CN108129336A - The preparation method of paraphenetidine - Google Patents
The preparation method of paraphenetidine Download PDFInfo
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- CN108129336A CN108129336A CN201711484141.5A CN201711484141A CN108129336A CN 108129336 A CN108129336 A CN 108129336A CN 201711484141 A CN201711484141 A CN 201711484141A CN 108129336 A CN108129336 A CN 108129336A
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- hydrogenation reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a kind of preparation methods of paraphenetidine.The present invention by paranitroanisole by carrying out continuous catalytic hydrogenation and then by sedimentation and membrane filtration, paraphenetidine is obtained, this method can reach that production efficiency is high, product quality is high, labor intensity is low, environmentally friendly and catalyst utilization is high, be conducive to industrialized effect.
Description
Technical field
The present invention relates to the preparation methods of paraphenetidine.
Background technology
Paraphenetidine is a kind of important fine-chemical intermediate, is mainly used for medicine and dye industry, due to production
Product are widely used, and domestic and international demand is larger.At present, the method for producing paraphenetidine has iron powder reducing, vulcanization sodium reduction
Method, hydrogenating reduction method and to hydrogen-based aniline process etc..It is and main still using vulcanization sodium reduction preparation to amino in industrial production
Methyl phenyl ethers anisole, but this method environmental pollution is serious；Although p-aminophenyl first is prepared using catalytic hydrogenation method in addition, industrially also having
Ether, but to there are problems that separation and recovery of catalyst utilization rate low etc. for existing catalytic hydrogenation method.
Therefore, it is low and environment amenable to amino that a kind of high production efficiency, product quality height, labor intensity how to be provided
The preparation method of methyl phenyl ethers anisole is the technical issues of those skilled in the art are badly in need of solving
Invention content
The technical problems to be solved by the invention are to overcome in the preparation process of paraphenetidine in the prior art
The problem of existing environmental pollution is serious, catalyst recovery utilization rate is low, product purity is low or production capacity is low, so as to provide one kind
The preparation method of paraphenetidine.It is low, friendly to environment that this method can reach high production efficiency, product quality height, labor intensity
Good and catalyst utilization is high, is conducive to industrialized effect.
The present invention is to solve above-mentioned technical problem by the following technical programs.
The present invention provides a kind of preparation methods of paraphenetidine, and it includes following steps：In methanol, in catalyst
Under the action of, paranitroanisole and hydrogen are subjected to continuous catalytic hydrogenation reaction, reacting rear material is through sedimentation and membrane filtration, i.e.,
It can；
The catalyst is Pd/Al2O3；
The catalytic hydrogenation reaction carries out in two or more flowing bed reactors；
The flow of the catalytic hydrogenation reaction is 5000L/h~6000L/h, and Hydrogen Vapor Pressure is 2~3MPa；
Or the flow of catalytic hydrogenation reaction is 5750~6250L/h, Hydrogen Vapor Pressure is 0.8~2.5MPa；Such as
6000L/h, pressure 1MPa；
The flow of the catalytic hydrogenation reaction enters the thermopnore for the material liquid that paranitroanisole and methanol are formed
Flow during reactor.
In the present invention, the continuous catalytic hydrogenation reaction is to be continuously added to the material liquid.For example, first by pair
Nitroanisole is pumped into after being configured to its corresponding methanol solution in the flowing bed reactor；It is described that stream can be used when being pumped into
Amount pump accurate measurement continuous feed, the continuity of the stably catalyzed hydrogenation reaction of stable flow velocity energy are reacted in time in guarantee raw material
While complete, the production capacity of flowing bed reactor is made full use of.
In the present invention, the reacting rear material refers in methanol, under the effect of the catalyst, by paranitroanisole and hydrogen
Gas carries out all materials in the reaction solution after continuous catalytic hydrogenation reaction.
In the present invention, the hydrogenation reaction, which uses, uses Pd/Al in this field2O3/H2Catalyst system and catalyzing nitro is restored
Hydrogenation mechanism for amino carries out.
In the present invention, preferably, when the flow of the catalytic hydrogenation reaction is 5000L/h, the Hydrogen Vapor Pressure for 2~
3Mpa；
When the flow of the catalytic hydrogenation reaction is 5750L/h, Hydrogen Vapor Pressure is 0.8~2.5Mpa；
When the flow of the catalytic hydrogenation reaction is 6250L/h, Hydrogen Vapor Pressure is 0.8~2.5Mpa；
When the flow of the catalytic hydrogenation reaction is 6000L/h, the Hydrogen Vapor Pressure is 1~3Mpa.
In the present invention, the temperature of the continuous catalytic hydrogenation reaction can be 80~90 DEG C or 90~100 DEG C.
More preferably, the temperature of the continuous catalytic hydrogenation reaction is 90~100 DEG C, and the flow of the catalytic hydrogenation reaction is
6000L/h, the Hydrogen Vapor Pressure are 1~3Mpa；
Alternatively, the temperature of the continuous catalytic hydrogenation reaction is 80~90 DEG C, the flow of the catalytic hydrogenation reaction is
5000L/h, the Hydrogen Vapor Pressure are 2~3Mpa；
Alternatively, the temperature of the continuous catalytic hydrogenation reaction is 80~90 DEG C, the flow of the catalytic hydrogenation reaction is
5750L/h, the Hydrogen Vapor Pressure are 0.8~2.5Mpa；
Alternatively, the temperature of the continuous catalytic hydrogenation reaction is 90~100 DEG C, the flow of the catalytic hydrogenation reaction is
6250L/h, the Hydrogen Vapor Pressure are 0.8~2.5Mpa.
In the present invention, sedimentation kettle can be used in when sedimentation；Kettle is isolated urges through the sedimentation for the reacting rear material
Agent and supernatant；The catalyst returns to the flowing bed reactor；The supernatant carries out the membrane filtration.
It is described reacting rear material is precipitated before, the reacting rear material reaches the Eligibility requirements of this field routine i.e.
It can；The process that example is reacted as mentioned may be used this field common detection methods (such as HPLC, TLC or NMR) and be monitored,
Generally with paranitroanisole residual volume≤0.2%, finished product purity >=99.5% is reaction qualification.
