etc.
The production technology of isoalkene of the present invention and/or tert-alkyl ether comprises also that when operation 1 and 2 exists operation 5 is (referring to accompanying drawing 2, Fig. 3), in operation 5, to mix by pipeline 8 with the fresh alcohol of sending into from pipeline 1b through pipeline 5 from least a portion cut O1 of the fractionating column C1 cat head of operation 2 and send into etherification reaction zone R2, mainly contained tert-alkyl ether, the unreacted hydrocarbon mixture, the product P 2 of unreacting alcohol and a small amount of low-molecular-weight ether light component, product P 2 is sent into fractionating column C2 through pipeline 9, mainly contained the unreacted hydrocarbon mixture, unreacting alcohol, the overhead fraction O2 (or O2a) of a small amount of low-molecular-weight ether light component, cut O2 (or O2a) can be used as Organic Chemicals or liquefied gas etc., also can send into next group methyltertiarvbutyl ether reactor and fractionating column (if also having unreacted isoalkene in this cut), also can remove alcohol processes, can also be partly through pipeline 10,10a, 18c, 18e and 18f are circulated to etherification reaction zone R1 and/or through pipeline 10,10a, 18c, 18d and 8 is circulated to etherification reaction zone R2 (can suppress the accessory substance generations such as low-molecular-weight ether, improve the selective of alcohol, referring to accompanying drawing 4), preferably remove alcohol and process. In order to reclaim the cut that is rich in tert-alkyl ether among the fractionating column C2, the present invention adopts following two kinds of technological processes: flow process 1 (referring to accompanying drawing 2): with the side line extraction of high-purity tert-alkyl ether fraction B 1a in the fractionating column C2 stripping section, the tower bottom distillate B2a that contains at least a kind of low polyisoolefines restructuring minute discharges through pipeline 12c. High-purity tert-alkyl ether fraction B 1a can be used as fuel additive, industrial chemicals or merges with fraction B 1 through pipeline 11 and is used for further cracking isoalkene; Fraction B 2a can be used as fuel additive etc. Flow process 2 (referring to accompanying drawing 3): the tower bottom distillate B3 that at least a portion is mainly contained at least a tert-alkyl ether and contain at least a kind of low polyisoolefines restructuring minute turns back to the fractionating column C1 of operation 2 through pipeline 12 and 12a, another part tower bottom distillate B3 sends into the ether storage tank through pipeline 12b, can be used as fuel additive or industrial chemicals.
For unreacted hydrocarbon mixture, a small amount of low-molecular-weight ether light component are separated with alcohol, the production technology of isoalkene of the present invention and/or tert-alkyl ether when operation 1,2 exists or operation 1,2,5 also comprise operation 6 (referring to accompanying drawing 4) when existing, in operation 6, at least a portion overhead fraction O1 that will obtain from the fractionating column C1 of operation 2 sends into alcohol washing Disengagement zone L1 through pipeline 5,5b, 8a and 10b, and/or send into alcohol washing Disengagement zone L1 from least a portion overhead fraction O2 (O2a) that the fractionating column C2 of operation 5 obtains through pipeline 10 and 10b, fresh water W1 enters alcohol washing Disengagement zone L1 through pipeline 14 and 13, obtains mainly moisture, pure aqueous phase B 4 and mainly contains the organic phase O4 of unreacted hydrocarbon mixture, a small amount of low-molecular-weight ether light component. Described alcohol washing Disengagement zone L1 selects at least one water scrubber T1 or at least one group of static mixer Mn and knockout drum Vn. From reduce cost of equipment, save floor space, the angle that simplifies the operation considers the alcohol washing preferred static mixer of Disengagement zone L1 of the present invention and knockout drum. Mainly moisture, pure aqueous phase B 4 can be sent into the waste water treatment plant or further separate to reclaim alcohol; The organic phase O4 that mainly contains unreacted hydrocarbon mixture, a small amount of low-molecular-weight ether light component can be used as Organic Chemicals or liquefied gas etc., also can further separate so that the unreacted hydrocarbon mixture separates with low-molecular-weight ether, can also part be circulated to etherification reaction zone R1 and/or be circulated to etherification reaction zone R2 through pipeline 16,16a, 18b, 18c, 18d and 8 through pipeline 16,16a, 18b, 18c, 18e and 18f and (can suppress the accessory substance generations such as low-molecular-weight ether, improve the selective of alcohol, referring to accompanying drawing 4), preferably further separate.
For the alcohol in the further recycle-water cut, the production technology of isoalkene of the present invention and/or tert-alkyl ether also comprises operation 8 (referring to accompanying drawing 4) when alcohol washing Disengagement zone L1 exists, in operation 8, to contain from least a portion in the operation 6 pure aqueous phase B 4 and send into alcohol recovery fractionating column C5 through pipeline 17, with aqueous distillate B8 and the rich pure cut O9 that obtains poor alcohol. The rich pure cut O9 that at least a portion cat head obtains is circulated to etherification reaction zone R1 and/or etherification reaction zone R2 through pipeline 28,28a, 2,3 and/or 28,28b, 5b, 8, aqueous distillate B8 enters alcohol washing Disengagement zone L1 through pipeline 29,29a and 13 at the bottom of at least a portion of fractionating column C5 (preferred most of) tower, water at the bottom of the tower of a small amount of fractionating column C5 can be discharged through pipeline 29,29b. When alcohol washing Disengagement zone L1 uses recycle-water (recirculated water), also can add a part of fresh water W1 to alcohol washing Disengagement zone L1 through pipeline 14 and 13.
For further light component among the organic phase O4 being separated with the unreacted hydrocarbon mixture, the production technology of isoalkene of the present invention and/or tert-alkyl ether also comprises operation 9 (referring to accompanying drawing 4) when alcohol washing Disengagement zone L1 exists, in operation 9, to wash organic phase O4 that at least a portion that Disengagement zone L1 obtains (preferential most of) mainly contains unreacted hydrocarbon mixture, a small amount of low-molecular-weight ether light component from alcohol and send into the fractionating column C3 of operation 9 through pipeline 16, and mainly be contained low molecule ether light component O5 and mainly contain the fraction B 5 of unreacted hydrocarbon mixture. Mainly containing unreacted hydrocarbon mixture B5 cut discharges through pipeline 19; Mainly containing low molecule ether light component O5 can discharge through pipeline 18, can also part return to etherification reaction zone R1 and/or return to etherification reaction zone R2 through pipeline 18a, 18b, 18c, 18d and 8 through pipeline 18a, 18b, 18c, 18e and 18f, preferred cycle is to etherification reaction zone R1 and/or R2, the accessory substances such as low-molecular-weight ether that can suppress among etherification reaction zone R1 and the R2 generate, and improve the selective of alcohol.
The production technology of isoalkene of the present invention and/or tert-alkyl ether comprises operation 1, operation 2, operation 3 and operation 4 (referring to accompanying drawing 5), in operation 1, at least the hydrocarbon mixture and at least a alcohol that contain a kind of isoalkene are sent into the etherification reaction zone R1 that catalyst for etherification is housed through pipeline 1,2 and 3 respectively, contained at least a kind of product P 1 of tert-alkyl ether. In operation 2, to obtain at least a portion etherification product P1 by operation 1 and send into fractionating column C1 through pipeline 4, mainly be contained the organic fraction O1 of unreacted hydrocarbon mixture, unreacting alcohol, a small amount of low-molecular-weight ether light component, by the high-purity tert-alkyl ether fraction B 1 of this tower side line extraction, by the fraction B 2 that mainly contains secondary alkyl ether, low polyisoolefines restructuring minute of discharging at the bottom of the tower. Organic fraction O1 can be used as Organic Chemicals or liquefied gas etc., also can further separate, can also partly send back to etherification reaction zone R1 and/or return to etherification reaction zone R2 through pipeline 5,5a, 18e, 18d and 8 through pipeline 5,5a and 18f and (can suppress the accessory substance generations such as low-molecular-weight ether, improve the selective of alcohol, referring to accompanying drawing 9), preferably further separate; High-purity tert-alkyl ether fraction B 1 can be delivered to fuel additive storage tank, industrial chemicals or be used for further cracking isoalkene through pipeline 6 and 6a; Fraction B 2 can be used as fuel additive etc. In operation 3, at least a portion is sent into the ether-splitting solution reaction zone R3 that ether-splitting solution catalyst is housed from the high-purity tertbutyl ether fraction B 1 of the fractionating column C1 of operation 2 through pipeline 6 and 6b, obtain containing the product P 3 of at least a alcohol of at least a isoalkene, the product P 3 that contains at least a alcohol of at least a isoalkene that will obtain from ether-splitting solution reaction zone R3 is delivered to operation 4. In operation 4, ether-splitting solution product P 3 is sent into fractionating column C4 through pipeline 20, mainly contained the cut O6 of isoalkene, pure and mild low-molecular-weight ether light component and contained the fraction B 6 of pure and mild not cracking tert-alkyl ether. The fraction B 6 that at least a portion is contained pure and mild not cracking tert-alkyl ether through pipeline 22,22a and 3 be back to etherification reaction zone R1 and/or through pipeline 22,22a and 22c to etherification reaction zone R2 (referring to Fig. 6), another part B6 cut can drain into the ether storage tank through pipeline 22 and 22b, can be used as fuel additive; The cut O6 that mainly contains isoalkene, pure and mild low-molecular-weight ether light component can be used as industrial chemicals or is used for further refining.
