CN106458846A

CN106458846A - Promotion of imine formation via cationic resin catalyst

Info

Publication number: CN106458846A
Application number: CN201580022117.2A
Authority: CN
Inventors: E·W-T·王; T·威尔克斯; M·R·乌利齐
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2014-03-04
Filing date: 2015-03-02
Publication date: 2017-02-22
Also published as: WO2015134401A1; EP3142998A4; EP3142998A1

Abstract

Methods and systems for purifying a crude aniline. The method can include contacting a crude aniline that can include aniline, water, and cyclohexanone with a cation exchange resin to produce a cyclohexanone-lean product that contains less cyclohexanone than the crude aniline. The cation exchange resin can be a solid, a semi-solid, or a combination thereof.

Description

Promote the formation of imines via cation resin catalyzing agent

Cross-Reference to Related Applications

This application claims submitting day is the preferential of U.S. Provisional Patent Application No.61/947,733 on March 4th, 2014 Power, is incorporated in the application by reference.

Background technology

Technical field

The embodiment of description is generally directed to the method and system of purification of crude aniline.More specifically, description Embodiment is related to method and system for the Ketohexamethylene concentration reducing in crude aniline.

Description of the prior art

Aromatic amine (inclusion aniline) is the precursor for preparing many industrial chemicals.The maximum purposes of aniline is that preparation is sub- Methyldiphenyl diisocyanate (MDI), methylenediphenyl diisocyanates can be with polyol reaction to prepare polyurethane.Benzene Amine can be by preparing catalytic hydrogenation of nitrobenzene, as shown in reaction 1.

Catalyst may include Raney's nickel；Palladium charcoal or nickel；Or the cobalt on kieselguhr, copper or nickel.But, reaction 1 may result in miscellaneous The formation of matter.A kind of such impurity is Ketohexamethylene, and it is difficult to remove by physical method from aniline.For example, aniline and hexamethylene Ketone can not be easily separated by distillation, because aniline is similar with the boiling point of Ketohexamethylene.

It is sub- ring that the crude aniline comprising Ketohexamethylene can be reacted in acid condition to form group with imine moiety or Schiff's base Hexyl aniline, as shown in reaction 2.

Then aniline can be carried out purification by removing higher molecular weight cyclohexylidene aniline.But, the reaction bar of reaction 2 Part is easily disturbed by upstream device and process conditions, and this may result in substandard product.

Accordingly, it would be desirable to be modified to the method and system of purification of crude aniline.

Description of Drawings

Fig. 1 describes the illustrative purification system schematic diagram according to one or more of embodiments, described purification system It is derived from the purification Aniline product of crude aniline for preparation, described purification system includes the anti-of cation exchange resin unit upstream Answer device.

Fig. 2 describes another the illustrative purification system schematic diagram according to one or more of embodiments, described pure Change system is used for the purification Aniline product from crude aniline for the preparation, and described purification system is included under cation exchange resin unit The reactor of trip.

Fig. 3 describes another the illustrative purification system schematic diagram according to one or more of embodiments, described pure Change system is used for the purification Aniline product from crude aniline for the preparation, and described purification system does not include cation exchange resin unit Upstream or the reactor in downstream.

Fig. 4 describes the demonstrative system schematic diagram according to one or more of embodiments, and described purification system is used for Prepare aniline and from wherein separate impurity.

Specific embodiment

The method and system of purification of crude aniline is provided.Methods described may include crude aniline and cation exchange resin To prepare the product containing a small amount of Ketohexamethylene, described crude aniline may include aniline, water and Ketohexamethylene for contact, described containing a small amount of hexamethylene The product of ketone comprises the Ketohexamethylene fewer than crude aniline.Cation exchange resin can be solid, semi-solid or a combination thereof.

Surprisingly and it was unexpectedly found that, by using reaction 2 heterogeneous reaction condition, its cationic Resin catalyst or cation exchange resin are used for providing sour environment, the Ketohexamethylene concentration in aniline charging or " crude aniline " Cyclohexylidene aniline can be prepared with aniline reaction and significantly reduce by Ketohexamethylene.The cation exchange resin of acid properties can Catalytic reaction and do not consume cation.Cation exchange resin can make the Ketohexamethylene concentration in crude aniline reduce at least 10%, At least 20%, at least 30%, at least 50%, at least 70%, or at least 90%.For example, crude aniline can be with cation exchange tree Fat contacts to prepare product or the purification Aniline product containing a small amount of Ketohexamethylene, and it is contacted with cation exchange resin with crude aniline Compare, Ketohexamethylene concentration reduces about 30%, about 40%, or about 50% to about 70%, about 80%, about 90%, or about 95% before Or it is more.In another example, cation exchange resin can make the Ketohexamethylene concentration in crude aniline reduce about 10% to about 50%, about 20% to about 50%, about 30% to about 60%, about 40% to about 65%, about 50% to about 70%, about 50% to about 75%, about 60% to about 90%.In another example, cation exchange resin can make the Ketohexamethylene concentration in crude aniline drop As little as lack 70%, at least 80%, at least 90%, or 95%, described crude aniline comprises about 100ppmw to about 15,000ppmw's Ketohexamethylene.

Also surprisingly and it was unexpectedly found that, cation exchange resin can make the Ketohexamethylene in crude aniline Concentration, less than 60 minutes, less than 45 minutes, less than 30 minutes, or reduces at least 20% less than in the time period of 15 minutes, extremely Few 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or at least 95%.For example, Cation exchange resin can make the Ketohexamethylene concentration in crude aniline at about 1 minute to about 15 minutes, about 5 minutes to about 20 points Clock, about 15 minutes to about 30 minutes, about 25 minutes to about 40 minutes, about 35 minutes to about 50 minutes, or about 40 minutes to about 60 Reduce at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least in the time period of minute 80%, at least 90%, or at least 95%.

Fig. 1 describes the schematic diagram of illustrative purification system 100, and described illustrative purification system 100 is used for by crude aniline 102 prepare purification Aniline product 134, and described illustrative purification system 100 includes reactor 110, described reactor 110 sun from The upstream of sub-exchange resin unit 122.Described system may include but be not limited to, one or more dewatering units, such as one or Multiple dehydrating towers 104, one or more Ketohexamethylene reduction reactors 110, one or more heat exchanger (two are shown as 114, 118), one or more cation exchange resin units 122, and one or more separator, for example one or more distillation column 130.Reactor 110 can be operated in homogeneous reaction condition.Crude aniline can be introduced to dewatering unit 104 via pipeline 102 Comprise the overhead of water with via pipeline 108 preparation dehydration crude aniline and via pipeline 106 preparation.In pipeline 102 Crude aniline may include but be not limited to, aniline, water, single Nitrobenzol, Ketohexamethylene, toluene, benzene, Hexalin, phenol, toluidines, Methyl cyclopentane, hexahydrotoluene, cyclohexylamine, one or more amine, one or more ketone or its any mixture.

The concentration that crude aniline in pipeline 102 can have aniline is low about 85wt%, about 88wt%, or about 92wt% is extremely High about 95wt%, about 97wt%, or about 99wt%.The concentration that crude aniline in pipeline 102 can have water is low about 1wt%, About 3wt%, or about 5wt% paramount about 8wt%, about 12wt%, or about 15wt%.Crude aniline in pipeline 102 can have ring The concentration of hexanone is the every million weight portions of low about 100 weight portions (" ppmw "), about 250ppmw, about 500ppmw, about 1, 000ppmw, or about 1,500ppmw paramount about 4,000ppmw, about 6,000ppmw, about 8,000ppmw, or about 10,000ppmw. The total concentration that crude aniline in pipeline 102 can have other impurities is low about 100ppmw, about 250ppmw, about 500ppmw, about 750ppmw, or about 1,000ppmw paramount about 1,250ppmw, about 1,500ppmw, about 1,750ppmw, or about 10,000ppmw, Described other impurities may include but be not limited to, benzene, toluene, phenol, single Nitrobenzol, toluidines, Hexalin, cyclohexylamine, methyl ring Pentane, hexahydrotoluene, and/or cyclohexylidene aniline.

Dewatering unit 104 can be separated at least a portion in water and/or other impurities to make via pipeline 108 with aniline Standby dehydration crude aniline and the overhead comprising water via pipeline 106 preparation.The tower top comprising water in pipeline 106 distillates Thing may include but be not limited to, water, toluene, benzene, Hexalin, phenol, methyl cyclopentane, hexahydrotoluene, Ketohexamethylene, cyclohexylamine or Its any mixture.Dewatering unit 104 may include any system, device, or system and/or the combination of device, and it can separate At least a portion comprising any water in the crude aniline being introduced into it via pipeline 102.For example, dewatering unit 104 can be one Individual or multiple distillation column or dephlegmator or include one or more distillation column or dephlegmator.Dewatering unit 104 can be at least about 100 DEG C operated at most about 215 DEG C of temperature, it can evaporate at least a portion of water and one or more other impurities extremely A few part, described one or more other impurities such as toluene, benzene, Hexalin, phenol, methyl cyclopentane, hexahydrotoluene, At least one of low boiling point of Ketohexamethylene, and/or cyclohexylamine, at least a portion of described water and one or more other impurities Temperature in dewatering unit 104.

Dewatering unit 104 can be empty, be partially filled with one or more material or be filled up completely with to improve mass transfer And/or water is separated with crude aniline.For example, packing material may include but be not limited to, structural material, random packing material, Tower tray, or its any combinations.Two or more packing materials can be configured in dewatering unit 104.For example, dewatering unit 104 can comprise random dumped packing, one or more tower trays, or a combination thereof.

Illustrative tower tray may include but be not limited to, perforated tray, sieve tray, bubble cap tray, float valve tray, standing valve Tower tray, tunnel type tower tray, whole section tower tray, double-pass tray, whole section tower tray, clasp float valve (snap-in valve) tower tray, riser Tower tray, slit (slit) tower tray, or its any combinations.As used in this application, term " packing material " may include but not It is limited to, one or more structuring and/or random shape material configure in dewatering unit 104.It is single that packing material can increase dehydration Effective surface area in unit 104, it can improve the mass transfer in dewatering unit 104 between liquid and/or gas phase.Packing material can be by Any suitable metal material is obtained.The illustrative example of random packing material may include but be not limited to, Raschig ring, Lessing ring, I- ring, saddle-shaped ring, Intalox saddle packing, Teller filler, Pall ring, U- ring, or its any combinations.Commercially available structuring The illustrative example of filler may include but be not limited to, structuring filling, corrugated plating, curl plate (crimped sheets), gauze, Grid, silk screen, integral honeycomb structure, or its any combinations.

