CN110483337A - A kind of separation and purification system and method for benzene dimethylene diisocyanate product - Google Patents
A kind of separation and purification system and method for benzene dimethylene diisocyanate product Download PDFInfo
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- CN110483337A CN110483337A CN201811038579.5A CN201811038579A CN110483337A CN 110483337 A CN110483337 A CN 110483337A CN 201811038579 A CN201811038579 A CN 201811038579A CN 110483337 A CN110483337 A CN 110483337A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
- C07C263/20—Separation; Purification
Abstract
The present invention provides a kind of separation and purification system and methods of benzene dimethylene diisocyanate product, and the system comprises desolventizing tower, weight-removing column, stabilizer mixing arrangement and product purification towers；Wherein, raw material to be processed enters desolventizing tower by the feed inlet that desolventizing tower is arranged, and the materials at bottom of tower outlet of desolventizing tower is connected with the material inlet of weight-removing column；The feed inlet of the middle part material outlet stable connection agent mixing arrangement of weight-removing column, the material outlet of stabilizer mixing arrangement connect product purification tower, and material outlet is arranged in the middle part of product purification tower.The separation system and method design science, structurally reasonable, energy saving, production cost and the quality of production are reliable, and simple process is easily operated, and highly-safe, low energy consumption, extract product purity height, and product separation yield is high, and XDI polymerization is few.
Description
Technical field
The invention belongs to separation field, it is related to separation and purification system and the side of a kind of benzene dimethylene diisocyanate product
Method.
Background technique
Benzene dimethylene diisocyanate (XDI) has excellent weatherability and color stability, is mainly used for high-grade poly-
The fields such as urethane coating and high-end resin eyeglass.XDI mainly uses phosgenation to produce at present, and raw material phosgene is hypertoxic and excessively program-controlled
It is imperative to develop non-phosgene route for higher cost processed.Mitsui chemical company is in CN 105143177A, CN
The technology path that carbamate pyrolysis prepares XDI is proposed in 105143178A and CN 105263903A, wherein CN
The product yield of XDI has reached 80% in 105263903A.Non-ammonia carbamate pyrolysismethod produces in the process route of XDI, comes
Contain XDI product, XMI (single-amido acid ester intermediate) intermediate, polymerization from the reaction solution of carbamate thermal decomposition unit
XDI and organic inert solvent.Therefore, the components such as XMI intermediate and polymerization XDI can be recycled while separating XDI product to Guan Chong
It wants.
Currently, the separation of XDI product purification is primarily present following problems: (1) XDI is heat-sensitive substance, meeting in distillation process
Cause it that polymerization side reactions occur, it is most important how to control separation process polymerization losses；(2) XMI intermediate and polymerization XDI boiling
Point is close, and the two separation is difficult.In this regard, patent CN 105143177A and CN 105263903A use rectification under vacuum method into
Row purification, using 10 blocks of theoretical trays, operating pressure is 66Pa~667Pa, and XDI purity reaches 99.7%, and separation and recovery rate reaches
To 93%.But separation process XDI polymerization losses is serious, and do not refer to how to separate and recover single-amido acid ester intermediate X MI and
It polymerize XDI.
Therefore, how to obtain high-purity XDI while reducing separation process XDI polymerization, and high efficiente callback separates high-purity XMI and uses
It is that non-phosgenation produces XDI urgent problem to be solved in circulation pyrolysis.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of points of benzene dimethylene diisocyanate product
From refining system and method, the system design science, structurally reasonable, energy saving, production cost, the quality of production are reliable, institute
It is simple, easily operated to state method, highly-safe, low energy consumption, extracts product purity height, and product separation yield is high.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of separation and purification system of benzene dimethylene diisocyanate (XDI) product,
The system comprises desolventizing tower, weight-removing column, stabilizer mixing arrangement, product purification towers；
Wherein, raw material to be processed is connected with the feed inlet of desolventizing tower, the materials at bottom of tower outlet of desolventizing tower and weight-removing column
Material inlet be connected；The middle part material outlet stable connection agent mixing arrangement of weight-removing column, the material of stabilizer mixing arrangement go out
Material outlet is arranged in mouth connection product purification tower, the middle part of product purification tower.
In the present invention, stabilizer mixing arrangement is set before product purification tower, XDI is avoided to divide by the way that stabilizer is added
From polymerization losses in the process.
Typical but non-limiting stabilizer mixing arrangement can be the blending tank etc. with stirring.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the system also includes reboiler, the reboiler is set to desolventizing tower
Materials at bottom of tower outlet the material inlet of weight-removing column between.
Preferably, the reboiler includes falling-film reboiler.Since the substances such as XDI and XMI are heat-sensitive substance, when long
Between be easy under the high temperature to cause polymerization, therefore falling-film reboiler is set to reduce the polymerization of product.
Preferably, material-handling pump is set between the materials at bottom of tower outlet and reboiler of desolventizing tower.
Preferably, the system also includes vacuum evacuation device, vacuum evacuation device independently with desolventizing column overhead, weight-removing column
Tower top is connected with product purification column overhead, provides the environment of high vacuum for desolventizing tower, weight-removing column and product purification tower.
As currently preferred technical solution, the feed inlet of the desolventizing tower is set in the middle part of desolventizing tower tower.
Preferably, the system also includes feed preheaters, are set on the feeding pipe of desolventizing tower.
Preferably, the system also includes desolventizing column overhead cooling components.
Preferably, the desolventizing column overhead cooling component includes the first condenser of desolventizing column overhead, desolventizing tower tower
Push up return tank and the second condenser of desolventizing column overhead, desolventizing column overhead material outlet and the first condenser of desolventizing column overhead
Feed inlet connection, the discharge port of the first condenser of desolventizing column overhead connect with desolventizing column overhead return tank, desolventizing tower
The material outlet of return tank of top of the tower is separately connected the second condenser of desolventizing column overhead material refluxing opening and desolventizing column overhead, takes off
The second condenser of solvent column overhead is connected with vacuum evacuation device.
Preferably, second condenser of desolventizing column overhead is connected with vacuum evacuation device by solvent tank.
As currently preferred technical solution, the system also includes weight-removing column tower top cooling components.
Preferably, the weight-removing column tower top cooling component includes sequentially connected the first condenser of weight-removing column tower top and de- weight
The second condenser of column overhead, the second condenser of weight-removing column tower top connect vacuum evacuation device.
Preferably, second condenser of weight-removing column tower top is connect by solvent recovery tank with vacuum evacuation device.
Preferably, first condenser of weight-removing column tower top is directly connect with weight-removing column main body.Due to solvent and other groups
Divide boiling point difference larger, while in order to reduce weight-removing column cost, therefore the first condenser of weight-removing column tower top and weight-removing column main body are connected
Be connected together (such as welding), and gas phase walks tube side, and condensation working medium walks shell side.
Preferably, the weight-removing column tower top cooling component output solvent.
Preferably, the tower bottom output of the weight-removing column polymerize benzene dimethylene diisocyanate.
