CN105348113A - N-(1-ethyl propyl)-3,4-dimethylaniline continuous production system and method - Google Patents
N-(1-ethyl propyl)-3,4-dimethylaniline continuous production system and method Download PDFInfo
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- 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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- 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 synthesis system 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 system 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, be specifically related to a kind of N-(1-ethyl propyl)-3,4-xylidine continuous production system and method.
Background technology
N-(1-ethyl propyl)-3,4-xylidines, molecular formula: C
13h
21n molecule: 191.3125, boiling point 290.2 DEG C, CAS:56038-89-2, structural formula is formula 1: be efficient, low toxicity, broad-spectrum weedicide pendimethalin main intermediate.
Formula 1
Existing synthesis N-(1-ethyl propyl)-3, the method of 4-xylidine is more, as, as EP630883 discloses a kind of synthetic method: 3,4-dimethyl nitrobenzene first through obtained 3, the 4-xylidine of iron powder reducing, then with propione condensation dewater and obtain imines under acid catalysis, imines obtains N-(1-ethyl propyl)-3,4-xylidines through hydrogenating reduction under rare metal catalyst action: the square formula 1 of synthetic line.This reaction scheme is long, and total recovery is low, also can produce a large amount of waste water and poisonous iron mud with iron powder reducing 3,4-dimethyl nitrobenzene, is not suitable for amplifying producing.
Equation 1
Industrial main employing 3, under catalyzer, directly there is hydro-reduction reaction in 4-dimethyl nitrobenzene and propione, o-Xylol is had to prepare N-(1-ethyl propyl)-3 as the publication number Chinese patent literature that is CN101302168A discloses one, the method of 4-xylidine, digestion reaction is there is under the present nitric-sulfuric acid of o-Xylol, obtained object product under the effect of digestion reaction product propione, catalyzer, the material of the method is recycle, and production process produces a large amount of refuses.
Publication number is the synthetic method that the Chinese patent of CN104250215A also discloses above-mentioned same routes, and carries out preferably to hydrogenation catalyst.
Existing methodical utilization of materials is not high, easily produces a large amount of wastewater and waste acid.
Summary of the invention
The invention provides continuous production system and the method for a kind of N-(1-ethyl propyl)-3,4-xylidine production process, realize the recycled of various materials, not only reduce production cost, improve the transformation efficiency of single batch of raw material.
A kind of serialization synthesis system of N-(1-ethyl propyl)-3,4-xylidines, comprises nitrification, washing system, distillation system, hydrogenation reactor and deep red film vapo(u)rization system; Nitrification forms by multiple stage horizontal double-doughnut nitrator is stacked, and washing system is in series by multistage labyrinth rinse bath; Distillation system is in series by Multistage rectifying tower; Deep red film vapo(u)rization system is the deep red film evaporator of plural serial stage; Also comprise the first phase-splitting groove be connected between nitrification and washing system; Be connected on the second phase-splitting groove between washing system and distillation system;
The outlet of last step double-doughnut nitrator is connected with the first phase-splitting groove entrance, the oil phase outlet of the first phase-splitting groove is connected with the entrance of the first step labyrinth rinse bath of washing system, the outlet of the last step labyrinth rinse bath of washing system is connected with the second phase-splitting groove entrance, the oil phase outlet of the second phase-splitting groove is connected with the entrance of the first step rectifying tower of distillation system, and the outlet of the last step rectifying tower of distillation system is connected with 4-nitro o-Xylol reservoir inlet;
4-nitro o-Xylol outlet is connected with hydrogenation reactor material inlet, the outlet of hydrogenation reactor is connected with strainer, the outlet of strainer is connected with the 3rd phase-splitting groove entrance, the oil phase of the 3rd phase-splitting groove enters the deep red film evaporator of the first step of deep red film vapo(u)rization system, the outlet of the deep red film evaporator of last step and N-(1-ethyl propyl)-3,4-xylidine storage tank connect.
As preferably, the aqueous phase outlet of the first phase-splitting groove is connected with dry thickening equipment entrance, and the outlet of dry thickening equipment is connected with nitric-sulfuric acid header tank entrance; The aqueous phase outlet of the second phase-splitting groove is connected with MVR concentration systems, and the phlegma of MVR concentration systems is by the rinse bath of pipeline access labyrinth, and as bath water reuse, the concentrated solution of MVR concentration systems is by pipeline access nitric-sulfuric acid header tank; The o-Xylol cut that distillation system is collected is by recycled in pipeline access o-Xylol header tank.
More preferably, the phlegma of MVR concentration systems is first back to nitric-sulfuric acid header tank cyclically utilizing again after super-dry thickening equipment drying treatment.