It is low about 98wt%, about 98.5wt% via the concentration that the dehydration crude aniline of pipeline 108 can have aniline, or about 99wt% paramount about 99.5wt%, about 99.9wt%, or about 99.99wt%.Dehydration crude aniline via pipeline 108 can have The concentration of water is low about 10ppmw, about 100ppmw, or about 200ppmw paramount about 1,000ppmw, about 3,000ppmw, or about 5, 000ppmw.The concentration that dehydration crude aniline in pipeline 108 can have Ketohexamethylene is low about 100ppmw, about 250ppmw, about 500ppmw, about 750ppmw, or about 1,000ppmw paramount about 2,000ppmw, about 3,000ppmw, about 4,000ppmw, or about 5, 000ppmw.The total concentration that dehydration crude aniline in pipeline 108 can have other impurities is low about 50ppmw, about 100ppmw, About 500ppmw, about 750ppmw, or about 1,000ppmw paramount about 2,500ppmw, about 3,500ppmw, about 4,250ppmw, or about 5,000ppmw, described other impurities may include but be not limited to, benzene, toluene, single Nitrobenzol, phenol, toluidines, Hexalin, hexamethylene Amine, methyl cyclopentane, hexahydrotoluene, and/or cyclohexylidene aniline.

Can be introduced in reactor 110 via the dehydration crude aniline of pipeline 108 and react with warp in the reactor 110 Prepare the product of Ketohexamethylene reduction by pipeline 112, compared with the dehydration crude aniline in pipeline 108, described Ketohexamethylene reduction Product comprises less Ketohexamethylene.Reactor 110 can be homogeneous reactor, and a wherein part for Ketohexamethylene can be in reactor 110 Interior reaction, to prepare group with imine moiety, such as cyclohexylidene aniline, is such as reacted as shown in 2.For example, Ketohexamethylene can be in catalyst example As in the presence of sulphuric acid with amine R-NH₂Reaction, to reduce the Ketohexamethylene concentration in dehydration crude aniline.For example, it is dehydrated rough benzene The reducible amount of Ketohexamethylene concentration in amine is low by about 10%, 20%, about 30%, or about 40% paramount about 50%, about 60%, about 70%, about 80%, or about 90%.

The concentration that in pipeline 112, the product of Ketohexamethylene reduction can have aniline is low about 98wt%, about 98.5wt%, or about 99wt% paramount about 99.9wt%, about 99.95wt%, or about 99.99wt%.In pipeline 112, the product of Ketohexamethylene reduction can have The concentration having water is low about 10ppmw, about 100ppmw, or about 200ppmw paramount about 1,000ppmw, about 3,000ppmw, or about 5,000ppmw.The Ketohexamethylene concentration that in pipeline 112, the product of Ketohexamethylene reduction can have is low about 10ppmw, about 50ppmw, about 100ppmw, about 300ppmw, or about 500ppmw paramount about 1,000ppmw, about 1,500ppmw, about 2,000ppmw, about 2, 500ppmw, or about 3,000ppmw.The concentration that in pipeline 112, the product of Ketohexamethylene reduction can have cyclohexylidene aniline is low about 50ppmw, about 100ppmw, about 500ppmw, about 750ppmw, or about 1,000ppmw paramount about 2,500ppmw, about 3, 500ppmw, about 4,250ppmw, or about 5,000ppmw.In pipeline 112, the product of Ketohexamethylene reduction can have the total of other impurities Concentration is low about 50ppmw, about 100ppmw, about 500ppmw, about 750ppmw, or about 1,000ppmw paramount about 2,500ppmw, About 3,500ppmw, about 4,250ppmw, or about 5,000ppmw, described other impurities may include but be not limited to, benzene, toluene, benzene Phenol, single Nitrobenzol, toluidines, Hexalin, cyclohexylamine, methyl cyclopentane, and/or hexahydrotoluene.

In pipeline 112, the product of Ketohexamethylene reduction can be introduced in one or more heat exchangers 114,118.First heat is handed over Parallel operation 114 and second heat exchanger 118 can be one of shell-tube type, sheet frame, winding, U-tube, bayonet type heat exchanger or many Kind, or its any combinations or one or more of inclusion shell-tube type, sheet frame, winding, U-tube, bayonet type heat exchanger, or its Any combinations.First heat exchanger 114 can cool down the product of the Ketohexamethylene reduction reclaimed from reactor 110 via pipeline 112, from And the Ketohexamethylene reduzate via pipeline 116 preparation first cooling.

Second heat exchanger 118 can cool down the Ketohexamethylene reduzate of the first cooling in pipeline 116 to make via pipeline 120 The Ketohexamethylene reduzate of standby second cooling.In pipeline 120, the pressure of the Ketohexamethylene reduzate of the second cooling can be about 300kPa, or about 500kPa to about 1,000kPa, about 1,500kPa, or about 2,000kPa.The hexamethylene of the second cooling in pipeline 120 The temperature of ketone reduzate can be low about 50 DEG C, about 70 DEG C, or about 90 DEG C paramount about 110 DEG C, about 130 DEG C, or about 150 DEG C.

Heat can be transferred to the heat transfer of one or more of first and second heat exchangers 114,118 from product indirectly The Ketohexamethylene reduzate to cool down via pipeline 116,120 preparation first and second respectively for the medium, and heating is from the first He The heat-transfer material of second heat exchanger 114,118.Illustrative heat-transfer material may include but be not limited to, cooling water, and boiler is given Water, low-pressure steam, middle pressure steam, ethylene glycol, the product containing a small amount of Ketohexamethylene, air and/or other gaseous fluids or it is any Mixture.Product via the Ketohexamethylene reduction of pipeline 112 can be by (not shown with cooling fluid such as water directly contact or mixing Go out) cooled down, thus the product via pipeline 116,120 preparation cooling.Product via the Ketohexamethylene reduction of pipeline 112 Thing can be cooled down by the combination of indirect heat exchange and directly contact cooling.

The Ketohexamethylene reduzate of the cooling via pipeline 120 can be introduced to cation exchange resin unit 122, thus Via the product containing a small amount of Ketohexamethylene for pipeline 126 preparation.Cation exchange resin unit 122 may include one or more cationes Exchange resin bed 124.Cation exchange resin bed 124 may include any one of cation exchange resin or multiple, described Cation exchange resin can catalysis of pimelinketone molecule to be converted into imines be cyclohexylidene aniline, as shown in reaction 2.Cation is handed over Change resin and may include H⁺Functional group, sulphuric acid, HSO₄ ^-One or more of functional group, or their any mixture or combination. Cation ion exchange resin may include but be not limited to, one or moreIon exchange resin, it can Derive from Dow Water＆Process Solution, one or moreSequence of ion exchanger resin, it can Derive from the Purolite Company, one or moreSequence of ion exchanger resin, it is available from the Lanxess Corp., or their any mixture.For example, cation exchange resin may be based on the styrene-diethyl of crosslinking The polymer of alkenyl benzene copolymer or the polymer including based on crosslinked styrene diethylene benzene copoly mer, it can comprise Sulfonic group.For example, cation exchange resin may include but be not limited to,36,CT- 151,2629 or its any mixture.

Cation exchange resin can be solid, semisolid, or the combination of solid and semi-solid structure.For example, cation is handed over Changing resin can be the form of solid particle, semi-solid granule, such as colloidal solid, or its mixture.Cation exchange resin can For macroporous granules, microporous particles, or its mixture or include macroporous granules, microporous particles, or its mixture.Solid cation is handed over Changing resin can be following form：Pill, beadlet, granule, thin slice, spheroid, cube, block, fiber, filamentous, threaded body or Its any mixture.As used in this application, term " semi-solid " and " semi-solid granule " refer to that itself does not dissolve in particular fluid Three dimensional structure in body.Three dimensional structure can absorb and retain a certain amount of liquid, thus being formed stable, generally soft and easily The structure of bending.Cation exchange resin can be solid and/or semi-solid structure, its configuration fixed bed, fluid or moving bed, Or in a combination thereof.In another example, to may be supported on one or more supporting members for example firm for solid and/or semi-solid structure On property supporting member, it is supported between two or more supporting members such as screen cloth and sheet material etc., or its any combinations.

Configuration producing depth of cation exchange resin in fixed bed can be low about 5cm, about 10cm, about 20cm, about 30cm, or the paramount about 70cm of about 40cm, about 85cm, about 100cm, about 150cm, about 200cm, or about 300cm.For example, configuration exists In fixed bed, cation exchange resin bed layer depth can be about 40cm to about 80cm, about 50cm to about 70cm, and about 60cm is to about 120cm, about 60cm are to about 200cm, or about 90cm to about 250cm.The fixed bed comprising cation exchange resin is configurable on sun In ion exchange resin unit 122.Cation exchange resin unit 122 can comprise or comprise additionally in one, two, four, six Individual, eight, ten, 12,15,20, or more discrete or single fixed bed.Each there is any Number fixed beds configure any number cation exchange resin units therein can relative to each other series, parallel or series connection with simultaneously Connection arrangement.Between any two cation exchange resin unit, the number of fixed bed, the size of fixed bed and configuration are each Certain cationic exchanger resin in individual fixed bed may be the same or different.

