CN107935862A - A kind of method of aniline continuous synthesizing diphenylamine - Google Patents

A kind of method of aniline continuous synthesizing diphenylamine Download PDF

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Publication number
CN107935862A
CN107935862A CN201711202766.8A CN201711202766A CN107935862A CN 107935862 A CN107935862 A CN 107935862A CN 201711202766 A CN201711202766 A CN 201711202766A CN 107935862 A CN107935862 A CN 107935862A
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Prior art keywords
reactor
aniline
reaction
heater
reactant
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CN201711202766.8A
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周松涛
冒圣华
冒莹莹
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NANTONG XINBANG CHEMICAL CO Ltd
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NANTONG XINBANG CHEMICAL CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/22—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of other functional groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention provides a kind of method of aniline continuous synthesizing diphenylamine, its reaction system is alternately connected using N stage reactors and multiple heaters, is passed through nitrogen in the reactor before aniline raw material enters reaction system, is specially：It will exchange heat in the reactant and feed exchanger of aniline feedstock transportation to two-stage tandem, material after heat exchange enters back into primary heater and is heated to predetermined temperature, subsequently into N number of reactor and multiple intermediate heaters, reactant is again introduced into after N number of reactor and multiple intermediate heaters successively alternation response with exchanging heat in feed exchanger, reaction mass after heat exchange enters back into ammonia and reaction liquid/gas separator, wherein, N is greater than or equal to 2, and solid-supported catalyst is provided with each reactor.The present invention improves reaction conversion ratio using cascade reaction, saves the energy, reduces production cost.