The production technology of isoalkene of the present invention and/or tert-alkyl ether is in operation 1,2,3 and 4 also comprise operation 5 (referring to accompanying drawing 6) when existing, in operation 5, will be from least a portion cut O1 of the fractionating column C1 cat head of operation 2 through pipeline 5 with the fresh alcohol of sending into from pipeline 1b and/or through pipeline 22, the fraction B that contains pure and mild not cracking tert-alkyl ether 6 mixing that 22a and 22c send into are sent into etherification reaction zone R2 by pipeline 8, mainly contained tert-alkyl ether, the unreacted hydrocarbon mixture, the product P 2 of unreacting alcohol and a small amount of low-molecular-weight ether light component, product P 2 is sent into fractionating column C2 through pipeline 9, mainly contained the unreacted hydrocarbon mixture, unreacting alcohol, the overhead fraction O2 (or O2a) of a small amount of low-molecular-weight ether light component, cut O2 (or O2a) can be used as Organic Chemicals or liquefied gas etc., also can send into next group etherification reaction zone and fractionator (if also having unreacted isoalkene in this cut), also can remove alcohol processes, can also be partly through pipeline 10,10a, 18c, 18e and 18f are circulated to etherification reaction zone R1 and/or through pipeline 10,10a, 18c, 18d and 8 is circulated to etherification reaction zone R2 (can suppress the accessory substance generations such as low-molecular-weight ether, improve the selective of alcohol, referring to accompanying drawing 9), preferably remove alcohol and process. In order to reclaim the cut that is rich in tert-alkyl ether among the fractionating column C2, the present invention adopts following two kinds of technological processes: flow process 1 (referring to accompanying drawing 6): with the side line extraction of high-purity tert-alkyl ether fraction B 1a in the fractionating column C2 stripping section, the tower bottom distillate B2a that contains at least a kind of low polyisoolefines restructuring minute discharges through pipeline 12c. High-purity tert-alkyl ether fraction B 1a can be used as fuel additive or is used for further cracking isoalkene with merging through pipeline 11 fraction B 1; Fraction B 2a can be used as fuel additive etc. Flow process 2 (referring to accompanying drawing 6): the tower bottom distillate B3 that at least a portion is mainly contained at least a tert-alkyl ether and contain at least a kind of low polyisoolefines restructuring minute turns back to the fractionating column C1 of operation 2 through pipeline 12 and 12a, another part tower bottom distillate B3 sends into the ether storage tank through pipeline 12b, can be used as fuel additive or industrial chemicals.
For ether synthesis technique unreacted hydrocarbon mixture, a small amount of low-molecular-weight ether light component are separated with alcohol, the production technology of isoalkene of the present invention and/or tert-alkyl ether when operation 1,2,3 and 4 exists or operation 1,2,3,4 and 5 also comprise operation 6 (referring to accompanying drawing 7) when existing, in operation 6, at least a portion overhead fraction O1 that will obtain from the fractionating column C1 of operation 2 sends into alcohol washing Disengagement zone L1 through pipeline 5,5b, 8a and 10b, and/or send into alcohol washing Disengagement zone L1 from least a portion overhead fraction O2 (O2a) that the fractionating column C2 of operation 5 obtains through pipeline 10 and 10b, fresh water W1 is sent into alcohol washing Disengagement zone L1 through pipeline 14, obtain mainly moisture, pure aqueous phase B 4 and mainly contain the organic phase O4 of unreacted hydrocarbon mixture, a small amount of low-molecular-weight ether light component. Described alcohol washing Disengagement zone L1 selects at least one water scrubber T1 or at least one group of static mixer Mn and knockout drum Vn. From reduce cost of equipment, save floor space, the angle that simplifies the operation considers the alcohol washing preferred static mixer in Disengagement zone of the present invention and knockout drum (referring to accompanying drawing 11,12). Mainly moisture, pure aqueous phase B 4 can be sent into the waste water treatment plant or further separate to reclaim alcohol; The organic phase O4 that mainly contains unreacted hydrocarbon mixture, a small amount of low-molecular-weight ether light component can be used as Organic Chemicals or liquefied gas etc., also can further separate so that the unreacted hydrocarbon mixture separates with low-molecular-weight ether, can also be circulated to etherification reaction zone R1 and/or be circulated to etherification reaction zone R2 through pipeline 16,16a, 18b, 18c, 18d and 8 through pipeline 16,16a, 18b, 18c, 18e and 18f that (can suppress the accessory substance such as low-molecular-weight ether generates, improve the selective of alcohol, referring to accompanying drawing 9), preferably further separate.
For the isoalkene with ether-splitting solution technique gained separates with alcohol, the production technology of isoalkene of the present invention and/or tert-alkyl ether when operation 1,2,3 and 4 exists or operation 1,2,3,4 and 5 when existing or operation 1,2,3,4,5 and 6 also comprise operation 7 (referring to accompanying drawing 7) when existing, in operation 7, to send into alcohol washing Disengagement zone L2 through pipeline 21 from the overhead fraction O6 of the fractionating column C4 of operation 4, fresh water is sent into alcohol washing Disengagement zone L2 through pipeline 24, obtain mainly moisture, pure aqueous phase B 7 and mainly contain the organic phase O8 of isoalkene, a small amount of low-molecular-weight ether light component. Described alcohol washing Disengagement zone L2 selects at least one water scrubber T2 or at least one group of static mixer Mm and knockout drum Vm. From reduce cost of equipment, save floor space, the angle that simplifies the operation considers the alcohol washing preferred static mixer in Disengagement zone of the present invention and knockout drum (referring to accompanying drawing 11,12). Mainly moisture, pure aqueous phase B 4 can be sent into the waste water treatment plant or further separate to reclaim alcohol; The organic phase O4 that mainly contains unreacted hydrocarbon mixture, a small amount of low-molecular-weight ether light component can be used as Organic Chemicals or liquefied gas etc., also can further separate to obtain purer isoalkene.
For the alcohol in the further recycle-water cut, the production technology of isoalkene of the present invention and/or tert-alkyl ether also comprises operation 8 (referring to accompanying drawing 8) at alcohol washing Disengagement zone L1 and/or pure the washing when Disengagement zone L2 exists, in operation 8, to contain from least a portion of operation 6 pure aqueous phase B 4 and send into alcohol recovery fractionating column C5 through pipeline 17, and/or will send into alcohol through pipeline 27 from containing of operation 7 of pure aqueous phase B 7 and reclaim fractionating column C5, with aqueous distillate B8 and the rich pure cut O9 that obtains poor alcohol. The rich pure cut O9 of at least a portion that cat head obtains (preferred most of) returns to etherification reaction zone R1 and/or etherification reaction zone R2 through pipeline 28,28a, 2,3 and/or 28,28b, 5b, 8, at least a portion at the bottom of the tower of fractionating column C5 (preferred most of) aqueous distillate B8 returns to alcohol washing Disengagement zone L1 and/or washing Disengagement zone L2, water at the bottom of the tower of a small amount of fractionating column C5 can be discharged through pipeline 29,29b. When alcohol washing Disengagement zone L1 and/or alcohol washing Disengagement zone L2 use recycle-water (recirculated water), can also add a part of fresh water W1 and/or W2 to alcohol washing Disengagement zone L1 and/or by pipeline 24,23 to alcohol washing Disengagement zone L2 by pipeline 14,13.
For further light component among the organic phase O4 being separated with the unreacted hydrocarbon mixture, the production technology of isoalkene of the present invention and/or tert-alkyl ether also comprises operation 9 (referring to accompanying drawing 9) when alcohol washing Disengagement zone L1 exists, in operation 9, to wash organic phase O4 that at least a portion that Disengagement zone L1 obtains (preferred most of) mainly contains unreacted hydrocarbon mixture, a small amount of low-molecular-weight ether light component from alcohol and send into the fractionating column C3 of operation 9 through pipeline 16, and mainly be contained low molecule ether light component O5 and mainly contain the fraction B 5 of unreacted hydrocarbon mixture. Mainly containing unreacted hydrocarbon mixture B5 cut discharges through pipeline 19; Mainly containing low molecule ether light component O5 can discharge through pipeline 18, can also return to etherification reaction zone R1 and/or return to etherification reaction zone R2 through pipeline 18a, 18b, 18c, 18d and 8 through pipeline 18a, 18b, 18c, 18e and 18f, preferred cycle is to etherification reaction zone R1 and/or R2, the accessory substances such as low-molecular-weight ether that can suppress among etherification reaction zone R1 and the R2 generate, and improve the selective of alcohol.
For further light component among the organic phase O8 being separated with isoalkene, to obtain the high-purity isoalkene, the production technology of isoalkene of the present invention and/or tert-alkyl ether also comprises operation 10 (referring to accompanying drawing 10) when alcohol washing Disengagement zone L2 exists, in operation 10, to wash the organic phase O8 that mainly contained isoalkene, a small amount of low-molecular-weight ether light component in the Disengagement zone from alcohol and send into the fractionating column C6 of operation 10 through pipeline 26, mainly be contained low molecule ether light component cut O10 and high-purity isoalkene fraction B 9. High-purity isoalkene B9 discharges through pipeline 31, can be used as polymer raw. Mainly containing low molecule ether light component cut O10 can discharge through pipeline 30, also at least a portion overhead fraction O10 can be returned etherification reaction zone R1 and/or returns etherification reaction zone R2 (referring to accompanying drawing 10) through pipeline 30,30a, 18b, 18c, 18d and 8 through pipeline 30,30a, 18b, 18c, 18e and 18f, preferred cycle is to etherification reaction zone R1 and/or R2, the accessory substances such as low-molecular-weight ether that can suppress among etherification reaction zone R1 and the R2 generate, and improve the selective of alcohol.
