CN109293482B

CN109293482B - The manufacturing device of MTBE, the manufacturing device of isobutene, the manufacturing method of the manufacturing method of MTBE and isobutene

Info

Publication number: CN109293482B
Application number: CN201811442680.7A
Authority: CN
Inventors: 村上能寿
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2018-03-30
Filing date: 2018-11-29
Publication date: 2019-09-10
Anticipated expiration: 2038-11-29
Also published as: JP2019178100A; CN109293482A; JP6440882B1

Abstract

The present invention relates to the manufacturing methods of the manufacturing device of MTBE, the manufacturing device of isobutene, the manufacturing method of MTBE and isobutene.The manufacturing device (300) of MTBE has: MTBE synthesis reactor (5), MTBE destilling tower (10), the first extractor (60), methanol destilling tower (50) and at least one of pipeline below (A) and pipeline (B): the pipeline (A (A1b, A2)) that MTBE synthesis reactor (5) is not connect with methanol destilling tower (50) via MTBE destilling tower (10) and the first extractor (60)；The pipeline (B) that MTBE synthesis reactor (5) is not connect with the first extractor (60) via MTBE destilling tower (10).

Description

The manufacturing device of MTBE, the manufacturing device of isobutene, the manufacturing method of MTBE and different The manufacturing method of butylene

Technical field

The present invention relates to the manufacturing devices and manufacturing method of MTBE and isobutene.

Background technique

Following method is described in patent document 1, and the method, which includes, to be made to include different in the hydrocarbon mixture of isobutene Butylene reacts in the presence of a catalyst with methanol, to obtain comprising methyl tertiary butyl ether(MTBE) (hereinafter, being recorded as " MTBE ") The MTBE synthesis procedure of reaction mixture；And the MTBE separation process of MTBE is isolated from reaction mixture by distilling.

MTBE is decomposed and is purified to obtain isobutene by distillation etc. in addition, describing in patent document 2 Method.

Existing technical literature

Patent document 1: Japanese Patent Publication 55-27159 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2007-269708 bulletin

Summary of the invention

The activity of catalyst used in MTBE synthesis procedure gradually decreases.Therefore, the case where catalyst activity reduces Under, it needs to stop MTBE synthetic reaction, then by MTBE synthesis reactor to atmosphere opening, and replaces internal catalyst.

After stopping MTBE synthetic reaction, remain in the catalyst of MTBE synthesis reactor the C4 such as isobutene hydrocarbon, MTBE and methanol.These compounds are flammable, thus preferably to before atmosphere opening in advance by these compounds from It is removed in the catalyst of MTBE synthesis reactor.Therefore, it is contemplated that methanol, water equal solvent are supplied into MTBE synthesis reactor, from And dissolve out the compound in catalyst into solvent.

However, dissolving out forming and usually operating by the cleaning stream (main component is solvent) of the compound in catalyst When the composition of stream (main component MTBE) that is supplied in the destilling tower for carrying out MTBE separation process vary considerably.Therefore, When being supplied in destilling tower as former state, the composition for the stream being supplied in subsequent handling from destilling tower substantially changes, to subsequent handling Generate adverse effect.

The present invention has been made in view of the above problems, synthesizes MTBE it is intended that providing suitably to handle The MTBE of cleaning stream and the manufacturing device of isobutene and use the manufacture that the inside of reactor generates when opening wide to atmosphere The MTBE of device and the manufacturing method of isobutene.

The manufacturing device of MTBE of the invention has:

MTBE synthesis reactor, the MTBE synthesis reactor include supply comprising methanol MTBE raw material entrance, with And the outlet of discharge reaction product；

MTBE destilling tower, the MTBE destilling tower include entrance, the tower with the outlet connection of the MTBE synthesis reactor Eject mouth and tower bottom outlet；

First extractor, first extractor is included to be entered with what the tower top outlet of the MTBE destilling tower was connect The water phase outlet of the water phase of water inlet, discharge comprising methanol of mouth, supply water and the oil of the oily phase of discharge mutually export；

Methanol destilling tower, the methanol destilling tower is included to be entered with what the outlet of the water phase of first extractor connected Mouth, tower top outlet and tower bottom outlet；And

At least one of pipeline (A) below and pipeline (B):

Pipeline (A), the pipeline (A) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction It is the outlet of any one of unitary reactor in the case where multiple unitary reactors of the device with series connection) and the first The entrance of alcohol destilling tower is not connected via the MTBE destilling tower and first extractor；

Pipeline (B), the pipeline (B) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction Device there are the multiple unitary reactors being connected in series in the case where be any one of unitary reactor outlet) with described the The entrance of one extractor is not connected via the MTBE destilling tower.

Here, above-mentioned MTBE synthesis reactor can have multiple unitary reactors of series connection,

The pipeline (A) can connect the entrance of pipeline and the methanol destilling tower between the unitary reactor,

The pipeline (B) can connect the entrance of pipeline and first extractor between the unitary reactor.

In addition, above-mentioned apparatus can be also equipped with: tank, the Yi Jilian being connect with the tower top outlet of the methanol destilling tower The reflux pipeline of the tank Yu the methanol destilling tower is connect,

The pipeline (A) can connect the MTBE synthesis reactor and the first via the tank and the reflux pipeline Alcohol destilling tower.

More specifically, the manufacturing device of MTBE of the invention has:

MTBE synthesis reactor, the MTBE synthesis reactor pass through the isobutene made in the hydrocarbon mixture comprising isobutene It is reacted with methanol and obtains the stream (F0) comprising MTBE, hydrocarbon mixture and methanol；

MTBE destilling tower, the MTBE destilling tower are generated mainly and distilling to the stream (F0) comprising MTBE Stream (F1) and it is main comprising hydrocarbon mixture and include methanol stream (F6)；

First extractor, first extractor are generated mainly mixed comprising hydrocarbon and contacting the stream (F6) and water Close object stream (F12) and it is main comprising water and include methanol stream (F3)；

Methanol destilling tower, the methanol destilling tower generate stream mainly comprising water and distilling to the stream (F3) It (F10) and mainly include the stream (F9) of methanol；And

At least one of pipeline (A) below and pipeline (B):

It should be noted that in the present specification, in the case where being recorded as " main includes the stream of ingredient α ", referring to The concentration of ingredient α is maximum in the concentration for each ingredient for including in the stream.

The manufacturing device of first isobutene of the invention has:

MTBE synthesis reactor, the MTBE synthesis reactor include entrance and the discharge reaction of supply MTBE raw material The outlet of product；

MTBE destilling tower, the MTBE destilling tower have entrance, the tower with the outlet connection of the MTBE synthesis reactor Eject mouth and tower bottom outlet；Or entrance, tower top outlet, tower bottom with the outlet connection with the MTBE synthesis reactor Outlet and side outlet；

MTBE decomposition reactor, the MTBE decomposition reactor is included to be exported with the tower bottom of the MTBE destilling tower Or the outlet of the MTBE decomposition product of entrance and discharge comprising isobutene and methanol of side outlet connection；

Decomposition product destilling tower, the decomposition product destilling tower is included to be connect with the outlet of the MTBE decomposition reactor Entrance, tower top outlet and tower bottom outlet；

Methanol destilling tower, the methanol destilling tower are included to export with the tower bottom of the decomposition product destilling tower and be connected Entrance, tower top outlet and tower bottom outlet；And

At least one of pipeline (A) below and pipeline (C):

Pipeline (A), the pipeline (A) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction It is the outlet of any one of unitary reactor in the case where multiple unitary reactors of the device with series connection) and the first The entrance of the alcohol destilling tower not company via the MTBE destilling tower, the MTBE decomposition reactor and the decomposition product destilling tower It connects；And

Pipeline (C), the pipeline (C) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction It is the outlet of any one of unitary reactor in the case where multiple unitary reactors of the device with series connection) and described point The entrance of solution product destilling tower is not connected via the MTBE destilling tower and the MTBE decomposition reactor.

Here, the MTBE synthesis reactor can have multiple unitary reactors of series connection,

The pipeline (C) can connect the entrance of pipeline and the decomposition product destilling tower between the unitary reactor.

More specifically, the manufacturing device of the first isobutene of the invention has:

MTBE decomposition reactor, the MTBE decomposition reactor are generated and decomposing the MTBE in the stream (F1) Stream (F2A) comprising methanol and isobutene；

Decomposition product destilling tower, the decomposition product destilling tower generate master and distilling to the stream (F2A) It will the stream (F7) comprising methanol and the main stream (F2B) comprising isobutene；

Methanol destilling tower, it includes water that the methanol destilling tower is generated main and distilling to the stream (F7) Stream (F10) and the main stream (F9) comprising methanol；And

At least one of pipeline (A) below and pipeline (C):

Pipeline (A), the pipeline (A) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction It is the outlet of any one of unitary reactor in the case where multiple unitary reactors of the device with series connection) and the first Alcohol destilling tower not via the MTBE destilling tower, the MTBE decomposition reactor and the decomposition product destilling tower entrance and company It connects；

The manufacturing device of second isobutene of the invention has:

Methanol destilling tower, the methanol destilling tower include with the tower bottom of the decomposition product destilling tower outlet and/or Entrance, tower top outlet and the tower bottom outlet of the water phase outlet connection of first extractor；And

At least one of pipeline (A) below~pipeline (C):

Pipeline (A), the pipeline (A) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction It is the outlet of any one of unitary reactor in the case where multiple unitary reactors of the device with series connection) and the first The entrance of alcohol destilling tower is not via the MTBE destilling tower, first extractor, the MTBE decomposition reactor and described point It solves product destilling tower and connects；

Pipeline (B), the pipeline (B) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction Device there are the multiple unitary reactors being connected in series in the case where be any one of unitary reactor outlet) with described the The entrance of one extractor is not connected via the MTBE destilling tower；And

Pipeline (C), the pipeline (C) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction It is the outlet of any one of unitary reactor in the case where multiple unitary reactors of the device with series connection) and described point The entrance of solution product destilling tower is not connected via the MTBE destilling tower with the MTBE decomposition reactor.