The mean cross-sectional dimension of ion exchange material such as ion exchange resin or length can be low about 0.01mm, about 0.05mm, about 0.1mm, about 0.3mm, or the paramount about 1mm of about 0.5mm, about 2mm, about 3mm, about 5mm, about 7mm, about 9mm, about 11mm, about 13mm, about 15mm, or about 20mm.The average pore size of ion exchange material such as ion exchange resin can be low by about 20 AngstromAboutOr aboutParamount aboutAboutAboutOr aboutFor example, cation is handed over The average pore size changing resin can be aboutTo aboutOr aboutTo aboutOr aboutTo aboutThe aperture of ion exchange material such as ion exchange resin can be low about 0.05mL/g, about 0.1mL/g, or about 0.15mL/g paramount about 0.3mL/g, about 0.5mL/g, or about I mL/g.For example, the aperture of cation exchange resin can be about 0.15mL/g to about 0.25mL/g, about 0.2mL/g are to about 0.4mL/g, or about 0.2mL/g to about 1mL/g.Ion exchange material example Surface area as ion exchange resin can be low about 10m²/ g, about 15m²/ g, or about 20m²The paramount about 30m of/g²/ g, about 40m²/ g, Or about 50m²/g.

It is at least partially dependent on the amount of certain cationic exchanger resin and/or Ketohexamethylene, the rough benzene in pipeline 108 In the product of Ketohexamethylene reduction in amine, pipeline 112, the Ketohexamethylene reduzate of the first cooling and/or pipeline 120 in pipeline 116 The Ketohexamethylene reduzate of the second cooling, can be contacted with following speed with cation exchange resin：About 0.1m³Crude aniline product Every 1m cation exchange resin is per hour to about 35m³The every 1m of raw product³Cation exchange resin is per hour.For example, pipeline 108 In crude aniline, in pipeline 112 Ketohexamethylene reduction product, in pipeline 116 first cooling Ketohexamethylene reduzate, and/ Or the Ketohexamethylene reduzate of the second cooling can be contacted with following speed with cation exchange resin in pipeline 120：Low about 1m³, About 3m³, about 5m³, or about 10m³Paramount about 15m³, about 20m³, about 25m³, or about 30m³The every 1m of raw product³Cation exchange resin Per hour.In another example, the crude aniline in pipeline 108, the product of Ketohexamethylene reduction in pipeline 112, in pipeline 116 The Ketohexamethylene reduzate of the first cooling, and/or in pipeline 120, the Ketohexamethylene reduzate of the second cooling can be with cation exchange Resin is contacted with following speed：About 1m³To about 8m³The every 1m of raw product^{3 sun}Ion exchange resin per hour, about 2m³To about 4m³Slightly The every 1m of product processed^{3 sun}Ion exchange resin per hour, about 3m³To about 5m³The every 1m of raw product^{3 sun}Ion exchange resin per hour, about 4m³To about 6m³The every 1m of raw product³Cation exchange resin per hour, about 10m³To about 27m³The every 1m of raw product³Cation is handed over Change resin per hour.Solid or semi-solid form can be kept when cation exchange resin is contacted with following material or after contact：Pipe Crude aniline in line 108, the product of Ketohexamethylene reduction in pipeline 112, in pipeline 116, the Ketohexamethylene of the first cooling is also original The Ketohexamethylene reduzate of the second cooling in thing, and/or pipeline 120.

It is at least partially dependent on specific ion exchange material, the crude aniline in pipeline 102, the dehydration in pipeline 108 are thick The product of Ketohexamethylene reduction in aniline processed, pipeline 112, the Ketohexamethylene reduzate of the first cooling and/or pipeline in pipeline 116 In 120, the Ketohexamethylene reduzate of the second cooling can be introduced to cation exchange resin unit 122 and in following temperature and sun Contacts ionic exchange resin：Low about 50 DEG C, about 60 DEG C, or about 70 DEG C paramount about 80 DEG C, about 90 DEG C, about 100 DEG C, about 110 DEG C, about 120 DEG C, about 130 DEG C, about 140 DEG C, about 150 DEG C, or about 155 DEG C.It is at least partially dependent on certain cationic exchanger resin, pipeline The product of Ketohexamethylene reduction in dehydration crude aniline in crude aniline in 102, pipeline 108, pipeline 112, the in pipeline 116 The Ketohexamethylene reduzate of the second cooling in the Ketohexamethylene reduzate of one cooling and/or pipeline 120, is being handed over described cation The pressure changing during resin contact can be low about 101kPa, about 200kPa, or about 500kPa paramount about 1,000kPa, about 1, 200kPa, or about 2,000kPa.

Cation exchange resin capacity close to exhausting, for example cation exchange resin no longer be present in crude aniline In enough hexamethylene reactive ketones when, cation exchange resin can use new ion exchange material to replace.In cation exchange resin Capacity close to exhaust when, cation exchange resin is renewable.For example, crude aniline is contacted with cation exchange resin and can stop Or steering other places, for example comprise the other positions of other cation exchange resiies, one or more regrown material can with exhaust Cation exchange resin contact to prepare the cation exchange resin of regeneration, the cation exchange resin of described regeneration can again with Following material contact：Crude aniline in pipeline 102, the dehydration crude aniline in pipeline 108, Ketohexamethylene reduction in pipeline 112 Product, in pipeline 116 first cooling Ketohexamethylene reduzate, and/or in pipeline 120 second cooling Ketohexamethylene also original Thing.

Cation exchange resin unit 122 can be to have the container of ion exchange material or include thering is ion exchange material Container, described ion exchange material for example comprises cation exchange resin therein.The appearance of cation exchange resin unit 122 Device can have various shapes, and described shape includes but is not limited to, cube, rectangle box, cylinder, prism, hyperboloid Structure, or some other shape or combinations thereof.For example, described container can be cylinder, and the cylindrical longitudinal axis can level take To or with respect to horizontal direction be in following angular orientation：About 1 °, about 5 °, about 10 °, about 20 °, or about 30 ° to about 60 °, about 70 °, or About 80 °.Container also can have the longitudinal axis, the described longitudinal axis can vertical orientated or with respect to vertical direction be in following angular orientation：About 1 °, about 5 °, about 10 °, about 20 °, or about 30 ° to about 60 °, about 70 °, or about 80 °.Cation exchange resin unit 122 or cation exchange The longitudinal axis of resin unit 122 can at least be substantially horizontally oriented.Cation exchange resin unit 122 or cation exchange resin list The longitudinal axis of unit 122 can at least be substantially vertically oriented.As used in this application, term " substantially vertical " refers to about -5 ° to about 5 °, about -3 ° to about 3 °, about -2 ° to about 2 °, about -1 ° to about 1 °, about -0.1 ° to about 0.1 °, or about -0.0001 ° to about 0.0001 °, with respect to vertical direction.

The concentration that in pipeline 126, the product containing a small amount of Ketohexamethylene can have aniline is low about 98wt%, about 98.5wt%, or About 99wt% paramount about 99.9wt, about 99.95wt%, or about 99.99wt%.The product containing a small amount of Ketohexamethylene in pipeline 126 can The concentration with water is low about 10ppmw, about 100ppmw, or about 200ppmw paramount about 1,000ppmw, about 3,000ppmw, or About 5,000ppmw.The Ketohexamethylene concentration that in pipeline 126, the product containing a small amount of Ketohexamethylene can have is low about 1ppmw, about 10ppmw, about 25ppmw, or the paramount about 60ppmw of about 40ppmw, about 70ppmw, about 85ppmw, or about 100ppmw.For example, warp 150ppmw is less than by the concentration that pipeline 126 can have Ketohexamethylene containing a small amount of cyclohexanone products, less than 100ppmw, is less than 50ppmw, less than 40ppmw, less than 30ppmw, less than 20ppmw, or is less than 10ppmw.A small amount of Ketohexamethylene is contained in pipeline 126 The concentration that product can have cyclohexylidene aniline is low about 50ppmw, about 100ppmw, about 500ppmw, about 750ppmw, or about 1, 000ppmw paramount about 2,500ppmw, about 3,500ppmw, about 4,250ppmw, or about 5,000ppmw.Contain a small amount of in pipeline 126 The total concentration that the product of Ketohexamethylene can have other impurities is low about 50ppmw, about 100ppmw, about 500ppmw, about 750ppmw, Or about 1,000ppmw paramount about 2,500ppmw, about 3,500ppmw, about 4,250ppmw, or about 5,000ppmw, it is described that other are miscellaneous Matter may include but be not limited to, benzene, toluene, phenol, single Nitrobenzol, Hexalin, toluidines, cyclohexylamine, methyl cyclopentane, and/or Hexahydrotoluene.

At least a portion containing a small amount of cyclohexanone products in pipeline 126 can be used as heat transfer medium to cool down entrance the first heat friendship Parallel operation 114 Ketohexamethylene reduction product, thus via pipeline 116 preparation first cooling Ketohexamethylene reduzate and via The product containing a small amount of Ketohexamethylene for pipeline 128 heating.Optionally, the product containing a small amount of Ketohexamethylene in pipeline 126 can bypass by pipe First heat exchanger 114 in line 128.The pressure containing a small amount of cyclohexanone products of heating can be low about 101kPa, about 300kPa, Or about 500kPa paramount about 1,000kPa, about 1,500kPa, or about 2,000kPa.In pipeline 128 heating containing a small amount of Ketohexamethylene The temperature of product can be low about 100 DEG C, about 110 DEG C, about 120 DEG C, or about 130 DEG C paramount about 150 DEG C, about 170 DEG C, or about 200 ℃.

Via pipeline 126 containing in a small amount of cyclohexanone products and/or pipeline 128 heating can be containing a small amount of cyclohexanone products For example carry out separating via distillation in separator 130, thus separating impurity and the aromatic amine product preparing purification.For example, warp Can be in separator 130 containing a small amount of cyclohexanone products containing heat in a small amount of cyclohexanone products and/or pipeline 128 by pipeline 126 In carry out separating, thus preparing final or purification Aniline product via pipeline 134, and comprise to discard via pipeline 132 preparation Thing or the impurity of a large amount of by-product.As garbage via pipeline 132 impurity detached with purification aniline may include except aniline with Outer any compound and/or component.Illustrative impurity may include but be not limited to, group with imine moiety, single Nitrobenzol, toluidines, Phenol or its any mixture.