In the present invention, inoranic membrane can be used in when membrane filtration, and the inoranic membrane is ceramics, metal or its composite material structure
Into symmetrically or non-symmetrically film.
In the present invention, average pore size 2nm~10 μm of the film.
In the present invention, preferably, the quantity of the film can be 2 or more；More preferably, the film is is connected in series with；
The film recycles the catalyst by pumping cycle in progress.
For example, when content of the catalyst in the inorganic film system reaches 10%~30%, by being recycled in pump
The catalyst is recycled.
In the present invention, the film after prolonged use, the catalyst molecule and the reacting rear material meeting
Filter membrane is blocked, preferably, being backwashed using methanol to the film, for example, methanol is pressed into film by the film outer chamber side
Inside it is rinsed.
In the present invention, the catalyst can be common particle catalyst, and fine for example, by using grain size 10nm~500 μm is urged
Agent.
In the present invention, the feed postition of the catalyst can be the mode of this field routine, such as add by catalyst
Batch can is added in into flowing bed reactor.
In the present invention, preferably, described two or more than two flowing bed reactors is are connected in series with, and the thermopnore
It is connection between reactor, such as makes to connect between each reactor by way of setting overflow pipe on each reactor
It is logical.
In the present invention, the single volume of the flowing bed reactor can be 10000L.
In the present invention, hydrogen is used for transmission preferably, being additionally provided between described two or more than two flowing bed reactors
Balance pipe, to keep connected state between each reactor.
In the present invention, described two or more than two flowing bed reactors can be that two or more add hydrogen kettle, such as
Level-one adds hydrogen kettle, secondary hydrogenation kettle, three-level to add hydrogen kettle, until N grades plus hydrogen kettle.
Preferably, when described two flowing bed reactors add hydrogen kettle and secondary hydrogenation kettle for level-one, the level-one adds hydrogen
It after material in kettle gradually increases, is flowed into the secondary hydrogenation kettle by overflow port, the reaction was continued to reaction conversion ratio qualification.
When reaction is to reaction conversion ratio qualification, residence time of the material in the autoclave series fluidized bed reactor is
About 2-3h.
In continuous catalytic hydrogenation reaction of the present invention, preferably first the methanol solution of the paranitroanisole is pumped
Enter the flowing bed reactor, then the catalyst is added in the flowing bed reactor, and put with inert gas
Reaction system is changed, then is passed through hydrogen displacement reaction system, then stirring, institute are opened under set reaction temperature and Hydrogen Vapor Pressure
While stating unlatching stirring, preferably continuously it is pumped into flow pump accurate measurement into the flowing bed reactor described to nitro
The methanol solution of methyl phenyl ethers anisole, while the continuous hydrogen that is passed through controls Hydrogen Vapor Pressure in set pressure limit.
Wherein, the dosage of the methanol solution of the paranitroanisole and the catalyst can be no more than the stream
In the range of the maximum reaction capacity of dynamic bed reactor optionally；The inert gas is preferably nitrogen；It is described with inert gas
Replace reaction system preferably three times and more than；It is described be passed through hydrogen displacement reaction system preferably three times and more than.
In the present invention, the Pd/Al2O3In Pd and Al2O3Mass ratio be (0.5~1)：100.
In the present invention, the weight ratio of the catalyst and the paranitroanisole can be 0.05:1-0.15:1, such as
0.1:1。
In the present invention, the mass ratio of the paranitroanisole and the methanol can be 1:4~1:10.
In the present invention, the catalyst is preferably added within the period of fixed intervals to ensure in continuous flow procedure
Its catalytic activity is stablized；The period of the fixed intervals is preferably 2-5h, such as 3h；The additional amount of the catalyst accounts for catalysis
The 1-2.5% of the weight percent of agent inventory, such as 2%.
In the present invention, filtrate of the reacting rear material through settling and membrane filtration obtains can also be post-processed, such as steam
It evaporates and/or crystallizes.
Wherein, the distillation can carry out in distillation still, and the solvent that the distillation obtains is recyclable.
Wherein, the crystallization can carry out in crystallization kettle.
The present invention provides a kind of preparation methods of paraphenetidine, include the following steps：
In the presence of hydrogen, catalyst, the mixed system of paranitroanisole and solvent is continuously added to thermopnore reaction
Continuous catalytic hydrogenation reaction is carried out in device；The flowing bed reactor is more than two-stage or two-stage adds the series connection of hydrogen kettle；Reaction solution
After carrying out continuous catalytic hydrogenation at different levels plus hydrogen kettle successively, settled into sedimentation kettle, by settling obtained catalysis
Agent is returned in the flowing bed reactor and is recycled, and realizes continuous catalytic hydrogenation；The supernatant that sedimentation obtains is led to
The membrane filter for crossing two or more series connection is filtered, and realizes interior cycle by pump between the membrane filter, filtrate is after
Handle to obtain paraphenetidine, you can；Wherein, when the flow of the mixed system is 5000L/h~6000L/h, the hydrogen
The pressure of gas is 2~3MPa；Or the flow of the mixed system be 5750L/h~6250L/h when, the pressure of the hydrogen
For 0.8~2.5MPa；When the flow of example mixed system as mentioned is 6000L/h, the pressure of the hydrogen is 1MPa；Described
Catalyst is Pd/Al2O3；The solvent is methanol.
In the present invention, the hydrogenation reaction, which uses, uses Pd/Al in this field2O3/H2Catalyst system and catalyzing nitro is restored
Hydrogenation mechanism for amino carries out.
In the present invention, preferably, when the flow of the catalytic hydrogenation reaction is 5000L/h, the Hydrogen Vapor Pressure for 2~
3Mpa；
When the flow of the catalytic hydrogenation reaction is 5750L/h, Hydrogen Vapor Pressure is 0.8~2.5Mpa；
When the flow of the catalytic hydrogenation reaction is 6250L/h, Hydrogen Vapor Pressure is 0.8~2.5Mpa；
When the flow of the catalytic hydrogenation reaction is 6000L/h, the Hydrogen Vapor Pressure is 1~3Mpa.
In the present invention, the temperature of the continuous catalytic hydrogenation reaction can be 80~90 DEG C or 90~100 DEG C.