Preferably, weight-removing column tower bottom quencher is set on the tower bottom export pipeline of the weight-removing column.
As currently preferred technical solution, the system also includes component is condensed back in the middle part of weight-removing column.
Preferably, it includes material storage tank and weight-removing column middle part object in the middle part of weight-removing column that component is condensed back in the middle part of the weight-removing column
Expect that condenser, middle part material outlet and the material condenser in the middle part of material storage tank in the middle part of weight-removing column and weight-removing column of weight-removing column successively connect
It connects, the outlet material of material condenser returns to weight-removing column in the middle part of weight-removing column.
Preferably, material conveying is set among material storage tank and weight-removing column middle part material condenser in the middle part of the weight-removing column
Pump.
Preferably, the middle part material outlet of the weight-removing column passes through material storage tank in the middle part of weight-removing column and stabilizer mixing arrangement
It is connected.
As currently preferred technical solution, the system also includes product purification column overhead cooling components.
Preferably, the product purification column overhead cooling component includes that sequentially connected product purification column overhead first condenses
The second condenser of device and product purification column overhead, the second condenser of product purification column overhead connect vacuum evacuation device.
Preferably, second condenser of product purification column overhead is connect by solvent recovery tank with vacuum evacuation device.
Preferably, first condenser of product purification column overhead is directly connect with product purification tower main body.
Preferably, the product purification column overhead cooling component output solvent.
Preferably, the system also includes be condensed back object in the middle part of component, including product purification tower in the middle part of product purification tower
Expect material condenser in the middle part of storage tank and product purification tower, material in the middle part of the middle part material outlet and product purification tower of product purification tower
Material condenser is sequentially connected in the middle part of storage tank and product purification tower, and the outlet material of material condenser returns in the middle part of product purification tower
Product purification tower.
Preferably, material storage tank and product purification tower middle part material condenser centre arranging thing in the middle part of the product purification tower
Material conveying pump.
Preferably, the middle part material outlet of the product purification tower is sub- by material storage tank in the middle part of product purification tower and benzene two
The connection of methyl diisocyanate storage tank.
Preferably, chilling is set between material storage tank and benzene dimethylene diisocyanate storage tank in the middle part of product purification tower
Device.
Preferably, reboiler is arranged in the tower bottom of the product purification tower.
Preferably, the reboiler is falling-film reboiler.
Preferably, the materials at bottom of tower outlet connection single-amido acid ester storage tank of the product purification tower.
Preferably, product purification is set between the materials at bottom of tower outlet and single-amido acid ester storage tank of the product purification tower
Tower tower bottom quencher, to reduce the polymerization of XDI, quencher quickly condenses XDI to 50 DEG C hereinafter, to reduce it in high-temperature region
Residence time.
Second aspect, the present invention provides using above-mentioned separation and purification system separation and refining method, the method includes
Following steps:
Raw material to be processed enters desolventizing tower and carries out desolventizing processing, desolventizing column overhead output solvent, desolventizing tower tower
Substrate material enter weight-removing column carry out it is de- handle again, weight-removing column tower bottom product material polymerize benzene dimethylene diisocyanate；De- weight
The material produced in the middle part of tower enters in product purification tower after mixing with stabilizer carries out refinement treatment, product purification tower tower bottom output
Single-amido acid ester, product purification midsection output benzene dimethylene diisocyanate.
It include solvent, benzene dimethylene diisocyanate, polymerization in the raw material as currently preferred technical solution
Benzene dimethylene diisocyanate and single-amido acid ester.
Preferably, benzene dimethylene diisocyanate, polymerization benzene dimethylene diisocyanate and monoamine in the raw material
The quality of carbamate and 10wt%~50wt% for total mass of raw material, such as 10wt%, 20wt%, 30wt%, 40wt%
Or 50wt% etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, remaining
For atent solvent.
Preferably, desolventizing tower is entered after raw material to be processed is preheated.
As currently preferred technical solution, the preheating temperature be 110 DEG C~200 DEG C, such as 110 DEG C, 120 DEG C,
130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG C etc., it is not limited to cited numerical value,
Other unlisted numerical value are equally applicable in the numberical range.
Preferably, the number of theoretical plate of the desolventizing tower be 5~30, such as 5,10,13,15,17,20,23,25,27 or
30 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, and preferably 20.
Preferably, the operating pressure of the desolventizing tower be 10kPa~50kPa, such as 10kPa, 20kPa, 30kPa,
40kPa or 50kPa etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable；
Bottom temperature is 90 DEG C~200 DEG C, such as 90 DEG C, 100 DEG C, 130 DEG C, 150 DEG C, 170 DEG C or 200 DEG C etc., it is not limited to
Cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable；Reflux ratio be 0.1~5, such as 0.1,0.5,
1,2,3,4 or 5 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, solvent quality score≤2wt% in the desolventizing tower materials at bottom of tower, such as 2wt%, 1.7wt%,
1.5wt%, 1.3wt%, 1wt% or 0.7wt% etc., it is not limited to cited numerical value, in the numberical range, other are not
The numerical value enumerated is equally applicable, preferably 1wt%~2wt%.
Preferably, the desolventizing tower materials at bottom of tower enters weight-removing column through reboiler and de- handle again.
Preferably, the reboiler is falling-film reboiler.
Preferably, the number of theoretical plate of the weight-removing column is 6~20, such as 6,10,12,14,16,18 or 20 etc., but not
It is only limitted to cited numerical value, other unlisted numerical value are equally applicable in the numberical range；Operating pressure be 0.2kPa~
2kPa, such as 0.2kPa, 0.4kPa, 0.6kPa, 1kPa, 0.2kPa, 1.4kPa, 1.6kPa or 2kPa etc., it is not limited to
Cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable；Bottom temperature is 160 DEG C~230 DEG C, such as
160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C or 230 etc., it is not limited to cited numerical value, interior other of the numberical range are not arranged
The numerical value of act is equally applicable.
Preferably, the weight-removing column overhead extraction solvent.
Preferably, the solvent of the weight-removing column overhead extraction recycles after condensing.
Preferably, polymerize in the material of the weight-removing column tower bottom extraction mass fraction of benzene dimethylene diisocyanate >=
90wt%.
As currently preferred technical solution, the material produced in the middle part of weight-removing column is divided into two-way, all the way through being condensed back,
Another way enters in product purification tower after being mixed with stabilizer.
Preferably, the stabilizer is BHT, para toluene sulfonamide, orthotoluene sulfonamide or p-methylphenyl sulphonyl isocyanic acid
Any one in ester or at least two combination, the combination is typical but non-limiting example has: BHT and para toluene sulfonamide
Combination, orthotoluene sulfonamide and the combination of p-methylphenyl sulfonyl isocyanate etc., preferably orthotoluene sulfonamide and p-methylphenyl
The mixture of sulfonyl isocyanate.
Preferably, the additive amount of the stabilizer is XDI and XMI gross mass in the material produced in the middle part of weight-removing column
‰~1wt of 0.1wt ‰, such as 0.1wt ‰, 0.3wt ‰, 0.5wt ‰, 0.7wt ‰ or 1wt ‰ etc., it is not limited to listed
The numerical value of act, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the material produced in the middle part of weight-removing column enters the packing section of product purification tower middle and lower part after mixing with stabilizer
It is handled.
