CN108191675A

CN108191675A - The method that paraphenetidine is prepared with the device catalytic hydrogenation of industrially scalable

Info

Publication number: CN108191675A
Application number: CN201711461473.1A
Authority: CN
Inventors: 王明和; 侍春明
Original assignee: Ningxia Zhongsheng New Technology Co Ltd
Current assignee: Ningxia Zhongsheng New Technology Co Ltd
Priority date: 2014-06-11
Filing date: 2015-06-10
Publication date: 2018-06-22
Also published as: CN108250085A; CN105294456B; CN105294456A

Abstract

The present invention relates to a kind of methods that device catalytic hydrogenation with industrially scalable prepares paraphenetidine, its be industrially scalable plus hydrogen kettle in, during each production cycle in a continuous manner or interruption mode add in raw material paranitroanisole, and real time monitoring adds the concentration of raw material and impurity in hydrogen kettle during the reaction, to obtain the paraphenetidine of more than 99.5% purity and 100% yield.The obtained paraphenetidine product of the present invention reaches more than 99.5% purity, can be used directly and sells；Further rectification process can also be passed through to obtain the paraphenetidine fine work of more than 99.9% purity, used for special dimension.

Description

The method that paraphenetidine is prepared with the device catalytic hydrogenation of industrially scalable

The application be the applying date on 06 10th, 2015, application No. is 201510312779.5, it is entitled " with industrialization The divisional application of the application for a patent for invention of the method that the device catalytic hydrogenation of scale prepares paraphenetidine ".

Technical field

The present invention relates to a kind of preparation method of paraphenetidine, more particularly, to a kind of device with industrially scalable The method for carry out catalytic hydrogenation and highly selective (high-purity), preparing paraphenetidine in high yield.

Background technology

Paraphenetidine, alternatively referred to as P-nethoxyaniline are important the intermediate of dyestuff, medicine and fragrance, with O-aminoanisole is compared, and application of the paraphenetidine in dye industry is more extensive.For example, in dye industry, it is right Aminoanisole be used to synthesize Fast Blue VB salt, purplish red base GP, azoic coupling component AS-SG, AS-RL, vat scarlet etc..In addition, using pair Aminoanisole can synthesize 2- amino -4- acetyl-anisidines, and the latter is the important source material of disperse dyes, can be used for into A series of disperse dyes of one-step synthesis, such as C.I. Disperse Blue-79s, 139,226,265,301, disperse violet 58, Disperse Navy Blue S-2GL Deng.In medical industry, paraphenetidine is mainly used for synthesizing atabrine, primary quinoline, indocin etc., and wherein indocin is to ammonia The bigger kind of base methyl phenyl ethers anisole consumption figure.

At the beginning of phase late 1980s, due to the backwardness and novel technique of traditional processing technology technology develop it is stagnant Afterwards, particularly catalytic hydrogenation new technology is difficult to break through, and paraphenetidine has been unable to meet downstream industry to product quality Requirements at the higher level, therefore, some main paraphenetidine manufacturing enterprises of the developed countries such as American-European and Japan sequentially switch off it Process units.And in contrast, with the emergence of China's dye industry, promote paraphenetidine capacity and output Rapid growth, China have become global paraphenetidine major producing country and supply country, there is thousands of tons of p-aminophenyl every year Ether products export, and China's paraphenetidine yield accounts for about 80% or so of global total output.

In traditional industrial process, domestic manufacturer is mostly to use " chemical reduction method ", i.e., with iron powder or Paranitroanisole is restored as reducing agent and prepares paraphenetidine by vulcanized sodium.But this production technology and In production technology, iron powder or a large amount of offal treatments that go out of vulcanization sodium reduction heel row are difficult, and cause serious pollution to the environment, and are advocated with China The developing direction of green non-pollution chemical industry led is runed counter to.It, not only can be significantly if carrying out harmless treatment to waste water, waste residue Increase production cost, it is also possible to cause secondary pollution when dealing with improperly.

For this purpose, those skilled in the art has carried out many researchs, and achieve the achievement of every aspect.

In document 1：" technical study that paraphenetidine is prepared by paranitroanisole ", using chemical industry, volume 32 the 6th Phase proposes to prepare sodium polysulfide for raw material using sulphur and sodium hydroxide in December, 2013, Wang Shuqing et al., then with more vulcanizations Sodium reduction paranitroanisole synthesizes paraphenetidine, and finally, the yield of paraphenetidine is 96%, purity 99%. Although this technique has been substantially solved using problem of environmental pollution caused by iron powder or vulcanized sodium as reducing agent, not It fundamentally can thoroughly solve the problems, such as " three wastes "；In addition, using sulphur and sodium hydroxide as primary raw material, will increase considerably Production cost；Meanwhile for the yield required by fine chemical product and purity, this synthesis technology also needs to further It improves.

In order to reduce the pollution to environment, product yield and purity are improved, especially reduces production cost, current research Direction is mostly to concentrate on to prepare paraphenetidine using " catalytic hydrogenation method ".The by-product of this method is only water, side reaction It is few；Environmentally friendly, high income, impurity is few, good product quality, is the ideal technology of substituted chemistry reduction method.

In document 2：" liquid phase catalytic hydrogenation method synthesizes paraphenetidine ", Chinese chlor-alkali, the 5th phase, in May, 2003, Jian Hua is disclosed using paranitroanisole as raw material, and skeleton nickel is catalyst, 115-130 DEG C of temperature of control, pressure 1-1.2MPa, Liquid phase catalytic hydrogenation reduction reaction is carried out under stiring, and using " when pressure no longer declines in kettle " as reaction end, is obtained Crude product obtains paraphenetidine product after vacuum distillation.This technique 150g paranitroanisoles disclosed in the document The order of magnitude on, crude product purity reaches as high as 99.31%, after distillation gained fine work purity reach as high as 99.83%, yield Reach as high as 92.7%.Since the method is only laboratory's stage, meanwhile, reaction solution, which has to pass through distillation processing, could improve production Product purity, and yield is relatively low, that is to say, that proportion of by-product is higher or raw material reaction is incomplete or distillation loss is larger, still not It can really realize the friendly production of cleaning.

In document 3：" backbone ruthenium nickel carbon selectivity catalytic hydrogenation prepares paraphenetidine ", fine chemistry industry, volume 23 the 5th Phase, it is backbone ruthenium nickel carbon Raney- to further improve the catalyst in catalytic hydrogenation reaction in May, 2006, Yuan Zhongyi et al. RuNiC, and Ru therein：Ni：C=1：1：2, the service life of catalyst is hence improved, and cause the selectivity of purpose product Higher than 99.4%.The research group discloses a kind of including main catalyst ruthenium, Yi Jiyou also in Chinese patent CN1775353 The skeleton ruthenium catalyst of the co-catalyst of Al, Ni, M (Fe, Mn, Mo or Cr) and C compositions adds hydrogen using the skeleton ruthenium catalyst Reaction may be such that 4g paranitroanisoles 100% are converted into paraphenetidine, and the yield of the product is 99%.But this Method is also only laboratory's stage, have no industrialization explanation, meanwhile, ruthenium catalyst it is expensive, production cost will substantially Degree improves.

In addition, in document 4：" Preparation of p-Anisidine by Liquid Phase Catalytic Hydrogenation ", Henan chemical industry, the 7th phase of volume 24, In June, 2007, horse is peaceful etc. to disclose 47g paranitroanisoles, 100ml ethyl alcohol and 2.3g moist catalysis as initial reactant, even The continuous preparation process for being passed through hydrogen, and with " not dropped as reaction end to hydrogen pressure ".Obtained product yield is 98.14%, purity 99.02%.Wherein, for the catalyst of one of the key of the technique, it is merely disclosed as " self-control nickel catalyst Agent " does not disclose other specifying informations.