The concentration that purification Aniline product in pipeline 134 can have aniline is the paramount about 99.99wt% of low about 99wt%.Pipe The concentration that purification Aniline product in line 134 can have aniline is at least 99wt%, at least 99.4wt%, or at least 99.5wt% To about 99.9wt% or about 99.95wt%.The concentration that purification Aniline product in pipeline 134 can have Ketohexamethylene is low about 1ppmw, about 5ppmw, about 10ppmw, about 15ppmw, about 20ppmw, or about 30ppmw paramount about 50ppmw, about 65ppmw, about 75ppmw, about 85ppmw, or about 100ppmw.The concentration that purification Aniline product in pipeline 134 can have water is low about 10ppmw, about 50ppmw, about 100ppmw, about 500ppmw, about 750ppmw, or about 1,000ppmw paramount about 2,500ppmw, about 3,500ppmw, about 4,250ppmw, or about 5,000ppmw.Purification Aniline product in pipeline 134 can have cyclohexylidene aniline Concentration be low about 1ppmw, about 5ppmw, about 10ppmw, about 15ppmw, about 20ppmw, or the paramount about 50ppmw of about 30ppmw, About 65ppmw, about 75ppmw, about 85ppmw, or about 100ppmw.Purification Aniline product in pipeline 134 can have other impurities Total concentration be low about 50ppmw, about 100ppmw, about 200ppmw, or about 300ppmw paramount about 500ppmw, about 750ppmw, Or about 1,000ppmw, described other impurities may include but be not limited to, benzene, toluene, phenol, Hexalin, cyclohexylamine, single Nitrobenzol, Toluidines, methyl cyclopentane, and/or hexahydrotoluene.

Separator 130 can be similar in appearance to dewatering unit 104.For example, separator 130 may include any system, device, or system And/or the combination of device, it can make to be introduced at least a portion of impurity and aniline in dehydration product via pipeline 128 to it and Row separates.For example, separator 130 for one or more distillation column or dephlegmator or can include one or more distillation column or fractional distillation Post.Separator 130 can be sky, be partially filled with one or more tower tray and/or packing material or be filled up completely with to change Enter mass transfer and/or aniline is separated with dehydration product.

System for preparing purification Aniline product may include dewatering unit 104, described dewatering unit 104 be configured to via Pipeline 102 receives crude aniline and preparation dehydration crude aniline.Dehydration crude aniline can be via one or more pipeline 108 times Receive to prepare the product of Ketohexamethylene reduction, one or more of pipelines 108 are connected with dewatering unit 104 or and dewatering unit 104 are in fluid communication and are connected with reactor 110 or are in fluid communication with reactor 110.First heat exchanger 114 can be via pipeline The Ketohexamethylene reduzate to prepare the first cooling for the product of 112 cooling Ketohexamethylene reduction, the Ketohexamethylene of described first cooling is also Original thing can reclaim via one or more pipelines 116, one or more of pipelines 116 and first heat exchanger 114 and the Two heat exchangers 118 are connected or are in fluid communication with first heat exchanger 114 and second heat exchanger 118.Second heat exchanger 118 The Ketohexamethylene reduzate of the first cooling can be cooled down further, the Ketohexamethylene reduzate of described first cooling is via pipeline 216 Reclaim from first heat exchanger 114, thus preparing the Ketohexamethylene reduzate of the second cooling, the Ketohexamethylene of described second cooling is also Original thing can be via 120 recovery.

Ketohexamethylene reduzate via the second cooling of pipeline 120 can be introduced to one or more cation exchange resiies Unit 122 is to prepare the product containing a small amount of Ketohexamethylene.Cation exchange resin unit 122 may include a kind of or many as above Plant cation exchange resin 124.Product containing a small amount of Ketohexamethylene can reclaim via one or more pipelines 126, one or Multiple pipelines 126 be connected with cation exchange resin unit 122 or be in fluid communication with cation exchange resin unit 122 and with First heat exchanger 114 is connected or is in fluid communication with first heat exchanger 114.Product containing a small amount of Ketohexamethylene can be used as heat transfer and is situated between Matter enters the Ketohexamethylene reduzate of first heat exchanger 114 to cool down, thus the hexamethylene via pipeline 116 preparation first cooling Ketone reduzate and can via one or more pipelines 128 and one or more separator 130 reclaim heating containing a small amount of ring Hexanone product, one or more of pipelines 128 are connected with first heat exchanger 114 or are connected with first heat exchanger 114 fluid Logical.Dewatering unit 104, first heat exchanger 114, second heat exchanger 118, cation exchange resin unit 122, reactor 110, and separator 30 can be described in as mentioned above or in this application other places.

Can be distilled in separator 130 via the product containing a small amount of Ketohexamethylene for the pipeline 212 or be separated, thus via Pipeline 234 is prepared final or purification Aniline product and is prepared garbage or a large amount of by-product via pipeline 232a.Via pipeline 234 purification Aniline product and can be described in as mentioned above and in this application other places via the garbage of pipeline 232.

Showing of another illustrative purification system 200 of purification Aniline product 234 is prepared in Fig. 2 description by crude aniline 102 It is intended to, another illustrative purification system 200 described includes reactor 110, and described reactor 110 is in cation exchange resin list The downstream of unit 222.Purification system 200 may include one or more dewatering units 104, one or more heat exchangers 114,118, One or more cation exchange resin units 222, one or more reactors 110, one or more separators 130, or its Any combinations.Dehydration crude aniline in pipeline 108 can be introduced to heat exchanger 114, thus cold via pipeline 216 preparation first But dehydration crude aniline.

In pipeline 216, the dehydration crude aniline of the first cooling can be introduced to second heat exchanger 118, thus via pipeline The dehydration crude aniline of 220 preparation the second coolings.In pipeline 220, the temperature of the dehydration crude aniline of the second cooling can be low by about 50 DEG C, about 75 DEG C, or about 100 DEG C paramount about 115 DEG C, about 130 DEG C, or about 150 DEG C.In pipeline 220, the dehydration of the second cooling is rough The pressure of aniline can be low about 300kPa, about 500kPa, about 750kPa, or about 1,000kPa to about high by about 1,250kPa, about 1, 500kPa, about 1,750kPa, or about 2,000kPa.

In pipeline 220 second cooling dehydration crude aniline can have with reference Fig. 1 above-mentioned pipeline 108 in dehydration thick The same or analogous composition of aniline processed.In pipeline 220, the dehydration crude aniline of the second cooling can be introduced to cation exchange resin Unit 222, thus prepare the product of Ketohexamethylene reduction via pipeline 226.Cation exchange resin unit 222 may include one or Multiple cation exchange resin bed 124 and one or more cation exchange resin therein.Cation exchange resin unit 222 can be same or similar with the above-mentioned cation exchange resin unit with reference to Fig. 1.

In pipeline 226, the product of Ketohexamethylene reduction may include aniline, water, single Nitrobenzol, phenol, toluidines, Ketohexamethylene, first Benzene, benzene, Hexalin, methyl cyclopentane, hexahydrotoluene, cyclohexylamine, one or more amine, one or more ketone or it is any mixed Compound.The concentration that in pipeline 226, the product of Ketohexamethylene reduction can have aniline is low about 98wt%, about 98.3wt%, or about 98.5wt% paramount about 98.7wt%, about 98.9wt%, or about 99wt%.In pipeline 226, the product of Ketohexamethylene reduction can have The concentration of water is low about 10ppmw, about 50ppmw, about 100ppmw, about 500ppmw, about 750ppmw, or about 1,000ppmw is paramount About 2,500ppmw, about 3,500ppmw, about 4,250ppmw, or about 5,000ppmw.In pipeline 226, the product of Ketohexamethylene reduction can The concentration with Ketohexamethylene is low about 10ppmw, about 50ppmw, about 100ppmw, about 250ppmw, about 500ppmw, or about 750ppmw paramount about 1,250ppmw, about 1,750ppmw, about 2,250ppmw, about 2,600ppmw, or about 3,000ppmw.Pipeline The concentration that in 226, the product of Ketohexamethylene reduction can have cyclohexylidene aniline is low about 50ppmw, about 100ppmw, about 500ppmw, about 750ppmw, or about 1,000ppmw paramount about 2,500ppmw, about 3,500ppmw, about 4,250ppmw, or about 5, 000ppmw.The total concentration that in pipeline 226, the product of Ketohexamethylene reduction can have other impurities is low about 50ppmw, about 100ppmw, about 500ppmw, about 750ppmw, or about 1,000ppmw paramount about 2,500ppmw, about 3,500ppmw, about 4, 250ppmw, or about 5,000ppmw, described other impurities may include but be not limited to, benzene, toluene, phenol, single Nitrobenzol, toluene Amine, Hexalin, cyclohexylamine, methyl cyclopentane, and/or hexahydrotoluene.

In pipeline 226, the product of Ketohexamethylene reduction can heat with via pipeline 228 in one or more heat exchangers 114 The Ketohexamethylene reduzate of preparation heating.In pipeline 226, the product of Ketohexamethylene reduction can be used as heat transfer medium to cool down entrance the The dehydration crude aniline of one heat exchanger 114, thus via pipeline 216 preparation first cooling dehydration crude aniline and via The Ketohexamethylene reduzate of pipeline 228 preparation heating.In another example, in pipeline 226, the product of Ketohexamethylene reduction can be Heat in 3rd heat exchanger (not shown).3rd heat exchanger can be similar or identical with second heat exchanger 118 as described above. In another example, in pipeline 226 product of Ketohexamethylene reduction can be directly introduced into reactor 110 and not first in any heat Heat in exchanger.

Ketohexamethylene reduzate via the heating of pipeline 228 can be introduced to reactor 110, thus making via pipeline 212 The standby product containing a small amount of Ketohexamethylene.The Ketohexamethylene reduzate of heating can react in the reactor 110 to remove any of presence At least a portion of Ketohexamethylene.The amount that the Ketohexamethylene reduzate of heating removes Ketohexamethylene from reactor 110 can be low about 30%, about 40%, or about 50% paramount about 60%, about 70%, about 80%, or about 90%.A small amount of Ketohexamethylene is contained in pipeline 212 The temperature of product can be low about 150 DEG C, about 155 DEG C, or about 160 DEG C paramount about 163 DEG C, about 166 DEG C, or about 170 DEG C, pipeline The pressure containing the product of a small amount of Ketohexamethylene in 212 is the paramount about 160kPa of low about 101kPa, about 120kPa, or about 140kPa, about 180kPa, or about 200kPa.

