CN104478738B - Reaction method for continuously synthesizing diphenylamine from aniline - Google Patents
Reaction method for continuously synthesizing diphenylamine from aniline Download PDFInfo
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- CN104478738B CN104478738B CN201410661655.3A CN201410661655A CN104478738B CN 104478738 B CN104478738 B CN 104478738B CN 201410661655 A CN201410661655 A CN 201410661655A CN 104478738 B CN104478738 B CN 104478738B
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- 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
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Abstract
The invention discloses a reaction method for continuously synthesizing diphenylamine from aniline. The reaction flow is as follows: firstly introducing an aniline raw material into an aniline high-level slot, and then introducing the aniline raw material into a metering slot and a two-stage series heat exchanger which is used for enabling reactants and raw materials to exchange heat, thereby enabling the raw materials to exchange heat and heat up; heating the raw materials; sequentially introducing the raw materials to a reactor A, a relay heater B, a reactor B, a relay heater C, a reactor C, a relay heater D and a reactor D which are connected in series to perform material reaction, and finally discharging the reacted materials from the reactor D; enabling the reaction materials to exchange heat and cool in the two-stage series heat exchanger; and introducing the cooled reaction materials into an ammonia and reaction liquor separator, and finally introducing the cooled reaction materials to a follow-up separating system, and returning the aniline raw materials to the aniline high-level slot for recycling. The reaction method for continuously synthesizing diphenylamine from aniline disclosed by the invention can be used for improving the heat exchange efficiency, comprehensively utilizing heat energy, saving energy resources, enabling the un-reacted aniline to pass through the follow-up separating system, and returning the recycled aniline to the aniline high-level slot of the reaction system for recycling.
Description
Technical field
The present invention relates to a kind of reaction method of utilization aniline continuous synthesizing diphenylamine, belong to chemical production field.
Background technology
China Patent No. is cn87107052.9, about so that aniline is contacted with aluminium oxide catalyst to make between 380-475 DEG C
Standby diphenylamines；China Patent No. is cn95103700.5, discloses a kind of method by aniline syntehsizing diphenylamine.The present invention be with
Aniline is raw material, in hydrogen and β zeolite/al2o3The method of syntehsizing diphenylamine in the presence of catalyst, using lower feeding manner, reacts
Temperature is 250 ~ 400 DEG C, reaction pressure 1.5 ~ 4.5mpa, aniline Feed space velocities 0.05 ~ 1.0h-1, the volume ratio of hydrogen and aniline
20 ~ 600, with this understanding, in product diphenylamine content more than 22%, accessory substance < 0.5%.By vapour-liquid under reaction pressure
Separate, liquid reacting product, reaction generation ammonia and hydrogen are separated from each other by water absorption dehydrogenating and hydrogen desiccation, hydrogen circulation makes
With.
China Patent No. is cn02112535.x, discloses a kind of aniline syntehsizing diphenylamine adding nitrogen in reactor
Method, its processing step is followed successively by: aniline metering, and aniline raw material is passed through aniline measuring tank, measuring pump, the metering of nitrogen buffers packet
And send into aniline heater；Aniline heats, and the aniline raw material after metering carries out being heated up to 330-370 DEG C；Reaction, former after heating
Material aniline is located at equipped with the reactor of catalyst, adds nitrogen in reactor, and the pressure in reactor is 1.6-2.5mpa,
For 0.15-0.2/h, temperature is 320-360 DEG C, is then dropped by raw produce heat exchanger the air speed of aniline and catalyst ratio
Temperature, makes temperature reach 150 DEG C of the phase below.
China Patent No. is cn201110058065.8, and disclosing a kind of method is by amino benzenes compounds and phenol
Compound under high-temperature and high-pressure conditions, in the presence of the cyclohexanone and metallic catalyst of catalytic amount, by system internal condensation-dehydrogenation-
Hydrogenation process, is directly synthesized diphenylamine compound.
China Patent No. is cn201110313288.4, discloses a kind of method by aniline continuous synthesizing diphenylamine,
Aniline raw material is contacted with hydrogen before entering reactor, so that hydrogen is dissolved in aniline raw material, has dissolved the aniline raw material of hydrogen
Enter in aniline continuous synthesizing diphenylamine reactor, the aniline raw material having dissolved hydrogen passes through beds, carries out aniline conjunction
Become diphenlyamine reaction, in beds, there is not the hydrogen of gas phase.
China Patent No. is cn201210552308.8, discloses a kind of diphenlyamine reaction device of biphenyl heating, bag
Include biphenyl heat conducting oil boiler, described biphenyl heat conducting oil boiler is connected with biphenyl heater by pipeline, described biphenyl heater divides
It is not connected with reactor and raw produce heat exchanger, described raw produce heat exchanger is connected with flash tank, and described flash tank also connects
It is connected to flash condenser, described biphenyl heat conducting oil boiler is connected with water dust scrubber by pipeline.