A kind of method that paranitroanisole is prepared with catalytic hydrogenation method is disclosed in Chinese patent CN1861570.It should Method is using methanol as solvent, using nitrobenzoyl ether mixture as raw material, is catalyst using Raney-Ni or Pd-C, is passed through hydrogen Catalytic hydrogenating reduction reaction is carried out, terminates catalytic hydrogenation reaction when no longer consumption hydrogen.The technique is mainly for ortho-nitrophenyl The mixture of methyl ether and paranitroanisole is starting material, for only using paranitroanisole as the scheme of starting material, being somebody's turn to do Document does not provide the yield and purity results of product.

Applicant in this case discloses a kind of synthetic method of alkoxyl aniline, the party in Chinese patent CN101492379 Method is that alkoxyl nitrobenzene is generated alkoxyl aniline by adding in hydrogen reaction under catalysts conditions for raw material.In the patent In embodiment 2 disclosed in application, by 100g paranitroanisoles, 1g RaneyNi, 100mL methanol is added in reactor, And be passed through hydrogen in 80 DEG C and reacted, stop until hydrogen half an hour after is no longer inhaled in reaction.This method can obtain yield 95%, The paraphenetidine product of purity 99.8%, wherein paraphenetidine high selectivity are up to 99.5%.

A kind of aromatic nitro compound using low content of aluminium catalyst is disclosed in Chinese patent CN1332148A The commercial run of continuously hydrogen adding causes to reduce production capacity, this method in order to avoid the sediment of generation nickel aluminate structure Emphasize that total aluminium content in catalyst is at most 5.5%.This patent application is to be directed to dinitrotoluene (DNT) (DNT), reaction yield About 99%-99.2%.But evidence suggests the method is not suitable for the catalytic hydrogenation of other nitro compounds centainly yet Reduction, especially single nitro compound.

Therefore, paraphenetidine technique prepared with " catalytic hydrogenation method " published at present, although due to this The characteristic of technique in itself has avoided the problem of environmental pollution that " three wastes " discharge is brought, and still, industrialized demand is come It says, the aforementioned several prior arts are the applications rested in such as laboratory scale of 100g ranks.And people in the art Can member be understood that, really implement still up for the inspection of practice in industrialization.

For example, the synthetic method of alkoxyl aniline of the applicant in this case disclosed in Chinese patent CN101492379 It has been found：Although this method can be implemented in the lab, such as in the embodiment 2 of the patent application, by 100g to nitre Base methyl phenyl ethers anisole, 1g Raney Ni, 100mL methanol is added in reactor, and is passed through hydrogen in 80 DEG C and is reacted, until anti- Should no longer inhale hydrogen half an hour after stopping, this method can obtain yield 95%, purity 99.8% paraphenetidine product, Middle paraphenetidine high selectivity is up to 99.5%.But when being scaled up to industrial production, purity can only be obtained 96% crude product, and after vacuum distillation purifies, yield drops to 95%.That is, this be carried out in laboratory Method cannot obtain highly selective (high-purity), paraphenetidine in high yield at industrial scale at all, moreover, raw material Utilization rate it is relatively low, still cannot really realize the friendly production of cleaning.

In conclusion prior art preparation still also exists as follows problem in terms of industrial-scale production：(1) product Yield is low.For the production of chemical products, what industry was generally pursued is in high yield；Reaction yield is higher, it is meant that production It loses in the process less and pollution is smaller, subsequent treatment process is simpler, be correspondingly to bring production cost A series of usefulness such as decline, market competitiveness rising.But just at present, catalytic hydrogenation method prepares p-aminophenyl first Ether also can only reach 98% or 99% yield, the space also further promoted.(2) product purity cannot meet The application of higher demand.Product purity is always the element for the application range for restricting the product, and current technique is difficult anti- Should at the end of can reach demand, will usually pass through vacuum distillation, rectifying or recrystallization post processing etc. and complicated technologies and set Standby, this necessarily causes technique, equipment to complicate, and investment extension is required to increase in energy consumption and manpower and materials etc. A large amount of operating cost, is finally significantly increased production cost；Meanwhile a considerable amount of waste residues are generated, the wasting of resources is caused, is caused Secondary pollution.(3) it is difficult to industrial-scale production.

In fact, applicant in this case has found by the stable operation practice on 20000 tons/year of industrial production devices, Current various " catalytic hydrogenation methods " even if the technique for preparing paraphenetidine can be obtained in laboratory comparatively ideal yield and Purity still, is applied according to its technical conditions in industrial production device, also with regard to that can reach the purity of 94-97%.Cause this The main reason for one result may be：(1) industrially scalable and difference of the laboratory scale on device, lead to industrialized unit It can not realize or reach the process specifications of minisize reaction kettle (laboratory scale)；(2) industrially scalable and laboratory scale Often different on material purity, for reasons of cost, chemistry during industrialization using industrial goods rather than laboratory scale is pure Pure raw material is even analyzed, this would necessarily affect the yield of reaction and the purity of product；(3) due to the complexity of chemical reaction Property, the influence factor of reaction process when laboratory study work can not be grasped really and expect industrially scalable completely. Due to more than, the production technology of industrially scalable easily generates more by-products, therefore, if being showed using above-mentioned these There is technique, to obtain in high yield and the paraphenetidine of high-purity can only increase equipment on post-processing step with into traveling One step ground rectifying or recrystallization etc..

This may be also not publicly to prepare paraphenetidine with catalytic hydrogenation method in domestic and international existing report document Relevant industrialization example the reason of.

So in view of this field there is an urgent need for using industrially scalable catalytic hydrogenation device carry out highly selective (high-purity), The method for preparing paraphenetidine in high yield, applicant in this case are developed through further further investigation on industrially scalable Method really can smoothly implement, that paraphenetidine is prepared using catalytic hydrogenation, and can highly selective (high-purity), height Obtain target product to yield.

Invention content

The purpose of the present invention is to provide it is a kind of have both simultaneously highly selective (high-purity), in high yield and cleaning it is friendly and Can existing industrialization technology can be substantially solved with the preparation method of the paraphenetidine of industrial-scale production, this method Present in many disadvantages and deficiency.

In order to achieve the above-mentioned object of the invention, the present invention provides following technical solution：

Device provided by the invention using industrially scalable carries out catalytic hydrogenation and highly selective (high-purity), in high yield The method that ground prepares paraphenetidine is in industrially scalable plus hydrogen kettle, with continuous during each production cycle Mode (i.e. midway continual mode) or raw material paranitroanisole is added in a manner of interruption, and real during the reaction When monitoring plus hydrogen kettle in the concentration of raw material and impurity, to obtain the paraphenetidine of more than 99.5% purity and 100% yield.