It is low about 98wt% via the concentration that the product containing a small amount of Ketohexamethylene for the pipeline 212 can have aniline, about 98.5wt%, or the paramount about 99.5wt% of about 99wt%, about 99.9wt%, about 99.95wt%, or about 99.99wt%.Via pipe The concentration that the product containing a small amount of Ketohexamethylene of line 212 can have water is low about 10ppmw, about 50ppmw, about 100ppmw, about 500ppmw, about 750ppmw, or about 1,000ppmw paramount about 2,500ppmw, about 3,500ppmw, about 4,250ppmw, or about 5, 000ppmw.It is low about 1ppmw, about 5ppmw via the concentration that the product containing a small amount of Ketohexamethylene for the pipeline 212 can have Ketohexamethylene, About 10ppmw, or the paramount about 40ppmw of about 20ppmw, about 60ppmw, about 80ppmw, or about 100ppmw.Via containing of pipeline 212 The concentration that the product of a small amount of Ketohexamethylene can have cyclohexylidene aniline is low about 50ppmw, about 100ppmw, about 500ppmw, about 750ppmw, or about 1,000ppmw paramount about 2,500ppmw, about 3,500ppmw, about 4,250ppmw, or about 5,000ppmw.Pipe The total concentration that in line 212, the product containing a small amount of Ketohexamethylene can have other impurities is low about 50ppmw, about 100ppmw, about 500ppmw, about 750ppmw, or about 1,000ppmw paramount about 2,500ppmw, about 3,500ppmw, about 4,250ppmw, or about 5, 000ppmw, described other impurities may include but be not limited to, benzene, toluene, phenol, single Nitrobenzol, Hexalin, toluidines, hexamethylene Amine, methyl cyclopentane, and/or hexahydrotoluene.

Can distill in separator 130 via the product containing a small amount of Ketohexamethylene for the pipeline 212 or otherwise separate with Prepare final or purification Aniline product via pipeline 234 and prepare garbage or a large amount of by-product via pipeline 232.Pipeline The concentration that purification Aniline product in 234 can have aniline is that low about 99wt%, about 99.3wt%, or about 99.5wt% are paramount about 99.9wt%, about 99.95wt%, or about 99.99wt%.The concentration that purification Aniline product in pipeline 234 can have aniline is At least 99wt%, at least 99.4wt%, or at least 99.5wt% to about 99.9wt% or about 99.95wt%.Pure in pipeline 234 The concentration that change Aniline product can have Ketohexamethylene is low about 1ppmw, about 5ppmw, about 10ppmw, or about 20ppmw is paramount about 40ppmw, about 60ppmw, about 80ppmw, or about 100ppmw.The concentration that purification Aniline product in pipeline 234 can have water is Low about 10ppmw, about 50ppmw, about 100ppmw, about 500ppmw, about 750ppmw, or about 1,000ppmw paramount about 2, 500ppmw, about 3,500ppmw, about 4,250ppmw, or about 5,000ppmw.Purification Aniline product in pipeline 234 can have Asia The concentration of cyclohexyl aniline is low about 1ppmw, about 5ppmw, about 10ppmw, or about 20ppmw paramount about 40ppmw, about 60ppmw, About 80ppmw, or about 100ppmw.The total concentration that purification Aniline product in pipeline 234 can have other impurities is low about 50ppmw, about 100ppmw, about 500ppmw, about 750ppmw, or about 1,000ppmw paramount about 2,500ppmw, about 3, 500ppmw, about 4,250ppmw, or about 5,000ppmw, described other impurities may include but be not limited to, benzene, toluene, phenol, ring Hexanol, cyclohexylamine, single Nitrobenzol, toluidines, methyl cyclopentane, and/or hexahydrotoluene.

Showing of another illustrative purification system 300 of purification Aniline product 334 is prepared in Fig. 3 description by crude aniline 102 It is intended to, the schematic diagram of another illustrative purification system 300 described does not include cation exchange resin unit 322 upstream or downstream Reactor.One or more pipelines 102 comprising crude aniline can with one or more dewatering units (is shown as 104) even Connect or be in fluid communication with one or more dewatering units (is shown as 104), (one is shown as one or more of dewatering units 104) separable at least a portion comprising in any residue water therein and/or other impurities is to prepare dehydration crude aniline. Dehydration crude aniline can reclaim via one or more pipelines 108, and one or more of pipelines 108 are with dewatering unit 104 even Connect or be in fluid communication with dewatering unit 104 and be connected with first heat exchanger 114 or connect with first heat exchanger 114 fluid Logical.

Dehydration crude aniline in pipeline 108 can have identical with the above-mentioned dehydration crude aniline 108 with reference to Fig. 1 and/or 2 Or similar composition.First heat exchanger 114 can be via the crude aniline of pipeline 108 cooled dehydrated to prepare the de- of the first cooling Water crude aniline, the dehydration crude aniline of described first cooling can reclaim via one or more pipelines 316, one or many Individual pipeline 316 is connected with first heat exchanger 114 and second heat exchanger 118 or is handed over first heat exchanger 114 and the second heat Parallel operation 118 is in fluid communication.Second heat exchanger 118 can cool down the dehydration crude aniline of the first cooling further, and described first is cold But dehydration crude aniline reclaims via pipeline 316 from first heat exchanger 114, thus the rough benzene of dehydration preparing the second cooling Amine, the dehydration crude aniline of described second cooling can be via 320 recovery.

Dehydration crude aniline via the second cooling of pipeline 320 can be introduced to one or more cation exchange resin lists Unit 322 is with the product containing a small amount of Ketohexamethylene via pipeline 326 preparation.Cation exchange resin unit 322 may include one or many Individual cation exchange resin 324.Cation exchange resin unit 322 and cation exchange resin 324 can respectively with reference to Fig. 1 and 2 cation exchange resin units 122 and/or 222 as above and the identical or phase of cation exchange resin 124 and/or 224 Seemingly.Contain in pipeline 326 a small amount of Ketohexamethylene product can have with reference in Fig. 1 pipeline as described above 126 containing a small amount of Ketohexamethylene The similar composition of composition of product.In an example, the product containing a small amount of Ketohexamethylene in pipeline 326 can have and reference Fig. 1 Product identical composition containing a small amount of Ketohexamethylene in pipeline 126 as mentioned above.

The product containing a small amount of Ketohexamethylene in pipeline 326 may function as heat transfer medium with cooled dehydrated crude aniline, described de- Water crude aniline is introduced to first heat exchanger 114 via pipeline 108, thus the dehydration via pipeline 316 preparation first cooling Crude aniline and can via one or more pipelines 328 reclaim heating containing a small amount of cyclohexanone products, one or more of Pipeline 328 is connected with one or more separators 130 or is in fluid communication with one or more separators 130.Dewatering unit 104, First heat exchanger 114, second heat exchanger 118, cation exchange resin unit 322, and separator 130 can be as described above Or in this application described in other places.

Can the distilling in separator 130 containing a small amount of cyclohexanone products or otherwise divide of heating via pipeline 328 From thus preparing final or purification Aniline product via pipeline 334 and preparing garbage or a large amount of by-product via pipeline 332 Thing.Purification Aniline product via pipeline 334 and the garbage via pipeline 332 can be for as mentioned above and in this application Described in other places.

The concentration that purification Aniline product in pipeline 334 can have aniline is low about 99wt%, about 99.3wt% or about 99.5wt% paramount about 99.9wt%, about 99.95wt%, or about 99.99wt%.Purification Aniline product in pipeline 334 can have The concentration having aniline is at least 99wt%, at least 99.4wt%, or at least 99.5wt% is to about 99.9wt%, or about 99.95wt%.The concentration that purification Aniline product in pipeline 334 can have Ketohexamethylene is low about 1ppmw, about 5ppmw, about 10ppmw, or the paramount about 40ppmw of about 20ppmw, about 60ppmw, about 80ppmw, or about 100ppmw.Purification benzene in pipeline 334 The concentration that amine product can have water is low about 10ppmw, about 50ppmw, about 100ppmw, about 500ppmw, about 750ppmw, or about 1,000ppmw paramount about 2,500ppmw, about 3,500ppmw, about 4,250ppmw, or about 5,000ppmw.Pure in pipeline 334 The concentration that change Aniline product can have cyclohexylidene aniline is low about 1ppmw, about 5ppmw, about 10ppmw, or about 20ppmw is paramount About 40ppmw, about 60ppmw, about 80ppmw, or about 100ppmw.Purification Aniline product in pipeline 334 can have other impurities Total concentration be low about 50ppmw, about 100ppmw, about 200ppmw, or about 300ppmw paramount about 500ppmw, about 750ppmw, Or about 1,000ppmw, described other impurities may include but be not limited to, benzene, toluene, phenol, Hexalin, cyclohexylamine, single Nitrobenzol, Toluidines, methyl cyclopentane, and/or hexahydrotoluene.

Fig. 4 describes the schematic diagram of demonstrative system 400, and described demonstrative system 400 is used for preparing aniline and from wherein dividing From impurity.Described system 400 may include one or more hydrogenation reactors 406, one or more phase separators 410, and one Or multiple purification system 416.It is as described above that one or more purification systems 416 refer to Fig. 1-3.For example, one or more Purification system 416 can be purification system 100,200, and/or one or more of 300 or include purification system 100,200, One or more of and/or 300.

In operation, one or more aromatic nitro compound via pipeline 402 and the hydrogen via pipeline 404 can It is introduced to hydrogenation reactor 406 to prepare crude aniline product via pipeline 408.The composition of crude aniline product in pipeline 408 The certain aromatic nitro compound of hydrogenation or the combination of aromatic nitro compound can be at least partially dependent on.Illustrative fragrance Race's nitro compound may include but be not limited to, Nitrobenzol, Methylnitrobenzene, dinitrotoluene (DNT) (DNT), dinitro benzene (DNB) or its Any mixture.Before being further purified or processing, crude aniline product in pipeline 408 or product may include aniline with And the mixture of one or more impurity.Illustrative impurity may include but be not limited to, water, phenol, Nitrobenzol, benzene, Methylnitrobenzene, Dinitrotoluene (DNT) (DNT), dinitro benzene (DNB), many Nitrobenzol, methyl cyclopentane, hexahydrotoluene, MNT, nitro Dimethylbenzene, Ketohexamethylene, Hexalin, cyclohexylamine, Ketohexamethylene, cyclohexyl aniline, diphenylamines, phenylenediamine, cyclohexylidene aniline, toluene Amine, dimethylaniline, toluene or its any mixture.

