CN105348113B - N-(1-ethyl propyl)-3,4-dimethylaniline continuous production device and method - Google Patents
N-(1-ethyl propyl)-3,4-dimethylaniline continuous production device and method Download PDFInfo
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- CN105348113B CN105348113B CN201510939077.XA CN201510939077A CN105348113B CN 105348113 B CN105348113 B CN 105348113B CN 201510939077 A CN201510939077 A CN 201510939077A CN 105348113 B CN105348113 B CN 105348113B
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- HFZKOYWDLDYELC-UHFFFAOYSA-N Cc(cc1)c(C)cc1[N+]([O-])=O Chemical compound Cc(cc1)c(C)cc1[N+]([O-])=O HFZKOYWDLDYELC-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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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
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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Abstract
The invention discloses an N-(1-ethyl propyl)-3,4-dimethylaniline continuous production device and method. The method is characterized in that o-xylene and nitric-sulfuric acid carry out nitration reaction in a nitration system; a reaction liquid passes through a first split phase tank, a labyrinth washing system and a distillation system in sequence to undergo distillation treatment; collected 4-nitro-o-xylene and 3-pentanone carry out catalytic hydrogenation reaction in a hydrogenation reactor; then N-(1-ethyl propyl)-3,4-dimethylaniline is prepared through treatment carried out by a falling film evaporation system. The production device provided by the invention has the beneficial effects that all the materials are recycled, thus reducing the production cost; the raw material conversion rate of single batch production is effectively increased, thus reducing the amount of waste acid and wastewater.
Description
Technical field
The present invention relates to technical field of organic synthesis, and in particular to a kind of N- (1- ethyl propyls) -3,4- dimethylanilines
Continuous production device and method.
Background technology
N- (1- ethyl propyls) -3,4- dimethylanilines, molecular formula:C13H21N molecules:191.3125,290.2 DEG C of boiling point,
CAS:56038-89-2, structural formula is formula 1：It is efficient, low toxicity, the main intermediate of broad-spectrum herbicide Pendimethalin.
The method of existing synthesis N- (1- ethyl propyls) -3,4- dimethylanilines is more, and e.g., such as EP630883 discloses one
Plant synthetic method：3,4- dimethyl nitrobenzenes elder generation Jing iron powder reducings are obtained 3,4- dimethylanilines, then with propione in acid catalysiss
Lower condensation is simultaneously dehydrated and obtains imines, imines hydrogenated reduction under rare metal catalyst action obtain N- (1- ethyl propyls)-
3,4- dimethylanilines：Synthetic line square formula 1.The reaction scheme is long, and total recovery is low, with iron powder reducing 3,4- dimethyl nitre
Base benzene can also produce a large amount of waste water and poisonous iron cement, be not suitable for amplifying production.
It is industrial mainly to adopt 3,4- dimethyl nitrobenzenes and propione that hydro-reduction reaction directly occurs under catalyst,
Chinese patent literature such as Publication No. CN101302168A discloses one kind has o-Dimethylbenzene to prepare N- (1- ethyl propyls) -3,
, there is digestion reaction, digestion reaction product propione, catalysis under the present nitric-sulfuric acid of o-Dimethylbenzene in the method for 4- dimethylanilines
Purpose product is obtained in the presence of agent, to recycle, production process produces substantial amounts of waste to the material of the method.
The Chinese patent of Publication No. CN104250215A also discloses that the synthetic method of above-mentioned same routes, and to hydrogenation
Catalyst has been carried out preferably.
The utilization of materials of existing method is not high, is also easy to produce a large amount of wastewater and waste acids.
The content of the invention
The invention provides a kind of continuous production device of N- (1- ethyl propyls) -3,4- dimethylaniline production processes
And method, the recycled of various materials is realized, production cost is not only reduced, improve the transformation efficiency of single batch of raw material.
A kind of continuous production device of N- (1- ethyl propyls) -3,4- dimethylanilines, including nitrification, washing system
System, distillation system, hydrogenation reactor and falling film evaporation system；Nitrification by the horizontal Crossed Circle nitrator of multiple stage it is stacked and
Into washing system is in series by multistage labyrinth sink；Distillation system is in series by Multistage rectifying tower；Falling film evaporation system
For the falling film evaporator of plural serial stage；Also include the first split-phase groove being connected between nitrification and washing system；It is connected on
The second split-phase groove between washing system and distillation system；
The outlet of afterbody Crossed Circle nitrator is connected with the first split-phase groove entrance, and the oil phase of the first split-phase groove goes out
Mouthful be connected with the entrance of the first order labyrinth sink of washing system, the outlet of the afterbody labyrinth sink of washing system and
Second split-phase groove entrance connects, and the oil phase outlet of the second split-phase groove is connected with the entrance of the first order rectifying column of distillation system, essence
The outlet for evaporating the afterbody rectifying column of system is connected with 4- nitro o-Dimethylbenzene reservoir inlets；
4- nitro o-Dimethylbenzene outlets are connected with hydrogenation reactor material inlet, outlet and the filtration of hydrogenation reactor
Device is connected, and the outlet of filter is connected with the 3rd split-phase groove entrance, the oil phase of the 3rd split-phase groove into falling film evaporation system the
Stage falling-film evaporators, outlet and N- (1- ethyl propyls) -3, the 4- dimethylanilines storage tank of afterbody falling film evaporator connect
Connect.
