CN108047096A - The preparation method of 1-naphthylamine-5-sulfonic acid - Google Patents
The preparation method of 1-naphthylamine-5-sulfonic acid Download PDFInfo
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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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- 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
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a kind of preparation methods of 1 naphthylamines, 5 sulfonic acid.The present invention by 1 sulfonic group, 5 nitronaphthalene by carrying out continuous catalytic hydrogenation and then by sedimentation and membrane filtration, 1 naphthylamines, 5 sulfonic acid is obtained, 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 present invention relates to a kind of preparation methods of 1-naphthylamine-5-sulfonic acid.
Background technology
1-naphthylamine-5-sulfonic acid is a kind of important fine-chemical intermediate, is mainly used for medicine and dye industry, can be used for
Prepare intermediate and medicine, the intermediate of insecticide and antioxidant of azoic dyes black salt K.Production naphthalidine -5- sulphurs at present
The method of acid has 1- sulfonic group 5- nitronaphthalenes iron powder reducing, vulcanization sodium reduction, hydrogenating reduction method etc., special powder reduction and vulcanized sodium
Reduction, there are the three wastes are more, environmental pollution seriously and be unable to continuous production, production capacity is low the problem of.Therefore, how a kind of life is provided
It produces that efficient, product quality is high, labor intensity is low and the preparation method of environment amenable 1-naphthylamine-5-sulfonic acid, is still ability
The technical issues of field technique personnel are badly in need of solving.
The content of the invention
The technical problems to be solved by the invention be existing 1-naphthylamine-5-sulfonic acid preparation method severe reaction conditions,
Serious corrosion of equipment, the three wastes are more, environmental pollution is serious or catalyst recovery utilization rate is low, be unable to continuous production and product is pure
The defects such as degree or production capacity are low, and provide a kind of preparation method of 1-naphthylamine-5-sulfonic acid.This method is easy to operate, safe
And can continuous production, can reach that production efficiency is high, product quality is high, labor intensity is low, environmentally friendly and catalyst utilizes
Rate 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 1-naphthylamine-5-sulfonic acid, and it includes following steps：In methanol, it is being catalyzed
Under the action of agent, 1- sulfonic group 5- nitronaphthalenes and hydrogen are subjected to continuous catalytic hydrogenation reaction, reacting rear material is through sedimentation and film
Filtering, you can；
The catalyst is ReneyNi；
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 stream for the material liquid that 1- sulfonic group 5- nitronaphthalenes and methanol are formed
Flow during dynamic bed reactor.
In the present invention, the continuous catalytic hydrogenation reaction is to be continuously added to the material liquid.For example, first by the 1-
Sulfonic group 5- nitronaphthalenes are pumped into after being configured to its corresponding methanol 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, under the effect of the catalyst, by 1- sulfonic group 5- nitronaphthalenes
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 ReneyNi/H in this field2Catalyst system and catalyzing nitro is reduced
It is carried out for the hydrogenation mechanism of amino.
In the present invention, it is preferred that 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 employed this field common detection methods (such as HPLC, TLC or NMR) and be monitored,
Generally with 1- sulfonic group 5- nitronaphthalene 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, it is preferred that the quantity of the film can be 2 or more；More preferably, the film is to be connected in series；
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 cycled 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, it is preferred that 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 with 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 in into flowing bed reactor.
In the present invention, it is preferred that described two or more than two flowing bed reactors are to be connected in series, 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 it is preferred that 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 two or more hydrogenation kettles, such as
Level-one hydrogenation kettle, secondary hydrogenation kettle, three-level hydrogenation kettle, until N grades of hydrogenation kettles.
It is preferred that when described two flowing bed reactors are hydrogenated with kettle and secondary hydrogenation kettle for level-one, the level-one hydrogenation
It after material in kettle gradually increases, is flowed by overflow port in the secondary hydrogenation kettle, it is qualified to reaction conversion ratio that the reaction was continued.
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 of the 1- sulfonic group 5- nitronaphthalenes 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 flow pump accurate measurement into the flowing bed reactor described
The methanol solution of 1- sulfonic group 5- nitronaphthalenes, while the continuous hydrogen that is passed through controls Hydrogen Vapor Pressure in set pressure limit.