The isoalkene purifying of gained also can adopt the method (referring to accompanying drawing 13) of washing first aftercut after the production technology ether-splitting solution of isoalkene of the present invention and/or tert-alkyl ether, itself and the synthetic main distinction with the cracking process integration of above-mentioned tert-alkyl ether are: the alcohol washing Disengagement zone L2 that is introduced into operation 7 from the ether-splitting product P 3 of the ether cracking zone of operation 3, obtain moisture, pure aqueous phase B 7 and contain cracking tert-alkyl ether not, isoalkene, a small amount of organic phase O8a of low molecule ether light component, organic phase O8a from alcohol washing Disengagement zone L2 enters the fractionating column C4 of operation 4, mainly contained the cut O6a of isoalkene and low-molecular-weight ether and mainly contained the not fraction B 6a of cracking tert-alkyl ether, fractionating column C4 overhead fraction O6a enters fractionating column C6 tower, contain mainly not that the fraction B 6a of cracking tert-alkyl ether is circulated to ether-splitting solution reaction zone R3, the flow direction of other cut is synthetic identical with the cracking process integration with above-mentioned tert-alkyl ether.
The operating condition of each operation is as described below in the production technology of preparation isoalkene of the present invention and/or tert-alkyl ether: in operation 1, at least the reaction raw materials that contains a kind of mixing alkene of isoalkene and contain at least a kind of alcohol enters etherification reaction zone R1, and etherification reaction zone comprises at least one methyltertiarvbutyl ether reactor. The methyltertiarvbutyl ether reactor that prior art is announced all can be used for the present invention, as can be simple catalytic reactor, also can be the catalytic distillation reactor. Catalyst for etherification can be disclosed any catalyst that can be used for the isoalkene etherificate in the prior art, such as acidic catalyst (being generally the solid acid catalyst that is formed by organic acid esters) and mineral acid ester catalyst, the present invention preferentially selects solid acid resin catalyst such as Amberlyst15 or 35 (this catalyst can be bought from the market), the range of reaction temperature of etherification reaction zone R1 is 30 ℃～100 ℃, preferable range is 40 ℃～90 ℃, pressure limit is 0.1～4.0MPa, preferred pressure range is 0.1～2.5MPa, and the air speed scope of etherification reaction zone is 0.01～50hr-1, preferable range is 0.1～10hr-1 The alcohol that enters this etherification reaction zone can be the reuse alcohol from pure recovery tower C5, can be fresh alcohol also, and the alcohol that enters this etherification reaction zone is 0.3～5.0 with the scope that contains the hydrocarbon mixture weight ratio of isoalkene, and preferable range is 0.5～3.0.
The operating condition of fractionating column C1 in the operation 2 is as follows: the operating pressure scope of fractionating column C1 is at 0.1～3.0MPa, preferable range is 0.5～2.0MPa, the number of theoretical plate of this tower is between 3～80, preferable range between 10～50, the side line extraction position of this tower this tower stripping section 1/3～2/3 between.
The condition of the ether-splitting solution reaction zone in the operation 3 is as follows: ether-splitting solution reaction zone comprises at least one ether-splitting solution reactor, and the methyltertiarvbutyl ether reactor that prior art is announced all can be used for the present invention. Catalyst for etherification can be disclosed any catalyst that can be used for the ether-splitting solution in the prior art, preferably select solid acid catalyst, the present invention preferentially selects support type inorganic acid salt catalyst, this catalyst is to adopt the described method of GB1173128 patent to make, its acid quality general control is 20%～30%, the reaction pressure of this ether-splitting solution reaction zone is controlled between 0.1～3.0MPa, preferable range is between 0.1～1.2MPa, reaction temperature is between 50 ℃～300 ℃, preferable range is between 100 ℃～250 ℃, and the air speed of this ether-splitting solution reaction zone is at 0.5～50h-1Between, preferable range is at 1～10h-1Between.
The operating condition of fractionating column C4 in the operation 4 is as follows: the operating pressure scope is at 0.1～1.5MPa, and preferable range is 0.1～1.0MPa, and the number of theoretical plate of this tower is between 3～80, and preferable range is between 10～50.
Etherification reaction zone R2 operating condition in the operation 5 is as follows: the catalyst of packing among the etherification reaction zone R2 is with catalyst used in the operation 1, the scope of the reaction temperature of this etherification reaction zone is 30 ℃～100 ℃, preferable range is 40 ℃～90 ℃, the reaction pressure scope is 0.1～4.0Mpa, preferred pressure range is 0.1～2.5Mpa, and etherification reaction air speed scope is 0.01～50hr-1, preferable range is 0.1～5hr-1The alcohol that enters etherification reaction zone R2 can be the reuse alcohol from pure recovery tower C5, also can be fresh alcohol, can also be a part of fresh alcohol and a part of reuse alcohol, entering the alcohol of etherification reaction zone R2 and the scope of isoalkene weight ratio is 0.3～5.0, and preferable range is 0.5～3.0. The operating condition of fractionating column C2 in the operation 5 is as follows: the operating pressure scope is at 0.1～3.0MPa, and preferable range is 0.5～2.0MPa, and the number of theoretical plate of this tower is between 4～40.
The alcohol washing Disengagement zone L1 operating condition of operation 6 is as follows: the organic fraction that enters this washing Disengagement zone is 0.005～20 with the weight ratio that enters this Disengagement zone water, and preferable range is between 0.01～5. The operating pressure of this washing Disengagement zone is between 0.1～2.0MPa, and preferable range is between 0.1～1.5MPa, and operating temperature is 10 ℃～60 ℃.
The operating condition of the alcohol washing Disengagement zone L2 of operation 7 is as follows: containing pure cut is 0.005～20 with entering this Disengagement zone water weight ratio, and preferable range is between 0.01～5. The operating pressure of this washing Disengagement zone is between 0.1～2.0MPa, and preferable range is between 0.1～1.5MPa, and operating temperature is 10 ℃～60 ℃.
The operating condition of the fractionating column C5 of operation 8 is as follows: the operating pressure of this fractionating 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 operating condition of the fractionating column C3 of operation 9 is as follows: the operating pressure of this fractionating 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 5～50.
The operating condition of the fractionating column C6 of operation 10 is as follows: the operating pressure of this fractionating 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.
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 pure iso-butylene of cracking legal system (IB) and pure methyl-tert butylene ether (MTBE) 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.
Embodiment 1
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% (weight) in the mixed c 4 hydrocarbon, the material quantity that enters methyltertiarvbutyl ether reactor is 100kg/h, and Amberlyst15 solid acid resin catalyzer (ROHM ﹠amp is 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 separation column C1 through pipeline 4, the working pressure of separation column C1 is 0.9MPa, the number of theoretical plate of this tower is 35, the feed plate of this tower (is counted from first block of plate of cat head at the 17th block of plate, down with), the fraction B 1 that is rich in methyl tertiary butyl ether at the 25th block of plate of this tower through pipeline 6 extraction.Concrete technical process is referring to Fig. 1, and table 2 has provided the flow and the composition data of the side line extraction cut of separation column C1 in this technology.
Table 2
C1 tower side line B1 cut
????Wt％ ????Kg/hr
????H 2O ????0.007 ????0.002
????IB
All the other C4 ????0.028 ????0.008
????MeOH
????MTBE ????99.604 ????28.710
????MSBE ????0.045 ????0.013
????DME *
????TBA ????0.226 ????0.065
????DIB ????0.090 ????0.026
Add up to ????100.000 ????28.824
*The DME----dme
Embodiment 2
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 about 20% (weight) in the mixed c 4 hydrocarbon, the material quantity that enters methyltertiarvbutyl ether reactor is 100kg/h, catalyzer of loading in the methyltertiarvbutyl ether reactor and reactor operating condition are with embodiment 1, the working pressure of separation column C1 is 0.9MPa, the number of theoretical plate of this tower is 35, the feed plate of this tower is rich in the 23rd piece plate extraction of the fraction B 1 of methyl tertiary butyl ether at this tower at the 17th block of plate.Its flow process is seen accompanying drawing 1, and other condition is with embodiment 1, and table 3 has provided the flow and the composition data of the side line extraction cut of separation column C1 in this technology.
Table 3
C1 tower side line B1 cut
????Wt％ ????Kg/hr
????H 2O ????0.009 ????0.003
????IB
All the other C4 ????0.032 ????0.009
????MeOH
????MTBE ????99.601 ????28.709
????MSBE ????0.046 ????0.013
????DME
????TBA ????0.224 ????0.646
????DIB ????0.088 ????0.025
Add up to ????100.000 ????28.824
Embodiment 3
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 about 20% (weight) in the mixed c 4 hydrocarbon, the material quantity that enters methyltertiarvbutyl ether reactor is 100kg/h, catalyzer of loading in the methyltertiarvbutyl ether reactor and reactor operating condition are with embodiment 1, the working pressure of separation column C1 is 0.9MPa, the number of theoretical plate of this tower is 35, the feed plate of this tower is rich in the 28th piece plate extraction of the fraction B 1 of methyl tertiary butyl ether at this tower at the 17th block of plate.Its flow process is seen accompanying drawing 1, and other condition is with embodiment 1, and table 4 has provided the flow and the composition data of the side line extraction cut of separation column C1 in this technology.