More preferably, the temperature of the continuous catalytic hydrogenation reaction is 90~100 DEG C, and the flow of the catalytic hydrogenation reaction is
6000L/h, the Hydrogen Vapor Pressure are 1~3Mpa；
Alternatively, the temperature of the continuous catalytic hydrogenation reaction is 80~90 DEG C, the flow of the catalytic hydrogenation reaction is
5000L/h, the Hydrogen Vapor Pressure are 2~3Mpa；
Alternatively, the temperature of the continuous catalytic hydrogenation reaction is 80~90 DEG C, the flow of the catalytic hydrogenation reaction is
5750L/h, the Hydrogen Vapor Pressure are 0.8~2.5Mpa；
Alternatively, the temperature of the continuous catalytic hydrogenation reaction is 90~100 DEG C, the flow of the catalytic hydrogenation reaction is
6250L/h, the Hydrogen Vapor Pressure are 0.8~2.5Mpa.
In the present invention, more than the two-stage or two-stage plus hydrogen kettle can be that level-one adds hydrogen kettle, secondary hydrogenation kettle, three-level to add hydrogen
Kettle, until N grades plus hydrogen kettle.
In the present invention, in the flowing bed reactor, single described plus hydrogen kettle volume can be 10000L.
In the present invention, preferably, be connection more than the two-stage or two-stage plus between hydrogen kettle, such as it is described respectively plus hydrogen kettle
Between connected in a manner that overflow pipe is set.
In the present invention, preferably, being connected between the sedimentation kettle and described plus hydrogen kettle, such as the sedimentation kettle and institute
State plus hydrogen kettle between connected in a manner that overflow pipe is set.
The feed postition of the hydrogen can be the feed postition of this field routine, it may for example comprise following steps：To flowing
Nitrogen is passed through in bed reactor and/or sedimentation kettle and replaces air therein, displacement once or more (such as three times)；Later
It is passed through hydrogen again and replaces nitrogen therein, displacement once or more (such as three times), then continuously it is passed through hydrogen, you can.
The mass ratio of the paranitroanisole and the solvent can be 1:4~1:10.
The paranitroanisole and the mixed system of solvent can be that this field is conventional, such as is stirred in material kettle
Uniformly.
When the mixed system is continuously added to, the flow preferably uses flow pump accurate measurement.Stable stream
The continuity of the fast stably catalyzed hydrogenation reaction of energy while the reaction was complete in time for guarantee raw material, makes full use of thermopnore to react
The production capacity of device.
The feed postition of the catalyst can be the mode of this field routine, such as by catalyst shot tank to flowing
It is added in bed reactor.
The catalyst can be that this field is conventional with paranitroanisole mass percent, such as 5%~15% (again
Such as 8%~10%).Preferably, the catalyst is added to ensure into the flowing bed reactor at interval of 2~5h
Its catalytic activity is stablized, and the additional amount of the catalyst and the weight percent of initial charge are 1%~2.5%.
It is described reaction solution is precipitated before, the reaction solution reaches the Eligibility requirements of this field routine；Such as institute
The process for the reaction stated may be used this field common detection methods (such as HPLC, TLC or NMR) and be monitored, generally with right
Nitro-anisole residues amount≤0.2%, finished product purity >=99.5% are qualified for reaction.
The membrane filter can be the inoranic membrane of this field routine, and the inoranic membrane is ceramics, metal or its composite wood
Expect the symmetrically or non-symmetrically film formed.
The interior cycle can be by the catalyst concentration (such as being concentrated into 10-30%) in the supernatant, and will be dense
Catalyst pump after contracting is returned in catalyst shot tank, carries out cycling and reutilization.
In the present invention, in the membrane filter, the average pore size of film is preferably 2nm~10 μm.
After prolonged use, the catalyst molecule and reacting rear material can block filter membrane to the film, compared with
Goodly, using the solvent by film outer chamber side press-in film in backwashed, after material Impurity elution is clean, by feed liquid put to
Recycling design in distillation still, catalyst fine particle is dissolved with salpeter solution to be removed.
In the present invention, the catalyst can recycle, and the number of the cycle does not do specific restriction, as long as catalyst
The effect of catalysis meets the requirement of the present invention, and number can be 10 times or more.
Described post processing can be that this field is conventional, for example, through distilling, concentrating and/or crystallize, obtain described to ammonia
Base methyl phenyl ethers anisole；Recovered solvent recycles；Preferably the recovered solvent enters back into material kettle and is recycled after rectifying
It utilizes.
In the present invention, the preparation method is preferably comprised following steps：
(1) by the mixed system of the paraphenetidine and solvent, by the flow pump from the material
It is continuously added in kettle in the flowing bed reactor, the catalyst is added to institute by the catalyst coppers
It states in flowing bed reactor；The flowing bed reactor adds hydrogen kettle for two-stage, by adding the overflow pipe string set between hydrogen kettle
Connection；Hydrogen will be replaced into the flowing bed reactor；
(2) in the presence of the hydrogen and the catalyst, the mixture of the paranitroanisole and solvent
The level-one that system is continuously added to the flowing bed reactor adds progress catalytic hydrogenation reaction in hydrogen kettle；And every 3~5h to institute
It states in the level-one hydrogenation reaction kettle of flowing bed reactor and adds the catalyst；Reaction solution adds in hydrogen kettle gradually in the level-one
It after increasing, is flowed into secondary hydrogenation kettle by overflow port, carries out continuous catalytic hydrogenation at different levels plus hydrogen kettle successively；
(3) reaction solution after the continuous catalytic hydrogenation is overflow by what is set between the sedimentation kettle and described plus hydrogen kettle
Flow tube, which enters in the sedimentation kettle, to be settled, and is returned in the flowing bed reactor by settling the obtained catalyst pump
It is recycled；The supernatant that sedimentation obtains is filtered by the membrane filter of two series connection；Between the membrane filter
Interior cycle is carried out by pump, by the catalyst concentration in the supernatant, and the catalyst pump after concentration is returned to the catalysis
In agent feed pot, cycling and reutilization；
(4) filtrate being obtained by filtration through step (3) enters after distillation still distilled, and into crystallization kettle crystallize pure
Change, obtain paraphenetidine；The solvent of distillation recovery further after rectifying, is pumped back in material kettle and carries out cycling and reutilization.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition can be combined arbitrarily each preferably to get the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is：
(1) using continuous feed, continuously hydrogen adding reduces intermittent charging substitution gas and putting after reaction back and forth
Null process reduces the loss of protective gas nitrogen and hydrogen, and operation simplifies, and hydrogen utilization ratio is high, reduces exhaust gas discharge and causes
Environmental pollution, and the safety is improved.