Wherein, the methanol solution of the 1- sulfonic group 5- nitronaphthalenes and the dosage of the catalyst can be no more than described
Flowing bed reactor maximum reaction capacity in the range of optionally；The inert gas is preferably nitrogen；It is described with inertia
Gas displacement reaction system be preferably three times and more than；It is described be passed through hydrogen displacement reaction system be preferably three times and more than.
In the present invention, the weight ratio of the catalyst and the 1- sulfonic groups 5- nitronaphthalenes can be 0.05:1-0.15:1, example
Such as 0.1:1.
In the present invention, the mass ratio of the 1- sulfonic groups 5- nitronaphthalenes 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 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 1-naphthylamine-5-sulfonic acid, comprise the following steps：
In the presence of hydrogen, catalyst, the mixed system of 1- sulfonic group 5- nitronaphthalenes and solvent is continuously added to thermopnore
Continuous catalytic hydrogenation reaction is carried out in reactor；The flowing bed reactor is connected more than two-stage or two-stage to be hydrogenated with kettle；Instead
After liquid is answered to carry out continuous catalytic hydrogenation in hydrogenation kettles at different levels successively, settled into sedimentation kettle, obtained by sedimentation
Catalyst is returned in the flowing bed reactor and recycled, and realizes continuous catalytic hydrogenation；Obtained supernatant will be settled
Liquid is filtered by two or more membrane filters connected, and interior cycle, filtrate are realized by pump between the membrane filter
It is post-treated to obtain 1-naphthylamine-5-sulfonic acid, you can；Wherein, when the flow of the mixed system is 5000L/h~6000L/h, institute
The pressure for stating hydrogen is 2~3MPa；Or the flow of the mixed system be 5750L/h~6250L/h when, the hydrogen
Pressure is 0.8~2.5MPa；When the flow of example mixed system as mentioned is 6000L/h, the pressure of the hydrogen is 1MPa；Institute
The catalyst stated is ReneyNi；The solvent is methanol.
In the present invention, the hydrogenation reaction, which uses, uses ReneyNi/H in this field2Catalyst system and catalyzing nitro is reduced
It is carried out for the hydrogenation mechanism of amino.
In the present invention, it is preferred that 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.
It can be that level-one is hydrogenated with kettle, secondary hydrogenation kettle, three-level hydrogenation that kettle is hydrogenated in the present invention, more than the two-stage or two-stage
Kettle, until N grades of hydrogenation kettles.
In the present invention, in the flowing bed reactor, the volume of the single hydrogenation kettle can be 10000L.
In the present invention, it is preferred that be to connect between more than the two-stage or two-stage being hydrogenated with kettle, such as each hydrogenation kettle
Between connected in a manner that overflow pipe is set.
In the present invention, it is preferred that connected between the sedimentation kettle and the hydrogenation kettle, such as the sedimentation kettle and institute
State hydrogenation 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 displacement air therein is passed through in bed reactor and/or sedimentation kettle, displacement once or more (such as three times)；Afterwards
Hydrogen is passed through again 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 1- sulfonic groups 5- nitronaphthalenes and the solvent can be 1:4~1:10.
The 1- sulfonic group 5- nitronaphthalenes and the mixed system of solvent can be that this field is conventional, 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 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 1- sulfonic group 5- nitronaphthalenes mass percent, such as 5%~
15% (in another example 8%~10%).It is preferred that the catalysis is added into the flowing bed reactor at interval of 2~5h
Agent to ensure that its catalytic activity is stablized, the additional amount of the catalyst and the weight percent of initial charge for 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 employed this field common detection methods (such as HPLC, TLC or NMR) and be monitored, generally with 1-
Sulfonic group 5- nitronaphthalene residual volume≤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.
Interior the cycling 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 cycling 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 post processing can be that this field is conventional, for example, through distilling, concentrating and/or crystallize, obtain the 1- naphthalenes
Amine -5- sulfonic acid；Recovered solvent recycles；Preferably the recovered solvent enters back into material kettle and is followed after rectifying
Ring utilizes.