Further preferably, the 4-nitro o-Xylol cut that deep red film vapo(u)rization system is collected is back to 4-nitro o-Xylol storage tank by pipeline, and is again transferred in hydrogenation reactor, recycled.
Each material of production system provided by the invention realizes cyclically utilizing, reduces production cost, and effectively improves single series-produced feed stock conversion, reduces spent acid wastewater flow rate.Hydrogenation liquid is continuous treatment in multi-stage falling film evaporation system, higher compared to the production efficiency of existing cooking-pot type interval evaporation mode, and the product purity of N-(1-ethyl propyl)-3, the 4-xylidines of collection is higher.
In nitrification, every platform double-doughnut nitrator comprises:
Main channel, the end face of its one end is with opening for feed, and the bottom surface of the other end is with discharge port;
Article two, returning charge subchannel, in main channel both sides external and between the two ends being connected in parallel on main channel;
Pusher stirring rake, arrange along main channel length direction, direction of propulsion is that discharge port is to opening for feed;
The main channel arranged direction of adjacent two double-doughnut nitrators is contrary, and namely the discharge port of one, top is just to the opening for feed of one, below.
Double-doughnut nitrator provided by the invention compared to existing vertical tubular type nitrator, material diversion evenly, effectively can avoid the reflux of reaction solution, increase the touch opportunity of o-Xylol and nitric-sulfuric acid, improve the transformation efficiency of raw material; And heat interchanging area more fully, effectively can reduce side reaction.
As preferably, described double-doughnut nitrator is 8-shaped.
As preferably, described double-doughnut nitrator is the round and smooth cavity configuration of 8-shaped, so effectively can reduce mixture reflux phenomenon in reactor, contribute to the cycle operation of material in reactor, alleviate the cleaning difficulty of reactor simultaneously.
As preferably, the inwall of each double-doughnut nitrator adopts acid resisting material to make, and further preferably, the inwall of each double-doughnut nitrator has uneven surface.
Reactor wall is arranged to uneven surface, the noise of nitration reaction process can be reduced on the one hand, the touch opportunity of nitric-sulfuric acid and o-Xylol can be improved on the other hand, reduce the interfacial tension of oil phase and sour phase in mixture, further raising reaction-ure conversion-age, improves the yield of product.
As preferably, the main channel of described double-doughnut nitrator is circular cylindrical cavity, so contributes to the stirring puopulsion efficiency improving pusher stirring rake, mixture is fully contacted, and improves the transformation efficiency of reactant, reduces side reaction simultaneously.
As preferably, in every platform double-doughnut nitrator, two returning charge subchannels and main channel are in same plane, and mounting heat exchanger between two returning charge subchannels and main channel.
Returning charge subchannel and main channel are in same plane, are conducive to each double-doughnut nitrator stacked combination, improve nitration reaction efficiency.Two interchanger can be set in each reactor, can heat transfer effect be improved, be conducive to nitration reaction and move to forward.
Further preferably, each double-doughnut nitrator aligns layout up and down, and interchanger runs through all double-doughnut nitrators.
As preferably, in nitrification, the pusher stirring rake of each double-doughnut nitrator is synchronized with the movement by link gear.
Nitration reaction liquid enters layering in the first phase-splitting groove, and upper strata enters washing system and carries out labyrinth washing; Described washing system has the labyrinth rinse bath of plural serial stage to be in series.
As preferably, described washing system is in series by 1-3 level labyrinth rinse bath.
Further preferably, described washing system is in series by first step labyrinth rinse bath and labyrinth, second stage rinse bath, first step labyrinth rinse bath is provided with material inlet, the outlet of first step labyrinth rinse bath is connected with the entrance of labyrinth, second stage rinse bath, and the outlet of labyrinth, second stage rinse bath is connected with the entrance of the second phase-splitting groove.
The upper oil phase of the first phase-splitting groove is entered by the material inlet of first step labyrinth rinse bath, and after secondary maze washing, the acid that the upper strata of the first phase-splitting groove remains fully contacts with the water of washing system, and washings enters phase-splitting in the second phase-splitting groove in the lump.The upper strata of the second phase-splitting groove is product or the hydrophobicity material for reaction; Lower floor is sour water.
The sour water of the second phase-splitting groove lower floor enters MVR system and concentrates, and the phlegma of collection is water, recycled to washing system as bath water; The concentrated solution of MVR system is mainly acid, after drying treatment, is circulated in nitric-sulfuric acid header tank, recycled.
The upper strata separated of the second phase-splitting groove is transferred to distillation system and is separated.
As preferably, described distillation system is that 3-6 level rectifying tower is in series.