Preferably, the product purification column overhead produces solvent.
Preferably, the solvent of the product purification column overhead extraction recycles after condensing.
Preferably, the number of theoretical plate of the product purification tower is 10~30, such as 10,15,20,25 or 30 etc., but not
It is only limitted to cited numerical value, other unlisted numerical value are equally applicable in the numberical range；Operating pressure be 0.2kPa~
2kPa, such as 0.2kPa, 0.4kPa, 0.6kPa, 1kPa, 0.2kPa, 1.4kPa, 1.6kPa or 2kPa etc., it is not limited to
Cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable；Bottom temperature is 160 DEG C~230 DEG C, such as
160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C or 230 DEG C etc., it is not limited to cited numerical value, in the numberical range, other are not
The numerical value enumerated is equally applicable.
Preferably, the delivery temperature of the product purification tower bottom output single-amido acid ester is 60 DEG C~150 DEG C, such as 60
DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C or 150 DEG C etc., it is not limited to cited numerical value, in the numberical range other
Unlisted numerical value is equally applicable, to guarantee material in liquid phase state.
Preferably, the material produced in the middle part of product purification tower is divided into two-way, and all the way through being condensed back, another way is that benzene two is sub-
Methyl diisocyanate.
The separation and refining method of the benzene dimethylene diisocyanate product as a preferred technical solution, including such as
Lower step:
(1) by raw material to be processed through raw material preheating to entering theoretical tower from the position of the 5th~12 column plate after 110~200 DEG C
The desolventizing tower that plate number is 5~30 carries out desolventizing processing, and the operating pressure of desolventizing tower is 10kPa~50kPa, tower reactor operation
Temperature is 90~160 DEG C, and setting reflux ratio is 0.1~5；
(2) solvent of desolventizing column overhead output obtains the solvent that purity reaches 99wt%, the object of tower reactor output after cooling
Material includes XDI, the concentrate for polymerizeing XDI and XMI, solvent quality score≤2wt%；
(3) desolventizing tower materials at bottom of tower enters falling-film reboiler by pressure difference, through falling-film reboiler enter weight-removing column into
Row is de- to be handled again, and the number of theoretical plate of weight-removing column is 6~20 pieces, and tower reactor pressure is controlled in 0.2kPa~2kPa, tower reactor operation temperature
At 160 DEG C~230 DEG C, weight-removing column tower top material obtains solvent after condensing for control；Weight-removing column tower bottom product material is after chilling
Output polymerize XDI, and the condensation of material 10%~50% of the 2nd piece of column plate extraction is to flowing back after 20 DEG C~50 DEG C in the middle part of weight-removing column；
(4) remaining weight-removing column extraction material is input in stabilizer mixing arrangement, and into stabilizer mixing arrangement
The compound stabilizer that 0.1~1wt of XDI and XMI gross mass ‰ is added is mixed, and the compound stabilizer is orthotoluene sulfonamide
With the mixture of p-methylphenyl sulfonyl isocyanate；
(5) step (4) mixed material is entered into the middle and lower part product purification Ta Ta packing section, the tower reason of product purification tower
It is 10~30 pieces by plate number, the control of tower reactor pressure is controlled in 0.2kPa~2kPa, tower reactor operation temperature at 160~230 DEG C；Product
Treating column tower bottom extraction intermediate X MI, which is kept the temperature to 60~150 DEG C, enters storage tank with liquid phase；The 3rd block of column plate of product purification midsection
Produce XDI product, wherein 10%~50% is condensed to flowing back after 20 DEG C~50 DEG C, remaining XDI product condense to 50 DEG C with
Under, input product storage tank is added after product stabilizer to be refrigerated within 8 DEG C and is saved, product stabilizer include antioxidant and
The mixture of polymerization inhibitor.
Compared with prior art, the invention has the following advantages:
Separation system and method for the present invention are simple, easily operated, and highly-safe, low energy consumption, extract product purity height,
Product separation yield is high, and for XDI product one way separation yield up to 97% or more, purity is up to 99wt% or more, and XMI purity reaches
99wt% or more, XDI polymerization amount are less than 2%.
Detailed description of the invention
Fig. 1 is that the structure of the separation and purification system of benzene dimethylene diisocyanate product described in the embodiment of the present invention 1 is shown
It is intended to；
Wherein, 1- feed preheater, 2- desolventizing tower, 3- weight-removing column falling-film reboiler, 4- weight-removing column, the mixing of 5- stabilizer
Device, 6- product purification tower, 7- vacuum evacuation device, 8- desolventizing the first condenser of column overhead, 9- desolventizing column overhead return tank,
10- desolventizing the second condenser of column overhead, 11- weight-removing column the first condenser of tower top, 12- weight-removing column the second condenser of tower top, 13-
Material storage tank in the middle part of weight-removing column, 14- weight-removing column middle part material condenser, 15- product purification the first condenser of column overhead, 16- are produced
The second condenser of product refined tower top, 17- product purification tower middle part material storage tank, 18- product purification tower middle part material condenser,
19- product purification tower tower bottom quencher, 20- product purification tower falling-film reboiler.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
Specific embodiment of the invention part provides a kind of separation and purification system of benzene dimethylene diisocyanate product
System, the system comprises desolventizing tower, weight-removing column, stabilizer mixing arrangement, product purification towers；
Wherein, raw material to be processed is connected with the feed inlet of desolventizing tower, the materials at bottom of tower outlet of desolventizing tower and weight-removing column
Material inlet be connected；The middle part material outlet stable connection agent mixing arrangement of weight-removing column, the material of stabilizer mixing arrangement go out
Material outlet is arranged in mouth connection product purification tower, the middle part of product purification tower.