In an embodiment of the invention, the present invention provides a kind of device catalytic hydrogenation with industrially scalable and prepares The method of paraphenetidine, this method add in raw material paranitroanisole (continous way production), this method in a continuous manner Including the steps：

(1) atent solvent and catalyst are added in：Atent solvent, catalysis are sequentially added in hydrogen kettle to by adding for nitrogen displacement Agent；

Wherein, the nitrogen, which is replaced to this, adds oxygen content≤0.5v% (percent by volume) in hydrogen kettle；

The atent solvent accounts for plus the 10-60v% of hydrogen kettle dischargeable capacity；

The catalyst is quaternary Raney's nickel catalyst, and additive amount is the 0.10- of target product (paraphenetidine) 3.5wt% (weight percent)；

Wherein, by weight percentage, nickel 83.3-95.6wt%, aluminium are the main component of quaternary Raney's nickel catalyst 3.8-10.1wt%, molybdenum 0.05-7.2wt%, iron 0.05-1.7wt%；

In this case plus hydrogen kettle is industrially scalable, and the pilot scale stage is in 1000L hereinafter, being 1000- when industrializing 3000L, the big production phase is in more than 3000L, such as 16000L；

(2) continuous charging and hydrogenation reaction is carried out：

After should adding hydrogen kettle with nitrogen, hydrogen displacement successively, it is filled with pressure in hydrogen to kettle and reaches 0.5-2.5MPa；Unlatching is stirred It mixes and heats this and add hydrogen kettle, control 1-10 DEG C of heating rate/min, the temperature for adding hydrogen kettle is risen to 40-90 DEG C and maintains 5- 75min；

To adding in hydrogen kettle with 0.2-25.0m³The charging rate of/h is added continuously paranitroanisole, meanwhile, it maintains to add Pressure in hydrogen kettle, at 55-120 DEG C, carries out hydrogenation reaction in 0.5-2.5MPa and temperature；

During the continuous charging of paranitroanisole, at interval of 15-75 minutes, sampling carried out gas chromatographic analysis, with Just all impurity summations in paranitroanisole conversion ratio and reaction solution are monitored；When paranitroanisole conversion ratio 90% with On, and all impurity summations be not more than 0.3% when keep charging, until add predetermined amount or add hydrogen kettle liquid position reach 100%, stop adding in paranitroanisole；If above-mentioned requirements are not achieved in one of conversion ratio, impurity summation two indices, reduce Charging rate；

Wherein, oxygen content≤0.5v% in hydrogen kettle should extremely be added with nitrogen displacement plus hydrogen kettle；Should extremely it be added with hydrogen displacement nitrogen Hydrogen kettle hydrogen content >=90v%；

The speed of the stirring is 250-550rpm；

(3) stop hydrogenation reaction：Stop after adding in paranitroanisole, it is 0.5- to maintain to add the Hydrogen Vapor Pressure in hydrogen kettle 2.5MPa and temperature are 55-120 DEG C, the reaction was continued 10-60min；

Sampling carries out gas chromatographic analysis, and until paranitroanisole conversion ratio, (paranitroanisole surplus is several for 100% For 0%), and all impurity summations stop hydrogenation reaction no more than 0.4%；

Continuous cooling is carried out, controls 1-10 DEG C of cooling rate/min, until temperature reaches less than 30 DEG C；Stop stirring, it is quiet It puts, binder to catalyst separator；

(4) it detaches and purifies：The material that step (3) extrudes in catalyst separator is stood, is then by filtering System separates catalyst；The material mixture liquid of catalyst is filtered out by desolventizing, dewatering system, sloughs organic solvent and water, finally Obtain the paraphenetidine product that content is not less than 99.5%.

In an embodiment of the invention, the atent solvent of step (1) for methanol, ethyl alcohol, normal propyl alcohol, isopropanol, Benzene,toluene,xylene, Benzene Chloride, aniline, dichloromethane, chloroform, carbon tetrachloride, dichloroethanes etc..It is filtered in step (4) Except the material mixture liquid (i.e. not separated to go back original mixture) or target product of catalyst, atent solvent can be also used as, is added in In step (1).According to different solvents, the 10-60v% of hydrogen kettle dischargeable capacity is added to be advisable to account for about.

The Raney's nickel catalyst of step (1) of the present invention is made by routine fashion, i.e., according to needed for quaternary Raney's nickel catalyst Each component ratio, the nickel of accurate weighing, aluminium, molybdenum, iron high pure metal are fully fused in a furnace, quenching cooling after, will close Golden body mechanical lapping is into fine particle；It is sieved further according to the needs used and picks out the alloyed powder of suitable particle size, enter next Walk activation procedure；It, in a certain temperature conditions, will be in alloyed powder in certain density sodium hydroxide/potassium hydroxide solution Most of aluminium dissolution, formed skeleton nickel；Sodium hydroxide/potassium hydroxide solution, which is cleaned, with clean water reaches pH=7.8-10.1 Afterwards, it is sealed up for safekeeping with clean water or atent solvent, that is, forms the Raney's nickel catalyst of needs.

In an embodiment of the invention, the reaction temperature in step (2) plus in hydrogen kettle is at 55-120 DEG C.It is if anti- It is more than 120 DEG C of maximum temperature to answer temperature, largely generates side reaction product, is unfavorable for obtaining the product of high-purity；If reaction temperature Degree is less than 55 DEG C, then reaction speed is too slow, similary easily to generate side reaction product, influences the yield of final goal product and pure Degree.

In an embodiment of the invention, time of repose is 20-120min in step (3).

In an embodiment of the invention, time of repose is 30-120min in step (4).

In an embodiment of the invention, the catalyst that step (4) separates is timed, is indefinite again after treatment When or continuously recovery.These catalyst, which are largely recovered, to be applied mechanically, and small part is eliminated.

In an embodiment of the invention, the organic solvent sloughed in step (4) by desolventizing system can return Receipts are applied mechanically, such as are full recycled to abovementioned steps and are applied mechanically, and are lost seldom during recycled, clean manufacturing is fully achieved Technological requirement.

In an embodiment of the invention, the water sloughed in step (4) through dewatering system can enter preceding road and produce Process is continued cycling through and is applied mechanically as wash water.

In yet another embodiment of the present invention, the present invention provides a kind of device catalytic hydrogenation system with industrially scalable The method of standby paraphenetidine, this method add in raw material paranitroanisole (discontinuous production), the party in a manner of being interrupted Method includes the steps：

(1) it feeds for the first time：To by nitrogen replace plus hydrogen kettle in sequentially add atent solvent, catalyst after, by right Nitroanisole storage tank is pumped by feedstock transportation and adds in 0.5-2.0m³Paranitroanisole；

(2) hydrogenation reaction is carried out：After should adding hydrogen kettle with nitrogen, hydrogen displacement successively, it is filled with pressure in hydrogen to kettle and reaches 0.5-2.5MPa；It opens and stirs and heat this plus hydrogen kettle, control 1-10 DEG C of heating rate/min, the temperature for adding hydrogen kettle is risen to 40-90 DEG C and 5-75min is maintained, proceed by hydrogenation reaction；

The speed of the stirring is 250-550rpm；

(3) continuous charging again：Gas chromatographic analysis is carried out to the reaction solution sampling in step (2), until p-nitrophenyl Methyl ether conversion ratio is more than 90%, and when all impurity summations are not more than 0.3%, carry out the continuous again of paranitroanisole plus Material；

Maintain plus hydrogen kettle in pressure in 0.5-2.5MPa and temperature at 55-120 DEG C, to adding in hydrogen kettle with 0.2- 25.0m³The charging rate of/h is added continuously paranitroanisole again, continues hydrogenation reaction；

During the continuous feed of paranitroanisole, at interval of 15-75 minutes, sampling carried out gas chromatographic analysis, with Just all impurity summations in paranitroanisole conversion ratio and reaction solution are monitored；When paranitroanisole conversion ratio 90% with On, and all impurity summations be not more than 0.3% when continue to feed, until add predetermined amount or add hydrogen kettle liquid position reach 100%, stop adding in paranitroanisole；If above-mentioned requirements are not achieved in one of conversion ratio, impurity summation two indices, reduce Charging rate stops charging；

(4) stop hydrogenation reaction：Stop after adding in paranitroanisole, it is 0.5- to maintain to add the Hydrogen Vapor Pressure in hydrogen kettle 2.5MPa and temperature are 55-120 DEG C, the reaction was continued 10-60min；

(5) it detaches and purifies：The material that step (4) extrudes in catalyst separator is stood, is then by filtering System separates catalyst；The material mixture liquid of catalyst is filtered out by desolventizing, dewatering system, sloughs organic solvent and water, finally Obtain the paraphenetidine product that content is not less than 99.5%.

