CN109776247A

CN109776247A - The manufacturing method of isobutene and the manufacturing device of isobutene

Info

Publication number: CN109776247A
Application number: CN201910221197.4A
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: 2019-03-22
Publication date: 2019-05-21

Abstract

The present invention relates to the manufacturing method of isobutene and the manufacturing devices of isobutene.The present invention provides a kind of manufacturing method of good isobutene of the thermal efficiency using MTBE as raw material.This method is with the following process: the stream (F1) comprising MTBE is supplied the process into MTBE decomposition reactor to obtain the gas streams (F2) comprising isobutene and methanol by (A)；Process of (B) the cooling gas stream (F2) to obtain the stream (F3) including at least liquid phase.Process (B) is with the following process: the process that (B1) carries out heat exchange between gas streams (F2) and stream (F1)；(B2) is in the process for carrying out carrying out heat exchange between the gas streams (F2) after heat exchange and the process stream (FP) in addition to stream (F1).

Description

The manufacturing method of isobutene and the manufacturing device of isobutene

Technical field

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

Background technique

Methyl tertiary butyl ether(MTBE) (MTBE) is decomposed into isobutene and methanol known to previous, and by methanol point from decomposition product From the method to obtain isobutene.

Existing technical literature

Patent document 1: Japanese Unexamined Patent Application Publication 2012-531475 bulletin

Summary of the invention

Problem to be solved by the invention

In recent years, it is desirable that the manufacturing method of the better isobutene of the thermal efficiency.

The present invention has been made in view of the above problems, the thermal efficiency that its purpose is to provide a kind of using MTBE as raw material The manufacturing method of good isobutene and the manufacturing device of isobutene.On the other hand, the purpose of the present invention is to provide one kind It is more preferable using MTBE as the thermal efficiency of raw material, facilitate energy conservation and can reduce production cost to industrially extremely beneficial The manufacturing method of isobutene and the manufacturing device of isobutene.

The means used to solve the problem

The manufacturing method of isobutene according to the present invention is with the following process:

(A) stream (F1) comprising MTBE is supplied into MTBE decomposition reactor to obtain comprising isobutene and methanol Gas streams (F2) process；With

(B) process of the cooling gas streams (F2) to obtain the stream (F3) including at least liquid phase,

The process (B) is with the following process:

(B1) process of heat exchange is carried out between the gas streams (F2) and the stream (F1)；With

(B2) in the gas streams (F2) and the process stream in addition to the stream (F1) after the heat exchange (FP) process of heat exchange is carried out between.

Thereby, it is possible to the thermal energy in the gas streams (F2) for effectively recycling the high temperature being discharged from MTBE decomposition reactor While obtain the stream (F3) comprising liquid phase.

It is preferred here that the temperature of the process stream (FP) before heat exchange in the process (B2) is lower than institute The temperature of the stream (F1) before stating the heat exchange in process (B1).

In addition, the above method can be also with the following process:

To have and supply to one or be connected in series multiple lower than the stream (F0) of the MTBE concentration of the stream (F1) Process in first destilling tower to obtain the stream (F1),

The process stream (FP) can be the stream (F0), the stream flowed between first destilling tower or appoint The tower bottom liquid of one first destilling tower of meaning.

In the case where process stream (FP) is stream (F0) or the stream flowed between the first destilling tower, stream (F2) Heat is supplied to the entrance stream of any one the first destilling tower of purifying MTBE, is the first destilling tower at process stream (FP) Tower bottom liquid in the case where, the heat of stream (F2) is supplied to the tower bottom liquid of the first destilling tower, therefore in any one situation Under may be by the distillation of the heat of stream (F2) as purifying MTBE heat source a part.

In the case where process stream (FP) is the tower bottom liquid of the first destilling tower, can be set to outside the first destilling tower Make to again return to after being retracted to external tower bottom liquid and stream (F2) progress heat exchange in the first destilling tower in heat exchanger The bottom of first destilling tower.

In addition, the above method can be also with the following process:

To have and supply to one or be connected in series multiple lower than the stream (F0) of the MTBE concentration of the stream (F1) In first destilling tower, so that the concentration for obtaining the hydrocarbon that the stream (F1) and carbon atom number are 4 is higher than the stream (F1) simultaneously It and include the process of the stream (F6) of methanol；

Contact the stream (F6) with water, thus obtain with carbon atom number be 4 hydrocarbon based on stream (F16) and Main includes the process of water, the also stream (F15) comprising methanol；With

By the stream (F15) supply into third destilling tower, to obtain stream (F9) He Yishui based on methanol Based on stream (F10) process,

The process stream (FP) can be the tower bottom liquid of the stream (F15) or the third destilling tower.

The heat of stream (F2) is supplied to the entrance stream or tower bottom liquid of third destilling tower as a result, therefore can utilize The a part of the heat of stream (F2) as the heat source of distillation.

In addition, the above method can have following process:

By the stream (F3) supply into after-fractionating tower, so as to obtain mainly include isobutene, also includes in tower top The stream (F4) of methanol, in the process that tower bottom obtains the stream (F11) based on methanol；

Contact the stream (F4) with water, thus obtain stream (F5) based on isobutene and mainly comprising water, The also process of the stream (F8) comprising methanol；With

By the stream (F8) and the stream (F11) supply into third destilling tower, to obtain based on methanol The process of stream (F10) based on stream (F9) He Yishui,

The process stream (FP) can be the tower of the stream (F8), the stream (F11) or the third destilling tower Bottom liquid.

The heat of stream (F2) is supplied to the tower bottom liquid of after-fractionating tower or third destilling tower as a result, or third is steamed The entrance stream of tower is evaporated, therefore can be using the heat of stream (F2) as a part of the heat source of each distillation.

In addition, the above method can have following process:

Contact the stream (F3) with water, thus obtain stream (F5) based on isobutene and mainly comprising water, The also process of the stream (F8) comprising methanol；

By the stream (F5) supply into after-fractionating tower, to obtain the stream based on isobutene in tower top (F18), the process for obtaining being higher than with boiling point the stream (F19) based on the ingredient of isobutene in tower bottom；With

By the stream (F8) supply into third destilling tower, to obtain stream (F9) based on methanol and with water Based on stream (F10) process,

The process stream (FP) can be stream (F8), the tower bottom liquid of the after-fractionating tower or third distillation The tower bottom liquid of tower.

In addition, the above method can have following process:

Contact the stream (F3) with water, thus obtain stream (F5) based on isobutene and mainly comprising water, The also process of the stream (F8) comprising methanol；With

By the stream (F8) supply into third destilling tower, to obtain stream (F9) based on methanol and be with water The process of main stream (F10),

The process stream (FP) can be the tower bottom liquid of the stream (F8) or the third destilling tower.

In addition, the above method can have following process:

To have and supply to one or be connected in series multiple lower than the stream (F0) of the MTBE concentration of the stream (F1) In first destilling tower, thus the process for obtaining the stream (F1)；With

By the stream (F3) supply into after-fractionating tower, so as to obtain mainly include isobutene, also includes in tower top The stream (F4) of methanol, in the process that tower bottom obtains the stream (F11) based on methanol,

The process stream (FP) can be the stream (F0).

In addition, the above method can have following process:

To have and supply to one or be connected in series multiple lower than the stream (F0) of the MTBE concentration of the stream (F1) In first destilling tower, thus the process for obtaining the stream (F1)；

The process stream (FP) can be the stream (F0).

In addition, the above method can be also with the following process: by the hydrocarbon mixture comprising isobutene and methanol supply to In MTBE synthesis reactor, react the isobutene in hydrocarbon mixture with methanol, to obtain the stream (F0) comprising MTBE Process.