The processing method of the system includes:
Raw material to be processed enters desolventizing tower and carries out desolventizing processing, desolventizing column overhead output solvent, desolventizing tower tower
Substrate material enter weight-removing column carry out it is de- handle again, weight-removing column tower bottom product material polymerize benzene dimethylene diisocyanate；De- weight
The material produced in the middle part of tower enters in product purification tower after mixing with stabilizer carries out refinement treatment, product purification tower tower bottom output
Single-amido acid ester, product purification midsection output benzene dimethylene diisocyanate.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1:
The separation and purification system and its processing method of a kind of benzene dimethylene diisocyanate product are present embodiments provided,
As shown in Figure 1, the system comprises: the de- weight of feed preheater 1, desolventizing tower 2, desolventizing column overhead cooling component, weight-removing column
Tower falling-film reboiler 3, weight-removing column 4, weight-removing column tower top cooling component, weight-removing column middle part are condensed back component, stabilizer mixing dress
Set 5, product purification tower 6, product purification column overhead cooling component, product purification tower middle part condensing reflux component and vacuum evacuation device
7；
Wherein, raw material to be processed is connected through feed preheater 1 with the feed inlet at 2 middle part of desolventizing tower, the tower of desolventizing tower 2
Bottom material outlet is connected through weight-removing column falling-film reboiler 3 with the material inlet of weight-removing column 4；
Desolventizing column overhead cooling component includes the first condenser of desolventizing column overhead 8,9 and of desolventizing column overhead return tank
The second condenser of desolventizing column overhead 10, the charging of desolventizing tower 2 tower top material outlet and the first condenser of desolventizing column overhead 8
Mouth connection, the discharge port of the first condenser of desolventizing column overhead 8 are connect with desolventizing column overhead return tank 9, desolventizing column overhead
The material outlet of return tank 9 is separately connected 2 tower top material refluxing opening of desolventizing tower and the second condenser of desolventizing column overhead 10, takes off
The second condenser of solvent column overhead 10 is connected by solvent tank with vacuum evacuation device 7；
Weight-removing column tower top cooling component includes sequentially connected the first condenser of weight-removing column tower top 11 and weight-removing column tower top
Two condensers 12, the second condenser of weight-removing column tower top 12 connect vacuum evacuation device 7 by solvent recovery tank；
It includes material storage tank 13 and weight-removing column middle part material condenser in the middle part of weight-removing column that component is condensed back in the middle part of weight-removing column
14, middle part material outlet and the material condenser 14 in the middle part of material storage tank 13 in the middle part of weight-removing column and weight-removing column of weight-removing column 4 successively connect
It connects, the outlet material of material condenser 14 returns to weight-removing column 4 in the middle part of weight-removing column；Meanwhile the middle part material outlet of weight-removing column 4 passes through
Material storage tank 13 is connected with stabilizer mixing arrangement 5 in the middle part of weight-removing column；The material outlet connection product essence of stabilizer mixing arrangement 5
Tower 6 processed；
Product purification column overhead cooling component includes sequentially connected the first condenser of product purification column overhead 15 and product
The second condenser of refined tower top 16, the second condenser of product purification column overhead 16 connect vacuum evacuation device 7 by storage tank；
It is condensed back in the middle part of product purification tower in the middle part of component, including product purification tower in material storage tank 17 and product purification tower
Portion's material condenser 18, middle part material outlet and product purification tower the middle part material storage tank 17 and product purification of product purification tower 6
Material condenser 18 is sequentially connected in the middle part of tower, and the outlet material of material condenser 18 returns to product purification tower in the middle part of product purification tower
6；Material-handling pump is set among material storage tank 17 and product purification tower middle part material condenser 18 in the middle part of product purification tower；Product
The middle part material outlet for the treatment of column 6 is connected by material storage tank 17 in the middle part of product purification tower and benzene dimethylene diisocyanate storage tank
It connects, reboiler (such as product purification tower falling-film reboiler 20) is arranged in the tower bottom of product purification tower, and product purification tower 6 passes through product
Treating column tower bottom quencher 19 is connected with single-amido acid ester storage tank；
The materials at bottom of tower of desolventizing tower 2, which is exported, is arranged power transfer pump between weight-removing column falling-film reboiler 3；
Material-handling pump is set among material storage tank 13 and weight-removing column middle part material condenser 14 in the middle part of weight-removing column；
The first condenser of weight-removing column tower top 11 is directly connect with 4 main body of weight-removing column；
The first condenser of product purification column overhead 15 is directly connect with 6 main body of product purification tower；
Quencher is set between material storage tank 17 and benzene dimethylene diisocyanate storage tank in the middle part of product purification tower.
Using above system separation and refining method the following steps are included:
(1) by raw material to be processed through raw material preheating to entering theoretical tower from the position of the 5th~12 column plate after 110~200 DEG C
The desolventizing tower that plate number is 5~30 carries out desolventizing processing, and the operating pressure of desolventizing tower is 10kPa~50kPa, tower reactor operation
Temperature is 90~160 DEG C, and setting reflux ratio is 0.1~5；
(2) solvent of desolventizing column overhead output obtains the solvent that purity reaches 99wt%, the object of tower reactor output after cooling
Material includes XDI, the concentrate for polymerizeing XDI and XMI, solvent quality score≤2wt%；
(3) desolventizing tower materials at bottom of tower enters falling-film reboiler by pressure difference, through falling-film reboiler enter weight-removing column into
Row is de- to be handled again, and the number of theoretical plate of weight-removing column is 6~20 pieces, and tower reactor pressure is controlled in 0.2kPa~2kPa, tower reactor operation temperature
At 160 DEG C~230 DEG C, weight-removing column tower top material obtains solvent after condensing for control；Weight-removing column tower bottom product material is after chilling
Output polymerize XDI, and the condensation of material 10%~50% of the 2nd piece of column plate extraction is to flowing back after 20 DEG C~50 DEG C in the middle part of weight-removing column；
(4) remaining weight-removing column extraction material is input in stabilizer mixing arrangement, and into stabilizer mixing arrangement
The stabilizer that 0.1~1wt of XDI and XMI gross mass ‰ is added is mixed；
(5) step (4) mixed material is entered into the middle and lower part product purification Ta Ta packing section, the tower reason of product purification tower
It is 10~30 pieces by plate number, the control of tower reactor pressure is controlled in 0.2kPa~2kPa, tower reactor operation temperature at 160~230 DEG C；Product
Treating column tower bottom extraction intermediate X MI, which is kept the temperature to 60~150 DEG C, enters storage tank with liquid phase；The 3rd block of column plate of product purification midsection
Produce XDI product, wherein 10%~50% is condensed to flowing back after 20 DEG C~50 DEG C, remaining XDI product condense to 50 DEG C with
Under, input product storage tank is added after product stabilizer to be refrigerated within 8 DEG C and is saved, product stabilizer include antioxidant and
The mixture of polymerization inhibitor.