In an embodiment of the invention, the atent solvent of step (1) for methanol, ethyl alcohol, normal propyl alcohol, isopropanol, Benzene,toluene,xylene, Benzene Chloride, aniline, dichloromethane, chloroform, carbon tetrachloride, dichloroethanes etc..It is filtered in step (5) Except the material mixture liquid (i.e. not separated to go back original mixture) or target product of catalyst, atent solvent can be also used as, is added in In step (1).According to different solvents, the 10-60v% of hydrogen kettle dischargeable capacity is added to be advisable to account for about.

In an embodiment of the invention, the reaction temperature in step (3) plus in hydrogen kettle is at 55-120 DEG C.It is if anti- It is more than 120 DEG C of maximum temperature to answer temperature, largely generates side reaction product, is unfavorable for obtaining the product of high-purity；If reaction temperature Degree is less than 55 DEG C, then reaction speed is too slow, similary easily to generate side reaction product, influences the yield of final goal product and pure Degree.

In an embodiment of the invention, according to actual needs, step (3) may be repeated 1-3 times.

In an embodiment of the invention, time of repose is 20-120min in step (4).

In an embodiment of the invention, time of repose is 30-120min in step (5).

In an embodiment of the invention, the catalyst that step (5) separates is timed, is indefinite again after treatment When or continuously recovery.These catalyst, which are largely recovered, to be applied mechanically, and small part is eliminated.

In an embodiment of the invention, the organic solvent sloughed in step (5) by desolventizing system can return Receipts are applied mechanically, such as are full recycled to abovementioned steps and are applied mechanically, and are lost seldom during recycled, clean manufacturing is fully achieved Technological requirement.

In an embodiment of the invention, the water sloughed in step (5) through dewatering system can enter preceding road and produce Process is continued cycling through and is applied mechanically as wash water.

The obtained paraphenetidine product of above-mentioned preparation method according to the present invention reaches more than 99.5% purity Substantially 100% yield can be used directly and sell；Further rectification process can also be passed through to obtain more than 99.9% The paraphenetidine fine work of purity is used for special dimension.

The preparation method of paraphenetidine provided by the invention is to have carried out synthesis to the technique in many aspects to change It is kind, so as to obtain the success on industrially scalable, up to more than 99.5% can be obtained without post processing after the reaction Purity and substantially 100% yield, greatly reduce production cost.Compared with prior art, usefulness of the present invention It is：

The quaternary Raney's nickel catalyst that the present invention uses is selected by a large number of experiments room and industrially scalable experiment, With the catalyst used in the prior art, such as the low content of aluminium catalyst in CN1332148A, the skeleton in CN1775353A Ruthenium-based catalyst is compared, and more particularly to more improve the reaction speed that nitro is reduced to amino in industrial-scale production, is made It obtains intermediate reaction product of the paranitroanisole during hydrogenation reduction to be greatly lowered or avoid to generate, so as to drop Generation that is low or avoiding impurity.This is because could be aware that from the reaction mechanism of catalytic hydrogenation, middle transition product is can not to keep away Exempt from.But this case improves reaction speed by selecting catalyst, allows the middle transition product residence time is very short, and Transient transformation is Target product, time and chance without giving generation by-product, so as to improve the purity of target product and quality.From this case The catalyst that the embodiment of offer and the result of comparing embodiment can be seen that this case really can be in the production of industrially scalable The purity of target product is improved to more than 99.5% and yield to 100% (that is, in addition to the impurity in industrial goods raw material, to nitro Methyl phenyl ethers anisole be hydrogenated generation required product), be superior to or be equivalent to purity of aforementioned comparison's file in laboratory scale and Yield (generally 99%).Equally, using other experiments that can be obtained or industrializeding catalyst, using the inventive method of this case The big pilot production of industrially scalable is carried out, the production effect for meeting or exceeding this case catalyst can not be obtained.

The present invention monitors reaction process by timely sampling analysis, knows to add the hydrogenation reaction situation in hydrogen kettle in time, special It is not the generation situation of side reaction product, associated process conditions can be adjusted in time, " is finally controlled " with " process control " replacement, This with the prior art mostly using when hydrogen " no longer consume terminate catalytic hydrogenation reaction " compared with, to catalytic hydrogenation reaction process and The monitoring of terminal is more accurate, and can strictly control hydrogenation reaction to be allowed to 100% reaction without generating side reaction.

Charging order in catalytic hydrogenation process compared with the prior art, the present invention is according to certain order will be molten Agent, catalyst, paranitroanisole are put into plus hydrogen kettle stage by stage, and by during each production cycle discontinuously or continuously Ground add in paranitroanisole, and be aided with follow-up analysis come control plus hydrogen kettle in paranitroanisole concentration, take this producing Hydrogenating reduction speed is strictly controlled in technical process, so as to which the generation of intermediate product and the company of being reduced or avoided is reduced or avoided The generation of string reaction reduces impurity generation, finally improves the content of target product.And in contrast, in the prior art usually It is at the beginning of reaction, i.e., by paranitroanisole, solvent and catalyst disposably input plus hydrogen kettle, such as in CN101492379A Method.Such feeding mode is easy to carry out in metering and operation, this side is used when laboratory and industrialized production more Formula.In laboratory scale, since inventory is small, this feeding mode will not lead to the problem of it is too many, such as with Method disclosed in CN101492379A in the lab hydrogenates 100g paranitroanisoles, can obtain 100% turn really Rate and up to 99.8% purity.But when being amplified to industrially scalable, disposably feed intake often to will appear and much ask Topic, this may be when reacting too fast because of local raw material aggreation, due to no real time monitoring well and can not process Control, can only finally control so that the by-product generated in hydrogenation reaction is more or even very much, so as to be difficult to meet in the present invention Without post processing, it is disposable reach in high yield, the demand of high-purity.This may be also method in CN101492379A in industry The main reason for scale cannot succeed repeatedly.

The present invention due to high-purity, obtain target product in high yield, so for generality application for, without appoint What post processing can be used, and enormously simplifies technological process, reduces investment, reduce operating cost, reduce production cost, The generation of waste residue is avoided, realizes clean manufacturing.

From the point of view of common sense, the chemical reaction that can be realized under lab might not can obtain in industrialization Success, is all often that lab scale is preferable especially in terms of reaction effect, and can be deteriorated after being amplified to industrially scalable.But this Invention has obtained abundant inspection in production practices, by the preparation (p-aminophenyl of the continuous industry scale more than 2 years Methyl ether actual production 55-60t/d<Ton day>), it has sufficed to show that, catalytic hydrogenation system is come with preparation method provided by the invention Standby paraphenetidine, the purity and substantially 100% stable yield that can be up to 99.5% obtain target product, this knot Fruit is even all higher by much than this reaction can reach in the lab purity and yield.Therefore, the present invention is from theory Move towards an extremely successful example of practice.The paraphenetidine product of high-purity obtained by this case obtains downstream production The consistent favorable comment of producer, supply falls short of demand.