(2) recycling in catalyst, avoiding frequently filtering leads to catalyst loss and ingress of air, makes
Into catalyst inactivation, the service life of catalyst is improved, catalyst amount is few, and catalyst is after applying mechanically repeatedly, still not shadow
Ring the purity of product.
(3) using the catalyst of membrane filter, further recycling loss, the utilization rate of catalyst is improved.
(4) reaction process three wastes generate, and reduce environmental pollution.
(5) the paraphenetidine product of the catalytic hydrogenation production method production described in, liquid chromatogram content is up to 99%
More than.
Description of the drawings
Fig. 1 is the process flow chart that catalytic hydrogenating reduction prepares paraphenetidine in the embodiment of the present invention；
Flow contains material kettle 1 in figure, with stirring plus hydrogen kettle 2,3, catalyst sedimentation kettle 4, two sets of membrane filters 5,6,
Distillation still 7, rectifying still 8, condenser 9, receiving slit 10 recrystallize kettle 11, centrifuge 12, buried slot 13, catalyst coppers 14.
As shown in Figure 1, by solvent, material input material kettle 1, stir evenly, being continuously driven into level-one by pump control flow adds hydrogen kettle 2
In, catalyst adds in level-one by feed pot 14 and adds in hydrogen kettle 2, is passed through air in nitrogen exchange system, then with hydrogen exchange system
Interior gas opens stirring, controls temperature, opens charge pump continuous feed, controls gas reactor pressure, and reaction solution adds hydrogen by level-one
2 overflow of kettle enters secondary hydrogenation kettle 3, then overflow enters catalyst sedimentation kettle 4, and reaction solution is just detached through sedimentation, reducing solution with catalyst,
Upper strata reducing solution squeezes into membrane filter 5,6 by pumping, and the catalyst of lower floor's sedimentation is squeezed by pumping in level-one and secondary hydrogenation kettle 2,3,
Reducing solution is completely separated, reducing solution enters in distillation still 7, and part is mixed in membrane filter 5,6 after the filtering of membrane filter 5,6
The material of catalyst through pump carry out in recycle, when catalyst content is concentrated into 20-30%, catalyst shot tank 14 is driven by pump
In, for adding the catalyst for adding and being lost in hydrogen kettle.After reducing solution enters distillation still 7, solvent is distilled to recover, further through rectifying
After 8 rectifying of tower, condensed device 9 condenses, and is received by fluid reservoir 10, and recovered solvent can be driven into material kettle 1 by pump and be followed
Ring recycles, and the feed liquid after precipitation is put into recrystallization kettle 11, after recrystallization purification, is discharged to centrifuge, obtains product, mother liquor into
Enter in ground slots 13, recrystallized for next group.
Specific embodiment
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.Test method without specific conditions in the following example, according to conventional methods and conditions or according to quotient
Product specification selects.
Membrane filter is by the Jiangsu JWCM37*25 type purpose ceramic-film filters that my high-tech is sold long.
Embodiment 1
A kind of preparation method of paraphenetidine, using paranitroanisole as raw material, using Pd/Al2O3Catalyst,
Continuous catalytic hydrogenation reaction is carried out in reactor, for catalyst after separation and recovery, reducing solution obtains target product through precipitation, purification
Paraphenetidine.
Specific steps include：
(1) will methanol 5000kg, paranitroanisole 1250kg put into material kettle in, subsequently feed intake according to the ratio into
Row, stirs evenly, is squeezed into level-one hydrogenation reaction kettle with pump, adds in Pd/Al2O3Catalyst 125kg, the grain size of catalyst are
10nm is passed through nitrogen exchange system three times, then is passed through hydrogen exchange system three times, opens stirring, is warming up to 90-100 DEG C, with
The flow of 6000L/h adds the material liquid that paranitroanisole is pumped into hydrogen kettle to level-one, is passed through H2, the hydrogen pressure in control system
Power is 1.0MPa, and is added at interval of 3h into level-one hydrogenation reaction kettle into Pd/Al2O3Catalyst 2.5kg, level-one add in hydrogen kettle
Material gradually increase after, by overflow port flow into secondary hydrogenation kettle in, material is adding residence time about 2-3h in hydrogen kettle, reaction
After qualified (with paranitroanisole residual volume≤0.2%), through the overflow of secondary hydrogenation kettle to settling kettle.
(2) feed liquid is in sedimentation kettle through sedimentation, and lower catalyst agent is squeezed into through pump to be added in hydrogen kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by being recycled in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid pumped concentration, realizes internal recycle.Used in the step
Film is ceramic membrane, average pore size 2nm.
(3) into distillation still, after heating removes solvent methanol, feed liquid is put into crystallization kettle, is passed through for the reducing solution after filtering
Purification, obtains paraphenetidine product, content 99.9%, production capacity 950kg/h.
Embodiment 2
(1) methanol 5000kg, paranitroanisole 1250kg are put into material kettle, subsequently feeds intake according to the ratio, stir
It mixes uniformly, is squeezed into level-one hydrogenation reaction kettle with pump, add in Pd/Al2O3Catalyst 125kg, the grain size of catalyst is 500 μm；It is logical
Enter nitrogen exchange system three times, then be passed through hydrogen exchange system three times, open stirring, 80-90 DEG C is warming up to, with 5000L/h's
Flow adds the material liquid that paranitroanisole is pumped into hydrogen kettle to level-one, is passed through H2, the Hydrogen Vapor Pressure in control system is
3.0MPa, and added at interval of 3h into level-one hydrogenation reaction kettle into Pd/Al2O3Catalyst 2.5kg, level-one add the object in hydrogen kettle
It after material gradually increases, is flowed into secondary hydrogenation kettle by overflow port, material is adding residence time about 2-3h in hydrogen kettle, and reaction is qualified
After (with paranitroanisole residual volume≤0.2%), through the overflow of secondary hydrogenation kettle to settling kettle.