The pipeline (B) can connect the entrance of pipeline and first extractor between the unitary reactor,

More specifically, the manufacturing device of the second isobutene of the invention has:

Decomposition product destilling tower, the decomposition product destilling tower generate main packet and distilling to the stream (F2A) Stream (F7) and the main stream (F2B) comprising isobutene containing methanol；

Methanol destilling tower, the methanol destilling tower are given birth to and distilling to the stream (F7) and the stream (F3) At the main stream (F10) comprising water and the main stream (F9) comprising methanol；And

At least one of pipeline (A) below~pipeline (C):

Pipeline (A), the pipeline (A) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction It is the outlet of any one of unitary reactor in the case where multiple unitary reactors of the device with series connection) and the first The entrance of the alcohol destilling tower not company via the MTBE destilling tower, the MTBE decomposition reactor and the decomposition product destilling tower It connects；

Pipeline (B), the pipeline (B) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction Device there are the multiple unitary reactors being connected in series in the case where be any one of unitary reactor outlet) with described the The entrance of one extractor is not connected via the MTBE destilling tower；

The manufacturing device of third isobutene of the invention has:

Second extractor, second extractor include and the entrance of the outlet connection of the MTBE decomposition reactor, confession The water phase outlet of the water phase of water inlet, discharge comprising methanol of water supply and the oil that oily phase is discharged mutually export；

Methanol destilling tower, the methanol destilling tower is included to be entered with what the outlet of the water phase of second extractor connected Mouth, tower top outlet and tower bottom outlet；And

At least one of pipeline (A) below and pipeline (D):

Pipeline (A), the pipeline (A) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction It is the outlet of any one of unitary reactor in the case where multiple unitary reactors of the device with series connection) and the first The entrance of alcohol destilling tower is not connected via the MTBE destilling tower, the MTBE decomposition reactor and second extractor； And

Pipeline (D), the pipeline (D) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction Device there are the multiple unitary reactors being connected in series in the case where be any one of unitary reactor outlet) with described the The entrance of two extractors is not connected via the MTBE destilling tower and the MTBE decomposition reactor.

The pipeline (D) can connect the entrance of pipeline and second extractor between the unitary reactor.

More specifically, the manufacturing device of third isobutene of the invention has:

MTBE decomposition reactor, the MTBE decomposition reactor are generated and decomposing the MTBE in the stream (F1) Stream (F2) comprising methanol and isobutene；

Second extractor, second extractor is by generating the stream (F2) and water mainly and contact comprising isobutyl The stream (F5) of alkene and it is main comprising water and include methanol stream (F8)；

Methanol destilling tower, it includes water that the methanol destilling tower is generated main and distilling to the stream (F8) Stream (F10) and the main stream (F9) comprising methanol；And

At least one of pipeline (A) below and pipeline (D):

Pipeline (A), the pipeline (A) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction It is the outlet of any one of unitary reactor in the case where multiple unitary reactors of the device with series connection) and the first The entrance of alcohol destilling tower is not connected via the MTBE destilling tower, the MTBE decomposition reactor and second extractor；

The manufacturing device of 4th isobutene of the invention has:

Methanol destilling tower, the methanol destilling tower include with the water phase of first extractor outlet and/or it is described Entrance, tower top outlet and the tower bottom outlet of the water phase outlet connection of second extractor；And

At least one of pipeline (A), pipeline (B) and pipeline (D) below:

Pipeline (A), the pipeline (A) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction It is the outlet of any one of unitary reactor in the case where multiple unitary reactors of the device with series connection) and the first The entrance of alcohol destilling tower is not via the MTBE destilling tower, first extractor, the MTBE decomposition reactor and described Two extractors and connect；

Pipeline (B), the pipeline (B) is by the outlet of the MTBE synthesis reactor (wherein, in the MTBE synthetic reaction It is the outlet of the arbitrary unitary reactor in the case where multiple unitary reactors of the device with series connection) and described first The entrance of extractor is not connected via the MTBE destilling tower；

In addition, the manufacturing device of above-mentioned each isobutene can be also equipped with: the tower top outlet with the methanol destilling tower The tank of connection and the reflux pipeline of the connection tank and the methanol destilling tower,

More specifically, the manufacturing device of the 4th isobutene of the invention has:

MTBE synthesis reactor, the MTBE synthesis reactor pass through the isobutene made in the hydrocarbon mixture comprising isobutene It is reacted with methanol and obtains the stream (F0) comprising methyl tertiary butyl ether(MTBE) (MTBE), hydrocarbon mixture and methanol；

Methanol destilling tower, the methanol destilling tower are given birth to and distilling to the stream (F3) and the stream (F8) At the main stream (F10) comprising water and the main stream (F9) comprising methanol；And

At least one of pipeline (A), pipeline (B) and pipeline (D) below:

The manufacturing method of MTBE of the invention is to be had using the manufacturing method of the MTBE of the manufacturing device of above-mentioned MTBE Following process:

Into the MTBE synthesis reactor for contain catalyst supply comprising isobutene hydrocarbon mixture and methanol from And the process for manufacturing MTBE；

Stop the process of the supply of the hydrocarbon mixture into the MTBE synthesis reactor；

After the supply for stopping the hydrocarbon mixture, methanol is supplied in Xiang Suoshu MTBE synthesis reactor, to obtain The process that the hydrocarbon mixture and MTBE for including in the catalyst dissolve out the cleaning stream (a) into methanol；

Cleaning stream (a) is sent via the pipeline (A) to the methanol destilling tower or is sent via the pipeline (B) To the process of first extractor；

Water is further supplied into the MTBE synthesis reactor, to obtain the methanol for including in catalyst dissolution The process of cleaning stream (b) into water；

Cleaning stream (b) is sent via the pipeline (A) to the methanol destilling tower or is sent via the pipeline (B) To the process of first extractor.

The manufacturing method of first isobutene of the invention is the isobutene using the manufacturing device of above-mentioned first isobutene Manufacturing method has following process:

Into the MTBE synthesis reactor for contain catalyst supply comprising isobutene hydrocarbon mixture and methanol from And the process for manufacturing isobutene；

Cleaning stream (a) is sent via the pipeline (A) to the methanol destilling tower or is sent via the pipeline (C) To the process of the decomposition product destilling tower；

Cleaning stream (b) is sent via the pipeline (A) to the methanol destilling tower or is sent via the pipeline (C) To the process of the decomposition product destilling tower.

The manufacturing method of second isobutene of the invention is the isobutene using the manufacturing device of above-mentioned second isobutene Manufacturing method has following process:

Cleaning stream (a) is sent via the pipeline (A) to the methanol destilling tower；Or via the pipeline (B) It send to first extractor；Or it send via the pipeline (C) to the process of the decomposition product destilling tower；

Cleaning stream (b) is sent via the pipeline (A) to the methanol destilling tower；Or via the pipeline (B) It send to first extractor；Or it send via the pipeline (C) to the process of the decomposition product destilling tower.

The manufacturing method of third isobutene of the invention is the isobutene using the manufacturing device of above-mentioned third isobutene Manufacturing method has following process:

Cleaning stream (a) is sent via the pipeline (A) to the methanol destilling tower or is sent via the pipeline (D) To the process of second extractor；

Cleaning stream (b) is sent via the pipeline (A) to the methanol destilling tower or is sent via the pipeline (D) To the process of second extractor.

The manufacturing method of 4th isobutene of the invention is the isobutene using the manufacturing device of above-mentioned 4th isobutene Manufacturing method has following process:

Cleaning stream (a) is sent via the pipeline (A) to the methanol destilling tower；Or via the pipeline (B) It send to first extractor；Or it send via the pipeline (D) to the process of second extractor；

Cleaning stream (b) is sent via the pipeline (A) to the methanol destilling tower；Or via the pipeline (B) It send to first extractor；Or it send via the pipeline (D) to the process of second extractor.

According to the present invention, it provides suitably to handle and be generated when opening wide the inside of MTBE synthesis reactor to atmosphere Clean the isobutene of stream and the manufacturing device of MTBE and using the isobutene of described device and the manufacturing method of MTBE.

Detailed description of the invention

Fig. 1 is the flow chart of the manufacturing device of the isobutene of first embodiment.

Fig. 2 is the flow chart of the manufacturing device of the isobutene of second embodiment.

Fig. 3 is the flow chart of the manufacturing device of the MTBE of third embodiment.

Fig. 4 is the flow chart of the MTBE synthesis reactor for indicating other embodiment and the mode of bypass line.

Fig. 5 is the flow chart of the MTBE destilling tower and its peripheral equipment of other embodiment.

Appended drawing reference

5 ... MTBE synthesis reactor, 10 ... MTBE destilling towers, 20 ... MTBE decomposition reactors, the distillation of 30 ... decomposition products Tower, 40 ... second extractors, 50 ... methanol destilling towers, 55 ... tanks, 60 ... first extractors, the manufacture of 100,200 ... isobutenes Device, the manufacturing device of 300 ... MTBE.

Specific embodiment

(first embodiment: the manufacturing device and method of isobutene)

The manufacturing method of the isobutene of first embodiment of the invention is illustrated.

Firstly, being illustrated referring to Fig.1 to the manufacturing device 100 of the isobutene of present embodiment.

The manufacturing device 100 mainly has MTBE synthesis reactor 5, MTBE destilling tower 10, MTBE decomposition reactor 20, divides Solution product destilling tower 30, the second extractor 40, methanol destilling tower 50, the first extractor 60 and bypass line A1a~A1c, A2, B and C.

The methanol source MeOH and hydrocarbon mixture for supplying MTBE raw material are connected in the entrance 5i of MTBE synthesis reactor 5 Source C4.MTBE synthesis reactor 5 is that the reactor in container filled with catalyst is appropriate.MTBE synthesis reactor 5 can To be the fixed-bed reactor for being filled with catalyst in container.It can be to flow up to air-flow towards there is no limit, Or it flows downward.

It is acid-exchange resin in the example for synthesizing catalyst used in the reaction of MTBE by methanol and isobutene. As acid-exchange resin, can enumerate for example: the phenylethylene sulfonate resin that is crosslinked using divinylbenzene, And the phenol sulfonic acid resin being crosslinked using formaldehyde.Above-mentioned acid-exchange resin is preferably macroreticular resin.