Therefore, method of the invention not only avoids the pollution of iron slag, waste water or sulfur-bearing waste residue, waste water to environment (iron powder reducing method and sodium sulfide reducing method are《Industry restructuring guidance list》In national industrial policies limitation intermediate item), Improve working environment, reduce labor intensity, realize innoxious green production, comply fully with《Industry restructuring guidance list》In National industrial policies encourage the requirement of intermediate item, while the advantages that but also with high yield, highly selective and low by-product, be easy to Realize serialization or intervalization large-scale industrial production.

Specific embodiment

The preparation of catalyst

Embodiment 1, four-way catalyst I

By nickel (Gansu Jinchuan 1 of 83.3kg^#Nickel), the aluminium (electrolytic aluminium) of 10.1kg, 5.3kg molybdenum (chemistry pure), 1.3kg Iron (chemistry pure) be packed into smelting furnace, heat after mixing, all high pure metals meltings.Quenching cooling, by obtained alloy Body mechanical lapping is into fine particle；The alloyed powder of 0.2-300 micron granularities is picked out in sieving.

The alloyed powder filtered out is activated：It, will be in alloyed powder under the conditions of 95 DEG C in 20% sodium hydroxide solution Most of aluminium dissolution, formed skeleton nickel；It is cleaned after sodium hydroxide solution reaches pH=8.1 with clean water, is sealed up for safekeeping with clean water, Raney's nickel catalyst I is formed, for use.

Embodiment 2, four-way catalyst II

By nickel (Gansu Jinchuan 1 of 95.6kg^#Nickel), the aluminium (electrolytic aluminium) of 3.8kg, 0.05kg molybdenum (chemistry pure), The iron (chemistry is pure) of 0.55kg is packed into smelting furnace, heats after mixing, all high pure metal meltings.Quenching cooling, by obtained by Alloy body mechanical lapping into fine particle；The alloyed powder of 0.2-300 micron granularities is picked out in sieving.

The alloyed powder filtered out is activated：It, will be in alloyed powder under the conditions of 95 DEG C in 20% potassium hydroxide solution Most of aluminium dissolution, formed skeleton nickel；It is cleaned after sodium hydroxide solution reaches pH=8.1 with clean water, is sealed up for safekeeping with clean water, Raney's nickel catalyst II is formed, for use.

Embodiment 3, four-way catalyst III

By nickel (Gansu Jinchuan 1 of 87.7kg^#Nickel), the aluminium (electrolytic aluminium) of 5.05kg, 7.2kg molybdenum (chemistry pure), The iron (chemistry is pure) of 0.05kg is packed into smelting furnace, heats after mixing, all high pure metal meltings.Quenching cooling, by obtained by Alloy body mechanical lapping into fine particle；The alloyed powder of 0.2-300 micron granularities is picked out in sieving.

The alloyed powder filtered out is activated：It, will be in alloyed powder under the conditions of 95 DEG C in 20% potassium hydroxide solution Most of aluminium dissolution, formed skeleton nickel；It is cleaned after sodium hydroxide solution reaches pH=7.8 with clean water, is sealed up for safekeeping with clean water, Raney's nickel catalyst III is formed, for use.

Raw material paranitroanisole progress catalytic hydrogenation is added in a continuous manner prepares paraphenetidine

Embodiment 4, industrially scalable prepare paraphenetidine

In order to provide certain downstream user 6350kg paraphenetidine products, and it requires purity more than 99.5%, into The following preparation of row：

(1) atent solvent and catalyst are added in：

First add hydrogen kettle 3 times with nitrogen displacement 16000L, analyze oxygen content≤0.5v% (percent by volume), Ran Houxiang in kettle Add the methanol 6400L for being conveyed in hydrogen kettle and accounting for the 40v% for adding hydrogen kettle dischargeable capacity.By catalyst charging hole, add to adding in hydrogen kettle Enter Raney's nickel four-way catalyst I obtained in 8.5kg embodiments 1, the additive amount of the catalyst is required target product (to amino Methyl phenyl ethers anisole) 0.13wt% (weight percent).

(2) continuous charging and hydrogenation reaction is carried out：

First it should add hydrogen kettle with nitrogen displacement, until oxygen content≤0.5v% (percent by volume) in this plus hydrogen kettle.

Again with the nitrogen in hydrogen displacement plus hydrogen kettle, until this plus hydrogen kettle hydrogen content >=90v% (percent by volume).

Hydrogen valve is opened, pressure in hydrogen to kettle is filled with and reaches 1.5MPa.

Stirring is opened, control mixing speed is in 400rpm.

It should add hydrogen kettle with steam heating, and control 5 DEG C/min of heating rate, the temperature for adding hydrogen kettle is risen to 60 DEG C and is maintained 45min。

To adding in hydrogen kettle with 3.0m³The charging rate of/h is added continuously paranitroanisole (industrial goods, purity 99.67%), meanwhile, maintain to add the pressure in hydrogen kettle, at 75-80 DEG C, to carry out hydrogenation reaction in 1.5MPa and temperature；

During the continuous charging of paranitroanisole, at interval of 30 minutes, sampling carried out gas chromatographic analysis, to supervise Control all impurity summations in paranitroanisole conversion ratio and reaction solution；When paranitroanisole conversion ratio is more than 90%, And all impurity summations be not more than 0.3% when keep charging, until add predetermined amount paranitroanisole (industrial goods, it is pure 99.67%) about 7893kg is spent, closes the material inlet valve of paranitroanisole；If one of conversion ratio, impurity summation two indices reach Less than above-mentioned requirements, then charging rate is reduced.

(3) stop hydrogenation reaction：Stop after adding in paranitroanisole, it is 1.5M to maintain to add the Hydrogen Vapor Pressure in hydrogen kettle Pa and temperature are 75-80 DEG C, the reaction was continued 30min；

At interval of 15 minutes, sampling carried out gas chromatographic analysis, until paranitroanisole conversion ratio for 100% (to nitre Base methyl phenyl ethers anisole surplus is almost that 0%), and all impurity summations stop hydrogenation reaction no more than 0.4%.

Continuous cooling is carried out, controls 1 DEG C/min of cooling rate, until temperature reaches 28 DEG C；Stop stirring, stand 60min, Binder is to catalyst separator.

(4) it detaches and purifies：

(mixture after restoring, including paraphenetidine, water and methanol and is urged the material that step (3) is extruded Agent) 90min is stood in catalyst separator.

Then, catalyst is filtered out by filtration system.These catalyst are after treatment, most of still to again return to It is recovered and applies mechanically in this production technology, small part is eliminated.

The material mixture liquid of catalyst is filtered out by desolventizing, dewatering system, first alcohol and water is sloughed, finally obtains The paraphenetidine product of 6350.5kg, yield 100%.After testing, the purity of the paraphenetidine product is 99.6% (that is, the content of paraphenetidine therein is 6324.5kg, accounts for the 99.6% of product gross weight, impurity part is actually Brought by raw material paranitroanisole), this purity fully meets demand of the lower step process of dye industry to material purity, therefore can Directly use and sell.

For the methanol that desolventizing system is collected into, the abovementioned steps that can be recycled directly back in this production technology and be recovered It applies mechanically.And the water that dewatering system is collected into can enter preceding working procedure as wash water, continue cycling through and apply mechanically.

It if, can also be by above-mentioned to amino in order to meet the more harsh client of the purity needs to paraphenetidine Methyl phenyl ethers anisole product passes through further rectification process, to obtain the paraphenetidine fine work of 99.9% or more purity.