Description

A kind of method of aniline continuous synthesizing diphenylamine
Technical field
The present invention relates to diphenylamines production technology field, more particularly to a kind of aniline continuous synthesizing diphenylamine cascade reaction work Skill.
Background technology
CN87107052.9 is disclosed makes aniline be contacted with aluminium oxide catalyst to prepare hexichol between about 380-475 DEG C Amine.CN95103700.5 discloses a kind of method by aniline syntehsizing diphenylamine, it is using aniline as raw material, is boiled in hydrogen and β Stone/Al2O3The method of syntehsizing diphenylamine in the presence of catalyst, using lower feeding manner, reaction temperature is 250-400 DEG C, reaction pressure Power 1.5-4.5MPa, aniline Feed space velocities 0.05-1.0h-1, the volume ratio 20-600 of hydrogen and aniline, on this condition, product Middle diphenylamine content is more than 22%, accessory substance<0.5%, pass through vapor-liquid separation, water absorption dehydrogenating and hydrogen under reaction pressure Dry to be separated from each other liquid reacting product, reaction generation ammonia and hydrogen, hydrogen recycles.CN02112535.X discloses one Kind adds the aniline syntehsizing diphenylamine method of nitrogen in reactor, its processing step is followed successively by：Aniline measures, by aniline raw material Measured by aniline measuring tank, metering pump, nitrogen buffers packet and be sent into aniline heater；Aniline heats, and the aniline after metering is former Material carries out being heated up to 330-370 DEG C；Reaction, the raw material aniline after heating is located in the reactor equipped with catalyst, in reactor Interior addition nitrogen, the pressure in reactor are 1.6-2.5MPa, and the air speed ratio of aniline and catalyst is 0.15-0.2/h, and temperature is 320-360 DEG C, then cooled down by raw produce heat exchanger, temperature is reached below 150 DEG C of the phase.201110058065.8 Disclose by amino benzenes compounds and phenol compound under high-temperature and high-pressure conditions, urged in the cyclohexanone and metal of catalytic amount In the presence of agent, pass through system internal condensation-dehydrogenation-hydrogenation process, direct syntehsizing diphenylamine class compound.Chinese Patent Application No. 201110313288.4 disclose a kind of method by aniline continuous synthesizing diphenylamine, it is before aniline raw material enters reactor Contacted with hydrogen, hydrogen is dissolved into aniline raw material, the aniline raw material for having dissolved hydrogen enters aniline continuous synthesizing diphenylamine In reactor, the aniline raw material of hydrogen has been dissolved by catalyst bed, has carried out aniline syntehsizing diphenylamine reaction, catalyst bed In be not present gas phase hydrogen.It is anti-that Chinese Patent Application No. 201210552308.8 discloses a kind of diphenylamines heated with biphenyl Device, including biphenyl heat conducting oil boiler are answered, the biphenyl heat conducting oil boiler is connected with biphenyl heater, the biphenyl by pipeline Heater is connected to reactor and raw produce heat exchanger, and the raw produce heat exchanger is connected with flash tank, the sudden strain of a muscle Steaming pot is also associated with flash condenser, and the biphenyl heat conducting oil boiler is connected with water dust scrubber by pipeline.
The synthetic method of diphenylamines disclosed above, some reaction temperatures are 380-475 DEG C high；Some need adds hydrogen； Some need adds nitrogen during the reaction, it is necessary to which follow-up Ammonia recovery process needs constantly discharge not coagulate tail gas, continuous row It cannot not put solidifyingly tail gas and necessarily carry ammonia emission secretly.
Therefore, it is necessary to provide a kind of new technical solution.
The content of the invention
The defects of in order to overcome the above-mentioned prior art, the present invention provide a kind of method of aniline continuous synthesizing diphenylamine, its Nitrogen need not be added during the reaction, hydrogen is more not required, and reaction conversion ratio is improved using cascade reaction, saves energy Source, reduces production cost.
To achieve the above object, the method for a kind of aniline continuous synthesizing diphenylamine of the invention, its reaction system use N grades Reactor and multiple heaters are alternately connected, and are passed through nitrogen in the reactor before aniline raw material enters reaction system, are specially：
To exchange heat in the reactant and feed exchanger of aniline feedstock transportation to two-stage tandem, the material after heat exchange again into Enter primary heater and be heated to predetermined temperature, subsequently into N number of reactor and multiple intermediate heaters, through N number of reactor and multiple Intermediate heater is again introduced into reactant with exchanging heat in feed exchanger after alternation response successively, and the reaction mass after heat exchange is again Into ammonia and reaction liquid/gas separator, wherein, N is greater than or equal to 2, and solid-supported catalyst is provided with each reactor.
Further, N number of reactor includes first reactor, second reactor, the 3rd reactor and the 4th reactor, more A intermediate heater includes the first intermediate heater, the second intermediate heater and the 3rd intermediate heater,
The reactant of the two-stage tandem and feed exchanger, primary heater, first reactor, the first intermediate heater, Second reactor, the second intermediate heater, the 3rd reactor, the 3rd intermediate heater and the 4th reactor are sequentially connected in series.
Further, the solid-supported catalyst is porous solid-supported catalyst.
Further, the aniline raw material by metering pump with the speed of 3500kg/H enter two-stage tandem reactant with Feed exchanger.
Further, aniline raw material exchanges heat to more than 260 DEG C in the reactant and feed exchanger of two-stage tandem；
The primary heater heated material to 330 DEG C, wherein, heating-up temperature from 295 DEG C of gradient increased temperatures to 330 DEG C, heating Speed is 0.106 DEG C/day.
Further, first intermediate heater, the second intermediate heater and the 3rd intermediate heater are used to remain anti- It is 330 DEG C to answer temperature.
Further, the reaction mass exported through the 4th reactor is again introduced into the reactant of two-stage tandem and charging exchanges heat Less than 110 DEG C are cooled in device, the reaction mass through cooling enters ammonia and reaction liquid/gas separator by the pressure reducing valve automatically controlled Middle progress ammonia and reactor separation.