Embodiment 2
A kind of separation and refining method of the benzene dimethylene diisocyanate product using system described in embodiment 1, packet
Include following steps:
(1) (wherein, the mass fraction of XDI is 14wt% to raw material to be processed, and the mass fraction for polymerizeing XDI is 2wt%, XMI
Mass fraction be 4wt%, the mass fraction of solvent be 80wt%) through feed preheater 1 preheating after from number of theoretical plate for 7 position
The progress desolventizing processing of desolventizing tower 2 for entering that theoretical cam curve is 20 is set, the flow rate of raw material is 95kg/h, desolventizing tower 2
Operating pressure is 20kPa, and tower reactor operation temperature is 160 DEG C, and setting reflux ratio is 1；
(2) solvent of 2 tower top output of desolventizing tower can obtain purity after desolventizing column overhead cooling component carries out cooling
Up to the solvent of 99wt%, the material of tower reactor output includes XDI, polymerization XDI and XMI concentrate, and XDI content is 76wt%, and XMI contains
Amount is 19wt%, and XDI polymer content is 5wt%；
(3) 2 materials at bottom of tower of desolventizing tower, which enters, enters weight-removing column falling-film reboiler 3 by pressure difference, through weight-removing column falling liquid film
Reboiler 3 take off into weight-removing column 4 and be handled again, and the number of theoretical plate of weight-removing column 4 is 8, and the control of tower reactor pressure is in 1kPa, tower reactor behaviour
Make temperature control at 190 DEG C, 4 tower top material of weight-removing column obtains solvent after the condensation of weight-removing column tower top cooling component；4 tower of weight-removing column
Bottom product material output after chilling polymerize XDI, the material (XDI and XMI mixture) of 4 middle parts of weight-removing column the 2nd block of column plate extraction
About 50% squeezes into 4 overhead reflux of weight-removing column through metering pump after material condenser 14 in the middle part of weight-removing column is condensed to 30 DEG C；
(4) remaining weight-removing column extraction material is input in stabilizer mixing arrangement 5, into stabilizer mixing arrangement 5
The compound stabilizer of XDI and XMI gross mass 1wt ‰ is added, compound stabilizer is specially orthotoluene sulfonamide and p-methylphenyl sulphur
The mixture of acyl isocyanates；
(5) material enters 6 tower middle and lower part packing section of product purification tower after mixing, and the tower number of theoretical plate of product purification tower 6 is
15 pieces, the control of tower reactor pressure controls within 190 DEG C in 1.2kPa, tower reactor operation temperature；The extraction of 6 tower bottom of product purification tower is intermediate
Body XMI, which is kept the temperature to 85 DEG C, enters storage tank with liquid phase；The 3rd block of 6 middle section of product purification tower column plate produces XDI product, and about 50% through cold
Condenser is condensed to squeezing into tower top through metering pump after 50 DEG C.The XDI product of extraction is cold through being condensed back component in the middle part of product purification tower
It coagulates to 30 DEG C, then enters product storage tank by gravity, be refrigerated within 8 DEG C and save after XDI product addition product stabilizer, product
Stabilizer is the mixture of antioxidant and polymerization inhibitor.
Whole process guarantees vacuum degree by vacuum evacuation device 7.
It adopts the device and the method, gained XDI product and recycling design quality are as follows
| Index name | XDI purity wt% | Recycling design accounts for the mass percentage wt% of former solvent |
| Purity | >99.1 | 98.3 |
| Hydrolyzable chloride content ppm | <100 | |
| NCO content % | ≤43.0 | |
| Coloration APHA | ≤20 | ≤20 |
Embodiment 3
A kind of separation and refining method of the benzene dimethylene diisocyanate product using system described in embodiment 1, packet
Include following steps:
The separation and refining method of the benzene dimethylene diisocyanate product, includes the following steps:
It (1) is 30 to theoretical cam curve is entered from the position of the 12nd column plate after 110 DEG C through raw material preheating by raw material to be processed
Desolventizing tower carry out desolventizing processing, the flow rate of raw material is 95kg/h, and the operating pressure of desolventizing tower is 50kPa, tower reactor behaviour
Making temperature is 160 DEG C, and setting reflux ratio is 5；
(2) solvent of desolventizing column overhead output obtains the solvent that purity reaches 99wt%, the object of tower reactor output after cooling
Material includes XDI, the concentrate for polymerizeing XDI and XMI, solvent quality score≤2wt%；
(3) desolventizing tower materials at bottom of tower enters falling-film reboiler by pressure difference, through falling-film reboiler enter weight-removing column into
Row is de- to be handled again, and the number of theoretical plate of weight-removing column is 20 pieces, and in 2kPa, tower reactor operation temperature is controlled at 230 DEG C the control of tower reactor pressure,
Weight-removing column tower top material obtains solvent after condensing；Weight-removing column tower bottom product material output after chilling polymerize XDI, in weight-removing column
The condensation of material 10% of portion's the 2nd block of column plate extraction is to flowing back after 20 DEG C；
(4) remaining weight-removing column extraction material is input in stabilizer mixing arrangement, and into stabilizer mixing arrangement
The BHT that XDI and XMI gross mass 1wt ‰ is added is mixed；
(5) step (4) mixed material is entered into the middle and lower part product purification Ta Ta packing section, the tower reason of product purification tower
It is 30 pieces by plate number, the control of tower reactor pressure is controlled in 2kPa, tower reactor operation temperature at 230 DEG C；In the extraction of product purification tower tower bottom
Mesosome XMI, which is kept the temperature to 150 DEG C, enters storage tank with liquid phase；The 3rd block of column plate of product purification midsection produces XDI product, about 10% warp
Condensation is to flowing back after 50 DEG C, and remaining XDI product is condensed to 50 DEG C hereinafter, input product storage tank, after adding product stabilizer
It is refrigerated within 8 DEG C and saves, product stabilizer includes the mixture of antioxidant and polymerization inhibitor.
Whole process guarantees vacuum degree by vacuum evacuation device 7.
It adopts the device and the method, gained XDI product and recycling design quality are as follows:
| Index name | XDI purity wt% | Recycling design accounts for the mass percentage wt% of former solvent |
| Purity | >99.2 | 99.3 |
| Hydrolyzable chloride content ppm | <100 | |
| NCO content % | ≤43.0 | |
| Coloration APHA | ≤20 | ≤20 |
Embodiment 4
A kind of separation and refining method of the benzene dimethylene diisocyanate product using system described in embodiment 1, packet
Include following steps:
It (1) is 5 to theoretical cam curve is entered from the position of the 5th column plate after 110 DEG C through raw material preheating by raw material to be processed
Desolventizing tower carries out desolventizing processing, and the flow rate of raw material is 95kg/h, and the operating pressure of desolventizing tower is 10kPa, tower reactor operation
Temperature is 90 DEG C, and setting reflux ratio is 0.1；
(2) solvent of desolventizing column overhead output obtains the solvent that purity reaches 99wt%, the object of tower reactor output after cooling
Material includes XDI, the concentrate for polymerizeing XDI and XMI, solvent quality score≤2wt%；
(3) desolventizing tower materials at bottom of tower enters falling-film reboiler by pressure difference, through falling-film reboiler enter weight-removing column into
Row is de- to be handled again, and the number of theoretical plate of weight-removing column is 6 pieces, and the control of tower reactor pressure is controlled in 0.2kPa, tower reactor operation temperature 160
DEG C, weight-removing column tower top material obtains solvent after condensing；Weight-removing column tower bottom product material output after chilling polymerize XDI, takes off weight
The condensation of material 50% of 2nd piece of column plate extraction is to flowing back after 20 DEG C in the middle part of tower；
(4) remaining weight-removing column extraction material is input in stabilizer mixing arrangement, and into stabilizer mixing arrangement
The para toluene sulfonamide that XDI and XMI gross mass 0.1wt ‰ is added is mixed；
(5) step (4) mixed material is entered into the middle and lower part product purification Ta Ta packing section, the tower reason of product purification tower
It is 10 pieces by plate number, the control of tower reactor pressure is controlled in 0.2kPa, tower reactor operation temperature at 160 DEG C；The extraction of product purification tower tower bottom
Intermediate X MI, which is kept the temperature to 60 DEG C, enters storage tank with liquid phase；The 3rd block of column plate of product purification midsection produces XDI product, about 50% warp
Condensation is to flowing back after 50 DEG C, and remaining XDI product is condensed to 50 DEG C hereinafter, input product storage tank, after adding product stabilizer
It is refrigerated within 8 DEG C and saves, product stabilizer includes the mixture of antioxidant and polymerization inhibitor.