The outlet 5o of MTBE synthesis reactor 5 is connect with the entrance 10i of MTBE destilling tower 10 by pipeline L1.It is steamed in MTBE The tower top outlet 10t for evaporating tower 10 is connected with pipeline L2, and in tower bottom outlet, 10b is connected with pipeline L3, exports in the side of tower side 10s is connected with pipeline L4.

The entrance 60i of first extractor 60 is connect with pipeline L2.The entrance 20i and pipeline L4 of MTBE decomposition reactor 20 connect It connects.

The outlet 20o of MTBE decomposition reactor 20 is connect with the entrance 30i of decomposition product destilling tower 30 via pipeline L5. MTBE decomposition reactor 20 is the reactor filled with aftermentioned solid catalyst, MTBE can be decomposed into isobutene and methanol.

It is connected with pipeline L6 in the tower top outlet 30t of decomposition product destilling tower 30,30b is connected with pipeline in tower bottom outlet L7.Pipeline L6 is connect with the entrance 40i of the second extractor 40.Pipeline L7 is connect with the entrance 50ia of methanol destilling tower 50.

The pipeline L14 of supply water is connected in the water inlet 40wi of the second extractor 40.It is being located at the second extractor 40 Mutually outlet 40oo is connected with pipeline L8 to the oil of tower top, is connected with pipeline L9 in the water phase outlet 40wo for being located at tower bottom.

The pipeline L20 of supply water is connected in the water inlet 60wi of the first extractor 60.It is being located at the first extractor 60 Mutually outlet 60t is connected with pipeline L15 to the oil of tower top, is connected with pipeline L13 in the water phase outlet 60b for being located at tower bottom.

Pipeline L7 from decomposition product destilling tower 30 is connect with the entrance 50ia of methanol destilling tower 50, is extracted from second The pipeline L9 of device 40 and pipeline L13 from the first extractor 60 are connect with the entrance 50ib of methanol destilling tower 50.It is steamed in methanol The tower top outlet 50t for evaporating tower 50 is connected with pipeline L10, and in tower bottom outlet, 50b is connected with pipeline L11.

For methanol destilling tower 50, preferably pipeline L7 is connected at position more higher than pipeline L9 and pipeline L13.That is, It is preferred that entrance 50ia is higher than entrance 50ib.Due to the stream (F7) of pipeline L7 water concentration lower than pipeline L9 stream (F8) and The concentration of the water of the stream (F3) of pipeline L13, therefore pass through the separation effect so set, water and methanol in methanol destilling tower 50 Rate improves.

Methanol destilling tower 50 can be packed tower, it is preferred that being the plate column with multiple column plates (tower tray) 50a.In plate In the case where formula tower, for methanol destilling tower 50, the column plate 50a of connecting pipeline L7 is preferably made to be higher than connecting pipeline L9 and pipeline The column plate 50a of L13.The difference of the number of plates is 1 layer or more, or 2 layers or more.Total number of plates of plate column for example can be with It is set as 40 layers~60 layers.

It is provided on pipeline L10 by the tank 55 of heat exchanger 58 and storing liquid methanol that methanol condensed is liquid. Reflux pipeline L18 is provided on tank 55, the reflux pipeline L18 makes the returning to methanol destilling tower 50 of the liquid reflux in tank Inflow entrance 50r；And the liquid of tank 55 is discharged to the outside by pipeline L12, the pipeline L12.

Bypass line A1a is the pipeline of connecting pipeline L1 and pipeline L7, and bypass line A1b is connecting pipeline L1 and pipeline The pipeline of L13, bypass line A1c is the pipeline of connecting pipeline L1 and pipeline L9, respectively by the outlet 5o of MTBE synthesis reactor 5 It is not mentioned via MTBE destilling tower 10, MTBE decomposition reactor 20, second with the entrance 50ia or entrance 50ib of methanol destilling tower 50 It takes device 40, decomposition product destilling tower 30 and the first extractor 60 and connects.

Bypass line A2 is the pipeline of connecting pipeline L1 and tank 55, and the outlet 5o of MTBE synthesis reactor 5 and methanol are steamed The reflux inlet 50r of tower 50 is evaporated not via MTBE destilling tower 10, MTBE decomposition reactor 20, the second extractor 40, decomposition product Destilling tower 30 is connected via tank 55 with reflux pipeline L18 with the first extractor 60.

Bypass line B is the pipeline of connecting pipeline L1 and pipeline L2, and the outlet 5o of MTBE synthesis reactor 5 is mentioned with first The entrance 60i of device 60 is taken not connect via MTBE destilling tower 10.

Bypass line C is the pipeline of connecting pipeline L1 and pipeline L5, by the outlet 5o of MTBE synthesis reactor 5 and decomposes production The entrance 30i of object destilling tower 30 is not connected via MTBE destilling tower 10 and MTBE decomposition reactor 20.

In the state of synthesizing MTBE in MTBE synthesis reactor 5, by these bypass lines A1a, A1b, A1c, A2, B and C closing.

(manufacturing method of isobutene)

Then, the manufacturing method of the isobutene of present embodiment is illustrated first.

(generation of the stream (F0) comprising MTBE in MTBE synthesis reactor 5)

Firstly, hydrocarbon mixture and methanol are supplied in MTBE synthesis reactor 5, to obtain mixing comprising MTBE, hydrocarbon The stream (F0) of object and methanol.

Hydrocarbon mixture includes isobutene and the hydrocarbon in addition to isobutene.The example of hydrocarbon mixture are as follows: by the water of naphtha The carbon atom number that steam cracking obtains be 4 hydrocarbon-fraction (C 4 fraction) or by extract or select plus hydrogen therefrom remove 1,3- fourth Fraction (remaining BB fraction (スペ Application ト BB stay point) after diene)；The carbon atom number as obtained from fluid catalytic cracking is 4 Hydrocarbon mixture (FCC-C4)；Make the mixture obtained from dehydrogenation of isobutane comprising isobutene；It is recorded as the tert-butyl alcohol (below " TBA ") dehydration obtained from include isobutene mixture；And it is obtained by the skeletal isomerization of 1- butylene or 2- butylene The mixture comprising isobutene；And their mixture.The example of hydrocarbon in addition to isobutene are as follows: iso-butane, normal butane, The hydrocarbon that the carbon atom numbers such as 1- butylene, 2- butylene, 1,3- butadiene are 4；The carbon atom numbers such as propane, propylene, allene, propine are 3 Hydrocarbon；The hydrocarbon that the carbon atom numbers such as pentane, amylene, isopentane are 5.

The reaction temperature of MTBE synthesis can be set as 20 DEG C~90 DEG C, reaction pressure can be set as 0.2MPa~ 2.5MPa。

Pass through the compound that the stream (F0) being synthesized into includes in addition to MTBE, hydrocarbon mixture and methanol.It is described The example of compound is the alcohol in addition to methanol and the ether in addition to MTBE.

The example for the hydrocarbon mixture for including in stream (F0) are as follows: isobutene, iso-butane, normal butane, 1- butylene, 2- butylene, The hydrocarbon that the carbon atom numbers such as 1,3- butadiene are 4；The hydrocarbon that the carbon atom numbers such as Diisobutylene are 8；Propane, propylene, allene, propine Etc. carbon atom numbers be 3 hydrocarbon；The hydrocarbon that the carbon atom numbers such as pentane, amylene, isopentane are 5.

The example of alcohol in addition to methanol is TBA.

The example of ether in addition to MTBE is dimethyl ether, methyl sec-butyl ether.

Stream (F0) can wrap aqueous.

The concentration of MTBE in stream (F0) can be 10 mass of mass %~97 %.

(distillation in the MTBE destilling tower 10 of stream (F0))

Then, stream (F0) is supplied in MTBE destilling tower 10 via pipeline L1.The inlet of MTBE destilling tower 10 The temperature of stream (F0) can be set as 25 DEG C~490 DEG C.Pressure in MTBE destilling tower 10 can be set as 0.1MPa~ 1.2MPa。

By being distilled in MTBE destilling tower 10 to stream (F0), via pipeline L2 from tower top discharge mainly comprising hydrocarbon Mixture and include methanol stream (F6), via pipeline L3 from tower bottom exclusion mainly contain Diisobutylene, methyl Zhong Ding The streams (F17) of the higher-boiling compounds such as base ether is discharged, and via pipeline L4 from the lower and the position more top than tower bottom than tower top Discharge is set mainly comprising the stream (F1) of MTBE.

The stream (F1) as midbarrel is discharged from MTBE destilling tower 10 in order to steadily pass through pipeline L4, MTBE steams Evaporating tower 10 can be the plate column with multiple tower trays.Thereby, it is possible to midbarrel is suitably discharged from tower tray.Via pipeline L4 Temperature, the temperature of the tower tray of liquid i.e. side-draw in the exit of the MTBE destilling tower 10 of the stream (F1) of discharge can be set as 80 DEG C~200 DEG C.

(methanol is extracted in the slave stream (F6) in the first extractor 60)

So that stream (F6) is become liquid phase by heat exchange, is then supplied in the first extractor 60 via pipeline L2, and Liquid water is supplied into the first extractor 60 via pipeline L20.By the contact with water, the methanol being present in stream (F6) is molten It is extracted in Xie Yushui, via pipeline L13 from tower bottom stream (F3) is discharged in the form of the mixture of water and methanol.

On the other hand, it will be passed through as the stream (F12) comprising hydrocarbon mixture of oily phase with the state for sufficiently eliminating methanol It is discharged by pipeline L15 from tower top.

The temperature of first extractor 60 can be set as 15 DEG C~80 DEG C, pressure can be set as 0.2MPa-G~ 1.0MPa-G.The temperature of the stream (F3) in the tower bottom exit of the first extractor 60 can be set as 30 DEG C~80 DEG C.

(decomposition of the MTBE in MTBE decomposition reactor 20)

Then, the stream (F1) generated in MTBE destilling tower 10 is supplied to MTBE decomposition reactor 20 via pipeline L4 In.

In MTBE decomposition reactor 20, the MTBE decomposition in stream (F1) is obtained into the material comprising isobutene and methanol It flows (F2A (F2)).At least part MTBE in stream (F1) is decomposed, it can also be by whole MTBE in stream (F1) It decomposes.Stream (F2A) comprising isobutene and methanol generally comprises undecomposed MTBE.