(2) feed liquid is in sedimentation kettle through sedimentation, and lower catalyst agent is squeezed into through pump to be added in hydrogen kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by being recycled in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid pumped concentration, realizes internal recycle.Used in the step
Film is ceramic membrane, and average pore size is 10 μm.
(3) into distillation still, after heating removes solvent methanol, feed liquid is put into crystallization kettle, is passed through for the reducing solution after filtering
Purification, obtains paraphenetidine product, content 99.8%, production capacity 790kg/h.
Embodiment 3
(1) methanol 12500kg, paranitroanisole 1250kg are put into material kettle, are subsequently fed intake and are stirred according to the ratio
Uniformly, it stirs evenly, is squeezed into level-one hydrogenation reaction kettle with pump, add in Pd/Al2O3Catalyst 125kg, the grain size of catalyst are
10nm；It is passed through nitrogen exchange system three times, then is passed through hydrogen exchange system three times, open stirring, be warming up to 90-100 DEG C, with
The flow of 6000L/h adds the material liquid that paranitroanisole is pumped into hydrogen kettle to level-one, is passed through H2, the hydrogen pressure in control system
Power is 3.0MPa, and is added at interval of 3h into level-one hydrogenation reaction kettle into Pd/Al2O3Catalyst 2.5kg, level-one add in hydrogen kettle
Material gradually increase after, by overflow port flow into secondary hydrogenation kettle in, material is adding residence time about 2-3h in hydrogen kettle, reaction
After qualified (with paranitroanisole residual volume≤0.2%), through the overflow of secondary hydrogenation kettle to settling kettle.
(2) feed liquid is in sedimentation kettle through sedimentation, and lower catalyst agent is squeezed into through pump to be added in hydrogen kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by being recycled in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid pumped concentration, realizes internal recycle.Used in the step
Film is ceramic membrane, average pore size 2nm.
(3) into distillation still, after heating removes solvent methanol, feed liquid is put into crystallization kettle, is passed through for the reducing solution after filtering
Purification, obtains paraphenetidine product, content 99.2%, production capacity 430kg/h.
Embodiment 4
(1) methanol 5000kg, paranitroanisole 1250kg are put into material kettle, are subsequently fed intake according to the ratio, stirring
Uniformly, it is squeezed into level-one hydrogenation reaction kettle with pump, adds in Pd/Al2O3Catalyst 125kg, the grain size of catalyst is 100 μm；It is passed through
Nitrogen exchange system three times, then is passed through hydrogen exchange system three times, opens stirring, 80-90 DEG C is warming up to, with the stream of 5000L/h
The material liquid for adding to level-one and paranitroanisole being pumped into hydrogen kettle is measured, is passed through H2, the Hydrogen Vapor Pressure in control system is 2.0MPa,
And it is added at interval of 3h into level-one hydrogenation reaction kettle into Pd/Al2O3Catalyst 2.5kg, level-one add the material in hydrogen kettle gradually to increase
It after mostly, is flowed into secondary hydrogenation kettle by overflow port, material is adding residence time about 2-3h in hydrogen kettle, and reaction qualification is (with to nitre
Base anisole residues amount≤0.2%) after, through the overflow of secondary hydrogenation kettle to settling kettle.
(2) feed liquid is in sedimentation kettle through sedimentation, and lower catalyst agent is squeezed into through pump to be added in hydrogen kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by being recycled in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid pumped concentration, realizes internal recycle.Used in the step
Film is metal film, average pore size 2nm.
(3) into distillation still, after heating removes solvent methanol, feed liquid is put into crystallization kettle, is passed through for the reducing solution after filtering
Purification, obtains paraphenetidine product, content 99.0%, production capacity 790kg/h.
Embodiment 5
(1) methanol 5000kg, paranitroanisole 1250kg are put into material kettle, are subsequently fed intake according to the ratio, stirring
Uniformly, it is squeezed into level-one hydrogenation reaction kettle with pump, adds in Pd/Al2O3Catalyst 125kg, the grain size of catalyst is 250 μm；It is passed through
Nitrogen exchange system three times, then is passed through hydrogen exchange system three times, opens stirring, 80-90 DEG C is warming up to, with the stream of 5750L/h
The material liquid for adding to level-one and paranitroanisole being pumped into hydrogen kettle is measured, is passed through H2, the Hydrogen Vapor Pressure in control system is 0.8MPa,
And it is added at interval of 3h into level-one hydrogenation reaction kettle into Pd/Al2O3Catalyst 2.5kg, level-one add the material in hydrogen kettle gradually to increase
It after mostly, is flowed into secondary hydrogenation kettle by overflow port, material is adding residence time about 2-3h in hydrogen kettle, and reaction qualification is (with to nitre
Base anisole residues amount≤0.2%) after, through the overflow of secondary hydrogenation kettle to settling kettle.
(2) feed liquid is in sedimentation kettle through sedimentation, and lower catalyst agent is squeezed into through pump to be added in hydrogen kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by being recycled in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid pumped concentration, realizes internal recycle.Used in the step
Film is composite material film, average pore size 2nm.
(3) into distillation still, after heating removes solvent methanol, feed liquid is put into crystallization kettle, is passed through for the reducing solution after filtering
Purification, obtains paraphenetidine product, content 94.6%, production capacity 900kg/h.
Embodiment 6
(1) methanol 5000kg, paranitroanisole 1250kg are put into material kettle, are subsequently fed intake according to the ratio, stirring
Uniformly, it is squeezed into level-one hydrogenation reaction kettle with pump, adds in Pd/Al2O3Catalyst 125kg, the grain size of catalyst is 10nm, is passed through
Nitrogen exchange system three times, then is passed through hydrogen exchange system three times, opens stirring, 80-90 DEG C is warming up to, with the stream of 5750L/h
The material liquid for adding to level-one and paranitroanisole being pumped into hydrogen kettle is measured, is passed through H2, the Hydrogen Vapor Pressure in control system is 2.5MPa,
And it is added at interval of 3h into level-one hydrogenation reaction kettle into Pd/Al2O3Catalyst 2.5kg, level-one add the material in hydrogen kettle gradually to increase
It after mostly, is flowed into secondary hydrogenation kettle by overflow port, material is adding residence time about 2-3h in hydrogen kettle, and reaction qualification is (with to nitre
Base anisole residues amount≤0.2%) after, through the overflow of secondary hydrogenation kettle to settling kettle.