Preferably, the water of the first split-phase groove mutually exports and be dried the connection of concentrator entrance, going out for concentrator is dried
Mouth is connected with nitric-sulfuric acid head tank entrance；The water of the second split-phase groove is mutually exported and is connected with MVR concentration systems, MVR concentration systems
Condensed fluid accessed in the sink of labyrinth by pipeline, used as slurry reuse, the concentrated solution of MVR concentration systems passes through pipeline
Access nitric-sulfuric acid head tank；The o-Dimethylbenzene fraction that distillation system is collected is accessed in o-Dimethylbenzene head tank by pipeline and circulated
Apply mechanically.
It is further preferred that the condensed fluid of MVR concentration systems first passes through to be dried after concentrator dried to return again to nitre sulfur mix
Sour head tank circulating and recovering.
Further preferably, it is adjacent that the 4- nitro o-Dimethylbenzene fractions that falling film evaporation system is collected are back to 4- nitros by pipeline
Dimethylbenzene storage tank, and be transferred to again in hydrogenation reactor, recycled.
Each material of the process units that the present invention is provided realizes circulating and recovering, reduces production cost, and effectively improves single batch
The feed stock conversion of production, reduces spent acid wastewater flow rate.Hydrogenation liquid continuous treatment in multi-stage falling film evaporation system, compares
It is higher in the production efficiency of existing cooking-pot type interval evaporation mode, the product of N- (1- ethyl propyls) -3, the 4- dimethylanilines of collection
Thing purity is higher.
In nitrification, every Crossed Circle nitrator includes：
Main channel, the top surface of its one end carries charging aperture, and the bottom surface of the other end carries discharging opening；
Two returning charge subchannels, positioned at main channel both sides external and are connected in parallel between the two ends of main channel；
Pusher stirring paddle, along main channel length direction arrangement, direction of propulsion is discharging opening to charging aperture；
The main channel arranged direction of adjacent two Crossed Circle nitrators is conversely, i.e. the discharging opening of top one is just under
The charging aperture of Fang Yitai.
, compared to existing vertical tubular type nitrator, material diversion is more for the Crossed Circle nitrator that the present invention is provided
Uniformly, the reflux of reactant liquor can be prevented effectively from, increases o-Dimethylbenzene with the touch opportunity of nitric-sulfuric acid, the conversion of raising raw material
Rate；And heat exchange area is more abundant, can effectively reduce side reaction.
Preferably, described Crossed Circle nitrator is in 8-shaped.
Preferably, the Crossed Circle nitrator is the round and smooth cavity body structure of 8-shaped, mixing is so effectively reduced
Material reflux phenomenon in reactor, contributes to cycle operation of the material in reactor, while alleviating the cleaning of reactor
Difficulty.
Preferably, the inwall of each Crossed Circle nitrator is made using acid resisting material, and further preferably, each Crossed Circle
The inwall of nitrator has rough surface.
Reactor wall is arranged to into rough surface, the noise of nitration reaction process on the one hand can be reduced, on the other hand may be used
To improve the touch opportunity of nitric-sulfuric acid and o-Dimethylbenzene, the interfacial tension of oil phase and acid phase in mixed material is reduced, further
Reaction-ure conversion-age is improved, the yield of product is improved.
Preferably, the main channel of the Crossed Circle nitrator is circular cylindrical cavity, so help to improving propulsion
The stirring propulsive efficiency of formula stirring paddle, is fully contacted mixed material, improves the conversion ratio of reactant, while reducing side reaction.
Preferably, two returning charge subchannels and main channel are in same plane in every Crossed Circle nitrator, and
Heat exchanger is installed between two returning charge subchannels and main channel.
Returning charge subchannel and main channel are in same plane, are conducive to each Crossed Circle nitrator stacked combination, improve
Nitration reaction efficiency.Two heat exchangers can be set in each reactor, heat transfer effect can be improved, be conducive to nitration reaction to
Forward direction is mobile.
Further preferably, each Crossed Circle nitrator aligns up and down arrangement, and heat exchanger is anti-through all Crossed Circles nitrification
Answer device.
Preferably, in nitrification, the pusher stirring paddle of each Crossed Circle nitrator passes through link gear synchronization
Motion.
Nitration reaction liquid enters layering in the first split-phase groove, and upper strata carries out labyrinth washing into washing system；Described washes
The labyrinth sink that the system of washing has plural serial stage is in series.
Preferably, described washing system is in series by 1-3 levels labyrinth sink.
Further preferably, described washing system is by first order labyrinth sink and the series connection of second level labyrinth sink
Into first order labyrinth sink is provided with material inlet, the outlet of first order labyrinth sink and entering for second level labyrinth sink
Mouth connection, the outlet of second level labyrinth sink is connected with the entrance of the second split-phase groove.
The upper oil phase of the first split-phase groove is entered by the material inlet of first order labyrinth sink, through secondary maze washing
Afterwards, abundant and washing system the water contact of the acid of the upper strata residual of the first split-phase groove, cleaning mixture is entered in the lump in the second split-phase groove
Split-phase.The upper strata of the second split-phase groove is product or the hydrophobicity material for reaction；Lower floor is sour water.