It is appropriate that stream (F1), which is supplied in gaseous form in MTBE decomposition reactor 20,.MTBE decomposition reactor The temperature of the stream (F1) of 20 inlet can be set as 100 DEG C~500 DEG C.

MTBE can be decomposed by using the gas phase reaction of the MTBE decomposition reactor of fixed-bed type.Reaction temperature is usual It is 100 DEG C~500 DEG C, preferably 150 DEG C~350 DEG C.Reaction pressure is usually atmospheric pressure~2.0MPa-G (gauge pressure), preferably Atmospheric pressure~1.2MPa-G.The feed speed of raw material according to reaction temperature, pressure, MTBE conversion ratio etc. and select, when with weight Air speed (WHSV) meter, generallys use 0.1 hour^-1~50 hours^-1, it is preferred to use 1 hour^-1~20 hours^-1.WHSV by for The flow velocity (kg/ hours) of all streams of MTBE decomposition process is obtained divided by catalyst weight (kg).

The conversion ratio of MTBE in MTBE decomposition process is preferably 40%~99%, and more preferably 70%~98%, into one Step preferably 85%~96%.

In MTBE decomposition process, usually using solid catalyst.As solid catalyst, can enumerate for example: metal Oxide, nonmetal oxide and composite oxides.As metal oxide, can enumerate for example: aluminium oxide, titanium oxide and oxygen Change chromium.As nonmetal oxide, such as silica can be enumerated.It as composite oxides, can enumerate for example: oxidation Silicon-aluminium oxide and zeolite.They can be crystalline, or it is unbodied, alternatively, it is also possible to comprising sulphur, phosphorus, magnesium, The elements such as calcium, sodium, potassium.As the solid catalyst used in MTBE decomposition process, it is preferable to use comprising converting by aluminium oxide For 4 mass of mass %~30 % silicon source and be scaled the silicon source of 60 mass of mass %~95 % by silica and have 50m²/ g~450m²The silica-alumina of the BET surface area of/g.

MTBE decomposition process is preferably carried out in 100 DEG C or more and 500 DEG C of silica-aluminas used below.The reaction For the endothermic reaction, it is therefore desirable to from external heating.Heat supply can be by externally to being arranged in MTBE decomposition reactor 20 Heat exchanger tube (Den heat pipe) supplies thermal medium and carries out, can also be being heated to stream (F1) and in a manner of sensible heat It is supplied, them can also be combined.

It can be set as via the temperature of the stream (F2A) in the exit of the MTBE decomposition reactor 20 of pipeline L5 discharge 100 DEG C~500 DEG C, it is preferably set to 150 DEG C~350 DEG C.

For flowing through the stream (F1) of pipeline L4, can be supplied to after the water addition in MTBE decomposition reactor 20.With The additive amount of water is preferably 0 mass of mass %~10 %, more preferably 0.2 matter relative to the amount being discharged from MTBE destilling tower 10 The mode of the amount mass of %~5.0 % carries out.

(methanol is separated in the slave stream (F2A) in decomposition product destilling tower 30)

Then, stream (F2A) is supplied in decomposition product destilling tower 30 via pipeline L5.

Inlet temperature in the decomposition product destilling tower 30 of stream (F2A) can be set as 20 DEG C~480 DEG C, preferably set It is 20 DEG C~330 DEG C.

By the distillation in decomposition product destilling tower 30, by a part of separating methanol in stream (F2A).From decomposition product The tower bottom of destilling tower 30 is via pipeline L7 discharge mainly comprising the stream (F7) of methanol.It is passed through from the tower top of decomposition product destilling tower 30 Stream (F2B (F2)) after isolating a part of methanol, based on isobutene is discharged by pipeline L6.Although isolating one Stream (F2B) after dividing methanol, based on isobutene, but usually in addition to isobutene also include methanol.In stream (F2B) Methanol content it is fewer than the methanol content in stream (F7).Stream (F7) based on methanol usually also includes in addition to methanol Undecomposed MTBE.

The temperature of the tower top of decomposition product destilling tower 30 can be set as 10 DEG C~110 DEG C.Decomposition product destilling tower 30 The temperature of tower bottom can be set as 80 DEG C~200 DEG C.The pressure of decomposition product destilling tower 30 can be set as 0.1MPa-G~ 2.0MPa-G。

(methanol is extracted from isobutene using water in the second extractor 40)

Then, so that stream (F2B) is become liquid phase by heat exchange, be then supplied to the second extractor 40 via pipeline L6 In, and liquid water is supplied into the second extractor 40 via pipeline L14.By the contact with water, it is present in stream (F2B) Methanol be dissolved in the water and be extracted, from tower bottom via pipeline L9 by the form of the mixture of water and methanol be discharged stream (F8)。

On the other hand, it is passed through with the state for sufficiently eliminating methanol from tower top as the stream (F5) comprising isobutene of oily phase It is discharged by pipeline L8.

For stream (F5), can according to need by distillation etc. carry out the removing of the low-boiling compounds such as dimethyl ether to Carry out the further high purity of isobutene.

The temperature of second extractor 40 can be set as 15 DEG C~80 DEG C, pressure can be set as 0.2MPa-G~ 1.0MPa-G.The temperature of the stream (F8) in the tower bottom exit of the second extractor 40 can be set as 30 DEG C~80 DEG C.

(separation of water and methanol in methanol destilling tower 50)

It is supplied in methanol destilling tower 50 from decomposition product destilling tower 30 by stream (F7) via pipeline L7, is extracted from second Stream (F8) is supplied in methanol destilling tower 50 by device 40 via pipeline L9, from the first extractor 60 by stream (F3) via pipeline L13 is supplied in methanol destilling tower 50.As described above, into methanol destilling tower 50 more top than stream (F8) and stream (F3) Position is appropriate for feedstock flow (F7).

The temperature of the stream (F7) of the inlet of methanol destilling tower 50 can be set as 80 DEG C~200 DEG C.Methanol destilling tower The temperature of the stream (F8) of 50 inlet can be set as 30 DEG C~80 DEG C.The stream (F3) of the inlet of methanol destilling tower 50 Temperature can be set as 30 DEG C~200 DEG C.

In methanol destilling tower 50, by distillation, from tower top via pipeline L10 discharge mainly comprising the stream of methanol (F9), the stream (F10) based on water is discharged via pipeline L11 from tower bottom.Stream (F9) usually also includes in addition to methanol MTBE。

The temperature of tower top can be set as 60 DEG C~150 DEG C.The temperature of tower bottom can be set as 100 DEG C~200 DEG C.Methanol The pressure of destilling tower 50 can be set as atmospheric pressure~1.0MPa-G.

Stream (F9) is condensed using heat exchanger 58 and becomes liquid phase, and is stored in tank 55.Make a part of stream (F9) top of methanol destilling tower 50 is flowed back into via reflux pipeline L18, reduces the concentration of the water of stream (F9) thus to mention The purity of high methanol.

It may be used as the methanol being supplied in MTBE synthesis reactor 5 via the stream (F9) that pipeline L12 is discharged.In addition, Stream (F10) may be used as the water for being supplied to the second extractor 40 and the methanol extraction in the first extractor 60.

(replacement of the catalyst in MTBE synthesis reactor)

As described above, hydrocarbon mixture and methanol being supplied into MTBE synthesis reactor 5 in the form of stream (F0) When manufacturing MTBE, the activity of the catalyst in MTBE synthesis reactor 5 is reduced with the time sometimes.In this case it is desirable to Replace the catalyst in MTBE synthesis reactor 5.Hydrocarbon mixture, MTBE and methanol are contained due to absorption etc. in catalyst, Therefore, the method for removing them out of catalyst before more catalyst changeout is illustrated below.

Firstly, stopping the supply of the hydrocarbon mixture into MTBE synthesis reactor 5.

Then, methanol is supplied into MTBE synthesis reactor 5, to keep the hydrocarbon mixture for including in catalyst and MTBE molten Out into methanol, and cleaning stream (a) of the discharge comprising hydrocarbon mixture, MTBE and methanol from MTBE synthesis reactor 5.Supply The temperature of methanol can be set as 10 DEG C~150 DEG C.The pressure of MTBE synthesis reactor 5 can be set as 0.2MPaG~ 2.5MPaG。

It is opposite to catalyst supply in order to dissolve out the hydrocarbon mixture contained in catalyst and MTBE fully in methanol In the apparent volume of catalyst is 1 times or more, the methanol of preferably 10 times or more of volume is appropriate.Therefore, preferably will not Cleaning stream burns, and is appropriate by the Methanol Recovery in cleaning stream.However, MTBE destilling tower 10 be not suitable for cleaning stream (a) this The stream that the methanol concentration of sample is high is distilled.

Therefore, cleaning stream (a) liquid is sent via bypass line A1a, A1b, A1c or A2 to methanol destilling tower 50；Or It send via bypass line B to the first extractor 60；Or it send via bypass line C to decomposition product destilling tower 30.

In the case where that will clean stream (a) and send via bypass line A1a, A1b, A1c or A2 to methanol destilling tower 50, lead to Water is discharged from pipeline L11 from pipeline L10 discharge hydrocarbon mixture, the mixture of MTBE and methanol in the distillation of over cleaning stream (a).

In the case where that will clean stream (a) and send via bypass line B to the first extractor 60, in the first extractor 60, Contact by cleaning stream (a) with water, is discharged hydrocarbon mixture and MTBE via pipeline L15, via pipeline L13 in the form of oily phase First alcohol and water is discharged in the form of water phase and is fed in methanol destilling tower 50.In methanol destilling tower 50, by methanol It is separated from water, therefore can suitably recycle methanol.

In the case where that will clean stream (a) and send via bypass line C to decomposition product destilling tower 30, pass through cleaning stream (a) Distillation, from pipeline L6 be discharged hydrocarbon mixture, from pipeline L7 discharge MTBE and methanol mixture.

In the case where including a large amount of hydrocarbon mixtures and MTBE in cleaning stream (a), (a) is flowed into cleaning via bypass line B It send to the first extractor 60, and recycling hydrocarbon mixture and MTBE are appropriate in stream (F12).