Embodiment 5, industrially scalable prepare paraphenetidine

In order to provide certain downstream user 1600kg and paraphenetidine product of the purity more than 99.5%, carry out such as Under preparation：

(1) atent solvent and catalyst are added in：

First add hydrogen kettle 3 times with nitrogen displacement 4000L, analyze oxygen content≤0.5v% (percent by volume), Ran Houxiang in kettle Add the methanol 2400L for being conveyed in hydrogen kettle and accounting for the 60v% for adding hydrogen kettle dischargeable capacity.By catalyst charging hole, add to adding in hydrogen kettle Enter Raney's nickel four-way catalyst II obtained in 56kg embodiments 2, the additive amount of the catalyst is required target product (to amino Methyl phenyl ethers anisole) 3.5wt% (weight percent).

(2) continuous charging and hydrogenation reaction is carried out：

Hydrogen valve is opened, pressure in hydrogen to kettle is filled with and reaches 2.5MPa.

Stirring is opened, control mixing speed is in 550rpm.

It should add hydrogen kettle with steam heating, and control 10 DEG C/min of heating rate, the temperature for adding hydrogen kettle is risen to 90 DEG C and is maintained 5min。

To adding in hydrogen kettle with 1.2m³The charging rate of/h is added continuously paranitroanisole (industrial goods, purity 99.74%), meanwhile, maintain to add the pressure in hydrogen kettle, at 115-120 DEG C, to carry out hydrogenation reaction in 2.5MPa and temperature；

During the continuous charging of paranitroanisole, at interval of 15 minutes, sampling carried out gas chromatographic analysis, to supervise Control all impurity summations in paranitroanisole conversion ratio and reaction solution；When paranitroanisole conversion ratio is more than 90%, And all impurity summations be not more than 0.3% when keep charging, until add predetermined amount paranitroanisole (industrial goods, it is pure 99.74%) about 1989kg is spent, closes the material inlet valve of paranitroanisole；If one of conversion ratio, impurity summation two indices reach Less than above-mentioned requirements, then charging rate is reduced.

(3) stop hydrogenation reaction：Stop after adding in paranitroanisole, it is 2.5MPa to maintain to add the Hydrogen Vapor Pressure in hydrogen kettle It is 115-120 DEG C with temperature, the reaction was continued 10min；

At interval of 5 minutes, sampling carried out gas chromatographic analysis, until paranitroanisole conversion ratio for 100% (to nitro Methyl phenyl ethers anisole surplus is almost that 0%), and all impurity summations stop hydrogenation reaction no more than 0.4%.

Continuous cooling is carried out, controls 10 DEG C/min of cooling rate, until temperature reaches 28 DEG C；Stop stirring, stand 120min, binder to catalyst separator.

(4) it detaches and purifies：

(mixture after restoring, including paraphenetidine, water and methanol and is urged the material that step (3) is extruded Agent) 120min is stood in catalyst separator.

The material mixture liquid of catalyst is filtered out by desolventizing, dewatering system, first alcohol and water is sloughed, finally obtains 1600kg Paraphenetidine product, yield 100%.After testing, the purity of the paraphenetidine product for 99.7% (that is, its In paraphenetidine content for 1595kg, account for the 99.7% of product gross weight), this purity is fully met one under dye industry Demand of the step process to material purity, therefore can be used directly and sell.

Embodiment 6, industrially scalable prepare paraphenetidine

In order to provide certain downstream user 800kg and paraphenetidine product of the purity more than 99.5%, carry out as follows Preparation：

(1) atent solvent and catalyst are added in：

First add hydrogen kettle 3 times with nitrogen displacement 2000L, analyze oxygen content≤0.5v% (percent by volume), Ran Houxiang in kettle Add the methanol 200L for being conveyed in hydrogen kettle and accounting for the 10v% for adding hydrogen kettle dischargeable capacity.By catalyst charging hole, added in adding in hydrogen kettle Raney's nickel four-way catalyst III obtained in 8.0kg embodiments 3, the additive amount of the catalyst are required target products (to amino Methyl phenyl ethers anisole) 1.0wt% (weight percent).

(2) continuous charging and hydrogenation reaction is carried out：

Hydrogen valve is opened, pressure in hydrogen to kettle is filled with and reaches 0.5MPa.

Stirring is opened, control mixing speed is in 250rpm.

It should add hydrogen kettle with steam heating, and control 1 DEG C/min of heating rate, the temperature for adding hydrogen kettle is risen to 40 DEG C and is maintained 75min。

To adding in hydrogen kettle with 0.2m³The charging rate of/h is added continuously paranitroanisole (industrial goods, purity 99.7%), meanwhile, maintain to add the pressure in hydrogen kettle, at 55-60 DEG C, to carry out hydrogenation reaction in 0.5MPa and temperature；

During the continuous charging of paranitroanisole, at interval of 15 minutes, sampling carried out gas chromatographic analysis, to supervise Control all impurity summations in paranitroanisole conversion ratio and reaction solution；When paranitroanisole conversion ratio is more than 90%, And all impurity summations be not more than 0.3% when keep charging, until add predetermined amount paranitroanisole (industrial goods, it is pure 99.7%) about 998kg is spent, closes the material inlet valve of paranitroanisole；If one of conversion ratio, impurity summation two indices are not up to To above-mentioned requirements, then charging rate is reduced.

(3) stop hydrogenation reaction：Stop after adding in paranitroanisole, it is 0.5MPa to maintain to add the Hydrogen Vapor Pressure in hydrogen kettle It is 55-60 DEG C with temperature, the reaction was continued 60min；

At interval of 30 minutes, sampling carried out gas chromatographic analysis, until paranitroanisole conversion ratio for 100% (to nitre Base methyl phenyl ethers anisole surplus is almost that 0%), and all impurity summations stop hydrogenation reaction no more than 0.4%.

Continuous cooling is carried out, controls 5 DEG C/min of cooling rate, until temperature reaches 28 DEG C；Stop stirring, stand 20min, Binder is to catalyst separator.

(4) it detaches and purifies：

(mixture after restoring, including paraphenetidine, water and methanol and is urged the material that step (3) is extruded Agent) 30min is stood in catalyst separator.

The material mixture liquid of catalyst is filtered out by desolventizing, dewatering system, first alcohol and water is sloughed, finally obtains 803kg Paraphenetidine product, yield 100%.After testing, the purity of the paraphenetidine product for 99.6% (that is, its In paraphenetidine content for 800kg, account for the 99.6% of product gross weight), this purity is fully met one under dye industry Demand of the step process to material purity, therefore can be used directly and sell.

Comparative example 1

According to the synthetic method of alkoxyl aniline of the applicant in this case disclosed in Chinese patent CN101492379, by than Example is amplified to the preparation that commercial production scale carries out paraphenetidine.

By 1.5m³(about 1850kg) paranitroanisole (industrial goods, purity 99.73%), 18.5kg RaneyNi, 1850L methanol be added to 4000L nitrogen it is transposed plus hydrogen kettle in.After nitrogen, hydrogen displacement are qualified again, stirring is equal It is even, this plus hydrogen kettle are heated and open hydrogen valve, maintains plus hydrogen temperature in the kettle is to be passed through hydrogen at 80 DEG C to carry out hydrogenation reaction, Stop until hydrogen half an hour after is no longer inhaled in reaction.

With speed 1 DEG C/min continuous coolings until temperature reaches 28 DEG C；Stop stirring, stand 60min, binder and carry out with Separation and purifying as embodiment 4 filter out the material mixture liquid of catalyst by desolventizing, dewatering system, slough methanol and Water finally obtains the crude product of paraphenetidine, purity 96%, it is impossible to meet the use of downstream product, and need to further subtract Pressure distillation is purified.