Product via pipeline 408 can be gas, liquid, or its mixture.Water and/or aniline also can be introduced to add Hydrogen reactor 406 (not shown).Water can be used as quench fluid or medium, and it can be for adjusting or otherwise adjusting hydrogenation Temperature in reactor 406.Aniline can be used as the carrier fluid of one or more catalyst.Therefore, aniline may also comprise therein one Plant or multiple catalysts.In another example (not shown), one or more catalyst can introduce water and aniline.By-product or Garbage (not shown) also can reclaim from hydrogenation reactor 406.By-product or garbage can be gas, liquid, or its mixture. By-product may include water, used, exhausting or discarded catalyst, unreacted aromatic nitro compound, and phenol is miscellaneous Matter, aniline, or its mixture any.

In hydrogenation reactor 406, the hydrogenation of aromatic nitro compound or reduction can be continuous, semicontinuous and/or in batches Mode is carried out.The hydrogenation of aniline can be carried out under liquid-phase condition and/or gas phase condition.Hydrogenation can be carried out in following temperature：Low about 30 DEG C, about 50 DEG C, or about 80 DEG C paramount about 250 DEG C, about 300 DEG C, about 400 DEG C, or about 500 DEG C.Hydrogenation can be entered in following pressure OK：Low about 101kPa, about 150kPa, or about 200kPa paramount about 1,000kPa, about 2,000kPa, about 3,500kPa, or about 5, 000kPa.The time of staying that the reactant mixture of aromatic nitro compound can have during being hydrogenated with is about 1 minute to about three Hour.The mol ratio of hydrogen and aromatic nitro compound can have low by about 3:1, about 3.2:1, or about 3,4:1 paramount about 3.8: 1, about 4:1, or about 4.2:1.

The hydrogenation of aromatic nitro compound can be carried out in the presence of one or more catalyst.Use can promote virtue Any suitable catalyst of fragrant race nitro compound hydrogenation.Illustrative catalyst may include but be not limited to, nickel, ferrum, chromium, platinum, Copper, cobalt, palladium, rhodium, iridium, their oxide, their hydroxide, their carbonate, their formates or they Any mixture.Catalyst can be unsupported or load.Illustrative carrier material may include but be not limited to, carbon, aluminium oxide Deng.Supported catalyst concentration can be low about 0.1wt% to about 50wt%, the weight based on carrier material.Carrier material Granularity can be about 0.01 μm to about 100 μm.The surface area of carrier material can be about 10m²To about 1,000m²Every gram.

In addition to one or more catalyst, the hydrogenation of aromatic nitro compound also can exist in water and/or aniline Under carry out.Water and/or aniline can provide to the temperature of hydrogenation reaction at least some to control and/or can be easy to introduce catalyst.Example As catalyst can introduce carrier fluid such as aniline and/or water to hydrogenation reactor or hydrogenation zone.Used, exhaust and/or discarded Catalyst can be reclaimed as by-product or garbage from hydrogenation reactor or hydrogenation zone.

Aromatic nitro compound and aniline/catalyst mixture can be introduced to hydrogenation reactor with following weight ratio 406：About 1:0.45 to about 1:0.6, about 1:0.5 to about 1:0.6, about 1:0.5 to about 1:0.55, or about 1:0.45 to about 1: 0.55.Aromatic nitro compound and water can be introduced to hydrogenation reactor 406 with following weight ratio：About 1:0.9 to about 1: 1.25, about 1:1 to about 1:1.15, about 1:0.95 to about 1:1.1, or about 1:1 to about 1:1.1.Can be by aromatic nitro compound With hydrogen, hydrogenation reactor 406 is introduced to following weight ratio：About 30:1 to about 10:1, about 25:1 to about 10:1, about 20:1 to About 10:1, about 15:1 to about 10:1, or about 25:1 to about 12.5:1.Aromatic nitro compound and aniline/catalyst mixture Weight ratio can be about 1:0.5 to about 1:0.55, the weight ratio of aromatic nitro compound and water can be about 1:1 to about 1:1.1, The weight ratio of aromatic nitro compound and hydrogen can be about 12.5:1 to about 25:1.

Illustrative method for preparing aniline may include United States Patent (USP) Nos.:8,809,587,7,049,471 and 7, 692,042 and U.S. Patent Application Publication Nos.:2007/0203364, institute in 2007/0238901, and 2009/0065347 Those methods stated.

Aniline can be reacted with aminating agent by one or more phenol and prepare.Illustrative phenol may include but be not limited to, The o-, m- or p- isomery of phenol, 2- methylphenol, 3- methylphenol, 4- methylphenol, ethyl -phenol and/or isopropyl-phenol Body, and there is the alkylphenol of at least one alkyl substituent, such as xylenol, Methylethyl phenol, methyl isopropyl Base phenol, methyl butyl phenol, diethyl phenol, ethyl-butyl phenol, diisopropyl phenol, isopropyl butylphenol, two fourths Base phenol or its any mixture.Illustrative amines agent may include but be not limited to, ammonia, ammonium carbonate, ammonium sulfate, ethamine, n-propylamine, Dimethylamine, diethylamine, diisopropylamine, methyl ethyl-amine, cyclohexylamine, aminopyridine, aniline, monomethylaniline., MEA, positive third Base aniline, isopropyl aniline, dimethylaniline, diethylaniline, dipropyl aniline, Methylethyl aniline, methyl-propyl aniline Or its any mixture.The illustrative method that one or more phenol and one or more aminating agent react may include United States Patent (USP) No.:Method described in 5,545,753.

Can have the concentration about 15wt% to about 80wt% of aniline via the product of pipeline 408.For example, via pipeline In 408 product, the amount of aniline can be low about 20wt%, about 25wt%, about 35wt%, or about 45wt% is paramount about 60wt%, about 65wt%, about 70wt%, or about 75wt%.The concentration can via the product of pipeline 408 with water is about 25wt% to about 85wt%.For example, the amount via water in the product of pipeline 408 can be low about 25wt%, about 40wt%, about 45wt%, or the paramount about 60wt% of about 50wt%, about 65wt%, about 70wt%, or about 75wt%.Reaction via pipeline 408 Product may include about 35wt% to the water of the aniline of about 45wt%, about 55wt% to about 65wt%, and less than about 5wt% other Component.

Product via pipeline 408 can be cooled down to prepare the product of cooling.For example, from product Heat can indirect transfer to heat transfer medium to prepare the product of cooling and the heat transfer medium of heating.Illustrative heat-transfer material May include but be not limited to, cooling water, boiler feedwater, low-pressure steam, middle pressure steam, ethylene glycol, air and/or other gaseous fluids Or its any mixture.In another example, product can by with cooling fluid such as water directly contact or mix and Cooling, thus prepare the product of cooling.Product via pipeline 408 can be cold by indirect heat exchange and directly contact But combination is cooled down.

Temperature via the cooling product of pipeline 408 can be low about 0 DEG C, about 25 DEG C, about 50 DEG C, or about 75 DEG C paramount About 150 DEG C, about 175 DEG C, or about 200 DEG C.Pressure via the cooling product of pipeline 408 can be low about 101kPa, about 300kPa, or about 500kPa paramount about 1,000kPa, about 1,500kPa, or about 2,000kPa.

Via the cooling product of pipeline 408 can be introduced to phase separator 410 with from phase separator 410 via pipeline 412 separation waters, thus prepare semifinished product or crude aniline via pipeline 414.Crude aniline 414 can be thick via pipeline 102 Aniline processed or the crude aniline including via pipeline 102, it is with reference to Fig. 1-3 as mentioned above and described in other places in this application 's.Purification Aniline product via pipeline 420 and the garbage via pipeline 418 can be by one or more purification systems 416 Obtain.Purification Aniline product via pipeline 420 and the garbage via pipeline 418 can be for as mentioned above and in the application Described in middle other places.For example, the purification Aniline product via pipeline 420 can be the purification aniline via pipeline 134,234 and 334 Product or the purification Aniline product including via pipeline 134,234 and 334, the garbage via pipeline 418 can be via pipeline 132,232 and 332 garbage or include the garbage via pipeline 132,232 and 332.Aniline prepares and purifies the another of system Outer details can be known from the open No.2012/0172627 of United States Patent (USP) or United States Patent (USP) No.8,809,587.

Embodiment

In order to be better understood to offer discussed above, provide following non-limiting example.Except as otherwise noted, otherwise All of part, ratio and percentage ratio are by weight.

Embodiment 1

Carry out one group of test to measure the effect for reaction 2 for the cationic resin.Test two cationoid resins, i.e. type 13 (Ex.1) and Class1 4 (Ex.2) resin.Cationic resin uses wet, the identical terms of shipment, and is not previously dried.Type The upper limit of 13 resin operation temperature is about 120 DEG C, and the upper limit of Class1 4 resin operation temperature is about 150 DEG C.For in test Aniline is SILVER REAGENT aniline, and its moisture is less than 1,000ppmw.About 50mL aniline is added to single glass flask In, about 0.5g cationic resin is added in each flask.Aniline/resin compound is heated to reaction temperature, in vibration table Upper stirring.To each aniline/resin compound, about 0.15mL SILVER REAGENT Ketohexamethylene is added to comprise about 3,000ppmw hexamethylene to make The aniline solution of ketone.In 15 minutes, 30 minutes and sampling in 60 minutes, by gas chromatographic analysiss cyclohexanone content.Also to not wrapping A reference examples (CI) containing any cation exchange resin is tested.Test condition and result are shown in table 1 below.

