CN108276311A - A kind of preparation method of metanilic acid - Google Patents
A kind of preparation method of metanilic acid Download PDFInfo
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- CN108276311A CN108276311A CN201711484124.1A CN201711484124A CN108276311A CN 108276311 A CN108276311 A CN 108276311A CN 201711484124 A CN201711484124 A CN 201711484124A CN 108276311 A CN108276311 A CN 108276311A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a kind of preparation methods of metanilic acid.The present invention by m-nitrobenzene sulfonic acid by carrying out continuous catalytic hydrogenation and then by sedimentation and membrane filtration, obtain metanilic acid, this method is easy to operate, safe and can continuous production, it 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 invention belongs to chemical products production fields, and in particular to a kind of preparation method of metanilic acid.
Background technology
Metanilic acid is a kind of important reactive dye intermediate, for producing reactive brilliant red K-2B, bright red K-
2BP, bright red K-2G, bright red M-2B, bright red X-B, bright red X-10B, active purple k-3r etc..Using m-nitrobenzene sulfonic acid as raw material, I
The existing production method of state is mainly traditional iron powder reducing method, and this method uses iron powder, after reduction, needs a large amount of iron
Mud removes, and operating process is complicated, and the generation environmental pollution of a large amount of iron cements and its serious, in the shape that environmentally friendly trend is increasingly serious
Under formula, traditional production method has been no longer desirable for Chemical Manufacture.Nowadays, metanilic acid is prepared about catalytic hydrogenation
Method is it has been reported that as in CN101362710B, and using m-nitrobenzene sulfonic acid as raw material, in organic solvent, hydrogen is reducing agent,
2-10h is reacted under the conditions of 20-180 DEG C, metanilic acid is made.Although the method overcomes traditional iron powder reducing to environment
The defect polluted, but its technique is interval catalytic hydrogenation mode, operation is complicated, and due to batch production, adds every time
Before hydrogen charging, there will be replacement process, consume a large amount of nitrogen and hydrogen, the operations such as filtering are stood after reaction makes labor cost
Increasing, material and solvent loss can also be caused by recycling the process of catalyst, and catalyst service efficiency is low, therefore, intermittent life
Production, high energy consumption, safety is low, and material and human cost are high, low production efficiency.
Invention content
Technical problem to be solved by the present invention lies in order to overcome the preparation process of metanilic acid in the prior art
In or there is a problem of that environmental pollution is serious, or there are technological operations cumbersome, high energy consumption, safety are low, material and human cost
The problem of height, low production efficiency, thus provide a kind of preparation method of metanilic acid.The preparation method of the present invention is reachable
, product quality height high to production efficiency, labor intensity is low, environmentally friendly 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 metanilic acid, and it includes following steps：In methanol-water, urging
Under the action of agent, m-nitrobenzene sulfonic acid and hydrogen are subjected to continuous catalytic hydrogenation reaction, reacting rear material is through sedimentation and film mistake
Filter, 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；
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 is that the material liquid that m-nitrobenzene sulfonic acid and methanol-water are formed enters the flowing
Flow when bed reactor.
In the present invention, the continuous catalytic hydrogenation reaction is to be continuously added to the material liquid.For example, between first will be described
Nitrobenzene-sulfonic acid is pumped into after being configured to its corresponding methanol-water solution in the flowing bed reactor；It is described to adopt when being pumped into
With flow pump accurate measurement continuous feed, the continuity of the stably catalyzed hydrogenation reaction of stable flow velocity energy is ensureing that raw material is timely
While the reaction was complete, the production capacity of flowing bed reactor is made full use of.
In the present invention, the reacting rear material refers in methanol-water, under the effect of the catalyst, by m-nitrobenzene sulfonic acid
The all materials in the reaction solution after continuous catalytic hydrogenation reaction are carried out with hydrogen.
In the present invention, the hydrogenation reaction, which uses, uses Pd/Al in this field2O3/H2Catalyst system and catalyzing nitro is restored
It is carried out for the hydrogenation mechanism of amino.
In the present invention, preferably, when the flow of the catalytic hydrogenation reaction be 5000L/h when, the Hydrogen Vapor Pressure be 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, the methanol-water is the mixed solution of methanol and water, wherein the volume ratio of the methanol and the water
Can be 1:4~4:1, such as 1:1.