The sour water of the second split-phase groove lower floor is concentrated into MVR systems, and the condensed fluid of collection is water, and recycled is to washing
System is used as slurry；The concentrated solution of MVR systems is mainly acid, after dried, in being recycled to nitric-sulfuric acid head tank,
Recycled.
The upper strata for separating of the second split-phase groove is transferred to distillation system separation.
Preferably, described distillation system is in series for 3-6 level rectifying columns.
Further preferably, described distillation system is connected in series for first rectifying column, Second distillation column and third distillation column,
The outlet of the entrance of first rectifying column and the second split-phase groove upper strata be connected, the outlet of first rectifying column and the entrance of Second distillation column；
The outlet of Second distillation column and the entrance of third distillation column；The outlet of third distillation column is connected with each component storage tank.
The distillation system of Multistage rectifying tower series connection can improve the separating effect of each component, there is provided the component isolated it is pure
Degree.
The outlet of 4- nitro o-Dimethylbenzene storage tanks is connected with the material inlet of hydrogenation reactor, between connecting line on according to
Secondary series connection dosing pump and surge tank.Hydrogenation reactor top is additionally provided with propione entrance, auxiliary agent entrance and gas access.Hydrogenation is anti-
The outlet at bottom of device is answered to be connected with the entrance of filter, the filtrate (liquid of filter is connected with the entrance of the 3rd split-phase groove, the 3rd
The bottom aqueous phase outlet of split-phase groove is entered and accesses MVR concentration systems；The oil phase outlet on the top of the 3rd split-phase groove and falling film evaporation
The entrance connection of the first order falling film evaporator of system, the outlet of the afterbody falling film evaporator of falling film evaporation system and N-
(1- ethyl propyls) -3,4- dimethylanilines storage tank connects, and period also isolates more other components, wherein 4- nitros neighbour diformazan
Benzene accesses 4- nitro o-Dimethylbenzene storage tanks by pipeline, is recycled to response system recovery.
Preferably, in the continuous production device of the present invention, the Crossed Circle nitration reaction that nitrification is connected by level Four
Device is stacked to be formed, and washing system is in series by secondary maze sink, and distillation system is in series by level Four rectifying column, rectification
The o-Dimethylbenzene fraction of systematic collection and raw material mixing recovery.Further preferably, described falling film evaporation system is by two-stage
Falling film evaporator is in series.
3rd split-phase groove oil phase outlet be connected with the entrance of the first falling film evaporator, the outlet of the first falling film evaporator and
The entrance connection of the second falling film evaporator, outlet and N- (1- ethyl propyls) -3, the 4- dimethylanilines of the second falling film evaporator
Storage tank connects.
Present invention also offers synthesizing N- (1- ethyl propyls) -3,4- dimethylanilines using above-mentioned continuous production device
Method, i.e. 4- nitros o-Dimethylbenzene and propione carry out catalytic hydrogenation, then Jing falling film evaporations system in hydrogenation reactor
Controlling obtains N- (1- ethyl propyls) -3,4- dimethylanilines；Catalyst is one or more of Pt-Pd/C, Pd/C and Raney's nickel；
4- nitros o-Dimethylbenzene is 1 with the raw materials components mole ratio of propione:1.1-3；Hydrogen pressure is 0.5-1MPa, and reaction temperature is 65-80
℃。
Hydrogen preferential and nitroso reaction under the catalyst, generates aromatic amine, and aromatic amine is easy to the carbonyl with propione
Base reaction production group with imine moiety, group with imine moiety carries out again hydrogenation reaction, purpose product, synthetic line square formula 2 is obtained.
With propione raw material from as solvent, one kettle way is obtained product N- (1- ethyl propyls) -3,4- dimethylanilines to the present invention.Reduce
Operating procedure and corresponding refining step, reduce waste gas discharge, improve production efficiency.
In catalytic hydrogenation, general 4- nitros o-Dimethylbenzene and imines thing GC terminates reaction less than 1%.Further
It is preferred that, the time of catalytic hydrogenation is 0.5-3h, namely reactant mixture material time of staying in hydrogenation reactor is 0.5-
3h。
Preferably, the mole that adds of catalyst is 0.01-0.15 times of 4- nitro o-Dimethylbenzene moles.
Preferably, catalytic hydrogenation is carried out in acid condition, the mol ratio that adds of the acid is 4- nitros neighbour two
0.1-0.5 times of toluene.
Preferably, catalytic hydrogenation is carried out under conditions of pH is 5.5-7.
Further preferably, C is added in catalytic hydrogenation system2-12Carboxylic acid or sulfonic acid, and control pH for 6-7.
The preferred acetic acid of described carboxylic acid, propanoic acid, valeric acid, caproic acid, one or more of adipic acid；The preferred benzene of described sulfonic acid
Sulfonic acid, dodecyl sodium sulfonate, one or more of p-methyl benzenesulfonic acid.
This method also being continuously synthesizing to including 4- nitro o-Dimethylbenzenes：Nitre is pressed into after o-Dimethylbenzene and nitric-sulfuric acid mixing
Nitration reaction is carried out in change system, reactant liquor enters layering in the first split-phase groove, and upper oil phase carries out labyrinth into washing system
Washing；Cleaning mixture is layered in the second split-phase groove, and its upper strata carries out rectification process into distillation system, and it is adjacent that collection obtains 4- nitros
Dimethylbenzene.