Further preferably, described distillation system is the first rectifying tower, Second distillation column and the 3rd rectifying tower are connected in series, and the entrance of the first rectifying tower exports with the second phase-splitting groove upper strata and is connected, the outlet of the first rectifying tower and the entrance of Second distillation column; The outlet of Second distillation column and the entrance of the 3rd rectifying tower; The outlet of the 3rd rectifying tower is connected with each component storage tank.
The distillation system of Multistage rectifying tower series connection can improve the separating effect of each component, provides the purity of isolated component.
The outlet of 4-nitro o-Xylol storage tank is connected with the material inlet of hydrogenation reactor, between connecting pipeline on to connect successively volume pump and surge tank.Hydrogenation reactor top is also provided with propione entrance, auxiliary agent entrance and gas inlet.The outlet at bottom of hydrogenation reactor is connected with the entrance of strainer, and the filtrate outlet of strainer is connected with the entrance of the 3rd phase-splitting groove, and the bottom aqueous phase outlet of the 3rd phase-splitting groove enters access MVR concentration systems; The oil phase outlet on the top of the 3rd phase-splitting groove is connected with the entrance of the deep red film evaporator of the first step of deep red film vapo(u)rization system, the outlet of the deep red film evaporator of last step of deep red film vapo(u)rization system and N-(1-ethyl propyl)-3,4-xylidine storage tank connects, period also isolates other components more, wherein 4-nitro o-Xylol is by pipeline access 4-nitro o-Xylol storage tank, is circulated to reactive system recovery.
As preferably, in continuous production system of the present invention, the nitrification double-doughnut nitrator of being connected by level Four is stacked to be formed, washing system is in series by secondary maze rinse bath, distillation system is in series by level Four rectifying tower, the o-Xylol cut that distillation system is collected and raw material mixing recovery.Further preferably, described deep red film vapo(u)rization system is in series by the deep red film evaporator of two-stage.
The oil phase outlet of the 3rd phase-splitting groove is connected with the entrance of the first deep red film evaporator, the outlet of the first deep red film evaporator is connected with the entrance of the second deep red film evaporator, the outlet of the second deep red film evaporator and N-(1-ethyl propyl)-3,4-xylidine storage tank connect.
Present invention also offers and adopt above-mentioned continuous production system synthesis N-(1-ethyl propyl)-3, the method of 4-xylidine, namely, 4-nitro o-Xylol and propione carry out catalytic hydrogenation in hydrogenation reactor, N-(1-ethyl propyl)-3,4-xylidines are obtained again through deep red film vapo(u)rization system; Catalyzer is one or more of Pt-Pd/C, Pd/C and blue Buddhist nun's nickel; The raw materials components mole ratio of 4-nitro o-Xylol and propione is 1:1.1-3; Hydrogen-pressure is 0.5-1MPa, and temperature of reaction is 65-80 DEG C.
Hydrogen is preferential and nitroso reaction under described catalyzer, generates aromatic amine, and aromatic amine is easy to produce group with imine moiety with the carbonyl reaction of propione, and group with imine moiety carries out hydrogenation reaction again, obtained object product, the square formula 2 of synthetic line.The present invention is with propione raw material certainly as solvent, and one kettle way obtains product N-(1-ethyl propyl)-3,4-xylidines.Decrease operation steps and corresponding refining step, decrease exhaust gas emission, improve production efficiency.
Equation 2
In catalytic hydrogenation, general 4-nitro o-Xylol and the GC of imines thing be less than 1% end reaction.Further preferably, the time of catalytic hydrogenation is 0.5-3h, and also namely reaction mixture material residence time in hydrogenation reactor is 0.5-3h.
As preferably, catalyzer add molar weight be the 0.01-0.15 of 4-nitro o-Xylol molar weight doubly.
As preferably, catalytic hydrogenation is carried out in acid condition, described acid add mol ratio be the 0.1-0.5 of 4-nitro o-Xylol doubly.
As preferably, catalytic hydrogenation is carried out under pH is the condition of 5.5-7.
Further preferably, in catalytic hydrogenation system, C is added
2-12carboxylic acid or sulfonic acid, and control pH is 6-7.
One or more of the preferred acetic acid of described carboxylic acid, propionic acid, valeric acid, caproic acid, hexanodioic acid; One or more of the preferred Phenylsulfonic acid of described sulfonic acid, dodecyl sodium sulfonate, tosic acid.
Present method also comprises the serialization synthesis of 4-nitro o-Xylol: carry out nitration reaction in o-Xylol and nitric-sulfuric acid mixing rear press-in nitrification, reaction solution enters layering in the first phase-splitting groove, and upper oil phase enters washing system and carries out labyrinth washing; Washings layering in the second phase-splitting groove, its upper strata enters distillation system and carries out rectification process, collects and obtains 4-nitro o-Xylol.