Table 4
C1 tower side line B1 cut
????Wt％ ????Kg/hr
????H 2O ????0.004 ????0.001
????IB
All the other C4 ????0.022 ????0.006
????MeOH
????MTBE ????99.575 ????28.701
????MSBE ????0.043 ????0.012
????DME
????TBA ????0.256 ????0.074
????DIB ????0.100 ????0.029
Add up to ????100.000 ????28.824
Comparative Examples 1
Contain the mixed c 4 hydrocarbon of iso-butylene and methyl alcohol respectively through pipeline 1,2 and 3 enter methyltertiarvbutyl ether reactor R1, the content of iso-butylene is about 20% (weight) in the mixed c 4 hydrocarbon, the material quantity that enters methyltertiarvbutyl ether reactor is 100kg/h, catalyzer of loading in the methyltertiarvbutyl ether reactor and reactor operating condition are with embodiment 1, etherification product P1 enters through pipeline 4 and enters separation column C1a, the working pressure of separation column C1a is 0.9MPa, the number of theoretical plate of this tower is 25, the tower bottom distillate B1a of separation column C1a enters separation column C1b through pipeline 7a, the working pressure of separation column C1b is 1.3MPa, number of theoretical plate is 25, the cut of discharging through pipeline 7 at the bottom of the separation column C1b tower contains the dimerization tertiary olefin, the heavy constituent such as (MSBE) of methyl sec-butyl ether, the overhead fraction B1 of separation column C1b enters ether-splitting through pipeline 6 and separates reactor R3, its idiographic flow is referring to Figure 14, with 3.5 ten thousand tons of/year MTBE synthetic with cracking associating preparing high-purity iso-butylene production equipment be example, the energy consumption data of separation column C1b sees Table 5, and table 6 is the flow of relevant cut in this technical process and forms data.
Table 5
Embodiment 1 Comparative Examples 1
The C1 separation column The C1a separation column The C1b separation column *
Year steam consumption (ten thousand tons) ????70.7 ??70.7 ????16.4
Year cooling water amount (ten thousand tons) ????390.6 ??390.6 ????102.6
Year current consumption (KWH) ????7.85×10 5 ??7.85×10 6 ????2.7×10 5
*When going into operation per year several 7200
Table 6
B1a cut at the bottom of the C1a Tata C1b column overhead B1 cut
???Wt％ ????kg/hr ??Wt％ ????kg/hr
??H 2O ??0.007 ????0.002 ?0.007 ?0.002
??IB
All the other C4 ??0.027 ????0.008 ?0.028 ?0.008
??MeOH
??MTBE ??98.853 ????29.212 ?99.604 ?28.710
??MSBE ??0.044 ????0.013 ?0.045 ?0.013
??DME
??TBA ??0.220 ????0.065 ?0.226 ?0.065
??DIB ??0.849 ????0.251 ?0.090 ?0.026
Add up to ??100.000 ????29.551 ?100.000 ?28.824
As can be seen from Table 6, Diisobutylene in the tower bottom distillate of separation column C1 (DIB) content is higher, can not satisfy the requirement of cracking stock, separation column C1a tower bottom distillate is after separation column C1b is refining, though satisfied the requirement of cracking stock, because of having increased a separation column C1b, and the energy consumption (seeing Table 5) of this system that increases, simultaneously, the corresponding certain device expense that increased.The present invention adopts side line extraction methyl tertiary butyl ether (MTBE) then to overcome above-mentioned shortcoming at separation column C1.Embodiment 4
Contain the mixed c 4 hydrocarbon of iso-butylene and methyl alcohol respectively through pipeline 1,2 and 3 enter methyltertiarvbutyl ether reactor R1, the content of iso-butylene is about 20% (weight) in the mixed c 4 hydrocarbon, the material quantity that enters methyltertiarvbutyl ether reactor is 100kg/h, catalyzer of loading in the methyltertiarvbutyl ether reactor and reactor operating condition are with embodiment 1, etherification product P1 enters separation column C1 through pipeline 4, the operational condition of separation column C1 is with embodiment 1, separation column C1 overhead fraction O1 enters methyltertiarvbutyl ether reactor R2 through pipeline 5, the catalyzer that is equipped with in this reactor is with the catalyzer among the methyltertiarvbutyl ether reactor R1,50 ℃ of the temperature of reaction of this reactor, reaction pressure is 0.9MPa, the air speed 2hr of methyltertiarvbutyl ether reactor -1, the reaction product P2 of methyltertiarvbutyl ether reactor R2 enters separation column C2 through pipeline 9, and the working pressure of separation column C2 is 0.7MPa, and the number of theoretical plate of this tower is 30, and C2 separation column tower bottom distillate B3 is through pipeline 12, and 12a returns separation column C1.Idiographic flow is referring to Fig. 3, and the flow of the relevant cut of this flow process and composition data see Table 7.
Table 7
C1 tower side line B1 cut B2 cut at the bottom of the C2 Tata
??Wt％ ??kg/hr ??Wt％ ??kg/hr
????H 2O ??0.007 ?0.002
????IB ??0.003 ?0.001
All the other C4 ??0.276 ?0.008
????MeOH
????MTBE ??99.541 ?28.846 ????97.204 ??4.277
????MSBE ??0.045 ?0.013 ????0.182 ??0.008
????DME
????TBA ??0.276 ?0.080 ????1.614 ??0.071
????DIB ??0.100 ?0.029 ????1.000 ??0.044
Add up to ??100.000 ?28.979 ????100.000 ??4.400
Comparative Examples 2
Substantially with embodiment 2, just C2 separation column tower bottom distillate B3 does not return separation column C1.Its flow process is not referring to Fig. 3 (using pipeline 12a among the figure), and the operation of equipment condition in this flow process is with embodiment 4, and table 8 has provided the composition content of this flow process related component.
Table 8
C1 tower side line B1 cut B2 cut at the bottom of the C2 Tata
??Wt％ ????kg/hr ??Wt％ ??kg/hr
????H 2O ??0.004 ????0.001
????IB
All the other C4 ??0.027 ????0.007
????MeOH
????MTBE ??99.681 ????25.970 ??98.006 ??4.275
????MSBE ??0.031 ????0.008 ??0.183 ??0.008
????DME
????TBA ??0.157 ????0.041 ??0.802 ??0.035
????DIB ??0.100 ????0.026 ??1.009 ??0.044
Add up to ??100.000 ????26.053 ??100.000 ??4.362
As can be seen from Table 8, adopt at the bottom of the fractionation Tata the line of return to separation column C1 import, the fraction B 1 of separation column C1 tower side line extraction still can satisfy the requirement of cracking stock, can increase like this to enter the material quantity that ether-splitting is separated reactor, and its result increases the product volume of high-purity isoolefine.
Embodiment 5
Contain the mixed c 4 hydrocarbon of iso-butylene and methyl alcohol respectively through pipeline 1,2 and 3 enter methyltertiarvbutyl ether reactor R1, the content of iso-butylene is about 20% (weight) in the mixed c 4 hydrocarbon, the material quantity that enters methyltertiarvbutyl ether reactor is 100kg/h, catalyzer of loading in the methyltertiarvbutyl ether reactor and reaction conditions are with embodiment 1, etherification reaction product P 1 enters separation column C1 through pipeline 4, the operational condition of separation column C1 and appointed condition are with embodiment 1, separation column C1 overhead fraction O1 is through pipeline 5,5b enters methyltertiarvbutyl ether reactor R2, the reaction product P2 of methyltertiarvbutyl ether reactor R2 enters separation column C2 through pipeline 9, the operational condition of methyltertiarvbutyl ether reactor R2 and separation column C2 and appointed condition are with embodiment 4, C2 separation column tower bottom distillate B3 is through pipeline 12,12a returns separation column C1, C2 fractionator overhead cut O2 enters alcohol washing disengaging zone L1, two static mixers and two separating tanks (separating tank is the horizontal tank of band baffle plate) are adopted in this washing disengaging zone, C2 fractionator overhead cut O2 enters static mixer Mn1, mix after pipeline 15 enters separating tank Vn1 with fresh water W1, entering the fresh water W1 of static mixer and the weight ratio of organic fraction O2 is 0.5, isolated organic phase O3a enters static mixer Mn2 through pipeline 15a from Vn1, mix after pipeline 15b enters separating tank Vn2 with fresh water W1a, entering the fresh water W1a of static mixer Mn2 and the weight ratio of organic fraction O3a is 0.4, isolated organic phase O4 enters separation column C3 through pipeline 16 from Vn2, static mixer Mn1, Mn2 and separating tank Vn1, the working pressure of Vn2 is 0.6MPa, service temperature is 40 ℃, the working pressure of separation column C3 is 0.8MPa, number of theoretical plate is 25, C3 column overhead cut O5 is through pipeline 18,18b returns methyltertiarvbutyl ether reactor R1, the side line extraction fraction B 1 of separation column C1 enters ether-splitting through pipeline 6 and separates reactor R3, it is solid acid catalyst that the ether-splitting that is equipped with among the reactor R3 is separated catalyzer, this catalyzer is to adopt the described method of GB1173128 patent to make, its sulfate radical content is 20%, the reaction pressure that this ether-splitting is separated reactor is 0.55MPa, temperature of reaction is at 200 ℃, reaction velocity 2h -1Between, separate the product P 3 that reactor obtains from ether-splitting and enter separation column C4, the working pressure of separation column C4 is 0.8MPa, number of theoretical plate is 25, the overhead fraction O6 of separation column C4 enters static mixer Mm1, mix after pipeline 25 enters Vm1 with fresh water W2, the weight ratio of fresh water W2 and organic fraction O6 is 0.5, enter static mixer Mm2 from the isolated organic phase O7a of separating tank Vm1 through pipeline 25a, mix after pipeline 25b enters Vm2 with fresh water W2a, the weight ratio of fresh water W2 and organic fraction O7a is 0.4, enter separation column C6 from the isolated organic phase O8 of separating tank Vm2 through pipeline 26, static mixer Mm1, Mm2 and separating tank Vm1, the working pressure of Vm1 is 0.6Mpa, service temperature is 40 ℃, the working pressure of separation column C 6 is 0.7MPa, number of theoretical plate is 35, C6 column overhead cut O10 returns methyltertiarvbutyl ether reactor R1 through pipeline 30 and 18b, obtain purity at the bottom of the separation column C6 tower and be 99.95% iso-butylene, this product can be used as the monomer of polymerization product, its technical process is referring to Figure 15, and table 9～table 13 has provided the mass flow of each equipment of turnover in this technical process.
Table 9