The manufacturing device of isobutene according to the present invention has:

First destilling tower, first destilling tower include the entrance of stream (F0) of the supply comprising MTBE, tower top outlet, And tower bottom outlet；

MTBE decomposition reactor, the MTBE decomposition reactor include and the outlet of the tower bottom of the first destilling tower or side outlet The outlet of the stream (F2) of entrance and discharge comprising isobutene and methanol of connection；

After-fractionating tower, the after-fractionating tower is included to be gone out with entrance, the tower top of the outlet connection of MTBE decomposition reactor Mouth and tower bottom outlet；

Pipeline L1, the pipeline L1 are connect with the entrance of the first destilling tower；

Pipeline L4, the tower bottom outlet of the first destilling tower of the pipeline L4 connection or entering for side outlet and MTBE decomposition reactor Mouthful；With

Pipeline L5, the outlet of the pipeline L5 connection MTBE decomposition reactor and the entrance of after-fractionating tower,

Pipeline L5 includes: heat is carried out between the stream (F1) flowed in pipeline L4 and the stream (F2) flowed in pipeline L5 The heat exchanger HE2 of exchange；With

The heat that heat exchange is carried out between the stream (F2) flowed in pipeline L5 and the stream (F0) flowed in pipeline L1 is handed over Parallel operation HE4,

In pipeline L5, it is arranged relative to heat exchanger HE2, heat exchanger HE4 in downstream side.

Above-mentioned apparatus can be also equipped with:

First extractor, first extractor include the entrance connecting with the tower top outlet of after-fractionating tower, are supplied to Water inlet, tower top outlet and the tower bottom outlet of water；With

Methanol destilling tower, the methanol destilling tower include entrance, the tower with the tower bottom of the first extractor outlet connection Eject mouth and tower bottom outlet.

Above-mentioned apparatus can be also equipped with:

MTBE synthesis reactor, the MTBE synthesis reactor includes the entrance for being supplied to MTBE raw material and discharge includes The outlet of the stream (F0) of MTBE,

The pipeline L1 can be the pipeline of the entrance of the outlet and the first destilling tower of connection MTBE synthesis reactor.

Invention effect

According to the present invention, the manufacture for the good isobutene of the thermal efficiency that its purpose is to provide a kind of using MTBE as raw material The manufacturing device of method and isobutene.Preferred embodiment according to the present invention, the present invention are capable of providing one kind using MTBE as raw material The thermal efficiency it is more preferable, facilitate energy conservation and can reduce production cost to the manufacturer of industrially extremely beneficial isobutene The manufacturing device of method and isobutene.

Detailed description of the invention

Fig. 1 is the manufacturing flow chart of isobutene involved in first embodiment and embodiment 1 of the invention.

Fig. 2 is the manufacturing flow chart of isobutene involved in second embodiment of the present invention.

Fig. 3 is the purifying flow chart of MTBE involved in another embodiment of the present invention.

Fig. 4 is the manufacturing flow chart of isobutene involved in embodiment 2.

Fig. 5 is the manufacturing flow chart of isobutene involved in comparative example 1.

Appended drawing reference

20 ... MTBE decomposition reactors

10 ... first destilling towers

The first destilling tower of 10A, 10B, 10C ...

30 ... after-fractionating towers

40 ... first extractors

50 ... third destilling towers

60 ... second extractors

100, the manufacturing device of 200,400,500 ... isobutenes

Specific embodiment

In the present specification, isobutene refers to 2- metering system.

In the present specification, in the feelings for being recorded as " main includes the stream of ingredient α " or " stream based on ingredient α " Under condition, refer to that the concentration of ingredient α in the concentration of each ingredient included in the stream is maximum.

(first embodiment)

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

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

The manufacturing device 100 has: the raw material source S of base feed stream (F0), the first destilling tower 10, MTBE decomposition reaction Device 20, after-fractionating tower 30, the first extractor 40, third destilling tower 50, the second extractor 60 and heat exchanger HE2, HE4, HE6、HE8、HE10、HE12、HE14、HE16。

Raw material source S and the first destilling tower 10 are connected by pipeline L1.It is connected with pipeline L2 in the tower top of the first destilling tower 10, It is connected with pipeline L3 in tower bottom, is connected with pipeline L4 in the side of tower.It is provided on first destilling tower 10 and is discharged to tower bottom liquid The pipeline L21 in the first destilling tower 10 is returned again to behind outside.The heat exchange for heating tower bottom liquid is provided on pipeline L21 Device (reboiler) HE6.

Pipeline L4 is connect with MTBE decomposition reactor 20.MTBE decomposition reactor 20 and after-fractionating tower 30 pass through pipeline L5 Connection.

Heat exchanger HE2 carries out heat exchange between pipeline L4 and pipeline L5.Heat exchanger HE4 is in pipeline L1 and pipeline L5 Between carry out heat exchange.On pipeline L5, relative to heat exchanger HE4, heat exchanger HE2 is configured in upstream side, i.e. MTBE 20 side of decomposition reactor, relative to heat exchanger HE2, heat exchanger HE4 is arranged on downstream side, i.e. after-fractionating tower 30 1 Side.

It is connected with pipeline L6 in the tower top of after-fractionating tower 30, is connected with pipeline L7 in tower bottom.It is set on after-fractionating tower 30 It is equipped with the pipeline L22 returned again in after-fractionating tower 30 after being discharged to the outside tower bottom liquid.It is provided with and is used on pipeline L22 Heat heat exchanger (reboiler) HE8 of tower bottom liquid.

Pipeline L6 is connect with the first extractor 40.Water is supplied into the first extractor 40 by pipeline L14.It is extracted first The tower top of device 40 is connected with pipeline L8, is connected with pipeline L9 in tower bottom.

Second extractor 60 is connect with the pipeline L2 of the first destilling tower 10.It is supplied by pipeline L15 into the second extractor 60 Water supply.It is connected with pipeline L17 in the tower top of the second extractor 60, is connected with pipeline L16 in tower bottom.

Pipeline L7 from after-fractionating tower 30, the pipeline L9 from the first extractor 40 and come from the second extractor 60 Pipeline L16 respectively connect with third destilling tower 50.

The height of connecting pipeline L7 in third destilling tower 50 is higher than the height of connecting pipeline L9 and connecting pipeline L16.That is, Pipeline L7 supplies stream to the position for being higher than pipeline L9 and pipeline L16.

Third destilling tower 50 can be packed tower, or the plate column with multiple column plates (tower tray) 50a.Board-like In the case where tower, the height of the column plate 50a1 (50a) of connecting pipeline L7 in third destilling tower 50 is preferably made to be higher than connecting pipeline L9 With the height of the column plate 50a2 (50a) of pipeline L16.The difference of the number of plates is 1 layer or more, or 2 layers or more.

Be each provided on pipeline L7, pipeline L9 and pipeline L16 heat exchanger HE12, HE14 that stream is heated and HE10。

It is connected with pipeline L10 in the tower top of third destilling tower 50, is connected with pipeline L11 in tower bottom.On third destilling tower 50 It is provided with the pipeline L23 returned again in third destilling tower 50 after being discharged to the outside tower bottom liquid.It is arranged on pipeline L23 useful In heat exchanger (reboiler) HE16 of heating tower bottom liquid.

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

(feed stream (F0))

Firstly, preparing the feed stream (F0) comprising MTBE as raw material source S.

Feed stream (F0) includes MTBE (methyl tertiary butyl ether(MTBE)) and the compound in addition to MTBE.

The example of compound in addition to MTBE is hydrocarbon, the ether in addition to MTBE, alcohol.

The example of hydrocarbon is that the carbon atom numbers such as isobutene, iso-butane, normal butane, 1- butylene, 2- butylene, 1,3-butadiene are 4 Hydrocarbon；The hydrocarbon that the carbon atom numbers such as Diisobutylene are 8；The hydrocarbon that the carbon atom numbers such as propane, propylene, allene, propine are 3；Pentane, The hydrocarbon that the carbon atom numbers such as amylene, isopentane are 5.

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

The example of alcohol is methanol, the tert-butyl alcohol (TBA).

Feed stream (F0) can wrap aqueous.