Further, the reaction pressure in the first reactor, second reactor, the 3rd reactor and the 4th reactor Declined by 2.2MPa to 1.8MPa successively gradient.
Further, when the primary heater is identical with temperature in first reactor, the reaction pressure is down to 1.6MPa。
Further, the material in multiple reactors can be inversely by primary heater into aniline material storaging tank.
Compared with prior art, the invention has the advantages that：
(1) method of the invention, its from security standpoint in reactor at the beginning no material when need to be carried out with nitrogen Displacement, makes reaction system be in anaerobic state, need not add nitrogen during the reaction, hydrogen is more not required.
(2) method of the invention, its cascade reaction improve reaction conversion ratio, reactant and the raw material heat exchanger of two-stage tandem Heat integration saves the energy.
Embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to embodiment The present invention is described in further detail.
" one embodiment " or " embodiment " referred to herein refers to may be included at least one implementation of the present invention A particular feature, structure, or characteristic." in one embodiment " that different places occur in the present specification not refers both to same A embodiment, nor the single or selective embodiment mutually exclusive with other embodiment.
The present invention from safety considerations, in reactor at the beginning no material when need with nitrogen into line replacement, make Reaction system is in anaerobic state, need not add nitrogen during the reaction, hydrogen is more not required.
Embodiment 1
The present invention uses N stage reactors and multiple intermediate heater combined serial technologies.N number of reactor includes first Reactor, second reactor, the 3rd reactor and the 4th reactor, multiple intermediate heaters include the first intermediate heater, the Two intermediate heaters and the 3rd intermediate heater,
The reactant of the two-stage tandem and feed exchanger, primary heater, first reactor, the first intermediate heater, Second reactor, the second intermediate heater, the 3rd reactor, the 3rd intermediate heater and the 4th reactor are sequentially connected in series.
Aniline raw material in basin is pumped to aniline head tank, into measuring tank, metering pump with the charging rate of 3500kg/H, Into the reactant and feed exchanger of two-stage tandem, feeding temperature is exchanged heat to more than 260 DEG C, into primary heater, in master Feeding temperature is risen to 330 DEG C in heater, wherein, reaction temperature is gradient increased temperature, 0.106 DEG C/day of heating rate.With catalysis Agent usage time elapse, reaction temperature from 295 DEG C slowly gradual change increase to 330 DEG C, the material after primary heater is heated is successively Into first reactor, the first intermediate heater, second reactor, the second intermediate heater, the 3rd reactor, the 3rd centre add Reacted in hot device and the 4th reactor, wherein in first reactor, second reactor, the 3rd reactor and the 4th reactor It is equipped with porous solid-supported catalyst, the reaction in first reactor, second reactor, the 3rd reactor and the 4th reactor Pressure is declined by 2.2MPa to 1.8MPa successively gradient.Heating among first intermediate heater, the second intermediate heater and the 3rd Device additional heat maintains reaction temperature, and the reaction mass come out from the 4th reactor is changed by the reactant of two-stage tandem with charging Hot device, reaction mass temperature are down to less than 110 DEG C, by the pressure reducing valve automatically controlled, extremely divide into ammonia and reaction liquid/gas separator From system.
Cascade reaction technology of the present invention can improve reaction conversion ratio, and for aniline conversion in 32-16%, conversion ratio is one Progressive formation, initial stage, high conversion rate, can slowly reduce as the time elapses conversion ratio；When reaction temperature reaches 330 DEG C, and aniline Conversion ratio is below 16%, it is necessary to carry out regeneration treatment to catalyst.The reactant of the two-stage tandem of the present invention and raw material heat exchanger Heat integration, saves the energy.Unreacted aniline is back to reaction system by piece-rate system below, the aniline of recycling Aniline head tank reuse.
The present invention main chemical reaction be：2C6H5NH2=C6H5NHC6H5+NH3；
Wherein, aniline conversion and temperature, pressure during production and these conditions change of catalyst usage time are close in main reaction Cut phase is closed, and the aniline for having 65-85% or so in reaction solution does not react, and aniline head tank is returned after being separated with subsequent separation system Reuse.The diphenylamines of the method production of the present invention, its side reaction product total amount account for the 0.5%-1% of diphenylamines amount.
Embodiment 2
In reaction process, when running into the abnormal conditions such as tripping that have a power failure, slowly inversely pass through benzene using material in reactor Amine primary heater arrives emergency turnover material basin again, when the temperature in primary heater in temperature and first reactor maintains an equal level, When the pressure of reaction system is down to 1.6MPa, stops contrary operation and wait supply of electric power normal.The purpose of contrary operation of the present invention： Aniline primary heater is protected, technically prevents that material carbonization blocks initiation security incident in aniline primary heater.
The invention has the advantages that：
(1) method of the invention, its from security standpoint in reactor at the beginning no material when need to be carried out with nitrogen Displacement, makes reaction system be in anaerobic state, need not add nitrogen during the reaction, hydrogen is more not required.
(2) method of the invention, its cascade reaction improve reaction conversion ratio, reactant and the raw material heat exchanger of two-stage tandem Heat integration saves the energy.
Described above has fully disclosed the embodiment of the present invention.It is pointed out that it is familiar with the field Scope of the technical staff to any change that the embodiment of the present invention is done all without departing from claims of the present invention. Correspondingly, the scope of claim of the invention is also not limited only to previous embodiment.