In the present invention, sedimentation kettle can be used in when sedimentation；The reacting rear material is urged through the sedimentation kettle is isolated
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 m-nitrobenzene sulfonic acid residual volume≤0.2%, finished product purity >=99.5% is that reaction is qualified.
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
At 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 to be 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 to the film using methanol, 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 be added by catalyst
Batch can is added into flowing bed reactor.
In the present invention, preferably, described two or more than two flowing bed reactors are to be connected in series with, and the thermopnore
It is connection between reactor, such as makes to connect between each reactor by way of overflow pipe is arranged 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 add hydrogen kettle for two or more, 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 are that level-one adds hydrogen kettle and secondary hydrogenation kettle, 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.
It is preferably first that the methanol-water of the m-nitrobenzene sulfonic acid is molten in continuous catalytic hydrogenation reaction of the present invention
Liquid pump enters the flowing bed reactor, then the catalyst is added in the flowing bed reactor, and with indifferent gas
Body replaces reaction system, then is passed through hydrogen displacement reaction system, then opens and stir under set reaction temperature and Hydrogen Vapor Pressure
It mixes, while the unlatching is stirred, is preferably continuously pumped into the flowing bed reactor with flow pump accurate measurement described
The methanol-water solution of m-nitrobenzene sulfonic acid, while the continuous hydrogen that is passed through controls Hydrogen Vapor Pressure in set pressure limit.
Wherein, the dosage of the methanol-water solution of the m-nitrobenzene sulfonic acid and the catalyst can be no more than described
Flowing bed reactor maximum reaction capacity within the scope of optionally；The inert gas is preferably nitrogen；It is described with inertia
Gas displacement reaction system is preferably three times or more；It is described to be passed through hydrogen displacement reaction system preferably three times or more.
In the present invention, the Pd/Al2O3In Pd and Al2O3Mass ratio can be (0.5~1)：100.
In the present invention, the weight ratio of the catalyst and the m-nitrobenzene sulfonic acid can be 0.05:1-0.15:1, such as
0.1:1。
In the present invention, the mass ratio of the m-nitrobenzene sulfonic acid and the methanol-water can be 1:4~1:10.
In the present invention, the methanol-water is the mixed solution of methanol and water, wherein the volume ratio of the methanol and the water
Can be 1:4~4:1, such as 1:1.
In the present invention, the catalyst is preferably added within the period of fixed intervals to ensure in continuous production process
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 be steamed
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 metanilic acid comprising following steps：It is deposited in hydrogen, catalyst
Under, it is anti-that the mixed system of m-nitrobenzene sulfonic acid and solvent is continuously added to progress continuous catalytic hydrogenation in flowing bed reactor
It answers；The flowing bed reactor is two-stage or two-stage or more plus the series connection of hydrogen kettle；Reaction solution carries out at different levels plus hydrogen kettle successively
After continuous catalytic hydrogenation, into being settled in sedimentation kettle, reacted back to the thermopnore by settling obtained catalyst
It is recycled in device, realizes continuous catalytic hydrogenation；The supernatant that sedimentation is obtained is concatenated by two or more
Membrane filter is filtered, and interior cycle is realized by pump between the membrane filter, and filtrate is post-treated to obtain metanilic acid, i.e.,
It can；Wherein, when the flow of the mixed system is 5000L/h~6000L/h, the pressure of the hydrogen is 2~3MPa；Or
When the flow of the mixed system is 5750L/h~6250L/h, the pressure of the hydrogen is 0.8~2.5MPa；Such as it is described
The flow of mixed system when being 6000L/h, the pressure of the hydrogen is 1MPa；The catalyst is Pd/Al2O3；Described
Solvent is methanol-water.
In the present invention, the hydrogenation reaction, which uses, uses Pd/Al in this field2O3/H2Catalyst system and catalyzing nitro is restored
It is carried out for the hydrogenation mechanism of amino.
In the present invention, preferably, when the flow of the catalytic hydrogenation reaction be 5000L/h when, the Hydrogen Vapor Pressure be 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 the 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 be connected in such a way that overflow pipe is set.
In the present invention, preferably, be connected between the sedimentation kettle and described plus hydrogen kettle, such as the sedimentation kettle and institute
It states and is connected in such a way that overflow pipe is set between adding hydrogen kettle.
The feed postition of the hydrogen can be the feed postition of this field routine, it may for example comprise following steps：To flowing
It is passed through nitrogen 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 m-nitrobenzene sulfonic acid and the solvent can be 1:4~1:10.