The R1 cut (kg/h) that enters the mouth R1 exports P1 cut (kg/h) C1 tower import cut (kg/h) C1 cat head O1 cut (kg/h) C1 side line B1 cut (kg/h)
H2O ?0.027 ?0.029 ?0.029 ?0.027 ?0.002
IB ?19.969 ?3.103 ?3.103 ?3.103
All the other C4 ?68.371 ?68.366 ?68.366 ?68.358 ?0.008
MeOH ?12.019 ?2.408 ?2.408 ?2.408
MTBE ?26.202 ?29.213 ?0.001 ?28.710
MSBE ?0.008 ?0.013 ?0.013
DME ?0.102 ?0.162 ?0.162 ?0.162
TBA ?0.090 ?0.114 ?0.049 ?0.065
DIB ?0.120 ?0.151 ?0.026
Add up to 100.488 ?100.488 ?103.559 ?74.108 ?28.824
Table 10
B2 cut (kg/h) at the bottom of the C1 tower C2 tower import cut (kg/h) C2 cat head O2 cut (kg/h) B3 cut (kg/h) at the bottom of the C2 tower The Mn1 W1 (kg/h) of intaking
H 2O ????0.048 ????0.047 ????0.001 ???35.424
IB ????0.310 ????0.310
All the other C4 ????68.354 ????68.354
MeOH ????1.886 ????1.886
MTBE ?0.502 ????4.301 ????0.001 ????4.300
MSBE ????0.008 ????0.008
DME ????0.220 ????0.220
TBA ????0.064 ????0.029 ????0.035
DIB ?0.125 ????0.045 ????0.045
Add up to ?0.627 ????75.236 ????70.847 ????4.389 ??35.424
Table 11
The Mn2 W1a (kg/h) of intaking Vn2 exports organic phase O4 (kg/h) C3 cat head O5 cut (kg/h) B5 cut (kg/h) at the bottom of the C3 tower
H2O ?28.328 ????0.038 ????0.038
IB ????0.308 ??0.005 ????0.303
All the other C4 ????68.340 ??0.532 ????67.808
MeOH ????0.001 ??0.001
MTBE ????0.001 ????0.001
MSBE
DME ????0.140 ??0.136 ????0.004
TBA
DIB
Add up to 28.328 ????68.828 ??0.674 ????68.154
Table 12
R3 exports P3 cut (kg/h) C4 cat head O6 cut (kg/h) B6 cut (kg/h) at the bottom of the C4 tower The Mm1 W2 (kg/h) of intaking
??H 2O ????0.067 ??0.067 ??8.584
??IB ????16.294 ??16.294
All the other C4 ????0.008 ??0.008
?MeOH ????9.111 ??0.730 ??8.381
?MTBE ????3.129 ??3.129
?MSBE ????0.012 ??0.012
?DME ????0.135 ??0.135
?TBA ????0.013 ??0.013
?DIB ????0.055 ??0.055
Add up to ????28.824 ??17.167 ??11.657 ??8.584
Table 13
The Mm2 W2a (kg/h) of intaking Vm2 exports organic phase O8 (kg/h) C6 cat head O10 cut (kg/h) B9 cut (kg/h) at the bottom of the C6 tower
??H2O ??6.866 ????0.012 ??0.012
??IB ????16.294 ??0.234 ????16.060
All the other C4 ????0.008 ????0.008
???MeOH
???MTBE
???MSBE
???DME ????0.068 ??0.068
???TBA
???DIB
Add up to ??6.866 ????16.382 ??0.314 ????16.068
Embodiment 6
Substantially the same manner as Example 5, just separation column C3 overhead fraction O5 and separation column C6 overhead fraction O10 do not return the direct extraction of first methyltertiarvbutyl ether reactor.Its flow process is referring to Figure 15, do not use among the figure separation column C3 and separation column C6 to the return wire of methyltertiarvbutyl ether reactor R1.The operational condition of major equipment is with embodiment 5 in this technology, and table 14 has provided the interior technology of the present invention of certain hour and traditional technology optionally influences methyl alcohol in this system, and table 15～table 19 has provided the mass flow of each equipment of turnover in this technical process.
Table 14
Improve technology (embodiment 5) Traditional technology (embodiment 6)
Methyl alcohol selectivity (%) The etherification reaction time (0～6 month) ????99 ????99
The etherification reaction time (7 months) ????99 ????98
Table 15
The R1 cut (kg/h) that enters the mouth R1 exports P1 cut (kg/h) C1 tower import cut (kg/h) C1 cat head O1 cut (kg/h) C1 side line B1 cut (kg/h) B2 cut (kg/h) at the bottom of the C1 tower
H 2O ?0.027 ?0.038 ?0.039 ?0.037 ?0.002
IB ?19.849 ?3.085 ?3.086 ?3.085 ?0.001
All the other C4 ?68.105 ?68.101 ?68.852 ?68.844 ?0.008
MeOH ?12.019 ?2.428 ?2.428 ?2.428
MTBE ?26.045 ?29.039 ?28.846 ?0.193
MSBE ?0.007 ?0.013 ?0.013
DME ?0.086 ?0.086 ?0.086
TBA ?0.089 ?0.139 ?0.059 ?0.080
DIB ?0.121 ?0.150 ?0.029 ?0.121
Add up to 100.000 ?100.000 ?103.832 ?74.539 ?28.979 ?0.314
Table 16
B2 cut (kg/h) at the bottom of the C1 tower C2 tower import cut (kg/h) C2 cat head O2 cut (kg/h) B3 cut (kg/h) at the bottom of the C2 tower The Mn1 W1 (kg/h) of intaking
H 2O ????0.058 ????0.058 ?35.634
IB ????0.308 ????0.308
All the other C4 ????68.840 ????68.840
MeOH ????1.915 ????1.915
MTBE ?0.193 ????4.277 ????4.277
MSBE ????0.008 ????0.008
DME ????0.144 ????0.144
TBA ????0.074 ????0.003 ????0.071
DIB ?0.121 ????0.044 ????0.044
Add up to ?0.314 ????75.668 ????71.268 ????4.400 ??35.634
Table 17
The Mn2 W1a (kg/h) of intaking Vn2 exports organic phase O4 (kg/h) C3 cat head O5 cut (kg/h) B5 cut (kg/h) at the bottom of the C3 tower
H 2O ?28.507 ????0.038 ????0.038
IB ????0.305 ????0.005 ????0.300
All the other C4 ????68.827 ????0.540 ????68.287
MeOH ????0.001 ????0.001
MTBE
MSBE
DME ????0.092 ????0.088 ????0.004
TBA
DIB
Add up to ?28.507 ????69.263 ????0.634 ????68.629
Table 18
R3 exports P3 cut (kg/h) C4 cat head O6 cut (kg/h) B6 cut (kg/h) at the bottom of the C4 tower The Mm1 W2 (kg/h) of intaking
H 2O ??0.070 ????0.070 ????8.624
IB ??16.375 ????16.375
All the other C4 ??0.008 ????0.008
MeOH ??9.154 ????0.729 ????8.425
MTBE ??3.144 ????3.144
MSBE ??0.012 ????0.012
DME ??0.136 ????0.136
TBA ??0.016 ????0.016
DIB ??0.061 ????0.061
Add up to ??28.976 ????17.248 ????11.728 ????8.624
Table 19
The Mm2 W2a (kg/h) of intaking Vm2 exports organic phase O8 (kg/h) C6 cat head O10 cut (kg/h) B9 cut (kg/h) at the bottom of the C6 tower
H 2O ??6.900 ??0.012 ????0.012
IB ??16.373 ????0.201 ????16.172
All the other C4 ??0.008 ????0.008
MeOH
MTBE
MSBE
DME ??0.068 ????0.068
TBA
DIB
Add up to ???6.900 ??16.461 ????0.281 ????16.180
From embodiment 5 and Comparative Examples 3 as can be seen, set up separation column C3 overhead fraction O5 and to the return wire of methyltertiarvbutyl ether reactor R1 with set up the return wire of separation column C4 overhead fraction O7 to methyltertiarvbutyl ether reactor R1, can suppress the generation of the side reaction thing (dme) in the etherification reaction, improve the selectivity of methyl alcohol, promptly improve the utilization ratio of the methyl alcohol in the total system.
Embodiment 7
Substantially the same manner as Example 5, just alcohol washing disengaging zone L1 and L2 respectively adopt a water wash column, the fresh water and the organic weight ratio of heating up in a steamer four fens that enter these two water wash columns all are 0.9, the working pressure of two water wash columns is 0.6MPa, service temperature is 40 ℃, its flow process is referring to Figure 16, the operational condition of major equipment is with embodiment 5 in this technology, table 20～table 24 has provided the mass flow of each equipment of turnover in this technical process, and the cost of equipment of water wash column sees Table 25 in the static mixer among the embodiment 5 and the installation cost of separating tank and this example.
Table 20
The R1 cut (kg/h) that enters the mouth R1 exports P1 cut (kg/h) C1 tower import cut (kg/h) C1 cat head O1 cut (kg/h) C1 side line B1 cut (kg/h)
H 2O ?0.027 ?0.028 ?0.028 ?0.027 ?0.001
IB ?19.969 ?3.102 ?3.102 ?3.102
All the other C4 ?68.371 ?68.366 ?68.366 ?68.358 ?0.008
MeOH ?12.019 ?2.409 ?2.409 ?2.409
MTBE ?26.202 ?29.213 ?0.001 ?28.710
MSBE ?0.010 ?0.014 ?0.014
DME ?0.102 ?0.160 ?0.160 ?0.160
TBA ?0.090 ?0.114 ?0.049 ?0.065
DIB ?0.121 ?0.151 ?0.026
Add up to ?100.488 ?100.488 ?103.557 ?74.106 ?28.824
Table 21
B2 cut (kg/h) at the bottom of the C1 tower C2 tower import cut (kg/h) C2 cat head O2 cut (kg/h) B3 cut (kg/h) at the bottom of the C2 tower T1 import water W1 (kg/h)
??H 2O ????0.048 ??0.047 ????0.001 ??63.752
??IB ????0.311 ??0.311
All the other C4 ????68.354 ??68.354
??MeOH ????1.885 ??1.885
??MTBE ?0.502 ????4.301 ??0.001 ????4.300
??MSBE ????0.008 ????0.008
??DME ????0.220 ??0.220
??TBA ????0.064 ??0.029 ????0.035
??DIB ?0.125 ????0.045 ????0.045
Add up to ?0.627 ????75.236 ??70.847 ????4.389 ???63.752
Table 22
T1 exports organic phase O4 (kg/h) T1 exports aqueous phase B 4 (kg/h) C3 cat head O5 cut (kg/h) B5 cut (kg/h) at the bottom of the C3 tower
H 2O ?0.038 ????63.761 ????0.038
IB ?0.309 ????0.002 ??0.006 ????0.303
All the other C4 ?68.340 ????0.014 ??0.532 ????67.808
MeOH ?0.001 ????1.884 ??0.001
MTBE ?0.001 ????0.001
MSBE
DME ?0.140 ????0.080 ?0.136 ????0.004
TBA ????0.029
DIB
Add up to ?68.829 ????65.770 ?0.675 ????68.154
Table 23
R3 exports P3 cut (kg/h) C4 cat head O6 cut (kg/h) B6 cut (kg/h) at the bottom of the C4 tower The T2 W2 (kg/h) of intaking
H 2O ????0.067 ??0.067 ????15.450
IB ????16.295 ????16.295
All the other C4 ????0.008 ????0.008
MeOH ????9.112 ????0.731 ??8.381
MTBE ????3.127 ??3.127
MSBE ????0.012 ??0.012
DME ????0.135 ????0.135
TBA ????0.013 ??0.013
DIB ????0.055 ??0.055
Add up to ????28.824 ????17.169 ??11.655 ????15.450
Table 24
T2 exports organic phase O8 (kg/h) T2 exports aqueous phase B 7 (kg/h) C6 cat head O10 cut (kg/h) B9 cut (kg/h) at the bottom of the C6 tower
??H 2O ??0.012 ????15.438 ??0.012
??IB ??16.295 ??0.235 ?????16.060
All the other C4 ??0.008 ?????0.008
??MeOH ????0.731
??MTBE
??MSBE
??DME ??0.068 ????0.067 ??0.068
??TBA
??DIB
Add up to ??16.383 ????16.236 ??0.315 ????16.068
Table 25
Embodiment 5 Embodiment 7
Static mixer Separating tank Water wash column
Cost of equipment (ten thousand yuan) ????0.5 ????2.0 ????18
Add up to (ten thousand yuan) ????2.5 ????18
As can be seen from Table 25, adopt static mixer to replace water wash column can save certain device expense (about 17.5 ten thousand yuan) in alcohol washing disengaging zone, therefore, the present invention when choosing pure water wash zone equipment, preferred static mixer and separating tank.
In a word, illustrated that by above embodiment and Comparative Examples but the profit reduction and reserving section inside cord extraction at first separation column meets the different tert-alkyl ether product of high purity that cracking requires, like this when preparation tert-alkyl ether and/or isoolefine, can save cost of equipment and energy consumption, the present invention simultaneously is by setting up in second etherification reaction zone return wire at the bottom of the fractionation Tata, but meet the ether product innovation that cracking requires in the same extraction of the side line of separation column C1, the present invention also adopts isolated low-molecular-weight ether lighting end to be circulated to the ether synthesis reactor, the side reaction that can suppress in the etherification reaction generates, to improve the utilization ratio of this system's alcohol.Also that prior art is the used water wash column of the present invention changes static mixer and separating tank into, with further saving cost of equipment.