After the crude product is evaporated under reduced pressure, the paraphenetidine product of 1413kg purity 99.8% can be obtained, is received Rate is 95%.

It can be seen that the industrialized process for preparing compared to this case can obtain the product of more than 99.6% purity, compare The method of example 1 can only obtain the crude product that purity is 96%, well below this case.This is because what this case embodiment 4-6 was used The preparation method of paraphenetidine is to reduce or avoid hydrogenating reduction by selecting the quaternary Raney's nickel catalyst of high activity The generation of impurity in reaction process；By being added continuously paranitroanisole, and it is aided with follow-up analysis and adds in hydrogen kettle to control The concentration of paranitroanisole takes this strictly to control hydrogenating reduction speed in production process；And with " process control " generation It carries out and (in addition to raw material impurity, all being reacted) for " final control " more accurate and stringent control hydrogenation reaction 100%；Cause This, preparation method of the invention can obtain up to 99.6% purity and substantially 100% without post processing after the reaction Yield, greatly reduce production cost, meanwhile, avoid the generation of a large amount of hazardous waste bottoms, realize clean manufacturing.

Raw material paranitroanisole progress catalytic hydrogenation is added in a manner of interruption and prepares paraphenetidine

Embodiment 7, industrially scalable prepare paraphenetidine

(1) it feeds for the first time：

First add hydrogen kettle 3 times with nitrogen displacement 16000L, analyze oxygen content≤0.5v% (percent by volume), Ran Houxiang in kettle Add the methanol 6400L for being conveyed in hydrogen kettle and accounting for the 40v% for adding hydrogen kettle dischargeable capacity.

By catalyst charging hole, Raney's nickel four-way catalyst I obtained in 8.5kg embodiments 1 is added in hydrogen kettle to adding, The additive amount of the catalyst is the 0.13wt% (weight percent) of target product (paraphenetidine).

It is pumped from paranitroanisole storage tank by feedstock transportation and is added continuously 1.5m into above-mentioned plus hydrogen kettle³(about 1850kg) paranitroanisole (industrial goods, purity 99.683%).

(2) hydrogenation reaction is carried out：

Stirring is opened, control mixing speed is in 400rpm.

By adding hydrogen kettle kettle inner coil pipe and kettle external jacket, pair plus hydrogen kettle heating, control 5 DEG C/min of heating rate, hydrogen will be added The temperature of kettle rises to 60 DEG C and maintains 45min, and each reactant in hydrogen kettle is added to proceed by hydrogenation reaction.

(3) continuous charging again：

Gas chromatographic analysis is carried out to the reaction solution sampling in step (2), until paranitroanisole conversion ratio is 90% More than, and when all impurity summations are not more than 0.3%, carry out the continuous charging again of paranitroanisole.

Maintain plus hydrogen kettle in pressure in 1.5MPa, to adding in hydrogen kettle with 2.0m³The charging rate of/h is added continuously again Paranitroanisole, until add the paranitroanisole (industrial goods, purity 99.683%) (about 7886.5kg) of predetermined amount Remainder 6036.5kg stops adding in paranitroanisole.

During continuous feed, at interval of 30 minutes, sampling carried out gas chromatographic analysis, turned to monitor paranitroanisole All impurity summations in rate and reaction solution；When paranitroanisole conversion ratio is more than 90%, and all impurity summations Continue to feed during no more than 0.3%, until completing this step；If one of conversion ratio, impurity summation two indices are not achieved above-mentioned It is required that it then reduces charging rate or stops charging.

It feeds simultaneously, by adjusting cooling water flow, it is ensured that add the reaction temperature in hydrogen kettle at 75-80 DEG C.

(4) stop hydrogenation reaction：

When adding predetermined amount (about 7886.5kg) and stop charging, maintain plus hydrogen kettle in Hydrogen Vapor Pressure for 1.5MPa and Temperature is 75-80 DEG C, the reaction was continued 30min.

(5) it detaches and purifies：

(mixture after restoring, including paraphenetidine, water and methanol and is urged the material that step (4) is extruded Agent) 90min is stood in catalyst separator.

The material mixture liquid of catalyst is filtered out by desolventizing, dewatering system, sloughs first alcohol and water, ultimate yield is 100% ground obtains the paraphenetidine product of 6345kg.After testing, the purity of the paraphenetidine product is 99.6% (that is, the content of paraphenetidine therein is 6320kg, accounting for the 99.6% of product gross weight), this purity fully meets dyestuff row Demand of the lower step process of industry to material purity, therefore can be used directly and sell.

It is slightly produced without the paraphenetidine that subsequent vacuum distillation then can only obtain purity 96% with aforementioned comparative example 1 Condition ratio, the preparation method for the paraphenetidine that this case embodiment 7 uses is by the way that the quaternary Raney's nickel of high activity is selected to urge Agent and the generation for reducing or avoiding impurity during hydrogenation reduction；By in batches but during each production cycle Be added continuously paranitroanisole, and be aided with follow-up analysis come control plus hydrogen kettle in paranitroanisole concentration, take this Hydrogenating reduction speed is strictly controlled in production process；It is and more accurate and stringent with " process control " replacement " final control " Control hydrogenation reaction 100% carries out；Therefore, industrial production process of the invention can obtain height without post processing after the reaction Purity and substantially 100% yield up to 99.6%, greatly reduce production cost, meanwhile, avoid a large amount of hazardous wastes Clean manufacturing is realized in the generation of bottoms.

Embodiment 8, industrially scalable prepare paraphenetidine

It is essentially identical with the method for embodiment 7, the difference lies in：

When step (1) feeds for the first time：The ethyl alcohol 6400L for accounting for the 40v% for adding hydrogen kettle dischargeable capacity is conveyed in hydrogen kettle to adding； Catalyst is Raney's nickel four-way catalyst II obtained in embodiment 2, and the additive amount of the catalyst is target product (p-aminophenyl Methyl ether) 0.26wt% (weight percent)；Inlet amount is 2.0m³Paranitroanisole (industrial goods, purity 99.747%).

When step (2) carries out hydrogenation reaction：It is filled with pressure in hydrogen to kettle and reaches 2.5MPa；Mixing speed is in 550rpm； Add hydrogen kettle 10 DEG C/min of heating rate, the temperature for adding hydrogen kettle is risen to 55 DEG C and maintain 5min.

Step (3) again continuous charging when：Maintain plus hydrogen kettle in pressure in 2.5MPa, to adding in hydrogen kettle with 5.0m³/ h's Charging rate is added continuously paranitroanisole (industrial goods, purity 99.747%) again；Ensure to add the reaction temperature in hydrogen kettle Degree is at 110 DEG C；During continuous feed, at interval of 15 minutes, sampling carried out gas chromatographic analysis.

When step (4) stops hydrogenation reaction：Hydrogen Vapor Pressure in maintenance plus hydrogen kettle is 2.5MPa and temperature is 110 DEG C, after Continuous reaction 10min；Cooling rate when carrying out continuous cooling is controlled in 10 DEG C/min；120min, binder are stood after stopping stirring To catalyst separator.

When step (5) is detached and is purified：120min is stood in catalyst separator.

In this embodiment, ultimate yield obtains the paraphenetidine product of 6369kg for 100%.After testing, should The purity of paraphenetidine product is 99.7% (that is, the content of paraphenetidine therein is 6350kg, to account for product gross weight 99.7%), this purity fully meets demand of the lower step process of dye industry to material purity, therefore can be used directly and sell It sells.