Whole process guarantees vacuum degree by vacuum evacuation device 7.
It adopts the device and the method, gained XDI product and recycling design quality are as follows:
Embodiment 5
A kind of separation and refining method of the benzene dimethylene diisocyanate product using system described in embodiment 1:
It (1) is 22 to theoretical cam curve is entered from the position of the 9th column plate after 150 DEG C through raw material preheating by raw material to be processed
Desolventizing tower carries out desolventizing processing, and the flow rate of raw material is 95kg/h, and the operating pressure of desolventizing tower is 20kPa, tower reactor operation
Temperature is 120 DEG C, and setting reflux ratio is 2；
(2) solvent of desolventizing column overhead output obtains the solvent that purity reaches 99wt%, the object of tower reactor output after cooling
Material includes XDI, the concentrate for polymerizeing XDI and XMI, solvent quality score≤2wt%；
(3) desolventizing tower materials at bottom of tower enters falling-film reboiler by pressure difference, through falling-film reboiler enter weight-removing column into
Row is de- to be handled again, and the number of theoretical plate of weight-removing column is 10 pieces, and the control of tower reactor pressure is controlled in 1.5kPa, tower reactor operation temperature 200
DEG C, weight-removing column tower top material obtains solvent after condensing；Weight-removing column tower bottom product material output after chilling polymerize XDI, takes off weight
The condensation of material 30% of 2nd piece of column plate extraction is to flowing back after 30 DEG C in the middle part of tower；
(4) remaining weight-removing column extraction material is input in stabilizer mixing arrangement, and into stabilizer mixing arrangement
The orthotoluene sulfonamide that 0.1~1wt of XDI and XMI gross mass ‰ is added is mixed；
(5) step (4) mixed material is entered into the middle and lower part product purification Ta Ta packing section, the tower reason of product purification tower
It is 15 pieces by plate number, the control of tower reactor pressure is controlled in 1.5kPa, tower reactor operation temperature at 200 DEG C；The extraction of product purification tower tower bottom
Intermediate X MI, which is kept the temperature to 90 DEG C, enters storage tank with liquid phase；The 3rd block of column plate of product purification midsection produces XDI product, about 30% warp
Condensation is to flowing back after 50 DEG C, and remaining XDI product is condensed to 50 DEG C hereinafter, input product storage tank, after adding product stabilizer
It is refrigerated within 8 DEG C and saves, product stabilizer includes the mixture of antioxidant and polymerization inhibitor.
Whole process guarantees vacuum degree by vacuum evacuation device 7.
It adopts the device and the method, gained XDI product and recycling design quality are as follows:
| Index name | XDI purity wt% | Recycling design accounts for the mass percentage wt% of former solvent |
| Purity | >99.3 | 99.3 |
| Hydrolyzable chloride content ppm | <100 | |
| NCO content % | ≤43.0 | |
| Coloration APHA | ≤20 | ≤20 |
Embodiment 6
A kind of separation and refining method of the benzene dimethylene diisocyanate product using system described in embodiment 1:
It (1) is 28 to theoretical cam curve is entered from the position of the 10th column plate after 150 DEG C through raw material preheating by raw material to be processed
Desolventizing tower carry out desolventizing processing, the flow rate of raw material is 95kg/h, and the operating pressure of desolventizing tower is 40kPa, tower reactor behaviour
Making temperature is 110 DEG C, and setting reflux ratio is 3；
(2) solvent of desolventizing column overhead output obtains the solvent that purity reaches 99wt%, the object of tower reactor output after cooling
Material includes XDI, the concentrate for polymerizeing XDI and XMI, solvent quality score≤2wt%；
(3) desolventizing tower materials at bottom of tower enters falling-film reboiler by pressure difference, through falling-film reboiler enter weight-removing column into
Row is de- to be handled again, and the number of theoretical plate of weight-removing column is 18 pieces, and the control of tower reactor pressure is controlled in 0.8kPa, tower reactor operation temperature 220
DEG C, weight-removing column tower top material obtains solvent after condensing；Weight-removing column tower bottom product material output after chilling polymerize XDI, takes off weight
The condensation of material 20% of 2nd piece of column plate extraction is to flowing back after 25 DEG C in the middle part of tower；
(4) remaining weight-removing column extraction material is input in stabilizer mixing arrangement, and into stabilizer mixing arrangement
The p-methylphenyl sulfonyl isocyanate that XDI and XMI gross mass 0.5wt ‰ is added is mixed；
(5) step (4) mixed material is entered into the middle and lower part product purification Ta Ta packing section, the tower reason of product purification tower
It is 25 pieces by plate number, the control of tower reactor pressure is controlled in 1.5kPa, tower reactor operation temperature at 200 DEG C；The extraction of product purification tower tower bottom
Intermediate X MI, which is kept the temperature to 80 DEG C, enters storage tank with liquid phase；The 3rd block of column plate of product purification midsection produces XDI product, about 40% warp
Condensation is to flowing back after 50 DEG C, and remaining XDI product is condensed to 50 DEG C hereinafter, input product storage tank, after adding product stabilizer
It is refrigerated within 8 DEG C and saves, product stabilizer includes the mixture of antioxidant and polymerization inhibitor.
Whole process guarantees vacuum degree by vacuum evacuation device 7.
It adopts the device and the method, gained XDI product and recycling design quality are as follows:
| Index name | XDI purity wt% | Recycling design accounts for the mass percentage wt% of former solvent |
| Purity | >99.1 | 98.3 |
| Hydrolyzable chloride content ppm | <100 | |
| NCO content % | ≤43.0 | |
| Coloration APHA | ≤20 | ≤20 |
Comparative example 1
A kind of separation and refining method of the benzene dimethylene diisocyanate product using system described in embodiment 1, is removed
Step is added without outside stabilizer in (4), remaining is same as Example 2.
Whole process guarantees vacuum degree by vacuum evacuation device 7.
It adopts the device and the method, the XDI rate of recovery is 93%；Gained XDI product and recycling design quality are as follows:
| Index name | XDI purity wt% | Recycling design accounts for the mass percentage wt% of former solvent |
| Purity | >98.9 | 97.5 |
| Hydrolyzable chloride content ppm | <100 | |
| NCO content % | ≤42.0 | |
| Coloration APHA | ≤20 | ≤20 |
Comparative example 2
A kind of separation and refining method of the benzene dimethylene diisocyanate product using system described in embodiment 1, is removed
Compound stabilizer as described in example 2 is replaced with outside N- ethyl orthotoluene sulfonamide, remaining is same as Example 2.
Whole process guarantees vacuum degree by vacuum evacuation device 7.