Claims (65)

1. the production technique of isoolefine and/or tert-alkyl ether comprises following operation:
(1) hydrocarbon mixture and at least a alcohol that will contain a kind of isoolefine is at least sent into the etherification reaction zone (R1) that catalyst for etherification is housed, to make the product (P1) that contains a kind of tert-alkyl ether at least;
(2) at least a portion product (P1) that operation (1) is obtained is sent into separation column (C1), with the organic fraction (B1) of the organic fraction (O1) that obtains mainly to contain unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent, high purity tert-alkyl ether with mainly contain secondary alkyl oxide, hang down the cut (B2) of polyisoolefines heavy constituent;
It is characterized in that the side line extraction of the high purity tert-alkyl ether cut (B1) of operation (2) gained from first separation column (C1), this side line extraction mouth is located in the stripping section of this tower; The organic fraction (O1) that mainly contains unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent is discharged from cat head; And the cut (B2) that mainly contains secondary alkyl oxide, low polyisoolefines heavy constituent is discharged at the bottom of this Tata.
2. the production technique of isoolefine according to claim 1 and/or tert-alkyl ether is characterized in that described side line extraction mouth is located at the position of the 1/3-2/3 of this tower stripping section.
3. the production technique of isoolefine according to claim 1 and/or tert-alkyl ether is characterized in that also comprising operation (5), and operation (5) comprises at least one group of etherification reaction zone and separation column.
4. the production technique of isoolefine according to claim 3 and/or tert-alkyl ether, it is characterized in that at least a portion cut (O1) that will obtain from the separation column (C1) of operation (2) sends into etherification reaction zone (R2), make and mainly contain tert-alkyl ether, the unreacted hydrocarbon mixture, the product (P2) of unreacting alcohol and a spot of lower molecular weight ether light constituent, at least a portion product (P2) that again etherification reaction zone is made is sent into separation column (C2), to obtain mainly to contain the unreacted hydrocarbon mixture, unreacting alcohol, the overhead fraction (O2) of a small amount of lower molecular weight ether light constituent, the tower bottom distillate (B2a) and the high purity tert-alkyl ether side stream (B1a) that contain heavy constituent, the cut (B1a) of at least a portion high purity tert-alkyl ether of gained is directly sent into ether-splitting and is separated reaction zone (R3) from the interior side line extraction of first separation column (C1) stripping section.
5. the production technique of isoolefine according to claim 3 and/or tert-alkyl ether, it is characterized in that at least a portion cut (O1) that will obtain from the separation column (C1) of operation (2) sends into etherification reaction zone (R2), make and mainly contain tert-alkyl ether, the unreacted hydrocarbon mixture, the product (P2) of unreacting alcohol and a spot of lower molecular weight ether light constituent, at least a portion product (P2) that again etherification reaction zone is made is sent into separation column (C2), to obtain mainly to contain the unreacted hydrocarbon mixture, unreacting alcohol, the overhead fraction (O2a) of a small amount of lower molecular weight ether light constituent and mainly contain tert-alkyl ether, the tower bottom distillate (B3) that contains heavy constituent, at least a portion tower bottom distillate (B3) of gained is sent into the separation column (C1) of operation (2).
6. according to the production technique of each described isoolefine of claim 1-5 and/or tert-alkyl ether, it is characterized in that also comprising operation (6), in operation (6), at least a portion overhead fraction (O1) that will obtain from the separation column (C1) of operation (2) and/or at least a portion overhead fraction (O2) that obtains from the separation column of operation (5) or (O2a) send into alcohol washing disengaging zone (L1) are to obtain mainly moisture, pure water (B4) and mainly to contain unreacted hydrocarbon mixture, the organic phase (O4) of lower molecular weight ether light constituent on a small quantity.
7. the production technique of isoolefine according to claim 6 and/or tert-alkyl ether is characterized in that described alcohol washing disengaging zone (L1) selects at least one water wash column (T1) for use.
8. the production technique of isoolefine according to claim 6 and/or tert-alkyl ether is characterized in that described alcohol washing disengaging zone (L1) selects at least one group of static mixer (Mn) and separating tank (Vn) for use.
9. according to the production technique of each described isoolefine of claim 6-8 and/or tert-alkyl ether, it is characterized in that also comprising operation (8), in operation (8), to send into separation column (C5) from least a portion water (B4) of operation (6), with aqueous distillate (B8) and the rich pure cut (O9) that obtains poor alcohol.
10. the production technique of isoolefine according to claim 9 and/or tert-alkyl ether is characterized in that the pure cut of the described richness of at least a portion (O9) is circulated to the etherification reaction zone (R1) of operation (1) and/or the etherification reaction zone (R2) of operation (5).
11. the production technique of isoolefine according to claim 9 and/or tert-alkyl ether is characterized in that the described aqueous distillate of at least a portion (B8) is circulated to the alcohol washing disengaging zone (L1) of operation (6).
12., it is characterized in that fresh water (W1) is introduced alcohol washing disengaging zone (L1) according to the production technique of each described isoolefine of claim 6-11 and/or tert-alkyl ether.
13. production technique according to each described isoolefine of claim 6-11 and/or tert-alkyl ether, it is characterized in that also comprising operation (9), in operation (9), at least a portion organic phase (O4) of operation (6) is sent into separation column (C3), with the cut (B5) that obtains mainly to contain the light constituent cut (O5) of lower molecular weight ether and mainly contain the unreacted hydrocarbon mixture.
14. the production technique of isoolefine according to claim 13 and/or tert-alkyl ether is characterized in that the described overhead fraction of at least a portion (O5) is circulated to the etherification reaction zone (R1) of operation (1) and/or the etherification reaction zone (R2) of operation (5).
15. according to the production technique of each described isoolefine of claim 1-8 and/or tert-alkyl ether, at least a portion cut (O1) that it is characterized in that the separation column from operation (2) is obtained, at least a portion cut (O2) that obtains from the separation column of operation (5) or (O2a) or from least a portion organic phase (O4) that operation (6) obtains be circulated to the etherification reaction zone (R1) of operation (1) and/or the etherification reaction zone (R2) of operation (5).
16. the production technique of isoolefine and/or tert-alkyl ether comprises following operation:
(1) hydrocarbon mixture and at least a alcohol that will contain a kind of isoolefine is at least sent into the etherification reaction zone (R1) that catalyst for etherification is housed, to make the product (P1) that contains a kind of tert-alkyl ether at least;
(2) at least a portion product (P1) that operation (1) is obtained is sent into separation column (C1), with the organic fraction (B1) of the organic fraction (O1) that obtains mainly to contain unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent, high purity tert-alkyl ether with mainly contain secondary alkyl oxide, hang down the cut (B2) of polyisoolefines heavy constituent;
(3) side stream (B1) of at least a portion high purity tert-alkyl ether that operation (2) is obtained is sent into and ether-splitting is housed is separated the ether-splitting of catalyzer and separate reaction zone (R3), to make the product (P3) that contains at least a isoolefine and at least a alcohol;
(4) product (P3) that operation (3) is obtained is sent into separation column (C4), with the light constituent cut (O6) that obtains mainly to contain the resulting most of isoolefine of operation (3), a small amount of alcohol, a small amount of lower molecular weight ether with mainly contain alcohol, the cut of cracking tert-alkyl ether (B6) not;
It is characterized in that the side line extraction of the high purity tert-alkyl ether cut (B1) of operation (2) gained from first separation column (C1), this side line extraction mouth is located in the stripping section of this tower; The organic fraction (O1) that mainly contains unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent is discharged from cat head; And the cut (B2) that mainly contains secondary alkyl oxide, low polyisoolefines heavy constituent is discharged at the bottom of this Tata.
17. the production technique of isoolefine according to claim 16 and/or tert-alkyl ether is characterized in that described side line extraction mouth is located at the position of the 1/3-2/3 of this tower stripping section.
18. the production technique of isoolefine according to claim 16 and/or tert-alkyl ether is characterized in that at least a portion cut (B1) is sent into the fuel dope basin, rest part is sent into ether-splitting separate operation (3).
19. the production technique of isoolefine according to claim 16 and/or tert-alkyl ether is characterized in that also comprising operation (5), operation (5) comprises at least one group of etherification reaction zone and separation column.
20. the production technique of isoolefine according to claim 19 and/or tert-alkyl ether, it is characterized in that at least a portion cut (O1) that will obtain from the separation column (C1) of operation (2) sends into etherification reaction zone (R2), make and mainly contain tert-alkyl ether, the unreacted hydrocarbon mixture, the product (P2) of unreacting alcohol and a spot of lower molecular weight ether light constituent, at least a portion product (P2) that again etherification reaction zone is made is sent into separation column (C2), to obtain mainly to contain the unreacted hydrocarbon mixture, unreacting alcohol, the overhead fraction (O2) of a small amount of lower molecular weight ether light constituent, the tower bottom distillate (B2a) and the high purity tert-alkyl ether side stream (B1a) that contain heavy constituent, the cut (B1a) of at least a portion high purity tert-alkyl ether of gained is directly sent into ether-splitting and is separated reaction zone (R3) from the interior side line extraction of first separation column (C1) stripping section.
21. the production technique of isoolefine according to claim 19 and/or tert-alkyl ether, it is characterized in that at least a portion cut (O1) that will obtain from the separation column (C1) of operation (2) sends into etherification reaction zone (R2), make and mainly contain tert-alkyl ether, the unreacted hydrocarbon mixture, the product (P2) of unreacting alcohol and a spot of lower molecular weight ether light constituent, at least a portion product (P2) that again etherification reaction zone is made is sent into separation column (C2), to obtain mainly to contain the unreacted hydrocarbon mixture, unreacting alcohol, the overhead fraction (O2a) of a small amount of lower molecular weight ether light constituent and mainly contain tert-alkyl ether, the tower bottom distillate (B3) that contains heavy constituent, at least a portion tower bottom distillate of gained are sent into the separation column (C1) of operation (2).
22., it is characterized in that at least a portion cut (B6) is sent into reaction zone (R1) and/or reaction zone (R2) according to the production technique of claim 16 or 20 described isoolefine and/or tert-alkyl ether.
23. production technique according to claim 16,19,20 or 21 described isoolefine and/or tert-alkyl ether, it is characterized in that also comprising operation (6), in operation (6), at least a portion overhead fraction (O1) that will obtain from the separation column (C1) of operation (2) and/or at least a portion overhead fraction (O2) that obtains from the separation column of operation (5) or (O2a) send into alcohol washing disengaging zone (L1) are to obtain mainly moisture, pure water (B4) and mainly to contain unreacted hydrocarbon mixture, the organic phase (O4) of lower molecular weight ether light constituent on a small quantity.
24. the production technique of isoolefine according to claim 23 and/or tert-alkyl ether is characterized in that described alcohol washing disengaging zone (L1) selects at least one water wash column (T1) for use.
25., it is characterized in that described alcohol washing disengaging zone (L1) selects at least one group of static mixer (Mn) and separating tank (Vn) for use according to the production technique of claim 23 described isoolefine and/or tert-alkyl ether.
26. production technique according to claim 16,19,20 or 21 described isoolefine and/or tert-alkyl ether, it is characterized in that also comprising operation (7), at least a portion cut (O6) that will obtain from the separation column (C4) of operation (4) in operation (7) is sent into alcohol washing disengaging zone (L2), to obtain mainly moisture, pure water (B7) and mainly to contain isoolefine, the organic phase (O8) of lower molecular weight ether light constituent on a small quantity.
27. the production technique of isoolefine according to claim 26 and/or tert-alkyl ether is characterized in that described alcohol washing disengaging zone (L2) selects at least one water wash column (T2) for use.
28. the production technique of isoolefine according to claim 26 and/or tert-alkyl ether is characterized in that described alcohol washing disengaging zone (L2) selects at least one group of static mixer (Mm) and separating tank (Vm) for use.
29. production technique according to claim 23 or 26 described isoolefine and/or tert-alkyl ether, it is characterized in that also comprising operation (8), in operation (8), to send into separation column (C5) from least a portion water (B4) of operation (6) or from least a portion water (B7) of operation (7), with aqueous distillate (B8) and the rich pure cut (O9) that obtains poor alcohol.
30. the production technique of isoolefine according to claim 23 and/or tert-alkyl ether, it is characterized in that also comprising operation (8) when existing when the alcohol washing disengaging zone (L2) of carrying out operation (7), in operation (8), to send into separation column (C5) from least a portion water (B4) of operation (6) and/or from least a portion water (B7) of operation (7), with aqueous distillate (B8) and the rich pure cut (O9) that obtains poor alcohol.
31., it is characterized in that the pure cut of the described richness of at least a portion (O9) is circulated to the etherification reaction zone (R1) of operation (1) and/or the etherification reaction zone (R2) of operation (5) according to the production technique of claim 29 or 30 described isoolefine and/or tert-alkyl ether.