It, will be clear via bypass line A (A1a, A1b, A1c or A2) in the case where largely including methanol in cleaning stream (a) It washes stream (a) to send to methanol destilling tower 50, and recycling methanol is appropriate in stream (F9).In the case, since cleaning is flowed (a) methanol concentration is high, therefore in the case where being supplied in methanol destilling tower 50, using with the entrance that is higher than entrance 50ib The bypass line A1a of 50ia connection is appropriate.

The hydrocarbon mixture in catalyst and MTBE are substantially removed as a result, but in catalyst due to absorption etc. and Contain methanol.

Therefore, after dissolution is into methanol, water is further supplied into MTBE synthesis reactor 5, thus by catalyst In include methanol dissolve out into water, and from MTBE synthesis reactor 5 will dissolution have the water of methanol with clean stream (b) form Discharge.The temperature of the water of supply can be set as 0 DEG C~80 DEG C.The pressure of MTBE synthesis reactor 5 can be set as 0.2MPaG ~2.0MPaG.Usually when being initially supplied water, it is also supplied with methanol into MTBE synthesis reactor 5, slowly increases the water of supply Amount, reduce to accompanying this amount of the methanol of supply, be finally stopped supply methanol, be only supplied water.

In order to dissolve out the methanol contained in catalyst fully in water, the table relative to catalyst is supplied to catalyst It is appropriate for seeing the water for the volume that volume is 1 times or more, preferably 10 times or more.Therefore, preferably cleaning stream (b) is not discharged to Outside system, it is appropriate for being separated from water and respectively carry out recycling the methanol in cleaning stream.However, MTBE destilling tower 10 is uncomfortable The stream high to water concentration as cleaning stream (b) is closed to distill.

Therefore, cleaning stream (b) liquid is sent via bypass line A1a, A1b, A1c or A2 to methanol destilling tower 50；Or It send via bypass line B to the first extractor 60；Or it send via bypass line C to decomposition product destilling tower 30.

In the case where that will clean stream (b) and send via bypass line A1a, A1b, A1c or A2 to methanol destilling tower 50, lead to Distillation is crossed, methanol is discharged from pipeline L10, water is discharged from pipeline L11.

In the case where that will clean stream (b) and send via bypass line B to the first extractor 60, in the first extractor 60, Cleaning stream (b) is contacted with water, but is hardly formed oily phase, is arranged in the form of the water phase comprising first alcohol and water via pipeline L13 Cleaning stream (b) out, and be supplied in methanol destilling tower 50.In methanol destilling tower 50, methanol is separated from water, therefore can be fitted Locality recycling methanol, can also recycle water.

In the case where that will clean stream (b) and send via bypass line C to decomposition product destilling tower 30, pass through cleaning stream (b) Distillation, from pipeline L6 be discharged hydrocarbon mixture, from pipeline L7 discharge MTBE, methanol and water mixture.

As a result, other than hydrocarbon mixture and MTBE in catalyst, methanol is also substantially removed.

Then, the inside of the MTBE synthesis reactor is opened wide to atmosphere, and more catalyst changeout.

If implementing washing and the methanol replacement of catalyst to MTBE synthesis reactor 5, then after more catalyst changeout The supply for starting methanol and hydrocarbon mixture, then can restart the synthesis of MTBE.

It should be noted that as hydrocarbon mixture, MTBE and the methanol for including in catalyst is removed before more catalyst changeout Method can also enumerate following methods in addition to the method described above.

Firstly, stopping the supply of the hydrocarbon mixture and methanol into MTBE synthesis reactor 5.Then, MTBE will be remained in Hydrocarbon mixture, methanol and MTBE in synthesis reactor 5 are discharged from MTBE synthesis reactor 5.The extraction can use setting Drawing liquid pipeline L22 in MTBE synthesis reactor 5 is carried out.The amount of Extract is few and is flammable, therefore can be to the liquid Body suitably carries out burning disposal.

Even if after discharge remains in the liquid in MTBE synthesis reactor 5, in catalyst also due to absorption etc. and contain There are hydrocarbon mixture, MTBE, methanol.Therefore, then supply methanol into MTBE synthesis reactor 5, thus make include in catalyst Hydrocarbon mixture and MTBE dissolve out into methanol, discharge includes hydrocarbon mixture, MTBE and methanol from MTBE synthesis reactor 5 Cleaning stream (a).The pressure of the temperature of the methanol of supply, the volume of methanol and MTBE synthesis reactor 5 and it is aforementioned.It will be clear Stream (a) liquid is washed to send via bypass line A1a, A1b, A1c or A2 to methanol destilling tower 50；Or via bypass line B send to First extractor 60；Or via bypass line C send to decomposition product destilling tower 30 method also with it is aforementioned.

By the hydrocarbon mixture in catalyst and after MTBE sufficiently removes, further supplied into MTBE synthesis reactor 5 Water supply, thus make the methanol for including in catalyst dissolution into water, and will dissolution have the water of methanol with clean stream (b) form from It is discharged in MTBE synthesis reactor 5.Pressure of the temperature of the water of supply, the volume of water and MTBE synthesis reactor 5 etc. with it is preceding It states the same.Cleaning stream (b) liquid is sent via bypass line A1a, A1b, A1c or A2 to methanol destilling tower 50；Or via bypass Pipeline B is sent to the first extractor 60；Or send the method to decomposition product destilling tower 30 also with aforementioned one via bypass line C Sample.In the method, other than hydrocarbon mixture and MTBE in catalyst, methanol is also substantially removed.

(effect)

According to the present embodiment, have bypass line A1a, A1b, A1c, A2, B or C.Thereby, it is possible to will dissolve out to have MTBE The cleaning stream of the flammable compound contained in the catalyst of synthesis reactor 5 does not decompose via MTBE destilling tower 10, MTBE anti- It answers device 20, decomposition product destilling tower 30, the second extractor 40 and the first extractor 60 and is supplied in methanol destilling tower 50；Or It is not supplied in decomposition product destilling tower 30 via MTBE destilling tower 10 and MTBE decomposition reactor 20；Or not via MTBE Destilling tower 10 and be supplied in the first extractor 60.

Thereby, it is possible to suitable in the case where not generating adverse effect to MTBE destilling tower 10, decomposition product destilling tower 30 etc. Locality processing cleaning is flowed and is recycled.

(second embodiment)

It is illustrated referring to manufacturing method of the Fig. 2 to the isobutene of second embodiment of the present invention.

The point that the present invention is different from the first embodiment is illustrated.Fig. 2 is the manufacture of the isobutene of present embodiment The flow chart of device 200.

In the manufacturing device 200 of the isobutene of present embodiment, pipeline L5 is connect with the entrance 40i of the second extractor 40 Rather than it is connect with the entrance 30i of decomposition product destilling tower 30.In addition, by mutually going out from the oil for the tower top for being located at the second extractor 40 The stream (F5) of mouth 40oo discharge is supplied to the entrance 30i of decomposition product destilling tower 30 via pipeline L8.It will be mentioned from being located at second The water phase of the tower bottom of device 40 is taken to export the entrance that the stream (F8) that 40wo is discharged is supplied to methanol destilling tower 50 via pipeline L9 50ib.To send to burning boiler via pipeline L7 from the stream (F27) that the tower bottom of decomposition product destilling tower 30 outlet 30b is discharged and It is not to send to methanol destilling tower 50.

Bypass line A1b is the pipeline of connecting pipeline L1 and pipeline L13, and bypass line A1c is connecting pipeline L1 and pipeline The pipeline of L9, bypass line A1d are the pipeline of the entrance 50ia of connecting pipeline L1 and methanol destilling tower 50, they synthesize MTBE The outlet 5o of reactor 5 and the entrance 50ib or 50ia of methanol destilling tower 50 does not decompose via MTBE destilling tower 10, MTBE anti- It answers device 20, the second extractor 40, decomposition product destilling tower 30 and the first extractor 60 and connects.

Bypass line B, A2 are identical with first embodiment.

Bypass line D is the pipeline of connecting pipeline L1 and pipeline L5, and the outlet 5o of MTBE synthesis reactor 5 is mentioned with second The entrance 40i of device 40 is taken not connect via MTBE destilling tower 10 and MTBE decomposition reactor 20.

Then, the point that the manufacturing method of the MTBE of present embodiment and isobutene are different from the first embodiment is said It is bright.

(methanol is extracted from isobutene using water in the second extractor 40)

It will be supplied in the second extractor 40 from the stream (F2) being discharged in MTBE decomposition reactor 20 via pipeline L5, and And liquid water is supplied into the second extractor 40 via pipeline L14.By the contact with water, the methanol in stream (F2) is dissolved in It is extracted in water and from isobutene, from tower bottom via pipeline L9 stream (F8) is discharged in the form of the mixture of water and methanol.

On the other hand, the stream comprising isobutene as oil phase after removing methanol is discharged via pipeline L8 from tower top (F5).In stream (F5) comprising isobutene, in addition to isobutene, usually also comprising higher boilings such as MTBE and Diisobutylenes Close object.

The temperature of the stream (F2) of the inlet of second extractor 40 can be set as 30 DEG C~480 DEG C.Second extractor 40 temperature can be set as 15 DEG C~80 DEG C, and pressure can be set as 0.2MPa-G~1.0MPa-G.

(separation of isobutene and higher-boiling compound in decomposition product destilling tower 30)

Then, the stream (F5) comprising isobutene is supplied in decomposition product destilling tower 30 via pipeline L8.It decomposes and produces The temperature of the stream (F5) of the inlet of object destilling tower 30 can be set as 15 DEG C~80 DEG C.

By the distillation in decomposition product destilling tower 30, from the tower top of decomposition product destilling tower 30 via pipeline L6 be discharged with Stream (F26) based on isobutene includes Diisobutylene etc. via pipeline L7 discharge from the tower bottom of decomposition product destilling tower 30 The stream (F27) of higher-boiling compound.Burning disposal is usually carried out to stream (F27).

Temperature, the temperature of tower bottom, the pressure of decomposition product destilling tower 30 of the tower top of decomposition product destilling tower 30 can be set It is set to identical with first embodiment.