It adopts the device and the method, the XDI rate of recovery is 92%；Gained XDI product and recycling design quality are as follows:
| Index name | XDI purity wt% | Recycling design accounts for the mass percentage wt% of former solvent |
| Purity | >98.0 | 97.3 |
| Hydrolyzable chloride content ppm | <100 | |
| NCO content % | ≤42.0 | |
| Coloration APHA | ≤20 | ≤20 |
It is highly-safe from above-described embodiment as can be seen that separation system of the present invention and method are simple, easily operated,
Low energy consumption, extracts product purity height, product separation yield is high, and up to 97% or more, purity is up to XDI product one way separation yield
99wt% or more, XMI purity reach 99wt% or more.
It can be seen that from above-mentioned comparative example and be added without stabilizer or stabilizer is replaced with into other substances, extract product
Purity and separation yield are substantially reduced, and XMI purity is substantially reduced, and polymerization XDI yield is significantly raised.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of separation and purification system of benzene dimethylene diisocyanate product, which is characterized in that the system comprises precipitations
Agent tower, weight-removing column, stabilizer mixing arrangement and product purification tower；
Wherein, raw material to be processed enters desolventizing tower by the feed inlet that desolventizing tower is arranged, and the materials at bottom of tower of desolventizing tower goes out
Mouth is connected with the material inlet of weight-removing column；The feed inlet of the middle part material outlet stable connection agent mixing arrangement of weight-removing column is stablized
The material outlet of agent mixing arrangement connects product purification tower, and material outlet is arranged in the middle part of product purification tower.
2. separation and purification system according to claim 1, which is characterized in that the system also includes reboiler, it is described again
Device is boiled to be set between the materials at bottom of tower outlet of desolventizing tower and the material inlet of weight-removing column；
Preferably, the reboiler includes falling-film reboiler；
Preferably, material-handling pump is set between the materials at bottom of tower outlet and reboiler of desolventizing tower；
Preferably, the system also includes vacuum evacuation device, vacuum evacuation device independently with desolventizing column overhead, weight-removing column tower top
It is connected with product purification column overhead.
3. separation and purification system according to claim 1 or 2, which is characterized in that the feed inlet of the desolventizing tower is arranged
In the middle part of desolventizing tower tower；
Preferably, the system also includes feed preheaters, are set on the feeding pipe of desolventizing tower；
Preferably, the system also includes desolventizing column overhead cooling components；
Preferably, the desolventizing column overhead cooling component includes the first condenser of desolventizing column overhead, desolventizing column overhead time
Flow tank and the second condenser of desolventizing column overhead, desolventizing column overhead material outlet and the first condenser of desolventizing column overhead into
Material mouth connection, the discharge port of the first condenser of desolventizing column overhead are connect with desolventizing column overhead return tank, desolventizing column overhead
The material outlet of return tank is separately connected the second condenser of desolventizing column overhead material refluxing opening and desolventizing column overhead, desolventizing
The second condenser of column overhead is connected with vacuum evacuation device；
Preferably, second condenser of desolventizing column overhead is connected with vacuum evacuation device by solvent tank.
4. separation and purification system according to claim 1-3, which is characterized in that the system also includes weight-removing columns
Tower top cooling component；
Preferably, the weight-removing column tower top cooling component includes sequentially connected the first condenser of weight-removing column tower top and weight-removing column tower
The second condenser is pushed up, the second condenser of weight-removing column tower top connects vacuum evacuation device；
Preferably, second condenser of weight-removing column tower top is connect by solvent recovery tank with vacuum evacuation device；
Preferably, first condenser of weight-removing column tower top is directly connect with weight-removing column main body；
Preferably, the weight-removing column tower top cooling component output solvent；
Preferably, the tower bottom output of the weight-removing column polymerize benzene dimethylene diisocyanate；
Preferably, weight-removing column tower bottom quencher is set on the tower bottom export pipeline of the weight-removing column.
5. separation and purification system according to claim 1-4, which is characterized in that the system also includes weight-removing columns
Middle part is condensed back component；
Preferably, it includes that weight-removing column middle part material storage tank and weight-removing column middle part material are cold that component is condensed back in the middle part of the weight-removing column
Condenser, middle part material outlet and the material condenser in the middle part of material storage tank in the middle part of weight-removing column and weight-removing column of weight-removing column are sequentially connected,
The outlet material of material condenser returns to weight-removing column in the middle part of weight-removing column；
Preferably, material-handling pump is set among material storage tank and weight-removing column middle part material condenser in the middle part of the weight-removing column；
Preferably, the middle part material outlet of the weight-removing column passes through material storage tank in the middle part of weight-removing column and stabilizer mixing arrangement phase
Even.
6. separation and purification system according to claim 1-5, which is characterized in that the system also includes product essences
Column overhead cooling component processed；
Preferably, the product purification column overhead cooling component include sequentially connected the first condenser of product purification column overhead and
The second condenser of product purification column overhead, the second condenser of product purification column overhead connect vacuum evacuation device；
Preferably, second condenser of product purification column overhead is connect by solvent recovery tank with vacuum evacuation device；
Preferably, first condenser of product purification column overhead is directly connect with product purification tower main body；
Preferably, the product purification column overhead cooling component output solvent；
Preferably, the system also includes be condensed back material storage in the middle part of component, including product purification tower in the middle part of product purification tower
Material condenser in the middle part of tank and product purification tower, middle part material outlet and product purification tower the middle part material storage tank of product purification tower
It is sequentially connected with material condenser in the middle part of product purification tower, the outlet material of material condenser returns to product in the middle part of product purification tower
Treating column；
Preferably, setting material is defeated between material storage tank and product purification tower middle part material condenser in the middle part of the product purification tower
Send pump；
Preferably, the middle part material outlet of the product purification tower passes through material storage tank in the middle part of product purification tower and phenylenedimethylidyne
The connection of diisocyanate storage tank；
Preferably, quencher is set between material storage tank and benzene dimethylene diisocyanate storage tank in the middle part of product purification tower；
Preferably, reboiler is arranged in the tower bottom of the product purification tower；
Preferably, the reboiler is falling-film reboiler；
Preferably, the materials at bottom of tower outlet connection single-amido acid ester storage tank of the product purification tower；
Preferably, product purification tower tower is set between the materials at bottom of tower outlet and single-amido acid ester storage tank of the product purification tower
Bottom quencher.
7. a kind of separation and refining method using system as claimed in any one of claims 1 to 6, which is characterized in that the method
The following steps are included:
Raw material to be processed enters desolventizing tower and carries out desolventizing processing, desolventizing column overhead output solvent, desolventizing tower bottoms
Material take off into weight-removing column and be handled again, and weight-removing column tower bottom product material polymerize benzene dimethylene diisocyanate；In weight-removing column
The material of portion's extraction enters in product purification tower after mixing with stabilizer carries out refinement treatment, product purification tower tower bottom output monoamine
Carbamate, product purification midsection output benzene dimethylene diisocyanate.