Preferably, in nitration reaction, described nitric-sulfuric acid is the mixed solution of nitric acid and sulphuric acid, wherein, nitric acid and
The mol ratio of sulphuric acid is 1:0.1-1；With the molar amount of nitric acid in nitric-sulfuric acid, o-Dimethylbenzene is with the mol ratio of nitric-sulfuric acid
1:1.05-5；Nitration reaction temperature in each ring nitration reactor is 10-25 DEG C；O-Dimethylbenzene and nitric-sulfuric acid mixed material
Feed flow rate be 1.5-10m/s.
In the present invention, o-Dimethylbenzene is put in blender respectively with nitric-sulfuric acid by respective head tank, by nitrogen after mixing
Gas or other noble gases are pressed in horizontal Crossed Circle nitrator, under the promotion of the pusher stirring paddle, are mixed into
Material formation is backflowed, and in main channel and returning charge subchannel cycle operation, is fully contacted and occurs digestion reaction.Part mixes material exists
Flow through to during discharging opening and continue reaction into next stage Crossed Circle nitrator under the dual function of gravity and feed pressure,
Enter in the first split-phase groove after multistage nitration reaction and be layered.
The organic faciess of the first split-phase groove contain more product and raw material, and lower floor is sour phase, and acid is back to after drying
Circulating and recovering in nitric-sulfuric acid head tank.The organic faciess on upper strata through washing system, the split-phase in the second split-phase groove, second point
The sour water of Xiang Cao lower floors is recycled to washing system and recycles through concentration, condensed fluid (predominantly water), concentrated solution Jing
Cross after being dried and be back to circulating and recovering in nitric-sulfuric acid head tank.
The upper strata of the second split-phase groove enters distillation system, collects 4- nitro o-Dimethylbenzenes, o-Dimethylbenzene, 3- nitros neighbour's diformazan
Benzene and light phase component, wherein o-Dimethylbenzene are back to recycled in o-Dimethylbenzene head tank.
4- nitro o-Dimethylbenzenes are transferred in hydrogenation reactor by dosing pump, while the propione of stoichiometry is turned
Hydrogenation reactor is moved to, N is carried out to reactor2/H2Gas disposal is substituted, described temperature is then heated to, catalytic hydrogenation is carried out anti-
Should, reactant liquor is filtered, recovery catalyst；Filter liquor pump is layered into the 3rd split-phase groove, upper strata it is organic
Layer is entered in falling film evaporation system, collects product N- (1- ethyl propyls) -3,4- dimethylanilines, the unreacted raw material of collection
Apply mechanically as 4- nitros o-Dimethylbenzene and propione import hydrogenation reactor interior circulation by pipeline.
The 4- nitro o-Dimethylbenzenes chromatographic purity collected through multistage rectification is more than 99.5%, collects in storage tank.4- nitre
Base o-Dimethylbenzene storage tank is continuously squeezed in hydrogenation reactor with the material of propione storage tank by dosing pump, and adds catalyst；
N2/H2Displacement is multiple.Hydrogenation reactor carries out catalytic hydrogenation, and reactant liquor is flowed into by the outlet at bottom of hydrogenation reactor and filtered
In device, the filtrate of filtration contains the more water of catalytic hydrogenation production, filtrate split-phase in the 3rd split-phase groove again, the 3rd split-phase groove
Bottom aqueous phase outlet enter access MVR concentration systems, recovery catalytic hydrogenation synthesis water.The top of the 3rd split-phase groove
Oil phase enters the continuous evaporation of the falling film evaporation system of two-stage tandem and collects the storage of N- (1- ethyl propyls) -3,4- dimethylanilines
Tank, period also isolates more other components, and wherein 4- nitros o-Dimethylbenzene accesses 4- nitro o-Dimethylbenzene storage tanks by pipeline,
It is recycled to response system recovery.
The invention has the advantages that：
1st, the Crossed Circle nitrator for providing can ensure that sour phase is fully contacted with organic faciess, timely and effective exclusion heat,
Stirring is good, it is easy to control, and production capacity is big, and many nitro compounds of by-product and nitrophenols are reduced；
2nd, washed using labyrinth mode of washing, multistage counter flow washing ensure that oil phase (the first split-phase groove upper strata) and water
Phase (slurry) is fully contacted, and the effect being completely separated can be reached during layering, reduces time of repose and volume of equipment, carries
High layered effect, realizes washing serialization, and unit waste water yield is reduced；And recovery is carried out to waste water, further
Reduce wastewater flow rate.
3rd, using continuous rectification mode, improve product quality；And reaction raw materials are recycled, reduce production
Cost, while reducing amount of waste.
4th, continuous treatment is carried out to product using multi-stage falling film evaporation system, compared to existing cooking-pot type interval evaporation mode
Production efficiency it is higher, the product purity of collection is higher.
Description of the drawings
The top view of the Crossed Circle nitrator that Fig. 1 is provided for the present invention；
The continuous production device of N- (1- the ethyl propyls) -3,4- dimethylanilines that Fig. 2 is provided for the present invention.