As preferably, in nitration reaction, described nitric-sulfuric acid is the mixing solutions of nitric acid and sulfuric acid, and wherein, the mol ratio of nitric acid and sulfuric acid is 1:0.1-1; With the molar amount of nitric acid in nitric-sulfuric acid, the mol ratio of o-Xylol and nitric-sulfuric acid is 1:1.05-5; Nitration reaction temperature in each ring nitration reactor is 10-25 DEG C; The charging flow velocity of o-Xylol and nitric-sulfuric acid mixture is 1.5-10m/s.
In the present invention, o-Xylol and nitric-sulfuric acid put into mixing tank by respective header tank respectively, be pressed in horizontal double-doughnut nitrator by nitrogen or other rare gas elementes after mixing, under the promotion of described pusher stirring rake, parallel feeding is formed and backflows, in main channel and returning charge subchannel cycle operation, fully contact and digestion reaction occurs.Part mixes material enters next stage double-doughnut nitrator and continues reaction flowing through to the dual function at gravity and feed pressure during discharge port, enters layering in the first phase-splitting groove after multistage nitration reaction.
The organic phase of the first phase-splitting groove contains more product and raw material, and lower floor is sour phase, and acid is back to cyclically utilizing in nitric-sulfuric acid header tank after super-dry.The organic phase on upper strata is through washing system, enter phase-splitting in the second phase-splitting groove, the sour water of the second phase-splitting groove lower floor is through concentration, and phlegma (being mainly water) is circulated to washing system recycle, and concentrated solution is back to cyclically utilizing in nitric-sulfuric acid header tank after super-dry.
The upper strata of the second phase-splitting groove enters distillation system, and collect 4-nitro o-Xylol, o-Xylol, 3-nitro o-Xylol and light phase component, wherein o-Xylol is back to recycled in o-Xylol header tank.
4-nitro o-Xylol is transferred in hydrogenation reactor by volume pump, the propione of stoichiometry is transferred to hydrogenation reactor simultaneously, carries out N to reactor
2/ H
2substitute gas disposal, be then warming up to described temperature, carry out catalytic hydrogenation, reaction solution is filtered, recovery catalyzer; Layering in filter liquor pump to the 3rd phase-splitting groove, the organic layer on upper strata enters in deep red film vapo(u)rization system, collect product N-(1-ethyl propyl)-3,4-xylidine, the unreacted raw material of collection is applied mechanically as 4-nitro o-Xylol and propione import hydrogenation reactor internal recycle by pipeline.
The 4-nitro o-Xylol chromatographic purity collected through multistage rectification is greater than 99.5%, is collected in storage tank.The material of 4-nitro o-Xylol storage tank and propione storage tank is squeezed in hydrogenation reactor continuously by volume pump, and adds catalyzer; N
2/ H
2displacement repeatedly.Hydrogenation reactor carries out catalytic hydrogenation, reaction solution is by the outlet at bottom inflow filter of hydrogenation reactor, the filtrate of filtering contains the more water that catalytic hydrogenation is produced, filtrate phase-splitting in the 3rd phase-splitting groove again, the bottom aqueous phase outlet of the 3rd phase-splitting groove enters access MVR concentration systems, the water of recovery catalytic hydrogenation synthesis.The oil phase on the top of the 3rd phase-splitting groove enters consecutive evaporation collection N-(1-ethyl propyl)-3 of the deep red film vapo(u)rization system of two-stage tandem, 4-xylidine storage tank, period also isolates other components more, wherein 4-nitro o-Xylol is by pipeline access 4-nitro o-Xylol storage tank, is circulated to reactive system recovery.
The present invention has following beneficial effect:
1, the double-doughnut nitrator provided can ensure that acid fully contacts with organic phase mutually, timely and effective eliminating heat, stirs good, and be easy to control, throughput is large, and the many nitro compounds of by-product and nitrophenol reduce;
2, labyrinth mode of washing is adopted to wash, multistage counter flow washing ensure that oil phase (the first phase-splitting groove upper strata) fully contacts with aqueous phase (bath water), the effect be thoroughly separated can be reached during layering, decrease time of repose and volume of equipment, improve layered effect, achieve washing serialization, unit waste water generation reduces; And recovery is carried out to waste water, reduce wastewater flow rate further.
3, adopt continuous rectification mode, improve product quality; And reaction raw materials is recycled, reduce production cost, reduce refuse amount simultaneously.
4, adopt multi-stage falling film evaporation system to carry out continuous treatment to product, higher compared to the production efficiency of existing cooking-pot type interval evaporation mode, the product purity of collection is higher.
Accompanying drawing explanation
Fig. 1 is the vertical view of double-doughnut nitrator provided by the invention;
Fig. 2 is the serialization synthesis system of N-provided by the invention (1-ethyl propyl)-3,4-xylidines.