The mixed system of the m-nitrobenzene sulfonic acid and the solvent can be this field routine, such as in material kettle
It stirs evenly.
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 makes full use of thermopnore to react while the reaction was complete in time for guarantee raw material
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 with the m-nitrobenzene sulfonic acid mass percent can be that this field is conventional, such as 5%~
15% (in another example 8%~10%).Preferably, the catalysis is added into the flowing bed reactor at interval of 2~5h
To ensure that its catalytic activity is stablized, the additional amount of the catalyst and the weight percent of initial charge are 1~2.5% for agent.
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
Nitrobenzene-sulfonic acid residual volume≤0.2%, finished product purity >=99.5% are that reaction is qualified.
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 constituted.
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 returns 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 indentation 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.
The described post-processing can be that this field is conventional, for example, through distillation, concentration and/or crystallization, obtain it is described between ammonia
Base benzene sulfonic acid；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 metanilic acid and the solvent, by the flow pump from described
It is continuously added in material kettle in the flowing bed reactor, the catalyst is added by the catalyst coppers
Into the flowing bed reactor；The flowing bed reactor is that two-stage adds hydrogen kettle, by adding the overflow being arranged between hydrogen kettle
Pipe is connected；It will be replaced into hydrogen in the flowing bed reactor；
(2) in the presence of the hydrogen and the catalyst, the m-nitrobenzene sulfonic acid and the solvent it is mixed
The level-one that zoarium system is continuously added to the flowing bed reactor adds progress catalytic hydrogenation reaction in hydrogen kettle；And every 3~5h
The catalyst is added into the level-one hydrogenation reaction kettle of the flowing bed reactor；Reaction solution adds in the level-one in hydrogen kettle
It after gradually 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 be arranged 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 two concatenated membrane filters；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, obtains metanilic acid；The solvent of distillation recovery is pumped back in material kettle further after rectifying 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 that：
(1) continuous feed, continuously hydrogen adding is used to reduce 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
At 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) membrane filter, the catalyst that further recycling is lost in is used to improve the utilization rate of catalyst.
(4) reaction process three wastes generate, and reduce environmental pollution.
(5) the metanilic acid 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 of the embodiment of the present invention prepares metanilic acid；
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 is added 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 layer reducing solution squeezes into membrane filter 5,6 by pumping, and the catalyst of lower layer'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 cycle catalyst shot tank 14 is driven by pump when catalyst content is concentrated into 20-30%
In, for adding the catalyst for adding and being lost in hydrogen kettle.After reducing solution enters distillation still 7, it is distilled to recover solvent, further through rectifying
After 8 rectifying of tower, condensed device 9 condenses, and is received by fluid reservoir 10, 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 and is discharged to centrifuge after recrystallization purification, obtains product, mother liquor into
Enter in ground slots 13, is recrystallized for next group.
Specific implementation mode
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.In the following examples, the experimental methods for specific conditions are not specified, 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 metanilic acid, using m-nitrobenzene sulfonic acid 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
Metanilic acid.
Specific steps include：
(1) in 50% methanol aqueous solution 5000kg, m-nitrobenzene sulfonic acid 1250kg input material kettle, will subsequently feed intake by
It is carried out according to the ratio, stirs evenly, squeezed into level-one hydrogenation reaction kettle with pump, Pd/Al is added2O3Catalyst 125kg, catalyst
Grain size be 10nm, be passed through nitrogen exchange system three times, then be passed through hydrogen exchange system three times, open stirring, be warming up to 90-
100 DEG C, adds the material liquid for being pumped into m-nitrobenzene sulfonic acid in hydrogen kettle to level-one with the flow of 6000L/h, be passed through H2, in control system
Hydrogen Vapor Pressure be 1.0MPa, and added into level-one hydrogenation reaction kettle into Pd/Al at interval of 3h2O3Catalyst 2.5kg, level-one
It after adding the material in hydrogen kettle gradually to increase, is flowed into secondary hydrogenation kettle by overflow port, material is adding in hydrogen kettle the residence time about
2-3h, after reacting qualified (with m-nitrobenzene sulfonic acid 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 layer reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection realize that interior cycle, the catalyst in reducing solution are gradually concentrated into 10- by pump
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid for pumping concentration, realizes internal recycles.Used in the step
Film is ceramic membrane, average pore size 2nm.