Specific embodiment
Following examples press the enforcement of aforesaid operations method：
As shown in Figure 1 and Figure 2, the continuous production device of N- (1- ethyl propyls) -3,4- dimethylanilines, including by four
The stacked nitrification of the horizontal Crossed Circle nitrator 1 of platform, the washing system being in series by secondary maze sink
With the distillation system being in series by level Four rectifying column；Hydrogenation reactor 26 and falling film evaporation system；Two grades of falling film evaporator strings
The falling film evaporation system of connection；Also include the first split-phase groove 10 being connected between nitrification and washing system；It is connected on washing
The second split-phase groove 13 between system and distillation system.
The cross section of Crossed Circle nitrator 1 is in 8-shaped.Crossed Circle nitrator 1 is tied for the round and smooth cavity of 8-shaped
Structure.
Every Crossed Circle nitrator 1 includes main channel 3, returning charge subchannel 4, pusher stirring paddle 5：
Main channel 3, is circular cylindrical cavity, and the top surface of its one end carries charging aperture 2, and the bottom surface of the other end carries discharging opening 6；
Two returning charge subchannel 4 is located at the both sides external of main channel 3 and is connected in parallel between the two ends of main channel 3.Each Crossed Circle nitration reaction
The inwall (main channel 3 and returning charge subchannel 4) of device 1 is made using acid resisting material, and inwall has rough surface.
Two returning charge subchannels 4 and main channel 3 are in same plane in every Crossed Circle nitrator 1, and two are returned
Heat exchanger is installed between material for making clothes passage 4 and main channel 3.In nitrification, each Crossed Circle nitrator is stacked about 1 in multiple stage
Arrangement is aligned, and heat exchanger runs through all Crossed Circle nitrators 1.
Pusher stirring paddle 5, along the length direction of main channel 3 arrangement, direction of propulsion is discharging opening 6 to charging aperture 2；
The arranged direction of main channel 3 of adjacent two Crossed Circle nitrators 1 is conversely, i.e. the discharging opening 6 of top one is being just
To the lower section charging aperture 2 of；
The outlet of afterbody Crossed Circle nitrator 1 (fourth stage Crossed Circle nitrator) and the first split-phase groove 10
Entrance connects, and the water of the first split-phase groove 10 mutually exports and be dried the connection of the entrance of concentrator 24, is dried the outlet of concentrator 24
It is connected with the entrance of nitric-sulfuric acid head tank 7；The oil phase outlet of the first split-phase groove 10 and the first order labyrinth sink of washing system
11 entrance connection.
The outlet of the afterbody labyrinth sink (second level labyrinth sink 12) of washing system and the second split-phase groove 13
Entrance connects, and the water of the second split-phase groove 13 is mutually exported and is connected with MVR concentration systems 23, and the condensed fluid of MVR concentration systems 23 passes through
Pipeline imports labyrinth sink as slurry reuse, and the concentrated solution of MVR concentration systems 23 is accessed by pipeline and is dried concentration
Equipment 24, after being dried the recycled of nitric-sulfuric acid head tank 7 is back in the lump；The oil phase of the second split-phase groove 13 enters distillation system
Carry out multistage rectification process.
Distillation system is that the series connection of first rectifying column 14, Second distillation column 15, third distillation column 16 and the 4th rectifying column 17 connects
Connect, the outlet of the entrance of first rectifying column 14 and the upper strata of the second split-phase groove 13 be connected, the outlet of first rectifying column 14 and the second rectification
The entrance of tower 15；The outlet of Second distillation column 15 and the entrance of third distillation column 16；The outlet of third distillation column 16 is smart with the 4th
The entrance connection of tower 17 is evaporated, the outlet of the 4th rectifying column 17 is connected (o-Dimethylbenzene storage tank 21,4- nitros neighbour two with each component storage tank
Toluene tank 18,3- nitro o-Dimethylbenzenes storage tank 19, light phase storage tank 20).Rectifier bottoms outlets at different levels and organic waste materials storage tank
22 connections.The o-Dimethylbenzene fraction that distillation system is collected accesses recycled in o-Dimethylbenzene head tank 8 by pipeline.
4- nitro o-Dimethylbenzenes storage tank 18 is exported and propione storage tank 25 is connected respectively with the material inlet of hydrogenation reactor 26,
Hydrogenation reactor 26 is additionally provided with hydrogen inlet, and hydrogen pipeline is provided with many breather valve, and nitrogen pipeline is connected with many breather valve.The hydrogen
The outlet for changing reactor 26 is connected with filter 27, and the outlet of filter 27 is connected with the entrance of the 3rd split-phase groove 28.3rd split-phase
The bottom aqueous phase outlet of groove 28 is connected with MVR concentration systems 23.The oil phase of the 3rd split-phase groove 28 enters falling film evaporation system.Falling liquid film
Vapo(u)rization system is in series by the first falling film evaporator 29 and the second falling film evaporator 30, the entrance of the first falling film evaporator 29 with
The oil phase outlet connection of the 3rd split-phase groove 28, the outlet of the first falling film evaporator 29 connects with the entrance of the second falling film evaporator 30
Connect；The outlet of the second falling film evaporator 30 is connected with the storage tank of N- (1- ethyl propyls) -3,4- dimethylanilines storage tank 31.Wherein
The outlet of two falling film evaporators 30 is also connected with 4- nitro o-Dimethylbenzenes storage tank 18, and multiple-way valve fraction is adopted in actual production process
Flow direction.The height boiling waste material of falling film evaporator bottoms at different levels accesses organic waste materials storage tank 22 by pipeline.