Embodiment 9, industrially scalable prepare paraphenetidine

When step (1) feeds for the first time：The methanol 9600L for accounting for the 60v% for adding hydrogen kettle dischargeable capacity is conveyed in hydrogen kettle to adding； Catalyst is Raney's nickel four-way catalyst III obtained in embodiment 3, and the additive amount of the catalyst is target product (to amino Methyl phenyl ethers anisole) 2.0wt% (weight percent)；Inlet amount is 0.5m³Paranitroanisole (industrial goods, purity 99.672%).

When step (2) carries out hydrogenation reaction：It is filled with pressure in hydrogen to kettle and reaches 0.5MPa；Mixing speed is in 250rpm； Add hydrogen kettle 1 DEG C/min of heating rate, the temperature for adding hydrogen kettle is risen to 45 DEG C and maintain 75min.

Step (3) again continuous charging when：Maintain plus hydrogen kettle in pressure in 0.5MPa, to adding in hydrogen kettle with 0.2m³/ h's Charging rate is added continuously paranitroanisole (industrial goods, purity 99.672%) again；Ensure to add the reaction temperature in hydrogen kettle Degree is at 55-65 DEG C；During continuous feed, at interval of 15 minutes, sampling carried out gas chromatographic analysis.

When step (4) stops hydrogenation reaction：Hydrogen Vapor Pressure in maintenance plus hydrogen kettle is 0.5MPa and temperature is 55-65 DEG C, The reaction was continued 60min；Cooling rate when carrying out continuous cooling is controlled in 5 DEG C/min；20min, binder are stood after stopping stirring To catalyst separator.

When step (5) is detached and is purified：30min is stood in catalyst separator.

In this embodiment, ultimate yield obtains the paraphenetidine product of 6375kg for 100%.After testing, should The purity of paraphenetidine product is 99.6% (that is, the content of paraphenetidine therein is 6350kg, to account for product gross weight 99.6%), this purity fully meets demand of the lower step process of dye industry to material purity, therefore can be used directly and sell It sells.

Claims

1. a kind of method that device catalytic hydrogenation with industrially scalable prepares paraphenetidine, this method is in a manner of being interrupted Raw material paranitroanisole is added in, this method includes the steps：

(1) it feeds for the first time：Atent solvent, quaternary Raney's nickel catalyst are sequentially added to by adding in hydrogen kettle for nitrogen displacement Afterwards, it is pumped by paranitroanisole storage tank by feedstock transportation and adds in 0.5-2.0m³Paranitroanisole；

(2) hydrogenation reaction is carried out：After should adding hydrogen kettle with nitrogen, hydrogen displacement successively, it is filled with pressure in hydrogen to kettle and reaches 0.5- 2.5MPa；It opens and stirs and heat this plus hydrogen kettle, control 1-10 DEG C of heating rate/min, the temperature for adding hydrogen kettle is risen into 40-90 DEG C and maintain 5-75min, proceed by hydrogenation reaction；

Wherein, oxygen content≤0.5v% in hydrogen kettle should extremely be added with nitrogen displacement plus hydrogen kettle；It should extremely add hydrogen kettle with hydrogen displacement nitrogen Hydrogen content >=90v%；

The speed of the stirring is 250-550rpm；

(3) continuous charging again：Gas chromatographic analysis is carried out to the reaction solution sampling in step (2), until paranitroanisole Conversion ratio carries out the continuous charging again of paranitroanisole more than 90%, and when all impurity summations are not more than 0.3%；

Maintain plus hydrogen kettle in pressure in 0.5-2.5MPa and temperature at 55-120 DEG C, to adding in hydrogen kettle with 0.2-25.0m³/ h's Charging rate is added continuously paranitroanisole again, continues hydrogenation reaction；

During the continuous feed of paranitroanisole, at interval of 15-75 minutes, sampling carried out gas chromatographic analysis, to supervise Control all impurity summations in paranitroanisole conversion ratio and reaction solution；When paranitroanisole conversion ratio is more than 90%, And all impurity summations continue to feed when being not more than 0.3%, until add predetermined amount or hydrogen kettle liquid position is added to reach 100%, Stop adding in paranitroanisole；If above-mentioned requirements are not achieved in one of conversion ratio, impurity summation two indices, charging speed is reduced Degree stops charging；

(4) stop hydrogenation reaction：Stop after adding in paranitroanisole, it is 0.5-2.5MPa to maintain to add the Hydrogen Vapor Pressure in hydrogen kettle It is 55-120 DEG C with temperature, the reaction was continued 10-60min；

Sampling carries out gas chromatographic analysis, until paranitroanisole conversion ratio is 100%, and all impurity summations are not more than 0.4%, stop hydrogenation reaction；

Continuous cooling is carried out, controls 1-10 DEG C of cooling rate/min, until temperature reaches less than 30 DEG C；Stop stirring, stand, pressure Expect to catalyst separator；

(5) it detaches and purifies：The material that step (4) extrudes in catalyst separator is stood, then passes through filtration system point Go out catalyst；The material mixture liquid of catalyst is filtered out by desolventizing, dewatering system, organic solvent and water is sloughed, finally obtains Content is not less than 99.5% paraphenetidine product.

2. the method that the device catalytic hydrogenation according to claim 1 with industrially scalable prepares paraphenetidine, wherein, institute The atent solvent for stating step (1) accounts for the 10-60v% for adding hydrogen kettle dischargeable capacity.

3. according to the method for preparing paraphenetidine with the device catalytic hydrogenation of industrially scalable of claims 1 or 2, In, the atent solvent of the step (1) is methanol, ethyl alcohol, normal propyl alcohol, isopropanol, benzene,toluene,xylene, Benzene Chloride, aniline, Dichloromethane, chloroform, carbon tetrachloride or dichloroethanes.

4. according to the method for preparing paraphenetidine with the device catalytic hydrogenation of industrially scalable of claims 1 or 2, In, the atent solvent of the step (1) is the material mixture liquid that catalyst is filtered out in step (5).

5. the method that the device catalytic hydrogenation according to claim 1 with industrially scalable prepares paraphenetidine, wherein, institute The nitrogen for stating step (1) is replaced into so that should add oxygen content≤0.5v% in hydrogen kettle.

6. the method that the device catalytic hydrogenation according to claim 1 with industrially scalable prepares paraphenetidine, wherein, institute Stating the main component of the quaternary Raney's nickel catalyst of step (1) is：By weight percentage, nickel 83.3-95.6wt%, Aluminium is 3.8-10.1wt%, molybdenum 0.05-7.2wt%, iron 0.05-1.7wt%；The additive amount of the quaternary Raney's nickel catalyst 0.10-3.5wt% for target product.

7. the method that the device catalytic hydrogenation according to claim 1 with industrially scalable prepares paraphenetidine, wherein, institute The time of repose for stating step (4) is 20-120min.

8. the method that the device catalytic hydrogenation according to claim 1 with industrially scalable prepares paraphenetidine, wherein, institute State the catalyst that step (5) separates be timed again after treatment, not timing or continuously recovery.

9. the method that the device catalytic hydrogenation according to claim 1 with industrially scalable prepares paraphenetidine, wherein, institute It states the water sloughed in step (5) through dewatering system and enters preceding working procedure as wash water, continue cycling through and apply mechanically.

10. the method that the device catalytic hydrogenation according to claim 1 with industrially scalable prepares paraphenetidine, wherein, The time of repose of the step (5) is 30-120min.