(2) feed liquid is in sedimentation kettle through sedimentation, and lower catalyst agent is squeezed into through pump to be added in hydrogen kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by being recycled in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid pumped concentration, realizes internal recycle.Used in the step
Film is composite material film, and average pore size is 10 μm.
(3) into distillation still, after heating removes solvent methanol, feed liquid is put into crystallization kettle, is passed through for the reducing solution after filtering
Purification, obtains paraphenetidine product, content 98.9%, production capacity 900kg/h.
Embodiment 7
(1) methanol 5000kg, paranitroanisole 1250kg are put into material kettle, are subsequently fed intake according to the ratio, stirring
Uniformly, it is squeezed into level-one hydrogenation reaction kettle with pump, adds in Pd/Al2O3Catalyst 125kg, the grain size of catalyst is 30nm；It is passed through
Nitrogen exchange system three times, then is passed through hydrogen exchange system three times, opens stirring, 90-100 DEG C is warming up to, with the stream of 6250L/h
The material liquid for adding to level-one and paranitroanisole being pumped into hydrogen kettle is measured, is passed through H2, the Hydrogen Vapor Pressure in control system is 2.5MPa,
And it is added at interval of 3h into level-one hydrogenation reaction kettle into Pd/Al2O3Catalyst 2.5kg, level-one add the material in hydrogen kettle gradually to increase
It after mostly, is flowed into secondary hydrogenation kettle by overflow port, material is adding residence time about 2-3h in hydrogen kettle, and reaction qualification is (with to nitre
Base anisole residues amount≤0.2%) after, through the overflow of secondary hydrogenation kettle to settling kettle.
(2) feed liquid is in sedimentation kettle through sedimentation, and lower catalyst agent is squeezed into through pump to be added in hydrogen kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by being recycled in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid pumped concentration, realizes internal recycle.Used in the step
Film is ceramic membrane, average pore size 2nm.
(3) into distillation still, after heating removes solvent methanol, feed liquid is put into crystallization kettle, is passed through for the reducing solution after filtering
Purification, obtains paraphenetidine product, content 99.6%, production capacity 980kg/h.
Embodiment 8
(1) methanol 5000kg, paranitroanisole 1250kg are put into material kettle, are subsequently fed intake according to the ratio, stirring
Uniformly, it is squeezed into level-one hydrogenation reaction kettle with pump, adds in Pd/Al2O3Catalyst 125kg, the grain size of catalyst is 100nm；It is passed through
Nitrogen exchange system three times, then is passed through hydrogen exchange system three times, opens stirring, 90-100 DEG C is warming up to, with the stream of 6250L/h
The material liquid for adding to level-one and paranitroanisole being pumped into hydrogen kettle is measured, is passed through H2, the Hydrogen Vapor Pressure in control system is 0.8MPa,
And it is added at interval of 3h into level-one hydrogenation reaction kettle into Pd/Al2O3Catalyst 2.5kg, level-one add the material in hydrogen kettle gradually to increase
It after mostly, is flowed into secondary hydrogenation kettle by overflow port, material is adding residence time about 2-3h in hydrogen kettle, and reaction qualification is (with to nitre
Base anisole residues amount≤0.2%) after, through the overflow of secondary hydrogenation kettle to settling kettle.
(2) feed liquid is in sedimentation kettle through sedimentation, and lower catalyst agent is squeezed into through pump to be added in hydrogen kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by being recycled in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid pumped concentration, realizes internal recycle.Used in the step
Film is ceramic membrane, average pore size 200nm.
(3) into distillation still, after heating removes solvent methanol, feed liquid is put into crystallization kettle, is passed through for the reducing solution after filtering
Purification, obtains paraphenetidine product, content 99.2%, production capacity 970kg/h.
Comparative example 1
(1) methanol 5000kg, paranitroanisole 1250kg are put into material kettle, are subsequently fed intake according to the ratio, stirring
Uniformly, it is squeezed into level-one hydrogenation reaction kettle with pump, adds in Pd/Al2O3Catalyst 125kg, the grain size of catalyst is 10nm；It is passed through
Nitrogen exchange system three times, then is passed through hydrogen exchange system three times, opens stirring, 80-90 DEG C is warming up to, with the stream of 5000L/h
The material liquid for adding to level-one and paranitroanisole being pumped into hydrogen kettle is measured, is passed through H2, the Hydrogen Vapor Pressure in control system is 1.0MPa,
And it is added at interval of 3h into level-one hydrogenation reaction kettle into Pd/Al2O3Catalyst 2.5kg, level-one add the material in hydrogen kettle gradually to increase
After mostly, being flowed into secondary hydrogenation kettle by overflow port, material is adding residence time about 3-5h in hydrogen kettle, raw material residual volume >=
5.6% reaction is not qualified, and feed liquid is through the overflow of secondary hydrogenation kettle to settling kettle.
(2) feed liquid is in sedimentation kettle through sedimentation, and lower catalyst agent is squeezed into through pump to be added in hydrogen kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by being recycled in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid pumped concentration, realizes internal recycle.Used in the step
Film is ceramic membrane, average pore size 2nm.
(3) reducing solution after filtering, into distillation still, heating removing solvent methanol.
Comparative example 2
(1) the continuous dosing mode in embodiment 1 is changed to intermittent feeds, i.e., solvent, itrated compound, catalyst, which add in, adds
In hydrogen kettle, gas reactor is replaced, stirring is warming up to 90-100 DEG C, is passed through hydrogen, and pressure is maintained to react 5-6h, instead in 1.0MPa
Liquid is answered to go out catalyst filtration through settling kettle sedimentation and applied mechanically for next batch, reducing solution is obtained through distilling separating methanol after purification
Product, content 99.7%.
(2) second batch raw material inventory is same as above, and catalyst applies mechanically last consignment of recycling successively, and adds catalyst, adds
Amount such as following table, other operations are same as above, obtained paraphenetidine product purity and unit interval production capacity such as following table.