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

Such feed stream (F0) can be for by keeping isobutene in the hydrocarbon mixture comprising isobutene and methanol anti- Contain the stream of MTBE obtained from answering.

The manufacturing method of isobutene of the invention can be also with the following process: by hydrocarbon mixture and first comprising isobutene Alcohol is supplied into MTBE synthesis reactor, thus the process for obtaining the stream containing MTBE.

The example of hydrocarbon mixture comprising isobutyl alkene can be enumerated: the carbon atom obtained by the steam pyrolysis of naphtha Count the hydrocarbon-fraction (C 4 fraction) for being 4 or by extracting or selecting fraction (the remaining BB after adding hydrogen therefrom to remove 1,3- butadiene Fraction (スペ Application ト BB stay point))；The hydrocarbon mixture (FCC-C4) that the carbon atom number as obtained from fluid catalytic cracking is 4；Make It include the mixture of isobutene obtained from dehydrogenation of isobutane；It include the mixture of isobutene obtained from being dehydrated TBA；And Include the mixture of isobutene as obtained from the skeletal isomerization of 1- butylene or 2- butylene；And their mixture.Institute State the example of the hydrocarbon in addition to isobutene in hydrocarbon mixture are as follows: iso-butane, normal butane, 1- butylene, 2- butylene, 1,3- butadiene Etc. carbon atom numbers be 4 hydrocarbon；The hydrocarbon that the carbon atom numbers such as propane, propylene, allene, propine are 3；The carbon such as pentane, amylene, isopentane The hydrocarbon that atomicity is 5.

Acid-exchange resin can be used as by making isobutene and first in the hydrocarbon mixture comprising isobutene Alcohol reacts and synthesizes the catalyst of MTBE.It as acid-exchange resin, can enumerate for example: be carried out using divinylbenzene The phenylethylene sulfonate resin of crosslinking and the phenol sulfonic acid resin being crosslinked using formaldehyde.Above-mentioned acid ion exchange Resin is preferably macroreticular resin.

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。

(distillation of the feed stream in the first destilling tower 10)

Then, feed stream (F0) is supplied into the first destilling tower 10 by pipeline L1.

The temperature of the stream (F0) of the inlet of first destilling tower 10 can be set as 25 DEG C~490 DEG C.First destilling tower Interior 10 pressure can be set as 0.1MPa-G (gauge pressure)~1.2MPa-G (gauge pressure).

Feed stream (F0) is distilled in the first destilling tower 10, main packet is discharged from tower top from there through pipeline L2 Hydrocarbon that the carbon atom number of butylene containing 1- etc. is 4, also include methanol gas streams (F6), be discharged by pipeline L3 from tower bottom main The stream (F7) of liquid (tower bottom liquid) comprising higher-boiling compounds such as Diisobutylene, methyl sec-butyl ethers, and pass through pipe Line L4 from than tower top on the lower and the discharge of more top than tower bottom position mainly include MTBE stream (F1).The MTBE's of stream (F1) Mass concentration is higher than the mass concentration of the MTBE of stream (F6) and stream (F7).The matter for the hydrocarbon that the carbon atom number of stream (F6) is 4 Measure mass concentration of the concentration higher than the hydrocarbon that the carbon atom number of stream (F1) and stream (F7) is 4.

In order to which the stream (F1) as midbarrel is steadily discharged from the first destilling tower 10 by pipeline L4, first 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.Pass through pipeline L4 Temperature, the temperature of the tower tray of liquid i.e. side-draw in the exit of the first destilling tower 10 of the stream (F1) of discharge can be set as 80 DEG C~200 DEG C.

In distillation, the tower bottom liquid of the tower bottom generation in the first destilling tower 10 is heated in heat exchanger HE6, from And the heat required to the supply distillation of the first destilling tower.Tower bottom liquid, the i.e. outlet temperature of the stream (F7) of the first destilling tower 10, i.e. The temperature of tower bottom liquid can be set as 80 DEG C~200 DEG C.The gas phase temperature of tower top can be set as 10 DEG C~110 DEG C.Stream (F7) it may be used as boiler oil etc..

(decomposition of the MTBE in MTBE decomposition reactor 20)

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

In MTBE decomposition reactor 20, the MTBE in stream (F1) is decomposed, to obtain comprising isobutene and methanol Stream (F2).Stream (F2) comprising isobutene and methanol generally comprises undecomposed MTBE.

It is preferred that stream (F1) is supplied in gaseous form in MTBE decomposition reactor 20.MTBE decomposition reactor 20 The temperature of the stream (F1) of 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 (gauge pressure).The feed speed of raw material according to reaction temperature, pressure, MTBE conversion ratio etc. and select, In terms of weight (hourly) space velocity (WHSV) (WHSV), generally use 0.1 hour^-1~50 hours^-1, it is preferred to use 1 hour^-1~20 hours^-1.WHSV is logical It crosses to supply to the flow velocity (kg/ hours) of all streams of MTBE decomposition process and be 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, can enumerate for example: silica.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 specific surface area of/g.

MTBE decomposition process is preferably carried out in 100 DEG C or more and 500 DEG C silica-aluminas used below.The reaction is The endothermic reaction, it is therefore desirable to be externally supplied heat.The supply of heat can by externally to be arranged in MTBE decomposition reaction Thermal medium is supplied in heat-transfer pipe in device 20 and is carried out, and can also be supplied in a manner of sensible heat being heated to stream (F1) It gives, them can also be combined.

The temperature of the stream (F2) in the exit for the MTBE decomposition reactor 20 being discharged by pipeline L5 can be set as 100 DEG C~500 DEG C, it is preferably set to 150 DEG C~350 DEG C.The stream (F2) being discharged from MTBE decomposition reactor 20 is usually gas.

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

(liquid phase is formed by the cooling of stream (F2))

The stream (F2) being discharged from MTBE decomposition reactor 20 by pipeline L5 is cooling, to obtain that at least there is liquid The stream (F3) of phase.As described above, heat exchanger HE2 and heat exchanger HE4 are disposed with from upstream side on pipeline L5. Stream (F2) carries out heat exchange with the stream (F1) flowed in pipeline L4 in heat exchanger HE2 and is cooled, then in heat Heat exchange is carried out with the stream (F0) flowed in pipeline L1 in exchanger HE4 and is further cooled, and is formed in pipeline L5 Liquid phase.It should be noted that can by the heat exchange with heat exchanger HE2 generate liquid phase, can also by with heat exchanger The heat exchange of HE2 does not generate liquid phase and just generates liquid phase by the heat exchange with heat exchanger HE4.Stream (F3) passes through pipeline L5 is supplied in after-fractionating tower 30.

If keeping the temperature of the stream (F3) of the pipeline L5 after the heat exchange in heat exchanger HE2 and heat exchanger HE4 low Any higher one in the boiling point in methanol and MTBE under the pressure in pipeline L5, then available methanol and isobutyl The liquid phase mixture of alkene.From the viewpoint of the amount for increasing liquid phase, preferably the temperature of stream (F3) is adjusted to than in pipeline L5 The all low temperature of the boiling point of methanol and both isobutenes under interior pressure.

The inlet temperature of pipeline L5 in heat exchanger HE2 can be set as 100 DEG C~500 DEG C, preferably can be set as 150 DEG C~350 DEG C.The outlet temperature of pipeline L5 in heat exchanger HE2 and the entrance temperature of the pipeline L5 in heat exchanger HE4 Degree can be set as 80 DEG C~490 DEG C, preferably can be set as 80 DEG C~340 DEG C.The outlet of pipeline L5 in heat exchanger HE4 Temperature can be set as 20 DEG C~480 DEG C, preferably can be set as 20 DEG C~330 DEG C.

From the point of view of the object stream side for carrying out heat exchange with the stream of pipeline L5 (F2), in heat exchanger HE2, pass through Heat exchange is carried out with the stream (F2) flowed in pipeline L5, the stream (F1) flowed in pipeline L4 is heated.That is, In heat exchanger HE2, the inlet temperature of pipeline L5 is higher than the inlet temperature of pipeline L4.