8. the method according to the description of claim 7 is characterized in that including solvent, two isocyanide of phenylenedimethylidyne in the raw material
Acid esters, polymerization benzene dimethylene diisocyanate and single-amido acid ester；
Preferably, benzene dimethylene diisocyanate, polymerization benzene dimethylene diisocyanate and mono amino first in the raw material
The quality of acid esters and 10wt%~50wt% for total mass of raw material；
Preferably, desolventizing tower is entered after raw material to be processed is preheated；
Preferably, the preheating temperature is 110 DEG C~200 DEG C；
Preferably, the number of theoretical plate of the desolventizing tower is 5~30, preferably 20；
Preferably, the operating pressure of the desolventizing tower is 10kPa~50kPa, and bottom temperature is 90 DEG C~200 DEG C, reflux ratio
It is 0.1~5；
Preferably, solvent quality score≤2wt%, preferably 1wt%~2wt% in the desolventizing tower materials at bottom of tower；
Preferably, the desolventizing tower materials at bottom of tower enters weight-removing column through reboiler and de- handle again；
Preferably, the reboiler is falling-film reboiler；
Preferably, the number of theoretical plate of the weight-removing column is 6~20, and operating pressure is 0.2kPa~2kPa, and bottom temperature is 160 DEG C
~230 DEG C；
Preferably, the weight-removing column overhead extraction solvent；
Preferably, the solvent of the weight-removing column overhead extraction recycles after condensing；
Preferably, polymerize in the material of the weight-removing column tower bottom extraction mass fraction of benzene dimethylene diisocyanate >=
90wt%.
9. method according to claim 7 or 8, which is characterized in that the material produced in the middle part of weight-removing column is divided into two-way, all the way
Through being condensed back, another way enters in product purification tower after being mixed with stabilizer；
Preferably, the stabilizer is any in para toluene sulfonamide, orthotoluene sulfonamide or p-methylphenyl sulfonyl isocyanate
It is a kind of or at least two combination, the preferably mixture of orthotoluene sulfonamide and p-methylphenyl sulfonyl isocyanate；
Preferably, the additive amount of the stabilizer is the 0.1wt ‰ of XDI and XMI gross mass in the material produced in the middle part of weight-removing column
~1wt ‰；
Preferably, the material produced in the middle part of weight-removing column enters product purification tower middle and lower part packing section after mixing with stabilizer carries out
Processing；
Preferably, the product purification column overhead produces solvent；
Preferably, the solvent of the product purification column overhead extraction recycles after condensing；
Preferably, the number of theoretical plate of the product purification tower is 10~30, and operating pressure is 0.2kPa~2kPa, and bottom temperature is
160 DEG C~230 DEG C；
Preferably, the delivery temperature of the product purification tower bottom output single-amido acid ester is 60 DEG C~150 DEG C；
Preferably, the material produced in the middle part of product purification tower is divided into two-way, and all the way through being condensed back, another way is phenylenedimethylidyne
Diisocyanate.
10. according to the described in any item methods of claim 7-9, which is characterized in that described method includes following steps:
(1) by raw material to be processed through raw material preheating to entering theoretical cam curve from the position of the 5th~12 column plate after 110~200 DEG C
Desolventizing processing is carried out for 5~30 desolventizing tower, the operating pressure of desolventizing tower is 10kPa~50kPa, tower reactor operation temperature
It is 90~160 DEG C, setting reflux ratio is 0.1~5；
(2) solvent of desolventizing column overhead output obtains the solvent that purity reaches 99wt%, the material packet of tower reactor output after cooling
The concentrate for including XDI, polymerizeing XDI and XMI, solvent quality score≤2wt%；
(3) desolventizing tower materials at bottom of tower enters falling-film reboiler by pressure difference, enters weight-removing column through falling-film reboiler and is taken off
It handles again, the number of theoretical plate of weight-removing column is 6~20 pieces, and the control of tower reactor pressure is in 0.2kPa~2kPa, the control of tower reactor operation temperature
At 160 DEG C~230 DEG C, weight-removing column tower top material obtains solvent after condensing；Weight-removing column tower bottom product material output after chilling
It polymerize XDI, the condensation of material 10%~50% of the 2nd piece of column plate extraction is to flowing back after 20 DEG C~50 DEG C in the middle part of weight-removing column；
(4) remaining weight-removing column extraction material is input in stabilizer mixing arrangement, and is added into stabilizer mixing arrangement
The compound stabilizer of 0.1~1wt of XDI and XMI gross mass ‰ is mixed, and the compound stabilizer is orthotoluene sulfonamide and right
The mixture of tolylsulfonyl- isocyanates；
(5) step (4) mixed material is entered into the middle and lower part product purification Ta Ta packing section, the tower theoretical plate of product purification tower
Number is 10~30 pieces, and the control of tower reactor pressure is controlled in 0.2kPa~2kPa, tower reactor operation temperature at 160~230 DEG C；Product purification
Tower tower bottom extraction intermediate X MI, which is kept the temperature to 60~150 DEG C, enters storage tank with liquid phase；The 3rd piece of column plate extraction of product purification midsection
XDI product, wherein 10%~50% is condensed to flowing back after 20 DEG C~50 DEG C, remaining XDI product is condensed to 50 DEG C hereinafter, defeated
Enter product storage tank, add after product stabilizer to be refrigerated within 8 DEG C and save, product stabilizer includes antioxidant and polymerization inhibitor
Mixture.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979500A (en) * | 2021-05-10 | 2021-06-18 | 中国科学院过程工程研究所 | Device and method for purifying xylylene diisocyanate |
| CN114478321A (en) * | 2022-04-06 | 2022-05-13 | 中国科学院过程工程研究所 | Method, device and application for separating, refining and purifying intermediate m-xylylene diamino ethyl formate solution |
| CN114984601A (en) * | 2022-07-05 | 2022-09-02 | 中国科学院过程工程研究所 | Device system and method for separating and refining 1, 5-pentamethylene diisocyanate by non-phosgene method |
| CN115433086A (en) * | 2022-09-29 | 2022-12-06 | 四川元理材料科技有限公司 | Industrial recovery method of solvent in isophorone diamino formic acid n-butyl ester pyrolysis reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112979500A (en) * | 2021-05-10 | 2021-06-18 | 中国科学院过程工程研究所 | Device and method for purifying xylylene diisocyanate |
| CN114478321A (en) * | 2022-04-06 | 2022-05-13 | 中国科学院过程工程研究所 | Method, device and application for separating, refining and purifying intermediate m-xylylene diamino ethyl formate solution |
| CN114478321B (en) * | 2022-04-06 | 2022-07-26 | 中国科学院过程工程研究所 | Method, device and application for separating, refining and purifying intermediate m-xylylene diamino ethyl formate solution |
| CN114984601A (en) * | 2022-07-05 | 2022-09-02 | 中国科学院过程工程研究所 | Device system and method for separating and refining 1, 5-pentamethylene diisocyanate by non-phosgene method |
| CN115433086A (en) * | 2022-09-29 | 2022-12-06 | 四川元理材料科技有限公司 | Industrial recovery method of solvent in isophorone diamino formic acid n-butyl ester pyrolysis reaction |
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