(3) feed liquid is put into crystallization kettle, after heating removes solvent through carrying by filtered reducing solution into distillation still
It is pure, obtain metanilic acid product, content 99.9%, production capacity 950kg/h.
Embodiment 2
(1) in 50% methanol aqueous solution 5000kg, m-nitrobenzene sulfonic acid 1250kg input material kettle, will subsequently feed intake by
It according to the ratio, stirs evenly, is squeezed into level-one hydrogenation reaction kettle with pump, Pd/Al is added2O3Catalyst 125kg, the grain of catalyst
Diameter is 500 μm；It is passed through nitrogen exchange system three times, then is passed through hydrogen exchange system three times, open stirring, be warming up to 80-90 DEG C,
Add the material liquid for being pumped into m-nitrobenzene sulfonic acid in hydrogen kettle to level-one with the flow of 5000L/h, is passed through H2, the hydrogen in control system
Pressure is 3.0MPa, and is added into level-one hydrogenation reaction kettle into Pd/Al at interval of 3h2O3Catalyst 2.5kg, level-one add hydrogen kettle
After interior material gradually increases, flowed into secondary hydrogenation kettle by overflow port, material is adding residence time about 2-3h in hydrogen kettle, instead
After answering qualified (with m-nitrobenzene sulfonic acid 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 layer reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection realize that interior cycle, the catalyst in reducing solution are gradually concentrated into 10- by pump
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid for pumping concentration, realizes internal recycles.Used in the step
Film is ceramic membrane, and average pore size is 10 μm.
(3) feed liquid is put into crystallization kettle, after heating removes solvent through carrying by filtered reducing solution into distillation still
It is pure, obtain metanilic acid product, content 99.8%, production capacity 790kg/h.
Embodiment 3
(1) it by 50% methanol aqueous solution 12500kg, m-nitrobenzene sulfonic acid 1250kg input material kettles, subsequently feeds intake
It stirs evenly, stirs evenly according to the ratio, squeezed into level-one hydrogenation reaction kettle with pump, Pd/Al is added2O3Catalyst 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, open stirring, heating
To 90-100 DEG C, adds the material liquid for being pumped into m-nitrobenzene sulfonic acid in hydrogen kettle to level-one with the flow of 6000L/h, be passed through H2, control
Hydrogen Vapor Pressure in system is 3.0MPa, and is added into level-one hydrogenation reaction kettle into Pd/Al at interval of 3h2O3Catalyst
2.5kg after level-one adds the material in hydrogen kettle gradually to increase, is flowed by overflow port in secondary hydrogenation kettle, material is adding in hydrogen kettle
Residence time about 2-3h, after reacting qualified (with m-nitrobenzene sulfonic acid residual volume≤0.2%), through secondary hydrogenation kettle overflow to sedimentation
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 layer reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection realize that interior cycle, the catalyst in reducing solution are gradually concentrated into 10- by pump
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid for pumping concentration, realizes internal recycles.Used in the step
Film is ceramic membrane, average pore size 2nm.
(3) feed liquid is put into crystallization kettle, after heating removes solvent through carrying by filtered reducing solution into distillation still
It is pure, obtain metanilic acid product, content 99.2%, production capacity 430kg/h.
Embodiment 4
(1) in 50% methanol aqueous solution 5000kg, m-nitrobenzene sulfonic acid 1250kg input material kettle, will subsequently feed intake by
It according to the ratio, stirs evenly, is squeezed into level-one hydrogenation reaction kettle with pump, Pd/Al is added2O3Catalyst 125kg, the grain of catalyst
Diameter is 100 μm；It is passed through nitrogen exchange system three times, then is passed through hydrogen exchange system three times, open stirring, be warming up to 80-90 DEG C,
Add the material liquid for being pumped into m-nitrobenzene sulfonic acid in hydrogen kettle to level-one with the flow of 5000L/h, is passed through H2, the hydrogen in control system
Pressure is 2.0MPa, and is added into level-one hydrogenation reaction kettle into Pd/Al at interval of 3h2O3Catalyst 2.5kg, level-one add hydrogen kettle
After interior material gradually increases, flowed into secondary hydrogenation kettle by overflow port, material is adding residence time about 2-3h in hydrogen kettle, instead
After answering qualified (with m-nitrobenzene sulfonic acid 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 layer reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection realize that interior cycle, the catalyst in reducing solution are gradually concentrated into 10- by pump
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid for pumping concentration, realizes internal recycles.Used in the step
Film is metal film, average pore size 2nm.