The inlet temperature of pipeline L4 in heat exchanger HE2 can be set as 80 DEG C~200 DEG C, preferably can be set as 80 DEG C~150 DEG C, the outlet temperature of pipeline L4 can be set as 85 DEG C~500 DEG C, preferably can be set as 85 DEG C~350 DEG C.

Similarly, in heat exchanger HE4, by carrying out heat exchange with the stream flowed in pipeline L5, in pipeline The stream (F0) flowed in L1 is heated.That is, in heat exchanger HE4, inlet temperature the entering higher than pipeline L1 of pipeline L5 Mouth temperature.

The inlet temperature of the pipeline L1 of heat exchanger HE4 can be set as 20 DEG C~100 DEG C, preferably can be set as 20 DEG C ~80 DEG C, the outlet temperature of pipeline L1 can be set as 25 DEG C~490 DEG C, preferably can be set as 25 DEG C~340 DEG C.

Furthermore it is preferred that the entrance temperature of pipeline L4 of the inlet temperature of the pipeline L1 of heat exchanger HE4 lower than heat exchanger HE2 Degree.As long as the difference of the inlet temperature of the pipeline L4 of the inlet temperature and heat exchanger HE2 of the pipeline L1 of heat exchanger HE4 is 0 DEG C It is above, preferably 1 DEG C or more, more preferably 10 DEG C or more.The upper limit is not particularly limited, and can be set as 180 DEG C, can also To be set as 130 DEG C.

It should be noted that utilizing the heating amount of the stream (F1) of heat exchanger HE2 generation and utilizing heat exchanger HE4 It, can be suitably before and after the heat exchanger 4 on pipeline L1 and pipe in the insufficient situation of heating amount of the stream (F4) of generation Add heat exchanger in the front and back of heat exchanger HE2 on line L4.

Similarly, in the insufficient feelings of cooling heat of the stream (F2) generated using heat exchanger HE2 and heat exchanger HE4 Under condition, additional heat exchanger can be suitably set.

Pressure in pipeline L5 can be set as about 0.1MPa-G (gauge pressure)~about 2.0MPa-G (gauge pressure).

(separation of isobutene and methanol in after-fractionating tower 30)

Then, the stream (F3) comprising liquid phase is supplied in after-fractionating tower 30 by pipeline L5.

Inlet temperature in the after-fractionating tower 30 of stream (F3) can be set as 20 DEG C~480 DEG C, can preferably set It is 20 DEG C~330 DEG C.

By being distilled in after-fractionating tower 30, main packet is discharged from the tower top of after-fractionating tower 30 by pipeline L6 Stream (F4) containing isobutene, the stream (F11) by pipeline L7 from the discharge of the tower bottom of after-fractionating tower 30 based on methanol.Material Flow the mass concentration of isobutene of the mass concentration higher than stream (F11) of the isobutene of (F4), the quality of the methanol of stream (F11) The mass concentration of methanol of the concentration higher than stream (F4).The stream (F4) based on isobutene is gone back usually in addition to isobutene Include methanol.The stream (F11) based on methanol also includes undecomposed MTBE usually in addition to methanol.

The temperature of the gas phase of the tower top of after-fractionating tower 30 can be set as 10 DEG C~110 DEG C.The tower of after-fractionating tower 30 The temperature of the tower bottom liquid at bottom can be set as 80 DEG C~200 DEG C.The pressure of after-fractionating tower 30 can be set as 0.1MPa-G~ 2.0MPa-G.The temperature of tower bottom liquid, the i.e. stream (F11) in the tower bottom exit of after-fractionating tower 30 can be set as 80 DEG C~ 200℃。

In distillation, the tower bottom liquid of after-fractionating tower 30 is heated in heat exchanger HE8, thus to after-fractionating Heat needed for the supply distillation of tower 30.

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

Then, preferably so that stream (F4) is become liquid phase by heat exchange, the first extractor is then supplied to by pipeline L6 In 40, and liquid water is supplied in the first extractor 40 by pipeline L14.By the contact with water, it is present in stream (F4) methanol in is dissolved in the water and is extracted, the stream by pipeline L9 from tower bottom discharge as water and the mixture of methanol (F8).Stream (F8) mainly includes water, also includes methanol.

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

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 first 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 first extractor 40 can be set as 30 DEG C~80 DEG C.

(separation of methanol and C4 compound in the second extractor 60)

It is preferred that the material for the main hydrocarbon comprising carbon atom number 4 for making to be discharged from the tower top of the first destilling tower 10 by heat exchange Flowing (F6) becomes liquid phase, is then supplied in the second extractor 60 by pipeline L2, and supplied liquid water by pipeline L15 Into the second extractor 60.By the contact with water, the methanol being present in stream (F6) is dissolved in the water and is extracted, passes through The stream (F15) as water and the mixture of methanol is discharged from tower bottom by pipeline L16.Stream (F15) mainly includes water, also includes first Alcohol.

On the other hand, the stream (F16) as the main hydrocarbon for being 4 comprising carbon atom number of oily phase passes through pipeline L17 from tower Top row goes out.

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

Stream (F11) is supplied in third destilling tower 50 from after-fractionating tower 30 by pipeline L7, and passes through pipeline Stream (F8) is supplied in third destilling tower 50 by L9 from the first extractor 40, in addition, by pipeline L16 by stream (F15) from Second extractor 60 is supplied in third destilling tower 50.

Here, preferably by the heat of the heat exchanger HE12 of pipeline L7, the heat exchanger HE14 of pipeline L9 and pipeline L16 Exchanger HE10 respectively heats the stream flowed in each pipeline.

Specifically, the temperature of the stream (F11) of the inlet of third destilling tower 50 can be set as 80 DEG C~200 DEG C. The temperature of the stream (F8) of the inlet of third destilling tower 50 can be set as 30 DEG C~80 DEG C.The inlet of third destilling tower 50 The temperature of stream (F15) can be set as 30 DEG C~80 DEG C.

Here, being supplied it is preferred that making to be higher than into third destilling tower 50 for the position of feedstock flow (F11) into third destilling tower 50 The position of feedstock flow (F8) and stream (F15).

From methanol concentration (total quality relative to water and methanol in stream obtained in after-fractionating tower 30 (F11) Methanol mass ratio) W11 is higher than methanol concentration W8 from stream (F8) obtained in the first extractor 40 and from second Methanol concentration W15 in stream obtained in extractor 60 (F15).Therefore, pass through the third destilling tower to separation water and methanol In the stream (F11) that the position supply methanol concentration more top than stream (F8) and stream (F15) is high in 50, thus it is effectively performed The separation of water and methanol.

It can be 3 mass of mass %~30 %, W15 can be 3 matter that W11, which can be 75 mass of mass %~100 %, W8, Measure the mass of %~30 %.

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

The temperature of the gas phase of tower top can be set as 60 DEG C~150 DEG C.The temperature of the tower bottom liquid of tower bottom can be set as 100 DEG C~200 DEG C.The pressure of third destilling tower 50 can be set as atmospheric pressure~1.0MPa-G.In distillation, in heat exchanger The tower bottom liquid of third destilling tower 50 is heated in HE16, thus to heat needed for the supply distillation of third destilling tower 50.

The methanol that stream (F9) can be used as MTBE synthesis uses.In addition, stream (F10) can be supplied to pipeline L14 It is used with the water in pipeline L15 as the methanol extraction in the first extractor 40 and the second extractor 60.

(effect)

According to the present embodiment, it can use at least the one of the gas streams (F2) being discharged from MTBE decomposition reactor 20 Partial condensation and latent heat and sensible heat when becoming stream (F3) comprising liquid, to the material being supplied in MTBE decomposition reactor 20 Stream (F1) and the stream (F0) being supplied in the first destilling tower 10 are heated.The thermal efficiency improves as a result, facilitates energy conservation.