In sum, in technology disclosed in the above patent, some reaction temperatures are high 380-475 DEG C；Some needs add
Enter hydrogen；Have needs to add during the course of the reaction nitrogen, needs follow-up Ammonia recovery operation to need constantly discharge not coagulate tail gas,
Continuous discharge is not coagulated tail gas and is necessarily carried ammonia emission secretly, is unfavorable for the protection of environmental resource, and waste of resource, and operating process becomes
Loaded down with trivial details.
Content of the invention
Present invention aims to deficiency of the prior art, provide a kind of utilization aniline continuous synthesizing diphenylamine
Reaction method, does not have at the beginning to need to enter line replacement with nitrogen during material in reactor, makes reaction system be in anaerobic state,
Do not need during the course of the reaction to add nitrogen, more do not need hydrogen.
For solving above-mentioned technical problem, the technical solution used in the present invention is: one kind utilizes aniline continuous synthesizing diphenylamine
Reaction method, its innovative point is: reaction process is: (1) aniline raw material is introduced into aniline head tank, subsequently into metering
Groove, enters back into carrying out in the heat exchanger of heat exchange for reactant and raw material of two-stage tandem, carries out raw material heat exchange intensification；
(2) raw material after heat exchange is entered heater and carry out raw material heat temperature raising；
(3) raw material after heating up in step (2) is sequentially entered the reactor a of series connection, relays heater b, reactor b,
Relaying heater c, reactor c, relay heater d, and reactor d carries out material reaction, becomes finally d in reactor out
Reaction mass；
(4) reaction mass in step (3) is carried out the heat exchange of heat exchange through two-stage tandem for reactant and raw material
In device, carry out reaction mass heat exchange cooling；
(5) by the reaction mass after step (4) cooling, by the pressure-reducing valve automatically controlling in heat exchanger tube, enter
Ammonia and reaction liquid/gas separator, finally enter subsequent separation system, isolate aniline raw material and return the reuse of aniline head tank.
Further, the specifically comprising the following steps that of described reaction process
(1) from aniline material storaging tank, by raw material pump pump to aniline head tank, enter measuring tank, measuring pump again with
The charging rate of 3500kg/h, the reactant that is used for that raw material is pumped into two-stage tandem is carried out in the heat exchanger of heat exchange with raw material, will
Feeding temperature heat exchange is to 260～265 DEG C；
(2) raw material after heat exchange is entered heater and carry out raw material heat temperature raising, the feeding temperature of raw material is risen to 295～
330 DEG C, heating mode is set to gradient increased temperature, and heating rate is 0.106 DEG C/day；
(3) raw material being warming up to 295～330 DEG C in step (2) is sequentially entered the reactor a of series connection, relay heater
B, reactor b, relay heater c, reactor c, relay heater d, reactor d, the pressure of setting reactor a to d is all 2.2
Between mpa～1.8mpa, and the order according to reactor a to d, pressure value reduces successively, becomes finally d in reactor out
For reaction mass；
(4) reaction mass in step (3) is carried out the heat exchange of heat exchange through two-stage tandem for reactant and raw material
In device, carry out reaction mass heat exchange cooling, reaction mass temperature is down to less than 110 DEG C；
(5) by the reaction mass after step (4) cooling, by the pressure-reducing valve automatically controlling in heat exchanger tube, enter
Ammonia and reaction liquid/gas separator, finally enter subsequent separation system, isolate aniline raw material and return the reuse of aniline head tank.
Further, it is fitted with commercially available porous solid-supported catalyst in four reactors in described step (3).
Further, described four relaying heaters, in the whole course of reaction of step (3), are continuously replenished heat to reactor
Amount, maintains reactor reaction temperature-resistant.
The main reaction chemical principle of the present invention is as follows:
2c6h5nh2= c6h5nhc6h5+ nh3
Beneficial effects of the present invention are as follows:
(1) reaction method of the utilization aniline continuous synthesizing diphenylamine of the present invention, by by multiple reactor cascade reactions
Cascade reaction technology, improve syntehsizing diphenylamine reaction conversion ratio be 16～32%, two-stage tandem for reactant and raw material
The heat exchanger carrying out, improves heat exchange efficiency, and by heat integration, energy saving, simultaneously so that unreacted aniline leads to
Later the piece-rate system in face, the aniline of recovery is back to the aniline head tank reuse of reaction system.
(2) reaction method of the utilization aniline continuous synthesizing diphenylamine of the present invention, solves routine in reactor one
When starting not having material, need to enter line replacement with nitrogen, so that reaction system is in the problem of anaerobic state, during the course of the reaction
Do not need to add nitrogen, more do not need hydrogen.