Embodiment
Following examples are pressed aforesaid operations method and are implemented:
As shown in Figure 1 and Figure 2, N-(1-ethyl propyl)-3, the serialization synthesis system of 4-xylidine, comprises by stacked nitrification, the washing system be in series by secondary maze rinse bath and the distillation system be in series by level Four rectifying tower of four horizontal double-doughnut nitrators 1; Hydrogenation reactor 26 and deep red film vapo(u)rization system; The deep red film vapo(u)rization system of secondary deep red film evaporator series connection; Also comprise the first phase-splitting groove 10 be connected between nitrification and washing system; Be connected on the second phase-splitting groove 13 between washing system and distillation system.
The cross section of double-doughnut nitrator 1 is 8-shaped.Double-doughnut nitrator 1 is the round and smooth cavity configuration of 8-shaped.
Every platform double-doughnut nitrator 1 comprises main channel 3, returning charge subchannel 4, pusher stirring rake 5:
Main channel 3 is circular cylindrical cavity, and the end face of its one end is with opening for feed 2, and the bottom surface of the other end is with discharge port 6; Article two, returning charge subchannel 4 is in main channel 3 both sides external and between the two ends being connected in parallel on main channel 3.The inwall (main channel 3 and returning charge subchannel 4) of each double-doughnut nitrator 1 adopts acid resisting material to make, and inwall has uneven surface.
In every platform double-doughnut nitrator 1, two returning charge subchannels 4 and main channel 3 are in same plane, and mounting heat exchanger between two returning charge subchannels 4 and main channel 3.In nitrification, align layout at the stacked each double-doughnut nitrator about 1 of multiple stage, and interchanger runs through all double-doughnut nitrators 1.
Pusher stirring rake 5, arrange along main channel 3 length direction, direction of propulsion is discharge port 6 to opening for feed 2;
Main channel 3 arranged direction of adjacent two double-doughnut nitrators 1 is contrary, and namely the discharge port 6 of one, top is just to the opening for feed 2 of one, below;
The outlet of last step double-doughnut nitrator 1 (fourth stage double-doughnut nitrator) is connected with the first phase-splitting groove 10 entrance, the aqueous phase outlet of the first phase-splitting groove 10 is connected with dry thickening equipment 24 entrance, and the outlet of dry thickening equipment 24 is connected with nitric-sulfuric acid header tank 7 entrance; The oil phase outlet of the first phase-splitting groove 10 is connected with the entrance of the first step labyrinth rinse bath 11 of washing system.
The outlet of the last step labyrinth rinse bath (labyrinth, second stage rinse bath 12) of washing system is connected with the second phase-splitting groove 13 entrance, the aqueous phase outlet of the second phase-splitting groove 13 is connected with MVR concentration systems 23, the phlegma of MVR concentration systems 23 imports labyrinth rinse bath as bath water reuse by pipeline, the concentrated solution of MVR concentration systems 23 accesses dry thickening equipment 24 by pipeline, is back to nitric-sulfuric acid header tank 7 recycled after drying in the lump; The oil phase of the second phase-splitting groove 13 enters distillation system and carries out multistage rectification process.
Distillation system is the first rectifying tower 14, Second distillation column 15, the 3rd rectifying tower 16 and the 4th rectifying tower 17 are connected in series, and the entrance of the first rectifying tower 14 exports with the second phase-splitting groove 13 upper strata and is connected, the outlet of the first rectifying tower 14 and the entrance of Second distillation column 15; The outlet of Second distillation column 15 and the entrance of the 3rd rectifying tower 16; The outlet of the 3rd rectifying tower 16 is connected with the entrance of the 4th rectifying tower 17, and the outlet of the 4th rectifying tower 17 is connected with each component storage tank (o-Xylol storage tank 21,4-nitro o-Xylol storage tank 18,3-nitro o-Xylol storage tank 19, light phase storage tank 20).Rectifier bottoms outlet at different levels is connected with organic waste materials storage tank 22.The o-Xylol cut that distillation system is collected is by recycled in pipeline access o-Xylol header tank 8.