In addition, since the stream (F3) being supplied in after-fractionating tower 30 has the liquid phase comprising methanol and isobutene, because This good effect of separative efficiency with methanol and isobutene.

(second embodiment)

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

The point that the present invention is different from the first embodiment is illustrated.

In the isobutene manufacturing device 200 of present embodiment, pipeline L5 is connect with the first extractor 40, rather than with second Destilling tower 30 connects.In addition, by the second steaming is supplied to from the stream (F5) that the tower top of the first extractor 40 is discharged by pipeline L8 It evaporates in tower 30.The pipeline L7 connecting with the tower bottom of after-fractionating tower 30 is not connect with third destilling tower 50.With after-fractionating tower 30 Tower top connection pipeline L6 do not connect with the first extractor 40.In addition, being connected with pipeline in the side of after-fractionating tower 30 L24。

It will be supplied in third destilling tower 50 by pipeline L9 from the stream (F8) that the tower bottom of the first extractor 40 is discharged.This In embodiment, the stream F8 of the stream F15 of pipeline L16 and pipeline L9 is supplied to the sustained height of third destilling tower 50.

In addition, pipeline L5 from 20 side of MTBE decomposition reactor successively via heat exchanger HE2 and heat exchanger HE14 with The connection of first extractor 40.

Then, the manufacturing method about the isobutene of present embodiment says the point being different from the first embodiment It is bright.

(liquid phase is formed by the cooling of stream (F2))

The stream (F2) being discharged by pipeline L5 from MTBE decomposition reactor 20 is cooling, to obtain including at least liquid phase Stream (F3).In the present embodiment, heat exchanger HE2 and heat exchanger are disposed with from upstream side on pipeline L5 HE14.Stream (F2) carries out heat exchange with the stream (F1) flowed in pipeline L4 in heat exchanger HE2 and is cooled, then Heat exchange is carried out with the stream (F8) flowed in pipeline L9 in heat exchanger HE14 and is further cooled, in pipeline L5 Form liquid phase.

The entrance of the inlet temperature and outlet temperature of pipeline L5 in heat exchanger HE2, pipeline L4 in heat exchanger HE2 Temperature and outlet temperature can be set as identical with first embodiment.

In heat exchanger HE14, by carrying out heat exchange with the stream (F2) flowed in pipeline L5, in pipeline L9 The stream (F8) of middle flowing is heated.That is, the inlet temperature of pipeline L5 is higher than the entrance of pipeline L9 in heat exchanger HE14 Temperature.

The inlet temperature of the pipeline L5 of heat exchanger HE14 can be set as 80 DEG C~490 DEG C, preferably can be set as 80 DEG C~340 DEG C, the outlet temperature of the pipeline L5 of heat exchanger HE14 can be set as 30 DEG C~480 DEG C, preferably can be set as 30 DEG C~330 DEG C.The inlet temperature of the pipeline L9 of heat exchanger HE14 can be set as 30 DEG C~80 DEG C, heat exchanger HE14's The outlet temperature of pipeline L9 can be set as 35 DEG C~490 DEG C, preferably can be set as 35 DEG C~340 DEG C.

The inlet temperature of pipeline L4 of the inlet temperature of the pipeline L9 of preferred heat exchanger HE14 lower than heat exchanger HE2. As long as temperature difference is 0 DEG C or more, preferably 1 DEG C or more, more preferably 10 DEG C or more.The upper limit is not particularly limited, such as It can be 170 DEG C, or 120 DEG C.

It should be noted that in the insufficient situation of heating amount of the stream (F8) generated using heat exchanger HE14, it can Suitably to add heat exchanger before and after the heat exchanger HE14 on pipeline L9.Similarly, using heat exchanger HE2 and In the insufficient situation of cooling heat for the stream (F2) that heat exchanger HE14 is generated, additional heat exchange can be suitably set Device.

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

Then, stream (F3) is supplied in the first extractor 40 by pipeline L5, and passes through pipeline L14 for liquid water It is supplied in the first extractor 40.By the contact with water, the methanol in stream (F3) is dissolved in the water and is extracted, and passes through pipe The stream (F8) as water and the mixture of methanol is discharged from tower bottom by line L9.

On the other hand, the stream comprising isobutene as the oily phase for eliminating methanol is discharged by L8 clumps of tower tops of pipeline (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 (F3) of the inlet of first extractor 40 can be set as 30 DEG C~480 DEG C.First 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 MTBE in after-fractionating tower 30)

Then, the stream (F5) comprising isobutene is supplied in after-fractionating tower 30 by pipeline L8.After-fractionating tower The temperature of the stream (F5) of 30 inlet can be set as 15 DEG C~80 DEG C.

By being distilled in after-fractionating tower 30, it is discharged by pipeline L6 from the tower top of after-fractionating tower 30 with isobutyl Stream (F18) based on alkene is discharged the stream (F20) based on MTBE from the side of after-fractionating tower 30 by pipeline L24, leads to Pipeline L7 is crossed from stream (F19) of the tower bottom of after-fractionating tower 30 discharge comprising higher-boiling compounds such as Diisobutylenes.Stream (F19) it can supply to boiler.In addition, stream (F20) can be recycled in MTBE decomposition reactor.

The tower top temperature of after-fractionating tower 30, column bottom temperature, after-fractionating tower 30 pressure can be set as and first is real It is identical to apply mode.

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

Stream (F8) is supplied in third destilling tower 50 from the first extractor 40 by pipeline L9, it will by pipeline L16 Stream (F15) is supplied in third destilling tower 50 from the second extractor 60.The stream (F8) of the inlet of third destilling tower 50 Temperature can be set as 35 DEG C~490 DEG C, preferably can be set as 35 DEG C~340 DEG C.Other conditions can be set as and first Embodiment is identical.

In third destilling tower 50, by distillation, the stream (F9) based on methanol is discharged from tower top by pipeline L10, It is discharged by pipeline L11 from tower bottom and stream as main component (F10) is made with water.Distillation condition can be set as implementing with first Mode is identical.

According to this method, the methanol of the MTBE content high-purity fewer than first embodiment can be obtained.

It is identical with first embodiment, at least part for the stream (F10) being discharged by pipeline L11 can be supplied to In pipeline L14 and pipeline L15, utilized in the first extractor 40 and the second extractor 60.

(effect)

According to the present embodiment, it can use at least the one of the gas streams (F2) being discharged from MTBE decomposition reactor 20 Partial condensation and latent heat and sensible heat when becoming stream (F3) comprising liquid, to the material being supplied in MTBE decomposition reactor 20 Stream (F1) and the stream (F8) being supplied in third destilling tower 50 from the first extractor 40 are heated.The thermal efficiency mentions as a result, Height facilitates energy conservation.

In particular, in the present embodiment, pipeline L5 is not connect via after-fractionating tower 30 with the first extractor 40, it is It functions the first extractor 40 efficiently, so that the stream (F3) is fully cooled and is mentioned isobutene and methanol first Taking becomes liquid under the pressure in device 40, in the present embodiment, due to that can use a large amount of latent heat and sensible heat that generate at this time In the heating of the entrance stream of third destilling tower 50, thus it is high-efficient.

(other embodiment)

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

For example, after so that stream (F2) is carried out heat exchange with stream (F1) in heat exchanger HE2 in pipeline L5 and cooling down, The stream for carrying out the object of heat exchange to further cool down the stream (F2) after heat exchange is not limited to supply shown in FIG. 1 To in the first destilling tower 10 stream (F0) and the tower top shown in Fig. 2 from the first extractor 40 be discharged and be supplied to third distillation Stream (F8) in tower 50, the process stream (still, not including stream (F1)) being also possible in the manufacture of isobutene.