(3) in main reaction of the present invention, aniline conversion and the specific material of selection in production method of the present invention enter successively
Sequentially, the change of these conditions of temperature, pressure, catalyst use time etc. is closely related, remaining 65～85% benzene in reactant liquor
Amine does not react, and returns aniline head tank and reuse, than the utilization of conventional aniline raw material after separating with subsequent separation system
Rate is high by 5～8%.
(4) side reaction that the present invention produces can generate 2- picoline, 4- MEA, acridine, indoles, 4-(1- methyl
Ethyl-n- phenyl) aniline, side reaction product total amount only accounts for the 0.5～1% of product diphenylamines amount.
Specific embodiment
With reference to specific embodiment, technical scheme is elaborated.
Embodiment 1
A kind of reaction process of reaction method using aniline continuous synthesizing diphenylamine of the present invention specifically comprises the following steps that
(1) from aniline material storaging tank, by raw material pump pump to aniline head tank, enter measuring tank, measuring pump again with
The charging rate of 3500kg/h, the reactant that is used for that raw material is pumped into two-stage tandem is carried out in the heat exchanger of heat exchange with raw material, will
Feeding temperature heat exchange is to 260 DEG C；
(2) raw material after heat exchange is entered heater and carry out raw material heat temperature raising, the feeding temperature of raw material is risen to 295
DEG C, heating mode is set to gradient increased temperature, and heating rate is 0.106 DEG C/day；(with the passage of catalyst use time, reaction temperature
From 295 DEG C slowly gradual change increase to 330 DEG C).
(3) raw material being warming up to 295 DEG C in step (2) is sequentially entered the reactor a of series connection, relay heater b, reaction
Device b, relays heater c, reactor c, relays heater d, reactor d, and the porous being equipped with four reactors buying is immobilized
Change catalyst, pressure is followed successively by 2.2 mpa, 2.1mpa, 2.0mpa, 1.9mpa from reactor a to d, and relaying heater is in reaction
During give reactor additional heat, maintain reaction temperature, last material out, becomes reaction mass in reactor d；
(4) reaction mass in step (3) is carried out the heat exchange of heat exchange through two-stage tandem for reactant and raw material
In device, carry out reaction mass heat exchange cooling, reaction mass temperature is down to 110 DEG C；
(5) by the reaction mass after step (4) cooling, by the pressure-reducing valve automatically controlling in heat exchanger tube, enter
Ammonia and reaction liquid/gas separator, finally enter subsequent separation system, and the aniline raw material return aniline head tank isolating 65% repeats to make
With.
In the present embodiment, solve conventional in reactor when there is no material at the beginning, need to enter line replacement with nitrogen,
So that reaction system is in the problem of anaerobic state, does not need during the course of the reaction to add nitrogen, more do not need hydrogen.Synthesis
The reaction conversion ratio of diphenylamines is 32%, and remaining aniline raw material is 65%, exceeds 8% than the utilization rate of conventional production process, side reaction
Product total amount only accounts for the 1% of product diphenylamines amount.
Embodiment 2
On the basis of embodiment 1, change each step reaction parameter in reaction method, particularly as follows: feeding temperature changes
Heat to 265 DEG C, feeding temperature rise to 330 DEG C, pressure from reactor a to d be followed successively by 2.1mpa, 2.0mpa, 1.9mpa,
1.8mpa, reaction mass temperature are down to 100 DEG C；After final reaction thing enters subsequent separation system, isolate 75% aniline raw material
Return aniline head tank to reuse.
In the present embodiment, the reaction conversion ratio of syntehsizing diphenylamine is 26%, and remaining aniline raw material is 75%, than conventional producer
The utilization rate of method exceeds 6%, and side reaction product total amount only accounts for the 0.8% of product diphenylamines amount.
Embodiment 3
On the basis of embodiment 1 or 2, change each step reaction parameter in reaction method, particularly as follows: feeding temperature changes
Heat to 263 DEG C, feeding temperature rise to 300 DEG C, pressure from reactor a to d be followed successively by 2.2 mpa, 2.0mpa, 1.9mpa,
1.8mpa, reaction mass temperature are down to 110 DEG C；After final reaction thing enters subsequent separation system, isolate 85% aniline raw material
Return aniline head tank to reuse.
In the present embodiment, the reaction conversion ratio of syntehsizing diphenylamine is 18%, and remaining aniline raw material is 85%, than conventional producer
The utilization rate of method exceeds 5%, and side reaction product total amount only accounts for the 0.5% of product diphenylamines amount.