(separation of water and methanol in methanol destilling tower 50)

The distillation of stream (F3) and stream (F8) are carried out in methanol destilling tower 50.The material of the inlet of methanol destilling tower 50 Flow the temperature of (F8), the temperature of the stream (F3) of the inlet of methanol destilling tower 50, the temperature of the tower top of methanol destilling tower 50, tower The various conditions of the methanol destilling tower 50 such as the temperature at bottom and the pressure of methanol destilling tower 50 and the steaming in methanol destilling tower 50 It is identical with first embodiment to evaporate later operation.According to this method, it is fewer than first embodiment that MTBE content can be obtained The methanol of high-purity.

According to the present embodiment, in the same manner as first embodiment can using bypass line A1b, A1c, A1d, A2, B or D carries out the replacement of the catalyst of MTBE synthesis reactor 5.

In the case where that will clean stream (a) and send via bypass line D to the second extractor 40, lead in the second extractor 40 Hydrocarbon mixture and MTBE is discharged via pipeline L8, via pipeline L9 with water in contact of the over cleaning stream (a) with water in the form of oily phase The form discharge first alcohol and water of phase is simultaneously fed in methanol destilling tower 50.In methanol destilling tower 50, by methanol and moisture From, therefore can suitably recycle methanol.

In the case where including a large amount of methanol in cleaning stream (a), it will be cleaned via bypass line A (A1b, A1c, A1d, A2) Stream (a) is sent to methanol destilling tower 50, and recycling methanol is appropriate in stream (F9).In the case, the first of cleaning stream (a) Determining alcohol is high, thus will clean flow (a) and be supplied in methanol destilling tower 50 via bypass line A in the case where, using with height In the bypass line A1d of the entrance 50ia connection of entrance 50ib be appropriate.

In the case where that will clean stream (b) and send via bypass line D to the second extractor 40, in the second extractor 40, Cleaning stream (b) is contacted with water, but is hardly formed oily phase, cleaning flow (b) in the form of the water phase comprising first alcohol and water via Pipeline L9 discharge, and be supplied in methanol destilling tower 50.In methanol destilling tower 50, methanol is separated from water, therefore can be fitted When recycling methanol, water can also be recycled.

(third embodiment)

The manufacturing method of the MTBE of third embodiment of the present invention is illustrated.

Firstly, being illustrated referring to manufacturing device 300 of the Fig. 3 to the MTBE of present embodiment.

The manufacturing device 100 mainly has MTBE synthesis reactor 5, MTBE destilling tower 10, methanol destilling tower 50, first mentions Take device 60 and bypass line A1b, A1d, A2 and B.

About MTBE synthesis reactor 5, MTBE destilling tower 10, methanol destilling tower 50, the first extractor 60 and they Connection relationship, it is identical with first embodiment other than pipeline L13 directly connect this point with methanol destilling tower 50.

Bypass line A1b is the pipeline of connecting pipeline L and pipeline L13, and bypass line A1d is connecting pipeline L1 and methanol steams Evaporate the pipeline of the entrance 50ia of tower 50, they by MTBE synthesis reactor 5 outlet 5o and methanol destilling tower 50 entrance 50ib Or 50ia is not connected via MTBE destilling tower 10, the first extractor 60.

Bypass line A2 is the pipeline of connecting pipeline L1 and tank 55, and the outlet 5o of MTBE synthesis reactor 5 and methanol are steamed The reflux inlet 50r of tower 50 is evaporated not via MTBE destilling tower 10, the first extractor 60 and is connected via tank 55 and reflux pipeline L18 It connects.

In the state of synthesizing MTBE in MTBE synthesis reactor 5, these bypass lines A1b, A1d, A2 and B are sealed It closes.

(manufacturing method of MTBE)

Then, the manufacturing method of the MTBE of present embodiment is illustrated.

Firstly, the stream (F0) comprising MTBE is generated in MTBE synthesis reactor 5 in the same manner as first embodiment, Stream (F0) is distilled in MTBE destilling tower 10 and generates stream (F6), stream (F1) and stream (F17), is mentioned first It takes in device 60 and stream (F3) and stream (F12) is generated by stream (F6).Various conditions of each process etc. and first embodiment phase Together, therefore record is omitted.

(replacement of the catalyst in MTBE synthesis reactor)

As described above, in supply hydrocarbon mixture and methanol into MTBE synthesis reactor 5 and with the form system of stream (F5) When making MTBE, the activity of the catalyst in MTBE synthesis reactor 5 is reduced with the time sometimes.In this case it is desirable to more Change the catalyst in MTBE synthesis reactor 5.Hydrocarbon mixture, MTBE and methanol are contained due to absorption etc. in catalyst, because This removes them preferably before more catalyst changeout out of catalyst.Hereinafter, being illustrated to this method.

Firstly, stopping the supply of the hydrocarbon mixture into MTBE synthesis reactor 5.Then, it is supplied to MTBE synthesis reactor 5 To methanol, dissolve out the hydrocarbon mixture for including in catalyst and MTBE into methanol, and packet is discharged from MTBE synthesis reactor 5 The cleaning stream (a) of hydrocarbon-containing mixture, MTBE and methanol.The pressure of the temperature of the methanol of supply and MTBE synthesis reactor 5 can be with It is identical with first embodiment.

It is opposite to catalyst supply in order to dissolve out the hydrocarbon mixture contained in catalyst and MTBE fully in methanol In the apparent volume of catalyst is 1 times or more, the methanol of preferably 10 times or more of volume is appropriate.Therefore, preferably not right Cleaning stream is burned, and is appropriate by the Methanol Recovery in cleaning stream.However, MTBE destilling tower 10 is not suitable for flowing cleaning (a) the high stream of methanol concentration as is distilled.

Therefore, cleaning stream (a) liquid is sent via bypass line A1b, A1d or A2 to methanol destilling tower 50 or via bypass Pipeline B is sent to the first extractor 60.

In the case where that will clean stream (a) and send via bypass line A1b, A1d or A2 to methanol destilling tower 50, pass through cleaning Water is discharged from pipeline L11 from pipeline L10 discharge hydrocarbon mixture, the mixture of MTBE and methanol in the distillation for flowing (a).

In the case where that will clean stream (a) and send via bypass line B to the first extractor 60, in the first extractor 60, Contact by cleaning stream (a) with water, is discharged hydrocarbon mixture and MTBE via pipeline L15, via pipeline L13 in the form of oily phase First alcohol and water is discharged in the form of water phase and is fed in methanol destilling tower 50.In methanol destilling tower 50, by methanol with Water separation, therefore can suitably recycle methanol.

In the case where including a large amount of methanol in cleaning stream (a), cleaning is flowed via bypass line A (A1b, A1d, A2) (a) it send to methanol destilling tower 50, and recycling methanol is appropriate in stream (F9).In the case, cleaning stream (a) is due to first Determining alcohol is high, therefore in the case where being supplied in methanol destilling tower 50, connect using with the entrance 50ia higher than entrance 50ib Bypass line A1d be appropriate.

The hydrocarbon mixture in catalyst and MTBE are sufficiently removed as a result, but are contained in catalyst due to absorption etc. There is methanol.

Therefore, after dissolution is into methanol, water is further supplied into MTBE synthesis reactor 5, thus by catalyst In include methanol dissolve out into water, and will dissolution have the water of methanol with clean stream (b) form from MTBE synthesis reactor 5 Discharge.The temperature of the water of supply and the pressure of MTBE synthesis reactor 5 can be set as identical with first embodiment.Usually exist When being initially supplied water, it is also supplied with methanol into MTBE synthesis reactor 5, slowly increases the amount of the water of supply, accompanying this The amount for reducing the methanol of supply, is finally stopped supply methanol, is only supplied water.

In order to dissolve out the methanol contained in catalyst fully in water, the table relative to catalyst is supplied to catalyst It is appropriate for seeing the water for the volume that volume is 1 times or more, preferably 10 times or more.Therefore, preferably cleaning stream (b) is not discharged to Outside system, preferably the methanol in cleaning stream is separated from water and is respectively recycled.However, unsuitable pair of MTBE destilling tower 10 The high stream of water concentration as cleaning stream (b) is distilled.

Therefore, cleaning stream (b) liquid is sent via bypass line A1b, A1d or A2 to methanol destilling tower 50 or via side Stylet B is sent to the first extractor 60.

In the case where that will clean stream (b) and send via bypass line A1b, A1d or A2 to methanol destilling tower 50, pass through steaming It evaporates, methanol is discharged from pipeline L10, water is discharged from pipeline L11.

In the case where that will clean stream (b) and send via bypass line B to the first extractor 60, in the first extractor 60, Cleaning stream (b) is contacted with water, but is hardly formed oily phase, cleaning flow (b) in the form of the water phase comprising first alcohol and water via Pipeline L13 discharge, and be supplied in methanol destilling tower 50.In methanol destilling tower 50, methanol is separated from water, therefore can be fitted Locality recycling methanol, recycling is also able to carry out to water.

After more catalyst changeout, if implementing washing and the methanol replacement of catalyst to MTBE synthesis reactor 5, then The supply for starting methanol and hydrocarbon mixture, then can restart the synthesis of MTBE.

It should be noted that as hydrocarbon mixture, MTBE and the first for including in catalyst is removed before more catalyst changeout The method of alcohol can also enumerate following methods in addition to the method described above.

Even if after discharge remains in the liquid in MTBE synthesis reactor 5, in catalyst also due to absorption etc. and contain There are hydrocarbon mixture, MTBE, methanol.Therefore, then supply methanol into MTBE synthesis reactor 5, thus make include in catalyst Hydrocarbon mixture and MTBE dissolve out into methanol, and from MTBE synthesis reactor 5 discharge include hydrocarbon mixture, MTBE and methanol Cleaning stream (a).The pressure of the temperature of the methanol of supply, the volume of methanol and MTBE synthesis reactor 5 and it is aforementioned.It will Cleaning stream (a) liquid, which is sent via bypass line A1b, A1d or A2 to methanol destilling tower 50 or send via bypass line B to first, to be mentioned Take the method for device 60 also with it is aforementioned.

By the hydrocarbon mixture in catalyst and after MTBE sufficiently removes, further supplied into MTBE synthesis reactor 5 Water supply, thus make the methanol for including in catalyst dissolution into water, and will dissolution have the water of methanol with clean stream (b) form from It is discharged in MTBE synthesis reactor 5.Pressure of the temperature of the water of supply, the volume of water and MTBE synthesis reactor 5 etc. with it is preceding It states the same.Cleaning stream (b) liquid is sent via bypass line A1b, A1d or A2 to methanol destilling tower 50 or via bypass line B Send to the first extractor 60 method also with it is aforementioned.In the method, in addition in catalyst hydrocarbon mixture and MTBE with Outside, methanol is also substantially removed.