Table 1

As shown in table 1, when the aniline charging comprising Ketohexamethylene is contacted in about 110 DEG C of temperature with cation exchange resin When, Ketohexamethylene concentration significantly reduces.For example, the Ketohexamethylene concentration in embodiment 1 reduces about 58%, embodiment 2 afterwards within 60 minutes In Ketohexamethylene concentration reduce about 63%.By contrast, 60 minutes afterwards reference examples C1 comprise about 2,995ppmw Ketohexamethylene.

Embodiment 2

The cyclohexanone solution in aniline being about 1,000ppmw with preparation initial concentration, carries out second group of test.Will about 50mL aniline and about 0.05mL Ketohexamethylene are mixed with each other.About 0.5g cation exchange resin (Class1 3 and Class1 4) is added to In aniline and cyclohexanone mixture.Test condition and result are shown in table 2 below.

Table 2

As shown in table 2, when the aniline charging comprising Ketohexamethylene is contacted in about 110 DEG C of temperature with cation exchange resin When, Ketohexamethylene concentration significantly reduces.For example, the Ketohexamethylene concentration of embodiment 3 and 4 reduces about respectively afterwards within about 60 minutes 52.5% and about 85.2%.

Embodiment 3

The cyclohexanone mixture in aniline being about 1,000ppmw with preparation initial concentration, carries out the 3rd group of test.Will about 50mL aniline and about 0.05mL Ketohexamethylene are mixed with each other.About 1g cation exchange resin (Class1 3 and Class1 4) is added to benzene In amine and cyclohexanone mixture.Test condition and result are shown in table 3 below.

Table 3

As shown in table 3, when the aniline charging comprising Ketohexamethylene is contacted in about 110 DEG C of temperature with cation exchange resin When, Ketohexamethylene concentration significantly reduces.For example, the Ketohexamethylene concentration of embodiment 5 and 5 reduces about 52% respectively afterwards within about 60 minutes About 64%.

Embodiment 4

The cyclohexanone mixture in aniline being about 1,000ppmw with initial concentration, is tested.By about 50mL aniline and About 0.05mL Ketohexamethylene is mixed with each other.About 0.5g cation exchange resin (Class1 4) is added to aniline and cyclohexanone mixture In.Test condition and result are shown in table 4 below.

Table 4

As shown in table 4, when the Ketohexamethylene aniline comprising about 1,000ppmw feeds with cation exchange resin about 140 DEG C temperature contact when, Ketohexamethylene concentration reduce about 93.5%, 60 minutes are afterwards, and Ketohexamethylene concentration significantly reduces.

Embodiment 5

The cyclohexanone mixture in aniline being about 100ppmw with concentration, is tested.By about 50mL aniline and 0.005mL Ketohexamethylene is mixed with each other.About 0.5g cation exchange resin (Class1 4) is added to aniline and cyclohexanone mixture In.Test condition and result are shown in table 5 below.

Table 5

As shown in table 5, when the dry aniline charging comprising 100ppmw Ketohexamethylene and cation exchange resin are at about 140 DEG C Temperature contact when, Ketohexamethylene concentration reduce about 88%, 60 minutes are afterwards, and Ketohexamethylene concentration significantly reduces.

As shown in table 1-5, surprisingly and it was unexpectedly found that, by comprise Ketohexamethylene aniline feed with sun from Sub-exchange resin contacts in about 110 DEG C to about 140 DEG C of temperature, significantly reduces the Ketohexamethylene concentration in aniline charging.Ketohexamethylene The degree reducing or amount can be at least partially dependent on time of contact with resin, initial Ketohexamethylene concentration, resinous type, temperature, And the combination of these regulated variables.

Embodiment described herein further to in hypomere any one or more snippets：

1. the method being used for purification of crude aniline, is contained less with preparing including being contacted crude aniline with cation exchange resin The product of amount Ketohexamethylene, described crude aniline comprises aniline, water and Ketohexamethylene, and the described product containing a small amount of Ketohexamethylene comprises than thick The few Ketohexamethylene of aniline processed, wherein cation exchange resin are solid, semi-solid or a combination thereof.

2. section 1 method, it further includes：By nitrobenzene to prepare crude aniline；At least a portion by water Separate with crude aniline to prepare dehydration crude aniline；Contained with preparing with crude aniline will be dehydrated to be contacted with cation exchange resin The product of a small amount of Ketohexamethylene.

3. sections 2 method, it further includes：Cooled dehydrated crude aniline is to prepare the dehydration crude aniline of cooling；Will The dehydration crude aniline of cooling is contacted with cation exchange resin to prepare the product containing a small amount of Ketohexamethylene；A small amount of Ketohexamethylene will be contained Product be incorporated in knockout tower to prepare purification Aniline product.

4. sections 3 method, wherein crude aniline comprises about 85wt% to the aniline of about 99wt%, and about 1wt% is to about The water of 15wt%, and about 100ppmw is to the Ketohexamethylene of about 15,000ppmw.

5. sections 3 or 4 method, wherein dehydration crude aniline comprises about 98wt% to the aniline of about 99.9wt%, is less than The water of 0.5wt%, and about 100ppmw is to the Ketohexamethylene of about 5,000ppmw.

6. in sections 3 to 5 either segment method, wherein purification Aniline product comprises about 99wt% to the benzene of about 99.99wt% Amine, less than the water of 0.5wt%, and the Ketohexamethylene less than 100ppmw.

7. in sections 3 to 6 either segment method, wherein about 50 DEG C to about 150 DEG C temperature by the aniline being dehydrated with contact Cation exchange resin cools down time period of 1 minute to about 15 minutes, and wherein contain the product of a small amount of Ketohexamethylene comprise with slightly Aniline processed compares the Ketohexamethylene at least lacking 30%.

8. in sections 3 to 6 either segment method, wherein about 50 DEG C to about 150 DEG C temperature by the aniline being dehydrated with contact The time period less than 60 minutes for the cation exchange resin cooling, and wherein the product containing a small amount of Ketohexamethylene comprises and crude aniline Compare the Ketohexamethylene at least lacking 50%.

9. section 1 method, crude aniline is contacted by the wherein temperature at about 50 DEG C to about 150 DEG C with cation exchange resin The time period of 1 minute to about 15 minutes, and wherein contain a small amount of Ketohexamethylene product comprise at least few compared with crude aniline 30% Ketohexamethylene.

10. section 1 method, crude aniline is connect by the wherein temperature at about 50 DEG C to about 150 DEG C with cation exchange resin Touch the time period of 1 minute to about 15 minutes, and wherein contain the product of a small amount of Ketohexamethylene and comprise compared with crude aniline at least 40% few Ketohexamethylene.

Crude aniline is connect by 11. section 1 of method, the wherein temperature at about 50 DEG C to about 150 DEG C with cation exchange resin Touch time period of 1 minute to about 15 minutes, and wherein contain the product of a small amount of Ketohexamethylene comprise at least few compared with crude aniline 50% Ketohexamethylene.

Crude aniline is connect by 12. section 1 of method, the wherein temperature at about 50 DEG C to about 150 DEG C with cation exchange resin Touch the time period less than 60 minutes, and wherein contain the product of a small amount of Ketohexamethylene and comprise at least to lack 50% compared with crude aniline Ketohexamethylene.

Crude aniline is connect by 13. section 1 of method, the wherein temperature at about 50 DEG C to about 150 DEG C with cation exchange resin Touch less than time period of 60 minutes, and wherein containing the product of a small amount of Ketohexamethylene, to comprise compared with crude aniline at least 60% few Ketohexamethylene.

Crude aniline is connect by 14. section 1 of method, the wherein temperature at about 50 DEG C to about 150 DEG C with cation exchange resin Touch less than time period of 60 minutes, and wherein containing the product of a small amount of Ketohexamethylene, to comprise compared with crude aniline at least 70% few Ketohexamethylene.

The method of either segment in 15. section 1 to 14, wherein cation exchange resin comprises H⁺Functional group, sulphuric acid, HSO₄ ^-Sense Group or its any combinations.

The method of either segment in 16. section 1 to 15, the wherein form of cation exchange resin are pill, beadlet, granule, thin Piece, spheroid, cube, block, fiber, filamentous, threaded body or its any mixture.

The method of either segment in 17. section 1 to 16, wherein cation exchange resin comprise based on crosslinked styrene-diethyl The polymer of alkenyl benzene copolymer, described based on the polymer of crosslinked styrene diethylene benzene copoly mer comprise sulphuric acid and HSO₄ ^-Functional group.

The method of either segment in 18. section 1 to 17, the average pore size of wherein cation exchange resin is aboutTo about

The method of either segment in 19. section 1 to 18, the pore volume of wherein cation exchange resin is about 0.1mL/g to about 1mL/g.

The method of either segment in 20. section 1 to 19, the surface area of wherein cation exchange resin is about 10m²/ g to about 50m²/ g.

The method of either segment in 21. section 1 to 20, wherein by least a portion of crude aniline and cation exchange resin with Speed is about 0.1m³The every 1m of crude aniline³Cation exchange resin is per hour to about 30m³The every 1m of crude aniline³Cation exchange Resin is contacted per hour.

22. methods being used for purification of crude aniline, including：Aromatic nitro compound is hydrogenated to prepare crude aniline, It comprises about 85wt% to the aniline of about 99wt%, the water of about 1wt% to about 15wt% and about 100ppmw to about 15,000ppmw Ketohexamethylene；At least a portion of water is separated to prepare dehydration product with crude aniline, it comprises about 98wt% or bigger The Ketohexamethylene of aniline, the less than about water of 5,000ppmw and about 100ppmw to about 5,000ppmw；By Ketohexamethylene in dehydration product The part reaction of a part and aniline to prepare the product of Ketohexamethylene reduction, the product of described Ketohexamethylene reduction comprise with described Dehydration product compares few Ketohexamethylene；With the temperature at about 50 DEG C to about 150 DEG C, the product that Ketohexamethylene reduces is handed over cation Change resin to contact to prepare the product containing a small amount of Ketohexamethylene, the described product containing a small amount of Ketohexamethylene comprises to reduce with described Ketohexamethylene Product compare few Ketohexamethylene, wherein cation exchange resin be solid, semi-solid or a combination thereof.