O-Dimethylbenzene is put in blender 9 respectively with nitric-sulfuric acid by respective head tank, sleeping by nitrogen press-in after mixing
In formula Crossed Circle nitrator 1, under the promotion of pusher stirring paddle 5, mixed feeding is formed and backflowed, and main channel 3 and is being returned
The cycle operation of material for making clothes passage 4, is fully contacted and occurs digestion reaction.Part mixes material is when flowing through to discharging opening 6 in gravity
And the continuation reaction of next stage Crossed Circle nitrator 1 is entered under the dual function of feed pressure, after multistage nitration reaction
The layering in the first split-phase groove 10.The organic faciess of the first split-phase groove 10 contain more product and raw material, and lower floor is sour phase, sour phase
Circulating and recovering in nitric-sulfuric acid head tank 7 is back to after being dried concentrator 24 and being dried.The organic faciess on upper strata are through washing
System, the split-phase in the second split-phase groove 13, through concentration, condensate circulation is extremely for the sour water of the lower floor of the second split-phase groove 13
Washing system is recycled, and concentrated solution is back to circulating and recovering in nitric-sulfuric acid head tank 7.The upper strata of the second split-phase groove 13 enters
Distillation system, through level Four rectification process, collects 4- nitro o-Dimethylbenzenes, o-Dimethylbenzene and 3- nitro o-Dimethylbenzenes, wherein adjacent
Dimethylbenzene is back to recycled in o-Dimethylbenzene head tank 8.
4- nitro o-Dimethylbenzenes storage tank 18 with the material of propione storage tank 25 continuously squeezes into hydrogenation by dosing pump
In device 26, and add catalyst；N2/H2Displacement is multiple.Hydrogenation reactor 26 carries out catalytic hydrogenation, and reactant liquor is anti-by hydrogenating
Answer in the outlet at bottom inflow filter 27 of device 26, the filtrate of filtration contains the more water of catalytic hydrogenation production, and filtrate is again
Split-phase in 3rd split-phase groove 28, the bottom aqueous phase outlet of the 3rd split-phase groove 28 is entered and accesses MVR concentration systems 23, and recovery is urged
Change the water of hydrogenation synthesis.The oil phase on the top of the 3rd split-phase groove 28 enters the continuous evaporation of the falling film evaporation system of two-stage tandem and receives
Collection N- (1- ethyl propyls) -3,4- dimethylanilines storage tank 31, period also isolates more other components, wherein 4- nitros neighbour two
Toluene accesses 4- nitro o-Dimethylbenzenes storage tank 18 by pipeline, is recycled to response system recovery.
Embodiment 1：
O-Dimethylbenzene and nitric-sulfuric acid are put in blender by dosing pump by respective head tank, wherein, nitric-sulfuric acid
In, the mol ratio of nitric acid and sulphuric acid is 1:0.5-1；With the molar amount of nitric acid in nitric-sulfuric acid, o-Dimethylbenzene and nitric-sulfuric acid
Mol ratio be 1:1.5-2.After o-Dimethylbenzene and nitric-sulfuric acid mix in blender, Crossed Circle nitration reaction is pressed into by nitrogen
The feed flow rate of device, o-Dimethylbenzene and nitric-sulfuric acid mixed material is 1.5-2m/s.It is organic in mixed material press-in nitrification
Mutually mutually being fully contacted with acid carries out multistage nitration reaction.Controlling the temperature in ring nitration reactors at different levels by heat exchanger is
10-25℃。
Reactant liquor flows out nitrification and enters layering in the first split-phase groove, and the acid solution of the first split-phase Cao Nei lower floor is through drying
Nitric-sulfuric acid head tank is back to after equipment process to recycle；The oil phase on upper strata carries out secondary maze and washes into washing system
Wash.Cleaning mixture is layered in the second split-phase groove, and lower floor's sour water layer of the second split-phase groove enters MVR systems, and the condensed fluid of collection is returned
Washing system is back to, concentrated solution is back to nitric-sulfuric acid head tank.The upper strata of the second split-phase groove carries out level Four into distillation system
Rectification process, collection obtains 4- nitro o-Dimethylbenzenes.The o-Dimethylbenzene of collection is back to o-Dimethylbenzene head tank and recycles.
After continuous prodution terminates, the conversion ratio of o-Dimethylbenzene is 93%, and nitration reaction liquid (is nitrification afterbody
The reactant liquor of reactor discharging opening, samples once per 30min) in, the content of 4- nitro o-Dimethylbenzenes is more than 89%, and rectification is collected
4- nitro o-Dimethylbenzenes purity be more than 99.6% (GC area normalization method purity).