" process stream " in the manufacture of isobutene refers to: be supplied to the decomposition process of MTBE includes at least part The stream of MTBE (such as stream (F1), stream (F0), aftermentioned flows between the first destilling tower 10A and the first destilling tower 10B Stream (F1A), the aftermentioned stream (F1B) flowed between the first destilling tower 10B and the first destilling tower 10C, aftermentioned The tower bottom liquid of one destilling tower 10A, tower bottom liquid of aftermentioned first destilling tower 10B etc.), the decomposition process that is supplied to MTBE include By-product stream (such as stream (F6), stream (F7), the stream (F16), stream generated in the purification procedures of the stream of MTBE (F15), the tower bottom liquid of aftermentioned first destilling tower 10C, the tower bottom liquid of the first destilling tower 10), be supplied to MTBE decomposition process Comprising the stream of raw material (methanol and/or isobutene) synthesized for MTBE and include MTBE decomposition process in obtain Cleavage reaction product stream.

Include the example of the stream of cleavage reaction product obtained in the decomposition process of MTBE are as follows: comprising methanol and/or Stream (such as stream (F4), stream (F11), stream (F5), stream (F8), stream (F11), the stream (F9), stream of isobutene (F18), the tower bottom liquid of after-fractionating tower 30, the tower bottom liquid of third destilling tower 50), from cleavage reaction product purification of methanol and/ Or by-product stream (such as the tower of stream (F19), the tower bottom liquid of after-fractionating tower 30, third destilling tower 50 generated when isobutene Bottom liquid), include undecomposed object (MTBE) stream.For these streams, the behaviour such as reaction, distillation, extraction can be further added Make, in the case where further additional operation, due to further generating by-product stream, the quantity of process stream increases.

It as additional reaction, the specific example of distillation procedure, can enumerate: by the top stream of the first destilling tower 10 (F6) isobutene and methanol for including in are supplied in the reactor filled with acid-exchange resin to generate MTBE Stream；Or it is supplied into the second extractor 60 and is further supplied in destilling tower to make by the stream for including MTBE Stream etc. after the reduction of MTBE content.In the operation of the addition, it is not only the methanol in stream (F6) included, may be used also From external new addition methanol as reaction raw materials.In addition, MTBE obtained in the reaction can be supplied to MTBE decomposition reaction In device 20.

Specifically, for example in first embodiment (referring to Fig.1), after can carrying out heat exchange with stream (F1) Stream (F2) is not supplied in heat exchanger HE4, and is supplied in heat exchanger HE12 and makes the stream of itself and pipeline L7 (F11) heat exchange is carried out, can also be supplied in heat exchanger HE14 and make the stream (F8) of itself and pipeline L9 to carry out heat exchange, It can also be supplied in heat exchanger HE8 and make the tower bottom liquid of itself and after-fractionating tower 30 to carry out heat exchange, can also be supplied to In heat exchanger HE16 and the tower bottom liquid of itself and third destilling tower 50 is made to carry out heat exchange, heat exchanger HE6 can also be supplied to In and so that the tower bottom liquid of itself and the first destilling tower 10 is carried out heat exchange, can also be supplied in heat exchanger HE10 and make itself and pipe The stream (F15) of line L16 carries out heat exchange.

Make the tower bottom liquid of stream (F2) and stream (F11), stream (F8), stream (F15) and third destilling tower 50 into In the case where row heat exchange, heat source of the heat generated by the cooling of stream (F2) as third destilling tower 50 can use A part.In addition, can use logical in the case where making the tower bottom liquid of stream (F2) and after-fractionating tower 30 carry out heat exchange Supercooling and a part of the heat that generates as the heat source of after-fractionating tower 30.In addition, distilling stream (F2) with first In the case that the tower bottom liquid of tower 10 carries out heat exchange, it can use through the cooling heat generated as the first destilling tower 10 A part of heat source.

In addition, the stream (F2) after heat exchange can will be carried out with stream (F1) in second embodiment (referring to Fig. 2) It is not supplied in heat exchanger HE14, and is supplied in heat exchanger HE4 and makes the stream (F0) of itself and pipeline L1 to carry out heat Exchange can also be supplied in heat exchanger HE6 and the tower bottom liquid of itself and the first destilling tower 10 is made to carry out heat exchange, can also be for It is given in heat exchanger HE8 and makes the tower bottom liquid of itself and after-fractionating tower 30 to carry out heat exchange, heat exchanger can also be supplied to In HE16 and the tower bottom liquid of itself and third destilling tower 50 is made to carry out heat exchange, can also be supplied in heat exchanger HE10 and make it Heat exchange is carried out with the stream (F15) of pipeline L16.In these cases, same as described above, it can use through stream (F2) A part of heat source of cooling and generation the heat as the distillation in each destilling tower.

Additionally, it is preferred that being lower than with stream (F2) temperature for carrying out the process stream (FP) before heat exchange in heat exchanger HE2 In with stream (F2) carry out heat exchange before stream (F1) temperature.

In addition, in the above description, stream (F2) is supplied in heat exchanger HE2 and another heat exchanger, It is cooled down in total two heat exchangers, but other than heat exchanger HE2, above-mentioned heat exchanger can also be supplied to In any two more than combined heat exchanger in, cooled down using total three or more heat exchangers.About more The sequence of a heat exchanger, place preferably opposite with stream (F2) the progress higher stream of inlet temperature of object stream of heat exchange In upstream side.

In addition, the method that stream (F3) is separated into isobutene and methanol is also not limited to make as embodiment described above It passes through the method for 30 both sides of the first extractor 40 and after-fractionating tower.For example, it is also possible to which so that stream (F3) only passes through first The mode of extractor 40 and the either side in after-fractionating tower 30 is implemented.Alternatively, it is also possible to be separated by absorption.

In addition, in the above-described embodiment, the first destilling tower 10 has following composition: low from tower top extraction by pipeline L2 Boiler cuts extract higher-boiling compound fraction out from tower bottom by pipeline L3, are extracted out by pipeline L4 from the intermediate of tower Midbarrel.But as long as can be improved the concentration of MTBE compared with stream (F0), above-mentioned be constructed without is particularly limited to, Such as or it is used in series the composition of multistage (such as 2 grades, 3 grades etc.) destilling tower.I.e., it is possible in the destilling tower of the first order In, low-boiling compound is extracted out from tower top, extracts higher-boiling compound and midbarrel and the steaming for being supplied to rear stage out from tower bottom It evaporates in tower, in the destilling tower of rear stage, extracts midbarrel out from tower top and be supplied in MTBE decomposition reactor 20, from tower bottom Extract higher-boiling compound out.

For example, the first destilling tower 10 can be replaced using Distallation systm 10 ' shown in Fig. 3.The Distallation systm 10 ' has: First destilling tower 10A, the first destilling tower 10B and the first destilling tower 10C.It is distilled with the pipeline L1 of heat exchanger HE4 and first Tower 10A connection.

It is connected with pipeline L2 in the tower top of the first destilling tower 10A, is connected with pipeline L31 in tower bottom.On first destilling tower 10A It is provided with the pipeline L21A returned again in the first destilling tower 10A after being discharged to the outside tower bottom liquid.It is arranged on pipeline L21A There is heat exchanger (reboiler) HE6A for heating tower bottom liquid.

Heat exchanger HE102 is provided on pipeline L31, pipeline L31 is connect with the first destilling tower 10B.

It is connected with pipeline L101 in the tower top of the first destilling tower 10B, is connected with pipeline L32 in tower bottom.First destilling tower 10B On be provided with tower bottom liquid is discharged to the outside after return again to the pipeline L21B in the first destilling tower 10B.It is set on pipeline L21B It is equipped with heat exchanger (reboiler) HE6B for heating tower bottom liquid.

Heat exchanger HE103 is provided on pipeline L32, pipeline L32 is connect with the first destilling tower 10C.

It is connected with pipeline L4 in the tower top of the first destilling tower 10C, is connected with pipeline L103 in tower bottom.First destilling tower 10C On be provided with tower bottom liquid is discharged to the outside after return again to the pipeline L21C in the first destilling tower 10C.It is set on pipeline L21C It is equipped with heat exchanger (reboiler) HE6C for heating tower bottom liquid.