Claims (10)

  1. A kind of 1. method of aniline continuous synthesizing diphenylamine, it is characterised in that：Its reaction system using N stage reactors and it is multiple plus Hot device is alternately connected, and is passed through nitrogen in the reactor before aniline raw material enters reaction system, is specially：
    It will exchange heat in the reactant and feed exchanger of aniline feedstock transportation to two-stage tandem, the material after heat exchange enters back into master Heater is heated to predetermined temperature, subsequently into N number of reactor and multiple intermediate heaters, through N number of reactor and multiple centres Heater is again introduced into reactant with exchanging heat in feed exchanger after alternation response successively, and the reaction mass after heat exchange enters back into Ammonia and reaction liquid/gas separator, wherein, N is greater than or equal to 2, and solid-supported catalyst is provided with each reactor.
  2. 2. the method for aniline continuous synthesizing diphenylamine according to claim 1, it is characterised in that：
    N number of reactor includes first reactor, second reactor, the 3rd reactor and the 4th reactor, multiple intermediate heaters Including the first intermediate heater, the second intermediate heater and the 3rd intermediate heater,
    The reactant of the two-stage tandem and feed exchanger, primary heater, first reactor, the first intermediate heater, second Reactor, the second intermediate heater, the 3rd reactor, the 3rd intermediate heater and the 4th reactor are sequentially connected in series.
  3. 3. the method for aniline continuous synthesizing diphenylamine according to claim 1, it is characterised in that：
    The solid-supported catalyst is porous solid-supported catalyst.
  4. 4. the method for aniline continuous synthesizing diphenylamine according to claim 2, it is characterised in that：
    The aniline raw material enters the reactant and feed exchanger of two-stage tandem by metering pump with the speed of 3500kg/H.
  5. 5. the method for aniline continuous synthesizing diphenylamine according to claim 1, it is characterised in that：
    Aniline raw material exchanges heat to more than 260 DEG C in the reactant and feed exchanger of two-stage tandem；
    The primary heater heated material to 330 DEG C, wherein, heating-up temperature is from 295 DEG C of gradient increased temperatures to 330 DEG C, heating rate For 0.106 DEG C/day.
  6. 6. the method for aniline continuous synthesizing diphenylamine according to claim 2, it is characterised in that：
    It is 330 DEG C that first intermediate heater, the second intermediate heater and the 3rd intermediate heater, which are used to maintain reaction temperature,.
  7. 7. the method for aniline continuous synthesizing diphenylamine according to claim 2, it is characterised in that：
    The reaction mass exported through the 4th reactor, which is again introduced into the reactant and feed exchanger of two-stage tandem, is cooled to 110 Below DEG C, the reaction mass through cooling is entered in ammonia and reaction liquid/gas separator by the pressure reducing valve that automatically controls carries out ammonia and anti- Device is answered to separate.
  8. 8. the method for aniline continuous synthesizing diphenylamine according to claim 2, it is characterised in that：
    Reaction pressure in the first reactor, second reactor, the 3rd reactor and the 4th reactor by 2.2MPa extremely Gradient declines 1.8MPa successively.
  9. 9. the method for aniline continuous synthesizing diphenylamine according to claim 2, it is characterised in that：
    When the primary heater is identical with temperature in first reactor, the reaction pressure is down to 1.6MPa.
  10. 10. the method for aniline continuous synthesizing diphenylamine according to claim 2, it is characterised in that：
    Material in multiple reactors can be inversely by primary heater into aniline material storaging tank.
CN201711202766.8A 2017-11-27 2017-11-27 A kind of method of aniline continuous synthesizing diphenylamine Pending CN107935862A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3944613A (en) * 1973-09-10 1976-03-16 New Japan Chemical Company, Limited Process for preparing diphenylamine from aniline
CN1363550A (en) * 2002-01-14 2002-08-14 曹宏生 Process for synthesizing biphenylamine from phenylamine by adding nitrogen gas to reactor
CN104478738A (en) * 2014-11-19 2015-04-01 南通新邦化工科技有限公司 Reaction method for continuously synthesizing diphenylamine from aniline

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3944613A (en) * 1973-09-10 1976-03-16 New Japan Chemical Company, Limited Process for preparing diphenylamine from aniline
CN1363550A (en) * 2002-01-14 2002-08-14 曹宏生 Process for synthesizing biphenylamine from phenylamine by adding nitrogen gas to reactor
CN104478738A (en) * 2014-11-19 2015-04-01 南通新邦化工科技有限公司 Reaction method for continuously synthesizing diphenylamine from aniline

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