With propione pump to hydrogenation reactor, 4- nitros o-Dimethylbenzene rubs 4- nitros o-Dimethylbenzene with the charging of propione
You are than being 1:1.1-1.5, catalyst is Pt-Pd/C, and it is 0.1eqv (with 4- nitro o-Dimethylbenzenes as base that catalyst feeds intake equivalent
It is accurate).Enter line replacement 3～5 times to the air in autoclave respectively with nitrogen, hydrogen.Hydrogen inlet valve is opened, it is slow to open autoclave hydrogen
Gas intake valve, controls into hydrogen speed and pressure (0.2～0.5MPa), and line replacement 3～5 times, displacement are entered to the air in autoclave
Complete rear control pressure is in 0.75MPa or so.65-80 DEG C is warming up to, hydrogen air relief valve is adjusted, pressure≤1.0MPa in kettle is controlled,
Catalytic hydrogenation is carried out, is reacted the later stage, hydrogen usage is slow, sample analysis, as the GC of 4- nitros o-Dimethylbenzene in reactant liquor
(material time of staying in hydrogenation reactor is 1-2h), stopped reaction when content is less than 1%.
Reactant liquor is filtered, and the catalyst of recovery is back to hydrogenation reactor interior circulation and applies mechanically, at filtrate split-phase
Reason, water mutually enters MVR concentration systems；Oil phase enters falling film evaporation system, collects N- (1- ethyl propyls) -3,4- dimethylanilines
Fraction；The 4- nitros o-Dimethylbenzene of collection goes to recycled in respective storage tank by pipeline respectively with propione.
Through determining, the conversion ratio of 4- nitro o-Dimethylbenzenes is 99%, N- (1- ethyl propyls) -3,4- dimethylanilines
It is 99.5% that yield is 98.1%, GC purity.
Embodiment 2
Compare with embodiment 1, difference is, in nitric-sulfuric acid, the mol ratio of nitric acid and sulphuric acid is 1:0.1-0.44；With nitre
The molar amount of nitric acid in sulfur nitration mixture, o-Dimethylbenzene is 1 with the mol ratio of nitric-sulfuric acid:1.1-2；O-Dimethylbenzene and nitric-sulfuric acid
The feed flow rate of mixed material is 1.5-2m/s.It is 10-15 that the temperature in ring nitration reactors at different levels is controlled by heat exchanger
℃。
After continuous prodution terminates, the conversion ratio of o-Dimethylbenzene is 96.5%, nitration reaction liquid (for nitrification last
The reactant liquor of stage reactor discharging opening, samples once per 30min) in, the content of 4- nitro o-Dimethylbenzenes is more than 93%, and rectification is received
The purity of the 4- nitro o-Dimethylbenzenes of collection is more than 99.6% (GC area normalization method purity).
In catalytic hydrogenation, 4- nitros o-Dimethylbenzene is 1 with the raw materials components mole ratio of propione:1.5-2, catalyst is thunder
Buddhist nun's nickel, catalyst feeds intake equivalent for 0.1eqv (on the basis of 4- nitro o-Dimethylbenzenes).Control Hydrogen Vapor Pressure is in 0.6-
0.75MPa.65-80 DEG C is warming up to, material time of staying in hydrogenation reactor is 2-3h.
Through determining, the conversion ratio of 4- nitro o-Dimethylbenzenes is 99%, N- (1- ethyl propyls) -3,4- dimethylanilines
It is 99.5% that yield is 98.1%, GC purity.
Embodiment 3
Compare with embodiment 1, difference is, in catalytic hydrogenation, add in hydrogenation reactor
The dodecyl sodium sulfonate of 0.1-0.2eqv (on the basis of 4- nitro o-Dimethylbenzenes), the pH for controlling reaction system is
Between 5.5-6, the time of staying of the material in hydrogenation reactor is 0.5-1h.After continuous reaction terminates, through determining, 4- nitre
The conversion ratio of base o-Dimethylbenzene is 99.1%, GC purity for the yield of 99.6%, N- (1- ethyl propyls) -3,4- dimethylanilines
For 99.5%.
Claims (9)
1. a kind of continuous production device of N- (1- ethyl propyls) -3,4- dimethylanilines, it is characterised in that including nitrification system
System, washing system, distillation system, hydrogenation reactor and falling film evaporation system；Nitrification is anti-by the horizontal Crossed Circle nitrification of multiple stage
Answer device to be stacked to form, washing system is in series by multistage labyrinth sink；Distillation system is in series by Multistage rectifying tower；Drop
Film vapo(u)rization system is the falling film evaporator of plural serial stage；Also include the first split-phase being connected between nitrification and washing system
Groove；The second split-phase groove being connected between washing system and distillation system；
The outlet of afterbody Crossed Circle nitrator is connected with the first split-phase groove entrance, the outlet of the oil phase of the first split-phase groove with
The entrance connection of the first order labyrinth sink of washing system, the outlet and second of the afterbody labyrinth sink of washing system
Split-phase groove entrance connects, and the oil phase outlet of the second split-phase groove is connected with the entrance of the first order rectifying column of distillation system, rectification system
The outlet of the afterbody rectifying column of system is connected with 4- nitro o-Dimethylbenzene reservoir inlets；
4- nitro o-Dimethylbenzene outlets are connected with hydrogenation reactor material inlet, outlet and the filter phase of hydrogenation reactor
Even, the outlet of filter is connected with the 3rd split-phase groove entrance, and the oil phase of the 3rd split-phase groove enters the first order of falling film evaporation system
Falling film evaporator, outlet and N- (1- ethyl propyls) -3, the 4- dimethylanilines storage tank connection of afterbody falling film evaporator；
Every Crossed Circle nitrator includes：
Main channel, the top surface of its one end carries charging aperture, and the bottom surface of the other end carries discharging opening；
Two returning charge subchannels, positioned at main channel both sides external and are connected in parallel between the two ends of main channel；
Pusher stirring paddle, along main channel length direction arrangement, direction of propulsion is discharging opening to charging aperture；
The main channel arranged direction of adjacent two Crossed Circle nitrators is conversely, i.e. the discharging opening of top one is just to lower section one
The charging aperture of platform；
The cross section of described Crossed Circle nitrator is in 8-shaped.