Table 2
| Apply mechanically number | 1 | 2 | 3 | 4 | 5 | 6 |
| Cat additional amounts/% | 2.5 | 2.5 | 2.5 | 3.5 | 3.5 | 4.5 |
| Conversion ratio/% | 99.1 | 98.5 | 97.2 | 99.4 | 98.3 | 99.3 |
| Production capacity/(kg/h) | 205 | 212 | 217 | 209 | 211 | 213 |
It is as shown in the table, intermittent feeds, cat easy in inactivation, and needing, which increases cat dosages, could meet reaction requirement, and use
Intermittent feeds are required for carrying out the displacement of nitrogen and hydrogen every time before feeding intake, air-loss amount is big, and intermittent feeds unit
Time production capacity low compared with the production capacity of continuously hydrogen adding 70%.
Comparative example 3
Two autoclave serial hydrogenation kettles are changed to one plus hydrogen kettle, with embodiment 1, each batch of parametric results are as follows for other operations
Table 3.
Table 3
| Embodiment 1 | Comparative example 3-1 | Comparative example 3-2 | Comparative example 3-3 | |
| Reaction temperature/DEG C | 90-100 | 90-100 | 90-100 | 90-100 |
| Flow rate pump/L/h | 6000 | 4000 | 3000 | 2000 |
| Hydrogen Vapor Pressure/MPa | 1.0 | 1.0 | 1.0 | 1.0 |
| Purity/% | 99.9 | 98.1 | 98.5 | 99.1 |
| Production capacity/(kg/h) | 950 | 610 | 460 | 350 |
It is as shown in the table, using level-one plus hydrogen kettle, well below two autoclave serial hydrogenation kettles of unit interval production capacity.
Claims (10)
1. a kind of preparation method of paraphenetidine, which is characterized in that comprise the steps of：In methanol, in the work of catalyst
Under, paranitroanisole and hydrogen are subjected to continuous catalytic hydrogenation reaction, reacting rear material is through sedimentation and membrane filtration, you can；
The catalyst is Pd/Al2O3；
The catalytic hydrogenation reaction carries out in two or more flowing bed reactors；
The flow of the catalytic hydrogenation reaction is 5000L/h~6000L/h, and Hydrogen Vapor Pressure is 2~3MPa；
Alternatively, the flow of the catalytic hydrogenation reaction is 5750~6250L/h, Hydrogen Vapor Pressure is 0.8~2.5MPa；Such as
6000L/h, pressure 1MPa；
The flow of the catalytic hydrogenation reaction is reacted for the material liquid that paranitroanisole and methanol are formed into the thermopnore
Flow during device.
2. preparation method as described in claim 1, which is characterized in that the flow of the catalytic hydrogenation reaction be 5000L/h, institute
Hydrogen Vapor Pressure is stated as 2~3Mpa；
Alternatively, the flow of the catalytic hydrogenation reaction is 5750L/h, Hydrogen Vapor Pressure is 0.8~2.5Mpa；
Alternatively, the flow of the catalytic hydrogenation reaction is 6250L/h, Hydrogen Vapor Pressure is 0.8~2.5Mpa；
Alternatively, the flow of the catalytic hydrogenation reaction is 6000L/h, the Hydrogen Vapor Pressure is 1~3Mpa.
3. the preparation method, which is characterized in that the temperature of the continuous catalytic hydrogenation reaction is
80~90 DEG C or 90~100 DEG C；
Preferably, when the temperature of continuous catalytic hydrogenation reaction is 80~90 DEG C, the flow of the catalytic hydrogenation reaction is
5000L/h, the Hydrogen Vapor Pressure are 2~3Mpa；
The temperature of the continuous catalytic hydrogenation reaction is 80~90 DEG C, and the flow of the catalytic hydrogenation reaction is 5750L/h, described
Hydrogen Vapor Pressure is 0.8~2.5Mpa；
The temperature of continuous catalytic hydrogenation reaction is 90~100 DEG C, and the flow of the catalytic hydrogenation reaction is 6250L/h, institute
Hydrogen Vapor Pressure is stated as 0.8~2.5Mpa.
4. preparation method as described in claim 1, which is characterized in that using sedimentation kettle during the sedimentation；Object after the reaction
Material is through the isolated catalyst of the sedimentation kettle and supernatant；The catalyst returns to the flowing bed reactor；The supernatant
Liquid carries out the membrane filtration；
And/or formed for ceramics, metal or its composite material symmetrical using inoranic membrane, the inoranic membrane during membrane filtration
Or asymmetric membrane；
And/or described two or more than two flowing bed reactors are to connect to be connected in series with, and between the flowing bed reactor
Logical, such as make to connect between each reactor by way of setting overflow pipe on each reactor；
And/or the single volume of the flowing bed reactor is 10000L；
And/or the balance pipe for being used for transmission hydrogen is additionally provided between described two or more than two flowing bed reactors, to keep
Connected state between each reactor；
And/or described two or more than two flowing bed reactors add hydrogen kettle, such as level-one to add hydrogen for two or more
Kettle, secondary hydrogenation kettle, three-level add hydrogen kettle, until N grades plus hydrogen kettle.
5. preparation method as described in claim 1, which is characterized in that average pore size 2nm~10 μm of the film；
And/or the quantity of the film is 2 or more；Preferably, the film is is connected in series with；
And/or the film recycles the catalyst by pumping cycle in progress；
And/or the film is backwashed using methanol, for example, by methanol by being rushed in film outer chamber side press-in film
It washes；
And/or the fine catalyst that the catalyst is grain size 10nm~500 μm.
6. preparation method as described in claim 1, which is characterized in that the Pd/Al2O3In Pd and Al2O3Mass ratio be
(0.5~1)：100；
And/or the weight ratio of the catalyst and the paranitroanisole is 0.05:1-0.15:1, such as 0.1:1；
And/or the mass ratio of the paranitroanisole and the methanol is 1:4~1:10；
And/or the catalyst is added to ensure its catalytic activity within the period of fixed intervals in continuous flow procedure
Stablize；The period of the fixed intervals is preferably 2-5h, such as 3h；The additional amount of the catalyst accounts for catalyst inventory
The 1-2.5% of weight percent, such as 2%.