The outlet of 4-nitro o-Xylol storage tank 18 is connected with hydrogenation reactor 26 material inlet respectively with propione storage tank 25, and hydrogenation reactor 26 is also provided with hydrogen inlet, and hydrogen pipeline is provided with many breather valves, and nitrogen pipeline is connected with many breather valves.The outlet of this hydrogenation reactor 26 is connected with strainer 27, and the outlet of strainer 27 is connected with the 3rd phase-splitting groove 28 entrance.The bottom aqueous phase outlet of the 3rd phase-splitting groove 28 is connected with MVR concentration systems 23.The oil phase of the 3rd phase-splitting groove 28 enters deep red film vapo(u)rization system.Deep red film vapo(u)rization system is in series by the first deep red film evaporator 29 and the second deep red film evaporator 30, the entrance of the first deep red film evaporator 29 exports with the oil phase of the 3rd phase-splitting groove 28 and is connected, and the outlet of the first deep red film evaporator 29 is connected with the entrance of the second deep red film evaporator 30; Outlet and N-(1-ethyl propyl)-3,4-xylidine storage tank 31 storage tank of the second deep red film evaporator 30 connect.Wherein the outlet of the second deep red film evaporator 30 is also connected with 4-nitro o-Xylol storage tank 18, adopt in actual production process multiport valve distillate flow to.Height bottom deep red film evaporator at different levels boils waste material by pipeline access organic waste materials storage tank 22.
O-Xylol and nitric-sulfuric acid put into mixing tank 9 by respective header tank respectively, be pressed in horizontal double-doughnut nitrator 1 by nitrogen after mixing, under the promotion of pusher stirring rake 5, parallel feeding is formed and backflows, in main channel 3 and returning charge subchannel 4 cycle operation, fully contact and digestion reaction occurs.Part mixes material enters next stage double-doughnut nitrator 1 and continues reaction flowing through to the dual function at gravity and feed pressure during discharge port 6, enters layering in the first phase-splitting groove 10 after multistage nitration reaction.The organic phase of the first phase-splitting groove 10 contains more product and raw material, and lower floor is sour phase, and acid is back to cyclically utilizing in nitric-sulfuric acid header tank 7 after super-dry thickening equipment 24 drying.The organic phase on upper strata, through washing system, enters phase-splitting in the second phase-splitting groove 13, and the sour water of the second phase-splitting groove 13 lower floor is through concentration, and condensate circulation is to washing system recycle, and concentrated solution is back to cyclically utilizing in nitric-sulfuric acid header tank 7.The upper strata of the second phase-splitting groove 13 enters distillation system, and through level Four rectification process, collect 4-nitro o-Xylol, o-Xylol and 3-nitro o-Xylol, wherein o-Xylol is back to recycled in o-Xylol header tank 8.
Being squeezed into continuously in hydrogenation reactor 26 by volume pump with the material of propione storage tank 25 of 4-nitro o-Xylol storage tank 18, and add catalyzer; N
2/ H
2displacement repeatedly.Hydrogenation reactor 26 carries out catalytic hydrogenation, reaction solution is by the outlet at bottom inflow filter 27 of hydrogenation reactor 26, the filtrate of filtering contains the more water that catalytic hydrogenation is produced, filtrate phase-splitting in the 3rd phase-splitting groove 28 again, the bottom aqueous phase outlet of the 3rd phase-splitting groove 28 enters access MVR concentration systems 23, the water of recovery catalytic hydrogenation synthesis.The oil phase on the top of the 3rd phase-splitting groove 28 enters consecutive evaporation collection N-(1-ethyl propyl)-3 of the deep red film vapo(u)rization system of two-stage tandem, 4-xylidine storage tank 31, period also isolates other components more, wherein 4-nitro o-Xylol is by pipeline access 4-nitro o-Xylol storage tank 18, is circulated to reactive system recovery.
Embodiment 1:
O-Xylol and nitric-sulfuric acid put into mixing tank by volume pump by respective header tank, and wherein, in nitric-sulfuric acid, the mol ratio of nitric acid and sulfuric acid is 1:0.5-1; With the molar amount of nitric acid in nitric-sulfuric acid, the mol ratio of o-Xylol and nitric-sulfuric acid is 1:1.5-2.After o-Xylol and nitric-sulfuric acid mix in mixing tank, be pressed into double-doughnut nitrator by nitrogen, the charging flow velocity of o-Xylol and nitric-sulfuric acid mixture is 1.5-2m/s.In mixture press-in nitrification, organic phase and acid fully contact mutually carries out multistage nitration reaction.The temperature controlled in ring nitration reactor at different levels by interchanger is 10-25 DEG C.
Reaction solution flows out nitrification and enters layering in the first phase-splitting groove, and the acid solution of the first phase-splitting Cao Nei lower floor is back to the recycle of nitric-sulfuric acid header tank after drying plant process; The oil phase on upper strata enters washing system and carries out secondary maze washing.Washings layering in the second phase-splitting groove, lower floor's sour water layer of the second phase-splitting groove enters MVR system, and the phlegma of collection is back to washing system, and concentrated solution is back to nitric-sulfuric acid header tank.The upper strata of the second phase-splitting groove enters distillation system and carries out level Four rectification process, collects and obtains 4-nitro o-Xylol.The o-Xylol collected is back to the recycle of o-Xylol header tank.