2. the continuous production device of N- (1- ethyl propyls) -3,4- dimethylanilines as claimed in claim 1, its feature exists
In nitrification is formed by the Crossed Circle nitrator that level Four is connected is stacked, and washing system is connected by secondary maze sink
Form, distillation system is in series by three-level rectifying column；Falling film evaporation system has two-stage falling film evaporator to be in series.
3. the continuous production device of N- (1- ethyl propyls) -3,4- dimethylanilines as claimed in claim 2, its feature exists
In the water of the first split-phase groove mutually exports and be dried the connection of concentrator entrance, and the outlet for being dried concentrator is high with nitric-sulfuric acid
Position groove entrance is connected；The water of the second split-phase groove is mutually exported and is connected with MVR concentration systems, and the condensed fluid of MVR concentration systems is by pipe
Road accesses labyrinth sink as slurry reuse, and the concentrated solution of MVR concentration systems accesses a nitric-sulfuric acid high position by pipeline
Groove；The o-Dimethylbenzene fraction that distillation system is collected accesses recycled in o-Dimethylbenzene head tank by pipeline.
4. using the method for claim 1-3 any one continuous production device, it is characterised in that 4- nitros o-Dimethylbenzene and 3-
Pentanone carries out catalytic hydrogenation in hydrogenation reactor, then Jing falling film evaporation systems are obtained N- (1- ethyl propyls) -3,4- bis-
Monomethylaniline.；Catalyst is one or more of Pt-Pd/C, Pd/C and Raney's nickel；4- nitros o-Dimethylbenzene enters with propione
Material mol ratio is 1:1.1-3；Hydrogen pressure is 0.5-1MPa, and reaction temperature is 65-80 DEG C.
5. using the method described in claim 4, it is characterised in that catalytic hydrogenation is carried out under conditions of pH is 5.5-7.
6. using the method described in claim 5, it is characterised in that the time of catalytic hydrogenation is 0.5-3h.
7. using the method described in claim 6, it is characterised in that add C in catalytic hydrogenation system2-12Carboxylic acid or
Sulfonic acid, and pH is controlled for 6-7.
8. method as claimed in claim 4, it is characterised in that also being continuously synthesizing to including 4- nitro o-Dimethylbenzenes：Adjacent two
Being pressed in nitrification after toluene and nitric-sulfuric acid mixing carries out nitration reaction, and reactant liquor enters layering in the first split-phase groove, on
Layer oil phase carries out labyrinth washing into washing system；Cleaning mixture is layered in the second split-phase groove, and its upper strata is entered into distillation system
Row rectification process, collection obtains 4- nitro o-Dimethylbenzenes.
9. method as claimed in claim 8, it is characterised in that synthetic method as claimed in claim 6, it is characterised in that
In nitration reaction, described nitric-sulfuric acid is the mixed solution of nitric acid and sulphuric acid, wherein, the mol ratio of nitric acid and sulphuric acid is 1:
0.1-1；With the molar amount of nitric acid in nitric-sulfuric acid, o-Dimethylbenzene is 1 with the mol ratio of nitric-sulfuric acid:1.05-5；Each annular
Nitration reaction temperature in nitrator is 10-25 DEG C；The feed flow rate of o-Dimethylbenzene and nitric-sulfuric acid mixed material is
1.5-10m/s。
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| CN1793106A (en) * | 2006-01-17 | 2006-06-28 | 甘肃银光化学工业集团有限公司 | Process for continuous preparing diruitro methylbenzele and apparatus thereof |
| CN1944393A (en) * | 2006-06-05 | 2007-04-11 | 甘肃银光化学工业集团有限公司 | Process for continuously preparing nitro-xylene isomer monomer |
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| GB1442514A (en) * | 1973-06-25 | 1976-07-14 | American Cyanamid Co | N-alkyl-3,4-xylidines and their nitration |
| US4740621A (en) * | 1985-11-01 | 1988-04-26 | First Chemical Corporation | Co-production of an aromatic monoamine and an aromatic diamine directly from benzene or a benzene derivative through controlled nitration |
| CN101302168B (en) * | 2008-05-22 | 2012-11-28 | 青岛瀚生生物科技股份有限公司 | Preparation of N-(1- ethyl propyl)-3,4-methyl toluidine |
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| CN1944393A (en) * | 2006-06-05 | 2007-04-11 | 甘肃银光化学工业集团有限公司 | Process for continuously preparing nitro-xylene isomer monomer |
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