7. preparation method as described in claim 1, which is characterized in that, preferably first will be described in continuous catalytic hydrogenation reaction
The methanol solution of paranitroanisole is pumped into the flowing bed reactor, then the catalyst is added in the thermopnore
In reactor, and with inert gas replacement reaction system, then hydrogen displacement reaction system is passed through, then in set reaction temperature
It is stirred with being opened under Hydrogen Vapor Pressure, while the unlatching is stirred, preferably with flow pump accurate measurement continuously to the flowing
The methanol solution of the paranitroanisole is pumped into bed reactor, while the continuous hydrogen that is passed through controls Hydrogen Vapor Pressure.
8. a kind of preparation method of paraphenetidine, which is characterized in that include the following steps：In the presence of hydrogen, catalyst,
The mixed system of paranitroanisole and solvent is continuously added to carry out continuous catalytic hydrogenation reaction in flowing bed reactor；It is described
Flowing bed reactor be at least more than two-stage or two-stage plus the series connection of hydrogen kettle；Reaction solution carries out continuous at different levels plus hydrogen kettle successively
It after catalytic hydrogenation, is settled into sedimentation kettle, is returned in the flowing bed reactor by settling obtained catalyst
It is recycled, realizes continuous catalytic hydrogenation；The film mistake that the supernatant that sedimentation obtains is connected by two or more
Filter is filtered, and interior cycle is realized by pump between the membrane filter, and filtrate is post-treated to obtain paraphenetidine, you can；Its
In, when the flow of the mixed system is 5000L/h~6000L/h, the pressure of the hydrogen is 2~3MPa；It is or described
The flow of mixed system when being 5750L/h~6250L/h, the pressure of the hydrogen is 0.8~2.5MPa；Example is mixed as mentioned
When the flow of zoarium system is 6000L/h, the pressure of the hydrogen is 1MPa；The catalyst is Pd/Al2O3；The solvent
For methanol.
9. production method as claimed in claim 8, which is characterized in that in the flowing bed reactor, single described plus hydrogen
Autoclave body product is 10000L；
When the flow of the catalytic hydrogenation reaction is 5000L/h, the Hydrogen Vapor Pressure is 2~3Mpa；
When the flow of the catalytic hydrogenation reaction is 5750L/h, Hydrogen Vapor Pressure is 0.8~2.5Mpa；
When the flow of the catalytic hydrogenation reaction is 6250L/h, Hydrogen Vapor Pressure is 0.8~2.5Mpa；
When the flow of the catalytic hydrogenation reaction is 6000L/h, the Hydrogen Vapor Pressure is 1~3Mpa；
And/or it is described respectively plus hydrogen kettle between connected in a manner that overflow pipe is set；
And/or it is connected in a manner that overflow pipe is set between the sedimentation kettle and described plus hydrogen kettle；
And/or the feed postition of the hydrogen, include the following steps：Nitrogen is passed through into flowing bed reactor and/or sedimentation kettle
Gas replaces air therein, replaces once or more；It is passed through hydrogen again later and replaces nitrogen therein, displacement is primary or one
More than secondary, it is then continuously passed through hydrogen；
And/or the mass ratio of the paranitroanisole and the solvent is 1:4~1:10；
And/or the paranitroanisole and the mixed system of solvent stir evenly in material kettle；
And/or the mixed system, when being continuously added to, the flow uses flow pump accurate measurement；
And/or the catalyst is added in by catalyst shot tank into the flowing bed reactor；
And/or the catalyst and paranitroanisole mass percent are 5%~15%；
And/or the membrane filter is inoranic membrane, such as ceramics, metal or its composite material composition are symmetrically or non-symmetrically
Film；
And/or the interior cycle is by the catalyst concentration in the supernatant, and by the catalyst after concentration by being pumped back to
In catalyst shot tank, cycling and reutilization is carried out；
And/or in the membrane filter, the average pore size of film is 2nm~10 μm；
And/or the post processing is through distilling, concentrating and/or crystallize, obtain the paraphenetidine；That recycles is molten
Agent recycles.
10. preparation method as claimed in claim 8 or 9, which is characterized in that include the following steps：
(1) by the mixed system of the paranitroanisole and solvent, by the flow pump from the material kettle
It is continuously added in the flowing bed reactor, the catalyst is added in into the flowing by the catalyst coppers
In bed reactor；The flowing bed reactor adds hydrogen kettle for two-stage, by the way that the overflow pipe set between hydrogen kettle is added to connect；By institute
Hydrogen is replaced into the flowing bed reactor stated；
(2) in the presence of the hydrogen and the catalyst, the mixed system of the paranitroanisole and solvent connects
The continuous level-one for adding in the flowing bed reactor, which adds, carries out catalytic hydrogenation reaction in hydrogen kettle；And every 3~5h to the stream
The catalyst is added in the level-one hydrogenation reaction kettle of dynamic bed reactor；Reaction solution, which adds in the level-one in hydrogen kettle, gradually to be increased
Afterwards, it is flowed into secondary hydrogenation kettle by overflow port, carries out continuous catalytic hydrogenation at different levels plus hydrogen kettle successively；
(3) reaction solution after catalytic hydrogenation is settled by described described in the overflow pipe set between kettle and described plus hydrogen kettle entrance
It is settled in sedimentation kettle, is made by settling the obtained catalyst pump and returning in the flowing bed reactor recycle
With；The supernatant that sedimentation obtains is filtered by the membrane filter of two series connection；By in pump progress between the membrane filter
Cycle is returned to by the catalyst concentration in the supernatant, and by the catalyst pump after concentration in the catalyst shot tank,
Cycling and reutilization；
(4) filtrate enters after distillation still distilled, and carries out crystallization purifying into crystallization kettle, obtains paraphenetidine；It distills back
The solvent of receipts further after rectifying, is pumped back in material kettle and carries out cycling and reutilization.
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| CN111559966A (en) * | 2020-06-16 | 2020-08-21 | 浙江闰土股份有限公司 | Preparation method of p-anisidine and equipment for preparing p-anisidine |
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| CN101492379A (en) * | 2008-01-25 | 2009-07-29 | 南京理工大学 | Synthesis of alkoxyl aniline |
| CN106496046A (en) * | 2016-09-28 | 2017-03-15 | 连云港泰盛化工有限公司 | The method that solvent-free catalytic hydrogenation produces aminoanisole |
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