(3) feed liquid is put into crystallization kettle, after heating removes solvent through carrying by filtered reducing solution into distillation still
It is pure, obtain metanilic acid product, content 99.0%, production capacity 790kg/h.
Embodiment 5
(1) in 50% methanol aqueous solution 5000kg, m-nitrobenzene sulfonic acid 1250kg input material kettle, will subsequently feed intake by
It according to the ratio, stirs evenly, is squeezed into level-one hydrogenation reaction kettle with pump, Pd/Al is added2O3Catalyst 125kg, the grain of catalyst
Diameter is 250 μm；It is passed through nitrogen exchange system three times, then is passed through hydrogen exchange system three times, open stirring, be warming up to 80-90 DEG C,
Add the material liquid for being pumped into m-nitrobenzene sulfonic acid in hydrogen kettle to level-one with the flow of 5750L/h, is passed through H2, the hydrogen in control system
Pressure is 0.8MPa, and is added into level-one hydrogenation reaction kettle into Pd/Al at interval of 3h2O3Catalyst 2.5kg, level-one add hydrogen kettle
After interior material gradually increases, flowed into secondary hydrogenation kettle by overflow port, material is adding residence time about 2-3h in hydrogen kettle, instead
After answering qualified (with m-nitrobenzene sulfonic acid 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 layer reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection realize that interior cycle, the catalyst in reducing solution are gradually concentrated into 10- by pump
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid for pumping concentration, realizes internal recycles.Used in the step
Film is composite material film, average pore size 2nm.
(3) feed liquid is put into crystallization kettle, after heating removes solvent through carrying by filtered reducing solution into distillation still
It is pure, obtain metanilic acid product, content 94.6%, production capacity 900kg/h.
Embodiment 6
(1) in 50% methanol aqueous solution 5000kg, m-nitrobenzene sulfonic acid 1250kg input material kettle, will subsequently feed intake by
It according to the ratio, stirs evenly, is squeezed into level-one hydrogenation reaction kettle with pump, Pd/Al is added2O3Catalyst 125kg, the grain of catalyst
Diameter is 10nm, is passed through nitrogen exchange system three times, then is passed through hydrogen exchange system three times, opens stirring, is warming up to 80-90 DEG C,
Add the material liquid for being pumped into m-nitrobenzene sulfonic acid in hydrogen kettle to level-one with the flow of 5750L/h, is passed through H2, the hydrogen in control system
Pressure is 2.5MPa, and is added into level-one hydrogenation reaction kettle into Pd/Al at interval of 3h2O3Catalyst 2.5kg, level-one add hydrogen kettle
After interior material gradually increases, flowed into secondary hydrogenation kettle by overflow port, material is adding residence time about 2-3h in hydrogen kettle, instead
After answering qualified (with m-nitrobenzene sulfonic acid 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 layer reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection realize that interior cycle, the catalyst in reducing solution are gradually concentrated into 10- by pump
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid for pumping concentration, realizes internal recycles.Used in the step
Film is composite material film, and average pore size is 10 μm.
(3) feed liquid is put into crystallization kettle, after heating removes solvent through carrying by filtered reducing solution into distillation still
It is pure, obtain metanilic acid product, content 98.9%, production capacity 900kg/h.
Embodiment 7
(1) in 50% methanol aqueous solution 5000kg, m-nitrobenzene sulfonic acid 1250kg input material kettle, will subsequently feed intake by
It according to the ratio, stirs evenly, is squeezed into level-one hydrogenation reaction kettle with pump, Pd/Al is added2O3Catalyst 125kg, the grain of catalyst
Diameter is 30nm；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,
Add the material liquid for being pumped into m-nitrobenzene sulfonic acid in hydrogen kettle to level-one with the flow of 6250L/h, is passed through H2, the hydrogen in control system
Pressure is 2.5MPa, and is added into level-one hydrogenation reaction kettle into Pd/Al at interval of 3h2O3Catalyst 2.5kg, level-one add hydrogen kettle
After interior material gradually increases, flowed into secondary hydrogenation kettle by overflow port, material is adding residence time about 2-3h in hydrogen kettle, instead
After answering qualified (with m-nitrobenzene sulfonic acid 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 layer reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection realize that interior cycle, the catalyst in reducing solution are gradually concentrated into 10- by pump
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid for pumping concentration, realizes internal recycles.Used in the step
Film is ceramic membrane, average pore size 2nm.