32., it is characterized in that the described aqueous distillate of at least a portion (B8) is circulated to the alcohol washing disengaging zone (L1) of operation (6) and/or the alcohol washing disengaging zone (L2) of operation (7) according to the production technique of claim 29 or 30 described isoolefine and/or tert-alkyl ether.
33. according to the production technique of claim 23,24 or 25 described isoolefine and/or tert-alkyl ether, its feature is introduced alcohol washing disengaging zone (L1) with fresh water (W1).
34., it is characterized in that fresh water (W2) is introduced alcohol washing disengaging zone (L2) according to the production technique of claim 26,27 or 28 described isoolefine and/or tert-alkyl ether.
35. production technique according to claim 23,24 or 25 described isoolefine and/or tert-alkyl ether, it is characterized in that also comprising operation (9), in operation (9), at least a portion organic phase (O4) of operation (6) is sent into separation column (C3), with the cut (B5) that obtains mainly to contain the light constituent cut (O5) of lower molecular weight ether and mainly contain the unreacted hydrocarbon mixture.
36. the production technique of isoolefine according to claim 35 and/or tert-alkyl ether is characterized in that the described overhead fraction of at least a portion (O5) is circulated to the etherification reaction zone (R1) of operation (1).
37. according to the production technique of each described isoolefine of claim 16-25 and/or tert-alkyl ether, at least a portion cut (O1) that it is characterized in that the separation column from operation (2) is obtained, at least a portion cut (O2) that obtains from the separation column of operation (5) or (O2a) or be circulated to the etherification reaction zone (R1) of operation (1) from least a portion organic phase (O4) that operation (6) obtains.
38. production technique according to claim 26,27 or 28 described isoolefine and/or tert-alkyl ether, it is characterized in that also comprising operation (10), in operation (10), at least a portion organic phase (O8) of operation (7) is sent into separation column (C6), to obtain mainly to contain the light constituent cut (O10) and the high purity isoolefine cut (B9) of lower molecular weight ether.
39., it is characterized in that the described overhead fraction of at least a portion (O10) is circulated to the etherification reaction zone (R1) and/or the etherification reaction zone (R2) of operation (1) according to the production technique of described isoolefine of claim 38 and/or tert-alkyl ether.
40. the production technique of isoolefine according to claim 35 and/or tert-alkyl ether, it is characterized in that also comprising operation (10) when existing when the alcohol washing disengaging zone (L2) of carrying out operation (7), in operation (10), at least a portion organic phase (O8) of operation (7) is sent into separation column (C6), to obtain mainly to contain the light constituent cut (O10) and the high purity isoolefine cut (B9) of lower molecular weight ether.
41., it is characterized in that at least a portion is circulated to operation (1) from overhead fraction (O5) and/or at least a portion of operation (9) separation column (C3) from the overhead fraction (O10) of operation (10) separation column (C6) etherification reaction zone (R1) and/or etherification reaction zone (R2) according to the production technique of described isoolefine of claim 40 and/or tert-alkyl ether.
42. a production technique for preparing isoolefine and/or tert-alkyl ether comprises following operation:
(1) hydrocarbon mixture and at least a alcohol that will contain a kind of isoolefine is at least sent into the etherification reaction zone (R1) that catalyst for etherification is housed, to make the product (P1) that contains a kind of tert-alkyl ether at least;
(2) at least a portion product (P1) that operation (1) is obtained is sent into separation column (C1), with the organic fraction (B1) of the organic fraction (O1) that obtains mainly to contain unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent, high purity tert-alkyl ether with mainly contain secondary alkyl oxide, hang down the cut (B2) of polyisoolefines heavy constituent;
(3) side stream (B1) of at least a portion high purity tert-alkyl ether that operation (2) is obtained is sent into and ether-splitting is housed is separated the ether-splitting of catalyzer and separate reaction zone (R3), to make the product (P3) that contains at least a isoolefine and at least a alcohol, carry out operation (7) afterwards;
(7) product (P3) that operation (3) is obtained is sent into alcohol washing disengaging zone (L2), to obtain mainly moisture, pure water (B7) and mainly to contain isoolefine, the organic phase (O8a) of cracking tert-alkyl ether, a small amount of lower molecular weight ether light constituent not, carry out operation (4) afterwards;
(4) operation (7) is obtained at least a portion organic phase (O8a) and send into separation column (C4), with the light constituent cut (O6) that obtains mainly to contain the resulting most of isoolefine of operation (3), a small amount of lower molecular weight ether and the cut of cracking tert-alkyl ether (B6a) not; It is characterized in that the side line extraction of the high purity tert-alkyl ether cut (B1) of operation (2) gained from first separation column (C1), this side line extraction mouth is located in the stripping section of this tower; The organic fraction (O1) that mainly contains unreacted hydrocarbon mixture, unreacting alcohol, a small amount of lower molecular weight ether light constituent is discharged from cat head; And the cut (B2) that mainly contains secondary alkyl oxide, low polyisoolefines heavy constituent is discharged at the bottom of this Tata.
43., it is characterized in that described side line extraction mouth is located at the position of the 1/3-2/3 of this tower stripping section according to the production technique of described preparation isoolefine of claim 42 and/or tert-alkyl ether.
44., it is characterized in that at least a portion cut (B6a) is sent into reaction zone (R3) according to the production technique of described preparation isoolefine of claim 42 and/or tert-alkyl ether.
45. according to the production technique of described preparation isoolefine of claim 42 and/or tert-alkyl ether, it is characterized in that at least a portion cut (B1) is sent into the fuel dope basin, rest part sent into ether-splitting separate operation (3).
46. the production technique according to described preparation isoolefine of claim 42 and/or tert-alkyl ether is characterized in that also comprising operation (5), operation (5) comprises at least one group of etherification reaction zone and separation column.
47. production technique according to described preparation isoolefine of claim 46 and/or tert-alkyl ether, it is characterized in that at least a portion cut (O1) that will obtain from the separation column (C1) of operation (2) sends into etherification reaction zone (R2), make and mainly contain tert-alkyl ether, the unreacted hydrocarbon mixture, the product (P2) of unreacting alcohol and a spot of lower molecular weight ether light constituent, at least a portion product (P2) that again etherification reaction zone is made is sent into separation column (C2), to obtain mainly to contain the unreacted hydrocarbon mixture, unreacting alcohol, the overhead fraction (O2) of a small amount of lower molecular weight ether light constituent, the tower bottom distillate (B2a) and the high purity tert-alkyl ether side stream (B1a) that contain heavy constituent, the cut (B1a) of at least a portion high purity tert-alkyl ether of gained is directly sent into ether-splitting and is separated reaction zone (R3) from the interior side line extraction of first separation column (C1) stripping section.
48. production technique according to described preparation isoolefine of claim 46 and/or tert-alkyl ether, it is characterized in that at least a portion cut (O1) that will obtain from the separation column (C1) of operation (2) sends into etherification reaction zone (R2), make and mainly contain tert-alkyl ether, the unreacted hydrocarbon mixture, the product (P2) of unreacting alcohol and a spot of lower molecular weight ether light constituent, at least a portion product (P2) that again etherification reaction zone is made is sent into separation column (C2), to obtain mainly to contain the unreacted hydrocarbon mixture, unreacting alcohol, the overhead fraction (O2a) of a small amount of lower molecular weight ether light constituent and mainly contain tert-alkyl ether, the tower bottom distillate (B3) that contains heavy constituent, at least a portion tower bottom distillate of gained are sent into the separation column (C1) of operation (2).
49. production technique according to claim 42,46,47 or 48 described preparation isoolefine and/or tert-alkyl ether, it is characterized in that also comprising operation (6), in operation (6), at least a portion overhead fraction (O1) that will obtain from the separation column (C1) of operation (2) or at least a portion overhead fraction (O2) that obtains from the separation column of operation (5) or (O2a) send into alcohol washing disengaging zone (L1) are to obtain mainly moisture, pure water (B4) and mainly to contain unreacted hydrocarbon mixture, the organic phase (O4) of lower molecular weight ether light constituent on a small quantity.
50., it is characterized in that described alcohol washing disengaging zone (L1) selects at least one water wash column (T1) for use according to the production technique of described preparation isoolefine of claim 49 and/or tert-alkyl ether.
51., it is characterized in that described alcohol washing disengaging zone (L1) selects at least one group of static mixer (Mn) and separating tank (Vn) for use according to the production technique of described preparation isoolefine of claim 49 and/or tert-alkyl ether.
52., it is characterized in that described alcohol washing disengaging zone (L2) selects at least one water wash column (T2) for use according to the production technique of described preparation isoolefine of claim 42 and/or tert-alkyl ether.
53., it is characterized in that described alcohol washing disengaging zone (L2) selects at least one group of static mixer (Mm) and separating tank (Vm) for use according to the production technique of described preparation isoolefine of claim 42 and/or tert-alkyl ether.
54. production technique according to claim 42 or 49 described preparation isoolefine and/or tert-alkyl ether, it is characterized in that also comprising operation (8), in operation (8), to send into separation column (C5) from least a portion water (B4) of operation (6) and/or from least a portion water (B7) of operation (7), with aqueous distillate (B8) and the rich pure cut (O9) that obtains poor alcohol.
55., it is characterized in that the pure cut of the described richness of at least a portion (O9) is circulated to the etherification reaction zone (R1) of operation (1) and/or the etherification reaction zone (R2) of operation (5) according to the production technique of described preparation isoolefine of claim 54 and/or tert-alkyl ether.
56., it is characterized in that the described aqueous distillate of at least a portion (B8) is circulated to the alcohol washing disengaging zone (L1) of operation (6) and/or the alcohol washing disengaging zone (L2) of operation (7) according to the production technique of described preparation isoolefine of claim 54 and/or tert-alkyl ether.
57., it is characterized in that fresh water (W2) is introduced alcohol washing disengaging zone (L2) according to the production technique of described preparation isoolefine of claim 42 and/or tert-alkyl ether.
58., it is characterized in that fresh water (W1) is introduced alcohol washing disengaging zone (L1) according to the production technique of claim 49,50 or 51 described preparation isoolefine and/or tert-alkyl ether.
59. production technique according to claim 49,50 or 51 described preparation isoolefine and/or tert-alkyl ether, it is characterized in that also comprising operation (9), in operation (9), at least a portion organic phase (O4) of operation (6) is sent into separation column (C3), with the cut (B5) that obtains mainly to contain the light constituent cut (O5) of lower molecular weight ether and mainly contain the unreacted hydrocarbon mixture.
60., it is characterized in that the described overhead fraction of at least a portion (O5) is circulated to the etherification reaction zone (R1) of operation (1) according to the production technique of described preparation isoolefine of claim 59 and/or tert-alkyl ether.
61. according to the production technique of each described preparation isoolefine of claim 42-53 and/or tert-alkyl ether, at least a portion cut (O2) that at least a portion cut (O1) that it is characterized in that obtaining from the separation column from operation (2), the separation column of operation (5) obtain or (O2a) or be circulated to the etherification reaction zone (R1) and/or operation (5) etherification reaction zone (R2) of operation (1) from least a portion organic phase (O4) that operation (6) obtains.
62. production technique according to described preparation isoolefine of claim 42 and/or tert-alkyl ether, it is characterized in that also comprising operation (10), in operation (10), at least a portion organic phase (O8) of operation (7) is sent into separation column (C6), to obtain mainly to contain the light constituent cut (O10) and the high purity isoolefine cut (B9) of lower molecular weight ether.
63., it is characterized in that the described overhead fraction of at least a portion (O10) is circulated to the etherification reaction zone (R1) of operation (1) and/or the etherification reaction zone (R2) of operation (5) according to the production technique of described preparation isoolefine of claim 62 and/or tert-alkyl ether.
64. production technique according to described preparation isoolefine of claim 59 and/or tert-alkyl ether, it is characterized in that also comprising operation (10), in operation (10), at least a portion organic phase (O8) of operation (7) is sent into separation column (C6), to obtain mainly to contain the light constituent cut (O10) and the high purity isoolefine cut (B9) of lower molecular weight ether.
65., it is characterized in that at least a portion is circulated to the etherification reaction zone (R1) of operation (1) and/or the etherification reaction zone (R2) of operation (5) from the overhead fraction (O5) of operation (9) separation column (C3) and/or at least a portion from the overhead fraction (O10) of operation (10) separation column (C6) according to the production technique of described preparation isoolefine of claim 59 and/or tert-alkyl ether.
CNB001340921A 2000-12-13 2000-12-13 Productive process for isoalkene and/or tertiary alkyl ether Expired - Lifetime CN1158228C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB001340921A CN1158228C (en) 2000-12-13 2000-12-13 Productive process for isoalkene and/or tertiary alkyl ether