After continuous prodution terminates, the transformation efficiency of o-Xylol is 93%, nitration reaction liquid (is the reaction solution of nitrification last step reactor discharge port, every 30min sampling is once) in, the content of 4-nitro o-Xylol is greater than 89%, and the purity of the 4-nitro o-Xylol that rectifying is collected is greater than 99.6% (GC area normalization method purity).
4-nitro o-Xylol and propione pump are in hydrogenation reactor, and the raw materials components mole ratio of 4-nitro o-Xylol and propione is 1:1.1-1.5, and catalyzer is Pt-Pd/C, and the catalyzer equivalent that feeds intake is 0.1eqv (with 4-nitro o-Xylol for benchmark).Respectively displacement is carried out 3 ~ 5 times to the air in autoclave with nitrogen, hydrogen.Open hydrogen inlet valve, slowly open autoclave hydrogen gas valve, control, into hydrogen speed and pressure (0.2 ~ 0.5MPa), to carry out displacement 3 ~ 5 times to the air in autoclave, replace rear control pressure at about 0.75MPa.Be warming up to 65-80 DEG C, regulate hydrogen reducing valve, control still internal pressure≤1.0MPa, carry out catalytic hydrogenation, in the reaction later stage, hydrogen usage is slow, sampling analysis, when the GC content of 4-nitro o-Xylol in reaction solution is less than 1% (material residence time in hydrogenation reactor is 1-2h), stopped reaction.
Reaction solution is filtered, and the catalyzer of recovery is back to hydrogenation reactor internal recycle and applies mechanically, filtrate phase-splitting process, and aqueous phase enters MVR concentration systems; Oil phase enters deep red film vapo(u)rization system, collects N-(1-ethyl propyl)-3,4-xylidine cut; The 4-nitro o-Xylol collected and propione go to recycled in respective storage tank respectively by pipeline.
Through measuring, the transformation efficiency of 4-nitro o-Xylol is the yield of 99%, N-(1-ethyl propyl)-3,4-xylidines be 98.1%, GC purity is 99.5%.
Embodiment 2
Compare with embodiment 1, difference is, in nitric-sulfuric acid, the mol ratio of nitric acid and sulfuric acid is 1:0.1-0.44; With the molar amount of nitric acid in nitric-sulfuric acid, the mol ratio of o-Xylol and nitric-sulfuric acid is 1:1.1-2; The charging flow velocity of o-Xylol and nitric-sulfuric acid mixture is 1.5-2m/s.The temperature controlled in ring nitration reactor at different levels by interchanger is 10-15 DEG C.
After continuous prodution terminates, the transformation efficiency of o-Xylol is 96.5%, nitration reaction liquid (is the reaction solution of nitrification last step reactor discharge port, every 30min sampling is once) in, the content of 4-nitro o-Xylol is greater than 93%, and the purity of the 4-nitro o-Xylol that rectifying is collected is greater than 99.6% (GC area normalization method purity).
In catalytic hydrogenation, the raw materials components mole ratio of 4-nitro o-Xylol and propione is 1:1.5-2, and catalyzer is blue Buddhist nun's nickel, and the catalyzer equivalent that feeds intake is 0.1eqv (with 4-nitro o-Xylol for benchmark).Control hydrogen pressure at 0.6-0.75MPa.Be warming up to 65-80 DEG C, material residence time in hydrogenation reactor is 2-3h.
Through measuring, the transformation efficiency of 4-nitro o-Xylol is the yield of 99%, N-(1-ethyl propyl)-3,4-xylidines be 98.1%, GC purity is 99.5%.
Embodiment 3
Compare with embodiment 1, difference is, in catalytic hydrogenation, adds in hydrogenation reactor
The dodecyl sodium sulfonate of 0.1-0.2eqv (with 4-nitro o-Xylol for benchmark), the pH controlling reaction system is between 5.5-6, and the residence time of material in hydrogenation reactor is 0.5-1h.After continuous reaction terminates, through measuring, the transformation efficiency of 4-nitro o-Xylol is the yield of 99.6%, N-(1-ethyl propyl)-3,4-xylidines be 99.1%, GC purity is 99.5%.