The product of 23. section 22 of method, wherein Ketohexamethylene reduction contacts 1 minute to about 15 minutes with cation exchange resin Time period, and wherein contain the product of a small amount of Ketohexamethylene comprise compared with the product of Ketohexamethylene reduction at least less 30% hexamethylene Ketone.

24. section 22 or 23 method, wherein cation exchange resin comprises H⁺Functional group, sulphuric acid, HSO₄ ^-Functional group or its Any combinations.

The method of either segment in 25. section 22 to 24, wherein cation exchange resin comprise based on crosslinked styrene-diethyl The polymer of alkenyl benzene copolymer, described based on the polymer of crosslinked styrene diethylene benzene copoly mer comprise sulphuric acid, HSO₄ ^-, functional group.

The method of either segment in 26. section 22 to 25, wherein in about 100 DEG C to about 170 DEG C of temperature by one of Ketohexamethylene Divide a part of reaction response with aniline.

27. the method for either segment in section 22 to 26, the average pore size of wherein cation exchange resin is aboutTo about

The method of either segment in 28. section 22 to 27, the pore volume of wherein cation exchange resin is about 0.1mL/g to about 1mL/g.

The method of either segment in 29. section 22 to 28, the surface area of wherein cation exchange resin is about 10m²/ g is to about 50m²/g.

The system of 30. purification of crude aniline, including：Hydrogenation reactor is configured to make aromatic nitro compound hydrogenate to make The standby crude aniline comprising aniline, water and Ketohexamethylene；It is configured to crude aniline and cation exchange tree with cation exchange unit Fat contacts to prepare the product containing a small amount of Ketohexamethylene, and the described product containing a small amount of Ketohexamethylene comprises the hexamethylene fewer than crude aniline Ketone, wherein cation exchange resin are solid, semi-solid or a combination thereof.

31. section 30 of system, it comprises dewatering unit further, and described dewatering unit is configured to water and described rough benzene Amine separates to prepare dehydration crude aniline, and described dehydration crude aniline comprises the water fewer than described crude aniline, is wherein dehydrated single Unit is located at the upstream of cation exchange unit.

32. section 30 or 31 system, it comprises reactor further, described reactor configurations be make in dehydration crude aniline The part reaction of Ketohexamethylene is located at the upper of cation exchange unit to prepare the crude aniline of Ketohexamethylene reduction, wherein reactor Trip and the downstream of dewatering unit.

The system of either segment in 33. section 30 to 32, it comprises separator further, and described separator is configured to make any miscellaneous At least a portion of matter is separated with the product containing a small amount of Ketohexamethylene, thus preparing purification Aniline product.

Some embodiments and feature are described using one group of numerical upper limits and one group of numerical lower limits.Should manage Solution, except as otherwise noted, otherwise expect the combination that described scope includes any two value, for example any lower value with any relatively The combination of high level, the combination of any two lower value, and/or the combination of any two high value.Some lower limits, the upper limit and scope Occur in following claims one or more in.All numerical value are that " about " is equal to or " approximate " is in setting, and consider The experimental error that can anticipate to those skilled in the art and change.

Various terms have been described above defining.To a certain extent, the term for claim is not as defined above, such as Fruit term is reflected at least one printed publication or granted patent, then should provide broadest for those skilled in the art Definition.Additionally, all patents quoted in the application, test program and other documents are fully incorporated by reference so that institute State disclosure content to be consistent with the application, and in the range of all jurisdictions being incorporated to described in allowing to carry out.

Although the above is related to embodiments of the present invention, can design on the premise of without departing from its elemental range Other and the further embodiment of the present invention, the scope of the invention is determined by the claims that follow.

Claims

1. the method for purification of crude aniline, is contacted to prepare containing a small amount of Ketohexamethylene with cation exchange resin including by crude aniline Product, described crude aniline comprises aniline, water and Ketohexamethylene, and the described product containing a small amount of Ketohexamethylene comprises than described rough benzene The few Ketohexamethylene of amine, wherein said cation exchange resin is solid, semi-solid or a combination thereof.

2. the method for claim 1, it further includes：

By nitrobenzene to prepare described crude aniline；

At least a portion of described water is separated from described crude aniline to prepare dehydration crude aniline；With

Described dehydration crude aniline is contacted with described cation exchange resin to prepare the described product containing a small amount of Ketohexamethylene.

3. the method for claim 2, it further includes：

Cooling described dehydration crude aniline is to prepare the dehydration crude aniline of cooling；

The dehydration crude aniline of described cooling is contacted with described cation exchange resin with prepare described containing a small amount of Ketohexamethylene Product；With

The described product containing a small amount of Ketohexamethylene is incorporated in knockout tower to prepare purification Aniline product.

4. the method for claim 3, wherein said crude aniline comprises about 85wt% to the aniline of about 99wt%, about 1wt% extremely The water of about 15wt%, and about 100ppmw is to the Ketohexamethylene of about 15,000ppmw, wherein said dehydration crude aniline comprises about The aniline of 98wt% to about 99.9wt%, less than the water of 0.5wt%, and about 100ppmw is to the Ketohexamethylene of about 5,000ppmw, and And wherein purification Aniline product comprises about 99wt% to the aniline of about 99.99wt%, less than the water of 0.5wt%, and is less than The Ketohexamethylene of 100ppmw.

5. the method for claim 1 wherein that described crude aniline is handed over by the temperature at about 50 DEG C to about 150 DEG C with described cation Change resin and contact time period of about 1 minute to about 15 minutes, and the wherein said product containing a small amount of Ketohexamethylene comprise with described Crude aniline compares the Ketohexamethylene at least lacking 30%.

6. the method for claim 1 wherein that described crude aniline is handed over by the temperature at about 50 DEG C to about 150 DEG C with described cation Change the time period that resin contact was less than 60 minutes, and the wherein said product containing a small amount of Ketohexamethylene comprises and described crude aniline Compare the Ketohexamethylene at least lacking 50%.

7. the method for claim 1 wherein that described cation exchange resin comprises H⁺Functional group, sulphuric acid, HSO₄ ^-Functional group or its Any combinations.

8. the method for claim 1 wherein described cation exchange resin form be pill, beadlet, granule, thin slice, spheroid, Cube, block, fiber, filamentous, threaded body or its any mixture.

9. the method for claim 1 wherein that described cation exchange resin comprises based on crosslinked styrene-divinylbenzene altogether The polymer of polymers, described comprises sulphuric acid and HSO based on crosslinked styrene diethylene benzene copoly mer₄ ^-Functional group.

10. the method for claim 1 wherein that the average pore size of described cation exchange resin is aboutTo aboutHole Volume be about 0.1mL/g to about 1mL/g, surface area is about 10m²/ g to about 50m²/g.

11. the method for claim 1 wherein at least a portion of described crude aniline with described cation exchange resin with speed Rate is about 0.1m³The every 1m of crude aniline³Cation exchange resin is per hour to about 30m³The every 1m of crude aniline³Cation exchange tree Fat is contacted per hour.

The method of 12. purification of crude aniline, including：Aromatic nitro compound is hydrogenated to prepare crude aniline, it comprises about 85wt% to the aniline of about 99wt%, the water of about 1wt% to about 15wt% and about 100ppmw to about 15,000ppmw hexamethylene Ketone；

At least a portion of described water is separated from described crude aniline to prepare dehydration product, it comprises about 98wt% or more Aniline, the less than about water of 5,000ppmw and about 100ppmw to about 5,000ppmw Ketohexamethylene；

A part for a part for Ketohexamethylene in described dehydration product and described aniline is reacted to prepare the product of Ketohexamethylene reduction Thing, the product of described Ketohexamethylene reduction comprises few Ketohexamethylene compared with described dehydration product；With

In about 50 DEG C to about 150 DEG C of temperature, the product that described Ketohexamethylene reduces is contacted with cation exchange resin and contained with preparing The product of a small amount of Ketohexamethylene, the described product containing a small amount of Ketohexamethylene comprises few hexamethylene compared with the product of described Ketohexamethylene reduction Ketone, wherein said cation exchange resin is solid, semi-solid or a combination thereof.

The method of 13. claim 12, the product of wherein said Ketohexamethylene reduction contacts about 1 point with described cation exchange resin The Zhong Zhiyue time period of 15 minutes, and the wherein said product containing a small amount of Ketohexamethylene comprises the product with the reduction of described Ketohexamethylene Compare the Ketohexamethylene at least lacking 30%.

The method of 14. claim 13, wherein said cation exchange resin comprises H⁺Functional group, sulphuric acid, HSO₄ ^-Functional group or Its any combinations.

15. the method for claim 12, wherein said cation exchange resin comprises based on crosslinked styrene-divinylbenzene The polymer of copolymer, described comprises sulphuric acid, HSO based on crosslinked styrene diethylene benzene copoly mer₄ ^-, functional group.

The method of 16. claim 12, wherein about 100 DEG C to about 170 DEG C temperature by with the partial reaction of described aniline The part of described Ketohexamethylene is reacted.

The system of 17. purification of crude aniline, including：

Hydrogenation reactor, it is configured to make aromatic nitro compound hydrogenation comprise the rough of aniline, water and Ketohexamethylene to prepare Aniline；With

Cation exchange unit, it is configured to make crude aniline contact with cation exchange resin to prepare containing a small amount of Ketohexamethylene Product, the described product containing a small amount of Ketohexamethylene comprises the Ketohexamethylene fewer than described crude aniline, wherein said cation exchange tree Fat is solid, semi-solid or a combination thereof.

The system of 18. claim 17, it comprises dewatering unit further, and described dewatering unit is configured to water from described rough Aniline separates to prepare dehydration crude aniline, and described dehydration crude aniline comprises the water fewer than described crude aniline, wherein said Dewatering unit is located at the upstream of described cation exchange unit.

19. the system of claim 18, it comprises reactor further, and described reactor configurations are to make described dehydration crude aniline To prepare the crude aniline of Ketohexamethylene reduction, wherein said reactor is located at described cation and hands over for the part reaction of middle Ketohexamethylene Change the upstream of unit and the downstream of described dewatering unit.

The system of 20. claim 19, it comprises separator further, and described separator is configured to make at least the one of any impurity Part separates from the described product containing a small amount of Ketohexamethylene to prepare the Aniline product of purification.