(3) feed liquid is put into crystallization kettle, after heating removes solvent through carrying by filtered reducing solution into distillation still
It is pure, obtain metanilic acid product, content 99.6%, production capacity 980kg/h.
Embodiment 8
(1) in 50% methanol aqueous solution 5000kg, m-nitrobenzene sulfonic acid 1250kg input material kettle, will subsequently feed intake by
It according to the ratio, stirs evenly, is squeezed into level-one hydrogenation reaction kettle with pump, Pd/Al is added2O3Catalyst 125kg, the grain of catalyst
Diameter is 100nm；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, add the material liquid for being pumped into m-nitrobenzene sulfonic acid in hydrogen kettle to level-one with the flow of 6250L/h, is passed through H2, in control system
Hydrogen Vapor Pressure is 0.8MPa, and is added into level-one hydrogenation reaction kettle into Pd/Al at interval of 3h2O3Catalyst 2.5kg, level-one add
After material in hydrogen kettle gradually increases, flowed into secondary hydrogenation kettle by overflow port, material is adding residence time about 2- in hydrogen kettle
3h, after reacting qualified (with m-nitrobenzene sulfonic acid 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 layer reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection realize that interior cycle, the catalyst in reducing solution are gradually concentrated into 10- by pump
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid for pumping concentration, realizes internal recycles.Used in the step
Film is ceramic membrane, average pore size 200nm.
(3) feed liquid is put into crystallization kettle, after heating removes solvent through carrying by filtered reducing solution into distillation still
It is pure, obtain metanilic acid product, content 99.2%, production capacity 970kg/h.
Comparative example 1
(1) in 50% methanol aqueous solution 5000kg, m-nitrobenzene sulfonic acid 1250kg input material kettle, will subsequently feed intake by
It according to the ratio, stirs evenly, is squeezed into level-one hydrogenation reaction kettle with pump, Pd/Al is added2O3Catalyst 125kg, the grain of catalyst
Diameter is 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 80-90 DEG C,
Add the material liquid for being pumped into m-nitrobenzene sulfonic acid in hydrogen kettle to level-one with the flow of 5000L/h, is passed through H2, the hydrogen in control system
Pressure is 1.0MPa, and is added into level-one hydrogenation reaction kettle into Pd/Al at interval of 3h2O3Catalyst 2.5kg, level-one add hydrogen kettle
It after interior material gradually increases, is flowed into secondary hydrogenation kettle by overflow port, material is adding residence time about 3-5h in hydrogen kettle, former
Expect that the reaction of residual volume >=5.6% is not qualified, 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 layer reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection realize that interior cycle, the catalyst in reducing solution are gradually concentrated into 10- by pump
30%, it is squeezed into catalyst shot tank by the catalyst feed liquid for pumping concentration, realizes internal recycles.Used in the step
Film is ceramic membrane, average pore size 2nm.
(3) filtered reducing solution, into distillation still, heating removing solvent.
Comparative example 2
(1) the continuous dosing mode in embodiment 1 is changed to intermittent feeds, i.e. solvent, itrated compound, catalyst (Cat)
It is added in hydrogen kettle, replaces gas reactor, stirring is warming up to 90-100 DEG C, is passed through hydrogen, maintains pressure in 1.0MPa, reacts 5-
6h, reaction solution settle through settling kettle, catalyst filtration are gone out and is applied mechanically for next batch, and reducing solution is through distilling separating methanol, purification
After obtain 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 metanilic acid product purity and unit interval production capacity such as following table.
| 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, needs increase cat dosages that could meet reaction and requires, and uses
Intermittent feeds are required for carrying out the displacement of nitrogen and hydrogen before feeding intake every time, and 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.
| 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 metanilic acid, which is characterized in that comprise the steps of：In methanol-water, in catalyst
Under effect, m-nitrobenzene sulfonic acid 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；
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 that the material liquid that m-nitrobenzene sulfonic acid and the methanol-water are formed enters the flowing
Flow when bed reactor.