(effect)

According to the present embodiment, have bypass line A1b, A1d, A2 or B.Thereby, it is possible to will dissolve out to have MTBE synthesis anti- The cleaning stream of the flammable compound contained in the catalyst of device 5 is answered not supply via MTBE destilling tower 10 and the first extractor 60 It is given in methanol destilling tower 50 or can not be supplied in the first extractor 60 via MTBE destilling tower 10.

Thereby, it is possible in the case where not generating adverse effect to MTBE destilling tower 10, suitably processing cleaning is flowed and carried out Recycling.

(other embodiment)

The present invention is not limited to the above embodiments, may exist various modifications mode.

For example, MTBE synthesis reactor 5 can be the synthesis reactor for being connected in series multiple unitary reactors.Example Such as, as shown in figure 4, MTBE synthesis reactor 5 have unitary reactor 5A, unitary reactor 5B and unitary reactor 5C and In the case that they are connected with being sequentially connected in series from the upstream side by pipeline, not only can by bypass line A1a, A1b, A1c, A1d, A2, B, C, D diverge after unitary reactor 5C, can also be between unitary reactor 5A and unitary reactor 5B Pipeline and/or unitary reactor 5B and unitary reactor 5C between pipeline diverge.That is, in MTBE synthesis reactor 5 In the case where multiple unitary reactors (such as 5A~5C) with series connection, bypass line A1a, A1b, A1c, A1d, A2, B, C, D can be by the outlets of any one unitary reactor (for example, the outlet 5Ao of unitary reactor 5A, unitary reactor 5B Export the outlet 5Co of 5Bo or unitary reactor 5C) with entrance 50ia, 50ib, 50r, the first extractor of methanol destilling tower 50 The entrance 30i of 60 entrance 60i, the entrance 40i of the second extractor 40 or decomposition product destilling tower 30 are (hereinafter referred to as specific The entrance of equipment) connection.

For example, in the case where replacing the catalyst of all unitary reactor 5A, 5B, 5C, can be used and unit process The bypass line of the downstream connection of device 5C, i.e. connection are located at the outlet 5Co and particular device of the unitary reactor 5C of most downstream The bypass line of entrance.In addition, in the case where only replacing the catalyst of unitary reactor 5A and 5B, in use from unit process Bypass line, the i.e. connection of pipeline fork between device 5B and unitary reactor 5C is located at second middle of number from upstream side Unitary reactor 5B outlet 5Bo and particular device entrance bypass line when, can not to unitary reactor 5C produce More catalyst changeout in the case where raw influence.In addition, in the case where only replacing the catalyst of unitary reactor 5A, in use from list The unitary reactor 5A's of bypass line, i.e. connection most upstream that pipeline between elementary reaction device 5A and unitary reactor 5B diverges It, can be the case where not had an impact to unitary reactor 5B and 5C when exporting the bypass line of the entrance of 5Ao and particular device Under more catalyst changeout.

Especially, from the viewpoint of the deterioration of the catalyst for the unitary reactor for easily causing most upstream side, setting from The bypass line of the unitary reactor of most upstream side and the pipeline fork from most upstream side between second unitary reactor of number, It is appropriate for connecting the bypass line of the outlet 5Ao of the unitary reactor of most upstream side and the entrance of particular device.

In addition, having multiple bypass lines in the above-described embodiment, but can also only have any one.

In addition, the connection form of bypass line is also not necessarily limited to the form of diagram.In the present specification, " A device and B are filled Set the pipeline not connected via C device " refer to: as long as A device is not connect with B device via C device, can be The pipeline that A device and B device are directly connected to, is also possible to the pipe for connecting A device via other pipelines or device with B device Line.

For example, bypass line A1a, A1b or A1c are by pipeline L1 and manage in first embodiment~third embodiment Line L7, pipeline L13 or pipeline L9 connection, but can also by the entrance of pipeline L1 and methanol destilling tower 50 (for example, 50ia or It 50ib) connects, the outlet 5o of MTBE synthesis reactor 5 can also be connect with pipeline L13, pipeline L7 or pipeline L9, it can also be with The outlet 5o of MTBE synthesis reactor 5 is connect with the entrance (for example, 50ia or 50ib) of methanol destilling tower 50.

In addition, in second embodiment~third embodiment, bypass line A1d is by pipeline L1 and methanol destilling tower 50 Entrance 50ia connection, but can also by MTBE synthesis reactor 5 outlet 5o and methanol destilling tower 50 entrance 50ia connect It connects.

In addition, in the above-described embodiment, pipeline L1 is connect by bypass line A2 with tank 55, but can also be by pipeline L1 It connect, pipeline L1 can also be connect with reflux pipeline L18 with pipeline L10, it can also be by the outlet 5o of MTBE synthesis reactor 5 It connect, the outlet 5o of MTBE synthesis reactor 5 can also be connect with pipeline L10 or reflux pipeline L18 with tank 55.

In addition, in the above-described embodiment, pipeline L1 is connect by bypass line B with pipeline L2, but can also be by MTBE The outlet 5o of synthesis reactor 5 is connect with the entrance 60i of the first extractor 60, pipeline L1 can also be connect with entrance 60i, Outlet 5o can be connect with pipeline L2.

In addition, in the above-described embodiment, pipeline L1 is connect by bypass line C with pipeline L5, but can also be by pipeline L1 is connect with the entrance (such as 30i) of decomposition product destilling tower 30, by the outlet 5o of MTBE synthesis reactor 5 and can also be decomposed The entrance (such as 30i) of product destilling tower 30 connects.

In addition, in the above-described embodiment, pipeline L1 is connect by bypass line D with pipeline L5, but can also be by pipeline L1 is connect with the entrance (such as 40i) of the second extractor 40, the outlet 5o of MTBE synthesis reactor 5 and second can also be extracted The entrance (such as 40i) of device 40 connects.

In the above-described embodiment, the entrance 50ia of methanol destilling tower 50 is different from the height of entrance 50ib, but even if It is highly identical also to implement.

In addition, in the present specification, " device B has the entrance with the outlet connection of device A " not only includes going out for device A The case where mouth is not connect with the entrance of device B via other processing units, also comprising being connected via other processing units Situation.As other processing units, for example, make unreacted component again the latter stage reactor of secondary response, reduce accessory ingredient it is dense Separators such as the destilling tower of degree etc..

For example, can have the 2nd MTBE synthetic reaction in the pipeline L2 in first embodiment~third embodiment Device, the 2nd MTBE synthesis reactor pass through make from tower top outlet 10t be discharged stream (F6) in unreacted methanol with C4 hydrocarbon reaction and generate MTBE.In the case, the first extractor 60 has and connect with the tower top outlet 10t of MTBE destilling tower 10 Entrance 60i.

In addition, in the above-described embodiment, MTBE destilling tower 10 has following constitute: from tower top outlet 10t via pipeline Low-boiling compound is discharged in L2, and higher-boiling compound is discharged from tower bottom outlet 10b via pipeline L3, goes out from the side of the centre of tower Mouth 10s is discharged via pipeline L4 makees midbarrel as main component with MTBE, but does not have as shown in figure 5, also using sometimes There is the MTBE destilling tower 10 of side outlet 10s.It, can using the MTBE destilling tower 10 for exporting 10s without side The entrance 20i of tower bottom outlet 10b and MTBE decomposition reactor 20 to be directly connected to, but via 1 or multiple additions It is appropriate that destilling tower is connect with the entrance 20i of MTBE decomposition reactor 20.For example, as shown in figure 5, can be in the first order In MTBE destilling tower 10, low-boiling compound is extracted out from tower top outlet 10t, from tower bottom outlet 10b extraction with higher-boiling compound And MTBE makees midbarrel as main component, and is supplied in the destilling tower 10 ' of rear stage via pipeline L4 ', rear In the destilling tower 10 ' of level-one, is extracted out from 10 ' t of tower top outlet and midbarrel as main component is made with MTBE, and via pipeline L4 is supplied to the entrance 20i of MTBE decomposition reactor 20, exports 10 ' b from tower bottom and extracts higher-boiling compound out via pipeline L3.

In the case, additional destilling tower 10 ' is equivalent to the tower bottom outlet 10b and MTBE that MTBE destilling tower 10 is arranged in The processing unit of addition between the entrance 20i of decomposition reactor 20, in the case, the entrance of MTBE decomposition reactor 20 20i is connect via the destilling tower 10 ' of rear stage with the tower bottom of MTBE destilling tower 10 outlet 10b.

In addition, in the first embodiment, a part will be removed in decomposition product destilling tower 30 from MTBE decomposition reaction Stream (F2B (F2)) after the methanol in stream (F2A (F2)) that device 20 is discharged is supplied in the second extractor 40, real second It applies in mode, will be supplied to as former state in the second extractor 40 from the stream (F2) that MTBE decomposition reactor 20 is discharged, and by The oil of two extractors 40 is mutually supplied in decomposition product destilling tower 30.However, being not provided with decomposition product destilling tower 30 It is enough to implement.

In addition, decomposition product destilling tower 30 can have a reflux portion, the reflux portion by the gas being discharged from top layer again It is flowed back into destilling tower after secondary condensation.In addition, methanol destilling tower 50 and decomposition product destilling tower 30 can have reboiler, it is described Reboiler again returns in destilling tower after heating the liquid being discharged from lowest level.In addition, destilling tower is with multiple tower trays Plate column be appropriate, but may be packed tower.

In the above-described embodiment, as the second extractor 40 and the first extractor 60, the extractor of tower is illustrated, but It is not limited to this.As the extractor of tower, can be appropriately used such as tower, rotating circular disk tower and porous template by spraying Extractor, in addition, as the extractor in addition to tower, such as have the extractor etc. of the groove profiles such as mixing sedimentation type.