When feed stream (F0) being supplied in the first destilling tower 10A and distilled by pipeline L1, pass through pipeline L2 From tower top obtain with carbon atom number be 4 hydrocarbon based on stream (F6), the stream (F1A) based on MTBE is obtained from tower bottom.

Then, when stream (F1A) being supplied in the first destilling tower 10B and distilled by pipeline L31, pass through pipeline L101 obtains the stream (F100) for the hydrocarbon for being 5 comprising carbon atom numbers such as micro existing pentane, pentane, isopentane from tower top, from Tower bottom obtains the stream (F1B) based on MTBE.

Then, it when stream (F1B) being supplied in the first destilling tower 10C and distilled by pipeline L32, is obtained from tower bottom To comprising the stream (F103) based on the higher-boiling compounds such as methanol and Diisobutylene and methyl sec-butyl ether, from tower Top obtains the stream (F1) based on MTBE.

With such Distallation systm 10 ', the stream after heat exchange can will be carried out with stream (F1) (F2) it is supplied in heat exchanger HE102, HE103, HE6A, HE6B and HE6C, carries out hot friendship with the stream flowed in these It changes.In such a case, it is possible to which the heat generated using the cooling by stream (F2) is as the heat source of distillation.

The gas from uppermost discharge is set to be back to destilling tower after condensing again in addition, above-mentioned each destilling tower can have In reflux portion.It should be noted that destilling tower can be the plate column with multiple tower trays, it is also possible to packed tower.

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

Furthermore it is possible to further add the separation purification unit such as destilling tower on each pipeline.

The form of heat exchanger is not particularly limited, and can be used well known to package type, double-tube type, screw type, template etc. Various heat exchangers.

In addition, the flow direction of two kinds of fluids in heat exchanger can be adverse current, cocurrent, any one in cross-current Kind.

In addition, the constituent material of heat exchanger is also not particularly limited, it is each that copper, aluminium, steel, stainless steel, titanium etc. can be used Kind metal material.As the measure for preventing the corrosion as caused by acid, acid proof material can be used.

(embodiment 1)

Using the manufacturing device 100 of the isobutene of first embodiment shown in FIG. 1, isobutene has been manufactured.Isobutene Manufacturing device 100 successively has from the upstream side of pipeline L5: the heat exchange of heat exchange is carried out between pipeline L4 and pipeline L5 Device HE2, the heat exchanger HE4 that heat exchange is carried out between pipeline L1 and pipeline L5.

The details of technique:

(preparation of feed stream (F0))

It has obtained containing MTBE as obtained from reacting the isobutene in the hydrocarbon mixture comprising isobutene with methanol Stream.The stream of MTBE will be contained as feed stream (F0).As described later, the stream before heat exchange is carried out with stream (F2) (F0) temperature is 49 DEG C.MTBE concentration in stream (F0) is 57 mass %.

(distillation of the feed stream in the first destilling tower 10)

Feed stream (F0) is supplied in the first destilling tower 10 by pipeline L1.By in the first destilling tower 10 to original Material stream (F0) is distilled, and includes from the main hydrocarbon for being 4 comprising carbon atom numbers such as 1- butylene of tower top discharge, also by pipeline L2 The gas streams (F6) of methanol, it is mainly high boiling comprising Diisobutylene, methyl sec-butyl ether etc. from tower bottom discharge by pipeline L3 The stream (F7) of the liquid (tower bottom liquid) of point compound, by pipeline L4 from the lower and the position more top than tower bottom is discharged than tower top Main includes the liquid stream (F1) of MTBE.MTBE concentration in liquid stream (F1) is 96 mass %.At this point, finding out the first steaming Heat needed for evaporating the distillation in tower 10.

(separation of methanol and C4 compound in the second extractor 60)

So that the stream (F6) being discharged from the top of the first destilling tower 10 is become liquid phase, is then supplied to second by pipeline L2 In extractor 60, and liquid water is supplied in the second extractor 60 by pipeline L15.By the contact with water, it is present in Methanol in stream (F6) is dissolved in the water and is extracted, the mixture by pipeline L16 from tower bottom discharge as water and methanol Stream (F15).Just the temperature of the stream (F15) after being discharged in the second extractor is 60 DEG C.Water concentration in stream (F15) For 71 mass %, methanol concentration is 28 mass %.Flow the ratio between of the flow of stream (F15) relative to aftermentioned stream (F2) It (F15/F2) is 0.19.

(decomposition of the MTBE in MTBE decomposition reactor 20)

The stream (F1) generated in the first destilling tower 10 is supplied in MTBE decomposition reactor 20 by pipeline L4.? In MTBE decomposition reactor 20, the MTBE in stream (F1) is decomposed, to obtain the stream (F2) comprising isobutene and methanol. Shown in the composition table 1 described as follows of obtained stream (F2).

Table 1

(cooling of stream (F2))

The stream (F2) being discharged from MTBE decomposition reactor 20 by pipeline L5 is cooling, to obtain stream (F3). As described above, heat exchanger HE2 and heat exchanger HE4 are disposed on pipeline L5 from upstream side.Make stream (F2) in heat Carry out heat exchange with the stream (F1) that flows in pipeline L4 in exchanger HE2 and cool down, then in heat exchanger HE4 with The stream (F0) flowed in pipeline L1 carries out heat exchange and cools down.The temperature of the inlet of the heat exchanger HE2 of stream (F1) is 138℃.The temperature of the inlet of the heat exchanger HE2 of stream (F2) is 217 DEG C.The flow of stream (F1) is relative to stream (F2) The ratio between flow (F1/F2) be 1.The temperature of the inlet of the heat exchanger HE4 of stream (F0) is 49 DEG C.The flow of stream (F0) The ratio between flow relative to stream (F2) (F0/F2) is 1.6.Stream (F3) is supplied to after-fractionating tower 30 by pipeline L5 In.

(separation of isobutene and methanol in after-fractionating tower 30)

Stream (F3) is supplied in after-fractionating tower 30 by pipeline L5, by being steamed in after-fractionating tower 30 It evaporates, stream (F4) based on isobutene is discharged from the tower top of after-fractionating tower 30 by pipeline L6, by pipeline L7 from second The stream (F11) based on methanol is discharged in the tower bottom of destilling tower 30.At this point, the reflux ratio of after-fractionating tower 30 is 1.0.Stream (F4) isobutylene concentration in is 96 mass %.At this point, heat needed for finding out the distillation in after-fractionating tower 30.

For every 1kg isobutene in stream (F4), heat needed for the distillation in the first destilling tower 10 is 700kcal/ kg.Heat needed for distillation in after-fractionating tower 30 is 290kcal/kg.

For every 1kg isobutene in stream (F4), heat and after-fractionating needed for the distillation in the first destilling tower 10 The sum of heat needed for distillation in tower 30 is 990kcal/kg.

(embodiment 2)

The simulation of manufacture isobutene has been carried out using the manufacturing device 400 of isobutene shown in Fig. 4.The manufacture of isobutene fills 400 are set successively to have from the upstream side of pipeline L5: between pipeline L4 and pipeline L5 carry out heat exchange heat exchanger HE2, The heat exchanger HE10 that heat exchange is carried out between pipeline L16 and pipeline L5, by using the process simulation of AspenTech company The simulation of device (Aspen Plus V10) and in heat and after-fractionating tower 30 needed for finding out the distillation in the first destilling tower 10 Distillation needed for heat.In example 2, pipeline L5 does not have the heat friendship that heat exchange is carried out between pipeline L1 and pipeline L5 Parallel operation HE4.