General principle and principal character and the advantages of the present invention of the present invention have been shown and described above.The technology of the industry
, it should be appreciated that the present invention is not restricted to the described embodiments, the simply explanation described in above-described embodiment and specification is originally for personnel
The principle of invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these changes
Change and improvement both falls within scope of the claimed invention.Claimed scope by appending claims and its
Equivalent thereof.
Claims (2)
1. a kind of reaction method of utilization aniline continuous synthesizing diphenylamine it is characterised in that: the concrete steps of described reaction process
As follows:
(1) from aniline material storaging tank, by raw material pump pump to aniline head tank, enter measuring tank, measuring pump is again with 3500kg/
The charging rate of h, the reactant that is used for that raw material is pumped into two-stage tandem carries out in the heat exchanger of heat exchange with raw material, by feeding temperature
Heat exchange is to 260～265 DEG C；
(2) raw material after heat exchange is entered heater and carry out raw material heat temperature raising, the feeding temperature of raw material is risen to 295～330
DEG C, heating mode is set to gradient increased temperature, and heating rate is 0.106 DEG C/day；
(3) raw material being warming up to 295～330 DEG C in step (2) is sequentially entered the reactor a of series connection, relay heater b, instead
Answer device b, relay heater c, reactor c, relay heater d, reactor d, the pressure of setting reactor a to d is all in 2.2 mpa
Between～1.8mpa, and the order according to reactor a to d, pressure value reduces successively, becomes anti-finally d in reactor out
Answer material；
(4) reaction mass in step (3) is carried out in the heat exchanger of heat exchange through two-stage tandem for reactant and raw material,
Carry out reaction mass heat exchange cooling, reaction mass temperature is down to less than 110 DEG C；
(5) by the reaction mass after step (4) cooling, by the pressure-reducing valve automatically controlling in heat exchanger tube, enter ammonia and
Reaction liquid/gas separator, finally enters subsequent separation system, isolates aniline raw material and returns the reuse of aniline head tank；
It is fitted with commercially available porous solid-supported catalyst in four reactors in described step (3).
2. utilization aniline continuous synthesizing diphenylamine according to claim 1 reaction method it is characterised in that: described step
(3) in whole course of reaction, relaying heater is continuously replenished heat to reactor, maintains reactor reaction temperature-resistant.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105384683B (en) * | 2015-12-17 | 2018-04-10 | 南通新邦化工科技有限公司 | A kind of 2 picoline, the production method of 4 picolines |
| CN107935862A (en) * | 2017-11-27 | 2018-04-20 | 南通新邦化工科技有限公司 | A kind of method of aniline continuous synthesizing diphenylamine |
| CN114805086A (en) * | 2022-05-16 | 2022-07-29 | 杰超橡塑南通有限公司 | Process and system for producing diphenylamine by adopting aniline continuous condensation method |
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|---|---|---|---|---|
| JPS6051152A (en) * | 1983-08-31 | 1985-03-22 | Mitsui Petrochem Ind Ltd | Production of diphenylamine compound |
| EP0560157A1 (en) * | 1992-03-12 | 1993-09-15 | Bayer Ag | Fixed bed reactors with short catalyst bed in the direction of flow |
| US5648538A (en) * | 1994-06-29 | 1997-07-15 | Fushun Research Institute Of Petroleum And Petrochemicals | Process for preparing diarylamines from arylamines |
| CN2692150Y (en) * | 2004-04-08 | 2005-04-13 | 曹宏生 | Diphenyl amine production device |
| CN2892853Y (en) * | 2006-02-13 | 2007-04-25 | 南通新邦化工有限公司 | Apparatus for whole continuous producing diphenylamine from aniline |
-
2014
- 2014-11-19 CN CN201410661655.3A patent/CN104478738B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6051152A (en) * | 1983-08-31 | 1985-03-22 | Mitsui Petrochem Ind Ltd | Production of diphenylamine compound |
| EP0560157A1 (en) * | 1992-03-12 | 1993-09-15 | Bayer Ag | Fixed bed reactors with short catalyst bed in the direction of flow |
| US5648538A (en) * | 1994-06-29 | 1997-07-15 | Fushun Research Institute Of Petroleum And Petrochemicals | Process for preparing diarylamines from arylamines |
| CN2692150Y (en) * | 2004-04-08 | 2005-04-13 | 曹宏生 | Diphenyl amine production device |
| CN2892853Y (en) * | 2006-02-13 | 2007-04-25 | 南通新邦化工有限公司 | Apparatus for whole continuous producing diphenylamine from aniline |
Non-Patent Citations (2)
| Title |
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| 二苯胺的合成工艺及应用进展;宋丽芝等;《辽宁化工》;20021130(第10期);第439-441页 * |
| 二苯胺连续合成工艺的改进;周松涛;《小氮肥》;20021115(第11期);第13-15页 * |
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