Claims

1. a kind of manufacturing device of MTBE, has:

MTBE synthesis reactor, the MTBE synthesis reactor include entrance, the Yi Jipai of MTBE raw material of the supply comprising methanol The outlet of reaction product out；

MTBE destilling tower, the MTBE destilling tower is included to be gone out with entrance, the tower top of the outlet connection of the MTBE synthesis reactor Mouth and tower bottom outlet；

First extractor, first extractor include the entrance connecting with the tower top outlet of the MTBE destilling tower, supply The water phase outlet of the water phase of water inlet, discharge comprising methanol of water supply and the oil that oily phase is discharged mutually export；

Methanol destilling tower, the methanol destilling tower include entrance, the tower with the water phase of first extractor outlet connection Eject mouth and tower bottom outlet；And

At least one of pipeline A and pipeline B below:

Pipeline A, the pipeline A export the entrance with the methanol destilling tower not via described for the MTBE synthesis reactor MTBE destilling tower and first extractor and connect, wherein the MTBE synthesis reactor have be connected in series it is multiple The outlet of the MTBE synthesis reactor is the outlet of any one of unitary reactor in the case where unitary reactor；

Pipeline B, the pipeline B export the entrance with first extractor not via described for the MTBE synthesis reactor MTBE destilling tower and connect, wherein the MTBE synthesis reactor have be connected in series multiple unitary reactors the case where Under the MTBE synthesis reactor outlet be any one of unitary reactor outlet.

2. device as described in claim 1, wherein

The MTBE synthesis reactor has the multiple unitary reactors being connected in series,

The pipeline A connects the entrance of pipeline and the methanol destilling tower between the unitary reactor,

The pipeline B connects the entrance of pipeline and first extractor between the unitary reactor.

3. a kind of manufacturing device of isobutene, has:

MTBE synthesis reactor, the MTBE synthesis reactor include the entrance and discharge reaction product of supply MTBE raw material Outlet；

MTBE destilling tower, the MTBE destilling tower has to be gone out with entrance, the tower top of the outlet connection of the MTBE synthesis reactor Mouth and tower bottom outlet；Or the entrance with the outlet connection with the MTBE synthesis reactor, tower top outlet, tower bottom export And side outlet；

MTBE decomposition reactor, the MTBE decomposition reactor include with the tower bottom of the MTBE destilling tower outlet or The outlet of the MTBE decomposition product of entrance and discharge comprising isobutene and methanol of side outlet connection；

Decomposition product destilling tower, what the outlet that the decomposition product destilling tower includes with the MTBE decomposition reactor connected enters Mouth, tower top outlet and tower bottom outlet；

Methanol destilling tower, the methanol destilling tower is included to be entered with what the outlet of the tower bottom of the decomposition product destilling tower connected Mouth, tower top outlet and tower bottom outlet；And

At least one of pipeline A and pipeline C below:

Pipeline A, the pipeline A export the entrance with the methanol destilling tower not via described for the MTBE synthesis reactor MTBE destilling tower, the MTBE decomposition reactor and the decomposition product destilling tower and connect, wherein it is anti-in MTBE synthesis The outlet of the MTBE synthesis reactor is any one institute in the case where answering device to have the multiple unitary reactors being connected in series State the outlet of unitary reactor；

Pipeline C, the pipeline C by the outlet of the MTBE synthesis reactor and the entrance of the decomposition product destilling tower not via The MTBE destilling tower and the MTBE decomposition reactor and connect, wherein the MTBE synthesis reactor have series connection connect The outlet of the MTBE synthesis reactor is any one of unitary reactor in the case where the multiple unitary reactors connect Outlet.

4. device as claimed in claim 3, wherein

The pipeline C connects the entrance of pipeline and the decomposition product destilling tower between the unitary reactor.

5. a kind of manufacturing device of isobutene, has:

MTBE destilling tower, the MTBE destilling tower has to be gone out with entrance, the tower top of the outlet connection of the MTBE synthesis reactor Mouth and tower bottom outlet；Or the entrance with the outlet connection with the MTBE synthesis reactor, tower top outlet, tower bottom go out Mouth and side outlet；

Methanol destilling tower, the methanol destilling tower include with the tower bottom of the decomposition product destilling tower outlet and/or it is described Entrance, tower top outlet and the tower bottom outlet of the water phase outlet connection of first extractor；And

At least one of pipeline A~pipeline C below:

Pipeline A, the pipeline A export the entrance with the methanol destilling tower not via described for the MTBE synthesis reactor MTBE destilling tower, first extractor, the MTBE decomposition reactor and the decomposition product destilling tower and connect, In, the MTBE synthesis reactor in the case where the MTBE synthesis reactor has the multiple unitary reactors being connected in series Outlet be any one of unitary reactor outlet；

Pipeline B, the pipeline B export the entrance with first extractor not via described for the MTBE synthesis reactor MTBE destilling tower and connect, wherein the MTBE synthesis reactor have be connected in series multiple unitary reactors the case where Under the MTBE synthesis reactor outlet be any one of unitary reactor outlet；

6. device as claimed in claim 5, wherein

The pipeline B connects the entrance of pipeline and first extractor between the unitary reactor,

7. a kind of manufacturing device of isobutene, has:

Second extractor, second extractor include and the entrance of the outlet connection of the MTBE decomposition reactor, supply water The water phase of water inlet, discharge comprising methanol water phase outlet and the oil of oily phase be discharged mutually export；

Methanol destilling tower, the methanol destilling tower include entrance, the tower with the water phase of second extractor outlet connection Eject mouth and tower bottom outlet；And

At least one of pipeline A and pipeline D below:

Pipeline A, the pipeline A export the entrance with the methanol destilling tower not via described for the MTBE synthesis reactor MTBE destilling tower, the MTBE decomposition reactor and second extractor and connect, wherein in the MTBE synthesis reactor The outlet of the MTBE synthesis reactor is any one of list in the case where multiple unitary reactors with series connection The outlet of elementary reaction device；

Pipeline D, the pipeline D export the entrance with second extractor not via described for the MTBE synthesis reactor MTBE destilling tower and the MTBE decomposition reactor and connect, wherein the MTBE synthesis reactor have be connected in series The outlet of the MTBE synthesis reactor is the outlet of any one of unitary reactor in the case where multiple unitary reactors.

8. device as claimed in claim 7, wherein

The pipeline D connects the entrance of pipeline and second extractor between the unitary reactor.

9. a kind of manufacturing device of isobutene, has:

Methanol destilling tower, the methanol destilling tower include and the outlet of the water phase of first extractor and/or described second Entrance, tower top outlet and the tower bottom outlet of the water phase outlet connection of extractor；And

At least one of pipeline A, pipeline B and pipeline D below:

Pipeline A, the pipeline A export the entrance with the methanol destilling tower not via described for the MTBE synthesis reactor MTBE destilling tower, first extractor, the MTBE decomposition reactor and second extractor and connect, wherein in institute The outlet of the MTBE synthesis reactor in the case where MTBE synthesis reactor is stated with the multiple unitary reactors being connected in series For the outlet of any one of unitary reactor；

Pipeline B, the pipeline B export the entrance with first extractor not via described for the MTBE synthesis reactor MTBE destilling tower and connect, wherein the MTBE synthesis reactor have be connected in series multiple unitary reactors the case where Under the MTBE synthesis reactor outlet be any one of unitary reactor outlet；And

10. device as claimed in claim 9, wherein

11. a kind of manufacturing method of MTBE, to use the system of the MTBE of the manufacturing device of MTBE described in as claimed in claim 1 or 22 Method is made, has following process:

Into the MTBE synthesis reactor for contain catalyst supply comprising isobutene hydrocarbon mixture and methanol to The process for manufacturing MTBE；

After the supply for stopping the hydrocarbon mixture, methanol is supplied in Xiang Suoshu MTBE synthesis reactor, to obtain described The process that the hydrocarbon mixture and MTBE for including in catalyst dissolve out the cleaning stream a into methanol；

Cleaning stream a is sent via the pipeline A to the methanol destilling tower or is sent via the pipeline B to described first The process of extractor；

Supply water further into the MTBE synthesis reactor to obtain the methanol for including in catalyst dissolution to water In cleaning stream b process；

Cleaning stream b is sent via the pipeline A to the methanol destilling tower or is sent via the pipeline B to described first The process of extractor.

12. a kind of manufacturing method of isobutene, to use the isobutyl of the manufacturing device of isobutene described in claim 3 or 4 The manufacturing method of alkene, has:

Into the MTBE synthesis reactor for contain catalyst supply comprising isobutene hydrocarbon mixture and methanol to The process for manufacturing isobutene；

Cleaning stream a is sent via the pipeline A to the methanol destilling tower or is sent via the pipeline C to the decomposition The process of product destilling tower；

Water is further supplied into the MTBE synthesis reactor, to obtain the methanol for including in catalyst dissolution to water In cleaning stream b process；

Cleaning stream b is sent via the pipeline A to the methanol destilling tower or is sent via the pipeline C to the decomposition The process of product destilling tower.

13. a kind of manufacturing method of isobutene, to use the isobutyl of the manufacturing device of isobutene described in claim 5 or 6 The manufacturing method of alkene, has:

Cleaning stream a is sent via the pipeline A to the methanol destilling tower；Or it send via the pipeline B to described One extractor；Or it send via the pipeline C to the process of the decomposition product destilling tower；

Cleaning stream b is sent via the pipeline A to the methanol destilling tower；Or it send via the pipeline B to described One extractor；Or it send via the pipeline C to the process of the decomposition product destilling tower.

14. a kind of manufacturing method of isobutene, to use the isobutyl of the manufacturing device of isobutene described in claim 7 or 8 The manufacturing method of alkene, has:

Cleaning stream a is sent via the pipeline A to the methanol destilling tower or is sent via the pipeline D to described second The process of extractor；

Cleaning stream b is sent via the pipeline A to the methanol destilling tower or is sent via the pipeline D to described second The process of extractor.

15. a kind of manufacturing method of isobutene, to use the isobutyl of the manufacturing device of isobutene described in claim 9 or 10 The manufacturing method of alkene, has:

Cleaning stream a is sent via the pipeline A to the methanol destilling tower；Or it send via the pipeline B to described One extractor；Or it send via the pipeline D to the process of second extractor；

Cleaning stream b is sent via the pipeline A to the methanol destilling tower；Or it send via the pipeline B to described One extractor；Or it send via the pipeline D to the process of second extractor.