In the temperature of the inlet of the heat exchanger HE2 of MTBE concentration, stream (F1) in stream (F0), stream (F1) MTBE concentration, the just temperature of the stream (F15) after being discharged in the second extractor, the water concentration in stream (F15), stream (F15) temperature of inlet, the composition of stream (F2), the stream (F1) of the heat exchanger HE2 of methanol concentration, stream (F2) in The ratio between flow of the flow relative to stream (F2), stream (F0) the ratio between flow of the flow relative to stream (F2) and material The flow of stream (F15) is set as same as Example 1 relative to the ratio between the flow of stream (F2).The heat exchanger of stream (F15) The temperature of the inlet of HE10 is 60 DEG C.In example 2, since stream (F0) does not carry out heat exchange, stream with stream (F2) (F0) it is supplied at 49 DEG C in the first destilling tower.Isobutylene concentration in stream (F4) same as Example 1 is 96 mass %.

It should be noted that in example 2, in order to make, the isobutylene concentration in stream (F4) is same as Example 1 to be 96 mass % need for the flow as the stream of the quantity of distillate of after-fractionating tower 30 (F4) to be adjusted to the stream of embodiment 1 (F4) 0.41 times of flow, and the reflux ratio of after-fractionating tower 30 is adjusted to 2.5.

For every 1kg isobutene in stream (F4), heat needed for the distillation in the first destilling tower 10 is 2250kcal/ kg.Heat needed for distillation in after-fractionating tower 30 is 750kcal/kg.

For every 1kg isobutene in stream (F4), heat and after-fractionating needed for the distillation in the first destilling tower 10 The sum of heat needed for distillation in tower 30 is 3000kcal/kg.

(comparative example 1)

The simulation of manufacture isobutene has been carried out using the manufacturing device 500 of isobutene shown in fig. 5.The manufacture of isobutene fills It sets 500 and only has the heat exchanger HE2 for carrying out heat exchange between pipeline L4 and pipeline L5 on pipeline L5, by using The simulation of the process simulator (Aspen Plus V10) of AspenTech company and find out needed for the distillation in the first destilling tower 10 Heat and after-fractionating tower 30 in distillation needed for heat.In comparative example 1, pipeline L5 does not have in pipeline L1 and pipeline The heat exchanger HE4 of heat exchange is carried out between L5.

In the temperature of the inlet of the heat exchanger HE2 of MTBE concentration, stream (F1) in stream (F0), stream (F1) MTBE concentration, the just temperature of the stream (F15) after being discharged in the second extractor, the water concentration in stream (F15), stream (F15) temperature of inlet, the composition of stream (F2), the stream (F1) of the heat exchanger HE2 of methanol concentration, stream (F2) in The ratio between flow of the flow relative to stream (F2), stream (F0) the ratio between flow of the flow relative to stream (F2) and material The flow of stream (F15) is set as same as Example 1 relative to the ratio between the flow of stream (F2).In comparative example 1, due to stream (F0) heat exchange is not carried out with stream (F2), stream (F0) is supplied to the first destilling tower at 49 DEG C.Isobutyl in stream (F4) Alkene concentration same as Example 1 is 96 mass %.

It should be noted that in order to make, the isobutylene concentration in stream (F4) is same as Example 1 to be in comparative example 1 96 mass % need for the flow as the stream of the quantity of distillate of after-fractionating tower 30 (F4) to be adjusted to the stream of embodiment 1 (F4) 0.33 times of flow, and the second reflux ratio is adjusted to 3.2.

For every 1kg isobutene in stream (F4), heat needed for the distillation in the first destilling tower 10 is 2900kcal/ kg.Heat needed for distillation in after-fractionating tower 30 is 900kcal/kg.

For every 1kg isobutene in stream (F4), heat and after-fractionating needed for the distillation in the first destilling tower 10 The sum of heat needed for distillation in tower 30 is 3800kcal/kg.

In embodiment 1 and embodiment 2, it in order to obtain the 1kg isobutene of same purity in the 2nd destilling tower 30, needs The heat being externally supplied is less than comparative example 1, therefore confirmed that the thermal efficiency of the technique entirety of embodiment 1 and embodiment 2 is excellent.

Claims

1. a kind of manufacturing method of isobutene, with the following process:

(A) stream (F1) comprising methyl tertiary butyl ether(MTBE) (MTBE) is supplied into MTBE decomposition reactor to obtain comprising different The process of the gas streams (F2) of butylene and methanol；With

The process (B) is with the following process:

(B2) after the heat exchange the gas streams (F2) in addition to the stream (F1) process stream (FP) it Between carry out heat exchange process.

2. the method for claim 1, wherein process stream (FP) before the heat exchange in the process (B2) Temperature of the temperature lower than the stream (F1) before the heat exchange in the process (B1).

3. it is method according to claim 1 or 2, it is also with the following process: will to have the MTBE lower than the stream (F1) To obtain the work of the stream (F1) in multiple first destilling towers that the stream (F0) of concentration is supplied to one or is connected in series Sequence,

The process stream (FP) is the stream (F0), the stream flowed between first destilling tower or any one institute State the tower bottom liquid of the first destilling tower.

4. it is method according to claim 1 or 2, with the following process:

There to be the stream (F0) lower than the MTBE concentration of the stream (F1) to supply multiple first to one or be connected in series Process in destilling tower to obtain the stream (F1)；With

By the stream (F3) supply into after-fractionating tower, thus tower top obtain mainly include isobutene, also include methanol Stream (F4), in the process that tower bottom obtains the stream (F11) based on methanol,

The process stream (FP) is the stream (F0).

5. it is method according to claim 1 or 2, with the following process:

There to be the stream (F0) lower than the MTBE concentration of the stream (F1) to supply multiple first to one or be connected in series Process in destilling tower to obtain the stream (F1)；

By the stream (F3) supply into after-fractionating tower, thus tower top obtain mainly include isobutene, also include methanol Stream (F4), in the process that tower bottom obtains the stream (F11) based on methanol；

Contact the stream (F4) with water, to obtain the stream (F5) based on isobutene and include mainly water, also wrap The process of stream (F8) containing methanol；With

By the stream (F8) and the stream (F11) supply into third destilling tower, to obtain the stream based on methanol (F9) process of the stream based on He Yishui (F10),

The process stream (FP) is the stream (F0).

6. method as described in claim 4 or 5, also with the following process: by hydrocarbon mixture and methanol comprising isobutene Supply makes the isobutene and methanol reaction in hydrocarbon mixture, to obtain the stream comprising MTBE into MTBE synthesis reactor (F0) process.

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

First destilling tower, first destilling tower include the entrance for being supplied to the stream comprising MTBE (F0), tower top outlet, with And tower bottom outlet；

MTBE decomposition reactor, the MTBE decomposition reactor is included to be connect with the outlet of the tower bottom of the first destilling tower or side outlet The stream (F2) of entrance and discharge comprising isobutene and methanol outlet；

After-fractionating tower, the after-fractionating tower include with MTBE decomposition reactor outlet connection entrance, tower top outlet, And tower bottom outlet；

Pipeline L4, the tower bottom outlet of the first destilling tower of the pipeline L4 connection or the entrance of side outlet and MTBE decomposition reactor； With

Pipeline L5 includes: carrying out heat exchange between the stream (F1) flowed in pipeline L4 and the stream (F2) flowed in pipeline L5 Heat exchanger HE2；And

The heat exchanger of heat exchange is carried out between the stream (F2) flowed in pipeline L5 and the stream (F0) flowed in pipeline L1 HE4,

8. the manufacturing device of isobutene as claimed in claim 7, is also equipped with:

First extractor, first extractor include the entrance connecting with the tower top outlet of after-fractionating tower, are supplied to water Water inlet, tower top outlet and tower bottom outlet；With

Methanol destilling tower, the methanol destilling tower is included to be gone out with entrance, the tower top of the tower bottom of the first extractor outlet connection Mouth and tower bottom outlet.

9. the manufacturing device of isobutene as claimed in claim 7 or 8, is also equipped with:

MTBE synthesis reactor, the MTBE synthesis reactor includes the entrance for being supplied to MTBE raw material and discharge includes MTBE Stream (F0) outlet,

The pipeline L1 is outlet and the pipeline of the entrance of the first destilling tower for connecting MTBE synthesis reactor.