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB001340921A CN1158228C (en) 2000-12-13 2000-12-13 Productive process for isoalkene and/or tertiary alkyl ether

Publications (2)

Publication Number Publication Date
CN1358695A true CN1358695A (en) 2002-07-17
CN1158228C CN1158228C (en) 2004-07-21

Family

ID=4596028

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB001340921A Expired - Lifetime CN1158228C (en) 2000-12-13 2000-12-13 Productive process for isoalkene and/or tertiary alkyl ether

Country Status (1)

Country Link
CN (1) CN1158228C (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102884029A (en) * 2010-05-20 2013-01-16 鲁奇有限责任公司 Method and system for producing low-oxygenate olefin flows
CN103172483A (en) * 2011-12-23 2013-06-26 中国石油化工股份有限公司 Production process of high-purity isoolefine (tert-olefin)
CN103524309A (en) * 2012-07-03 2014-01-22 北京安耐吉能源工程技术有限公司 Purification method of crude methyl tertiary-butyl ether product and method for producing methyl tertiary-butyl ether

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4056549B1 (en) 2021-03-08 2024-05-08 Basf Se Process for obtaining isobutene from a c4-hydrocarbon mixture
CN117043125A (en) 2021-03-08 2023-11-10 巴斯夫欧洲公司 From C 4 Process for obtaining isobutene from hydrocarbon mixtures
WO2023217810A1 (en) 2022-05-13 2023-11-16 Basf Se Process for purifying a raw c4-hydrocarbon mixture

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102884029A (en) * 2010-05-20 2013-01-16 鲁奇有限责任公司 Method and system for producing low-oxygenate olefin flows
US9505684B2 (en) 2010-05-20 2016-11-29 Air Liquide Global E&C Solutions Germany Gmbh Method and system for producing low-oxygenate OLEFIN flows
CN103172483A (en) * 2011-12-23 2013-06-26 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)
CN103524309A (en) * 2012-07-03 2014-01-22 北京安耐吉能源工程技术有限公司 Purification method of crude methyl tertiary-butyl ether product and method for producing methyl tertiary-butyl ether
CN103524309B (en) * 2012-07-03 2015-08-26 北京安耐吉能源工程技术有限公司 The purification process of the thick product of methyl tertiary butyl ether and the method for production methyl tertiary butyl ether

Also Published As

Publication number Publication date
CN1158228C (en) 2004-07-21

Similar Documents

Publication Publication Date Title
CN1712391A (en) Process for the preparation of tert.-butanol from isobutene containing hydrocarbon mixtures
CN102372573B (en) Method for preparing propylene by using etherified C4 and ethylene
CN1075483C (en) Process and appts. for C4 and C5 olefine hydrocarbon fraction conversion into ether and propene
CN1174945C (en) Three step process for producing light olefins from methane and/or ethane
CN1852878A (en) Processing C4 olefin streams for the maximum production of propylene
CN1603290A (en) Process for the preparation of tert.-butanol
CN101198572A (en) Process for the double bond hydroisomerization of butenes
CN1122011C (en) Process for preparing alkyl ethers and mixtures thereof
CN1159272C (en) Productive process for isoalkene and/or tertiary alkyl ether
CN1102562C (en) Olefin skeletal isomerization process
CN103172487B (en) Production process of high-purity isoolefine (tert-olefin)
CN1158228C (en) Productive process for isoalkene and/or tertiary alkyl ether
CN1760342A (en) Catalytic cracking method and equipment for producing more propylene
CN1159273C (en) Productive process for isolakene and/or tertiary alkyl ether
CN102050690B (en) Isoolefine production method
CN1162387C (en) Process for preparing isoolefine and/or tertiary alkylether
CN104672046B (en) Method of increasing ethylene and propylene yields by freshening C-4 olefins in catalytic cracking or pyrolysis process after separation
CN1239444C (en) Isoalkene producing process
CN104250204B (en) A kind of complex etherified technique
CN1282734C (en) Technology process for efficientely catalyzing converting of C4 hydrocarbon kind
CN1182087C (en) Process for separating linear alpha olefins from a stream containing saturated hydrocarbons, internal olefins, branched olefins and linear alpha olefins
CN1070834C (en) Process for preparing alkyl ethers and mixtures thereof
CN1107134A (en) Method for producing tertether with C4 or C5, including two obtaining-distillating steps
CN1202060C (en) Ether product producing process
CN1286782C (en) Method for isomerization of light hydrocarbon

Legal Events

Date Code Title Description
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C06 Publication
PB01 Publication
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term

Granted publication date: 20040721

CX01 Expiry of patent term