Claims (10)
1. the serialization synthesis system of N-(1-ethyl propyl)-3,4-xylidines, is characterized in that, comprises nitrification, washing system, distillation system, hydrogenation reactor and deep red film vapo(u)rization system; Nitrification forms by multiple stage horizontal double-doughnut nitrator is stacked, and washing system is in series by multistage labyrinth rinse bath; Distillation system is in series by Multistage rectifying tower; Deep red film vapo(u)rization system is the deep red film evaporator of plural serial stage; Also comprise the first phase-splitting groove be connected between nitrification and washing system; Be connected on the second phase-splitting groove between washing system and distillation system;
The outlet of last step double-doughnut nitrator is connected with the first phase-splitting groove entrance, the oil phase outlet of the first phase-splitting groove is connected with the entrance of the first step labyrinth rinse bath of washing system, the outlet of the last step labyrinth rinse bath of washing system is connected with the second phase-splitting groove entrance, the oil phase outlet of the second phase-splitting groove is connected with the entrance of the first step rectifying tower of distillation system, and the outlet of the last step rectifying tower of distillation system is connected with 4-nitro o-Xylol reservoir inlet;
4-nitro o-Xylol outlet is connected with hydrogenation reactor material inlet, the outlet of hydrogenation reactor is connected with strainer, the outlet of strainer is connected with the 3rd phase-splitting groove entrance, the oil phase of the 3rd phase-splitting groove enters the deep red film evaporator of the first step of deep red film vapo(u)rization system, the outlet of the deep red film evaporator of last step and N-(1-ethyl propyl)-3,4-xylidine storage tank connect.
2. the serialization synthesis system of N-(1-ethyl propyl)-3,4-xylidines as claimed in claim 1, it is characterized in that, every platform double-doughnut nitrator comprises:
Main channel, the end face of its one end is with opening for feed, and the bottom surface of the other end is with discharge port;
Article two, returning charge subchannel, in main channel both sides external and between the two ends being connected in parallel on main channel;
Pusher stirring rake, arrange along main channel length direction, direction of propulsion is that discharge port is to opening for feed;
The main channel arranged direction of adjacent two double-doughnut nitrators is contrary, and namely the discharge port of one, top is just to the opening for feed of one, below.
3. N-(1-ethyl propyl)-3 as claimed in claim 2, the serialization synthesis system of 4-xylidine, it is characterized in that, the nitrification double-doughnut nitrator of being connected by level Four is stacked to be formed, washing system is in series by secondary maze rinse bath, and distillation system is in series by three grades of rectifying tower; Deep red film vapo(u)rization system has the deep red film evaporator of two-stage to be in series.
4. N-(1-ethyl propyl)-3 as claimed in claim 3, the serialization synthesis system of 4-xylidine, it is characterized in that, the aqueous phase outlet of the first phase-splitting groove is connected with dry thickening equipment entrance, and the outlet of dry thickening equipment is connected with nitric-sulfuric acid header tank entrance; The aqueous phase outlet of the second phase-splitting groove is connected with MVR concentration systems, and the phlegma of MVR concentration systems is by pipeline access labyrinth rinse bath as bath water reuse, and the concentrated solution of MVR concentration systems is by pipeline access nitric-sulfuric acid header tank; The o-Xylol cut that distillation system is collected is by recycled in pipeline access o-Xylol header tank.
5. adopt the method for any one of claim 1-4 serialization synthesis system, it is characterized in that, 4-nitro o-Xylol and propione carry out catalytic hydrogenation in hydrogenation reactor, then obtain N-(1-ethyl propyl)-3,4-xylidines through deep red film vapo(u)rization system; Catalyzer is one or more of Pt-Pd/C, Pd/C and blue Buddhist nun's nickel; The raw materials components mole ratio of 4-nitro o-Xylol and propione is 1:1.1-3; Hydrogen-pressure is 0.5-1MPa, and temperature of reaction is 65-80 DEG C.
6. adopt method according to claim 5, it is characterized in that, catalytic hydrogenation is carried out under pH is the condition of 5.5-7.
7. adopt method according to claim 6, it is characterized in that, the time of catalytic hydrogenation is 0.5-3h.
8. adopt method according to claim 7, it is characterized in that, in catalytic hydrogenation system, add C
2-12carboxylic acid or sulfonic acid, and control pH is 6-7.
9. method as claimed in claim 5, it is characterized in that, also comprise the serialization synthesis of 4-nitro o-Xylol: in o-Xylol and nitric-sulfuric acid mixing rear press-in nitrification, carry out nitration reaction, reaction solution enters layering in the first phase-splitting groove, and upper oil phase enters washing system and carries out labyrinth washing; Washings layering in the second phase-splitting groove, its upper strata enters distillation system and carries out rectification process, collects and obtains 4-nitro o-Xylol.
10. method as claimed in claim 9, it is characterized in that, in nitration reaction, described nitric-sulfuric acid is the mixing solutions of nitric acid and sulfuric acid, and wherein, the mol ratio of nitric acid and sulfuric acid is 1:0.1-1; With the molar amount of nitric acid in nitric-sulfuric acid, the mol ratio of o-Xylol and nitric-sulfuric acid is 1:1.05-5; Nitration reaction temperature in each ring nitration reactor is 10-25 DEG C; The charging flow velocity of o-Xylol and nitric-sulfuric acid mixture is 1.5-10m/s.
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