2. preparation method as described in claim 1, which is characterized in that the flow of the catalytic hydrogenation reaction is 5000L/h, institute
It is 2~3MPa to state Hydrogen Vapor Pressure；
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. preparation method as described in claim 1, which is characterized in that the temperature of the continuous catalytic hydrogenation reaction is 80~90
DEG C or 90~100 DEG C；
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 is 2~3MPa；
When the temperature of continuous catalytic hydrogenation reaction is 80~90 DEG C, the flow of the catalytic hydrogenation reaction is 5750L/h,
The Hydrogen Vapor Pressure is 0.8~2.5MPa；
When the temperature of 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.
4. preparation method as described in claim 1, which is characterized in that using sedimentation kettle when 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 inoranic membrane is used when the membrane filtration, it is symmetrical that the inoranic membrane is that ceramics, metal or its composite material are constituted
Or asymmetric membrane；
And/or described two or more than two flowing bed reactors are to be connected in series with, and are to connect between the flowing bed reactor
Logical, such as make to be connected between each reactor by way of overflow pipe is arranged on each reactor；
And/or the single volume of the flowing bed reactor is 10000L；
And/or it is additionally provided with the balance pipe for being used for transmission hydrogen 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 are that two or more add hydrogen kettle, such as level-one to add hydrogen
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 to be 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 indentation 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 m-nitrobenzene sulfonic acid is 0.05:1-0.15:1, such as 0.1:1；
And/or the mass ratio of the m-nitrobenzene sulfonic acid and the methanol-water is 1:4~1:10；
And/or the volume ratio of methanol described in the methanol-water solution and the water is 1:4~4:1, such as 1:1；
And/or the catalyst is added to ensure its catalytic activity within the period of fixed intervals in continuous production process
Stablize；The period of the fixed intervals is preferably 2~5h, such as 3h；The additional amount of the catalyst accounts for catalyst inventory
Weight percent 1~2.5%, 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-water solution of m-nitrobenzene sulfonic acid is pumped into the flowing bed reactor, then the catalyst is added to the stream
In dynamic bed reactor, and with inert gas replacement reaction system, then it is passed through hydrogen displacement reaction system, then in set reaction
Stirring is opened at temperature and Hydrogen Vapor Pressure, while the unlatching is stirred, preferably with flow pump accurate measurement continuously to described
The methanol-water solution of the m-nitrobenzene sulfonic acid is pumped into flowing bed reactor, while the continuous hydrogen that is passed through controls Hydrogen Vapor Pressure.
8. a kind of preparation method of metanilic acid, which is characterized in that include the following steps：In the presence of hydrogen, catalyst,
The mixed system of m-nitrobenzene sulfonic acid 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 at different levels plus hydrogen kettle continuous successively
After catalytic hydrogenation, into being settled in sedimentation kettle, returned in the flowing bed reactor by settling obtained catalyst
It is recycled, realizes continuous catalytic hydrogenation；The supernatant that sedimentation obtains is passed through into two or more concatenated film mistakes
Filter is filtered, and interior cycle is realized by pump between the membrane filter, and filtrate is post-treated to obtain metanilic acid, you can；Its
In, when the flow of the mixed system is 5000L/h~6000L/h, the pressure of the hydrogen is 2~3MPa；Or it is 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-water.
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 be connected in such a way that overflow pipe is set；
And/or it is connected in such a way 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：It is passed through nitrogen 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 m-nitrobenzene sulfonic acid and the solvent is 1:4~1:10；
And/or the volume ratio of methanol described in the methanol-water solution and the water is 1:4~4:1, such as 1:1；
And/or the mixed system of the m-nitrobenzene sulfonic acid and the solvent stirs 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 by catalyst shot tank into the flowing bed reactor；
And/or the catalyst and m-nitrobenzene sulfonic acid 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 to obtain the metanilic acid through distillation, concentration and/or crystallization；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 m-nitrobenzene sulfonic acid and the solvent, by the flow pump from the material
It is continuously added in kettle in the flowing bed reactor, the catalyst is passed through described in the catalyst coppers addition
In flowing bed reactor；The flowing bed reactor is that two-stage adds hydrogen kettle, by adding the overflow pipe being arranged between hydrogen kettle to connect；
It will be replaced into hydrogen in the flowing bed reactor；
(2) in the presence of the hydrogen and the catalyst, the mixture of the m-nitrobenzene sulfonic acid and the 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 catalytic hydrogenation is settled by described described in the overflow pipe being arranged 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 two concatenated membrane filters；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 metanilic acid；It distills back
The solvent of receipts is pumped back in material kettle further after rectifying and carries out cycling and reutilization.
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