In the present invention, the preparation method is preferably comprised following steps：
(1) by the mixed system of the 1-naphthylamine-5-sulfonic acid 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 is hydrogenated with kettle for two-stage, by being hydrogenated with the overflow pipe string set between kettle
Connection；Hydrogen will be replaced into the flowing bed reactor；
(2) in the presence of the hydrogen and the catalyst, the 1- sulfonic group 5- nitronaphthalenes and solvent it is mixed
Zoarium system is continuously added to carry out catalytic hydrogenation reaction in the level-one hydrogenation kettle of the flowing bed reactor；And every 3~5h
The catalyst is added into the level-one hydrogenation reaction kettle of the flowing bed reactor；Reaction solution is in the level-one hydrogenation kettle
It after gradually increasing, is flowed by overflow port in secondary hydrogenation kettle, carries out continuous catalytic hydrogenation in hydrogenation kettles at different levels successively；
(3) reaction solution after the continuous catalytic hydrogenation is overflow by what is set between the sedimentation kettle and the hydrogenation kettle
Flow tube is settled into described settle in kettle, is returned to by settling the obtained catalyst pump in the flowing bed reactor
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 1-naphthylamine-5-sulfonic acid；The solvent of distillation recovery further after rectifying, is pumped back in material kettle and is cycled profit again
With.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition can be combined 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 causes 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 membrane filter, the catalyst being lost in further is recycled, improves the utilization rate of catalyst.
(4) reaction process three wastes generate, and reduce environmental pollution.
(5) the 1-naphthylamine-5-sulfonic 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 prepares 1-naphthylamine-5-sulfonic acid in the embodiment of the present invention；
Flow contains material kettle 1 in figure, the hydrogenation kettle 2,3 with stirring, 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.
It as shown in Figure 1, by solvent, material input material kettle 1, stirs evenly, level-one hydrogenation kettle 2 is continuously driven by pump control flow
In, catalyst is added in by feed pot 14 in level-one hydrogenation kettle 2, is passed through air in nitrogen displacement system, then with hydrogen exchange system
Interior gas opens stirring, controls temperature, opens charge pump continuous feed, controls gas reactor pressure, and reaction solution is hydrogenated with by level-one
2 overflow of kettle enters secondary hydrogenation kettle 3, then overflow enters catalyst sedimentation kettle 4, and reaction solution is just separated 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 cycle, when catalyst content is concentrated into 20-30%, catalyst shot tank 14 is driven by pump
In, for adding the catalyst being lost in hydrogenation 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 scope.The experimental method of actual conditions is not specified in the following example, according to conventional methods and conditions or according to business
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 1-naphthylamine-5-sulfonic acid using 1- sulfonic group 5- nitronaphthalenes as raw material, is catalyzed using ReneyNi
Agent carries out continuous catalytic hydrogenation reaction in the reactor, and for catalyst after separation and recovery, reducing solution obtains mesh through precipitation, purification
Mark product 1-naphthylamine-5-sulfonic acid.
Specific steps include：
(1) methanol 5000kg, 1- sulfonic group 5- nitronaphthalenes 1250kg is put into material kettle, subsequently fed intake according to the ratio
It carries out, stirs evenly, squeezed into pump in level-one hydrogenation reaction kettle, add in ReneyNi catalyst 125kg, the grain size of catalyst is
10nm is passed through nitrogen displacement 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 is hydrogenated with the material liquid that 1- sulfonic group 5- nitronaphthalenes are pumped into kettle to level-one, is passed through H2, the hydrogen in control system
Atmospheric pressure is 1.0MPa, and is added at interval of 3h into level-one hydrogenation reaction kettle into ReneyNi catalyst 2.5kg, level-one hydrogenation
It after material in kettle gradually increases, is flowed by overflow port in secondary hydrogenation kettle, material residence time about 2-3h in hydrogenation kettle,
After reaction qualified (with 1- sulfonic group 5- nitronaphthalenes 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 in hydrogenation kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by cycle in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed by the catalyst feed liquid pumped concentration in catalyst shot tank, 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 1-naphthylamine-5-sulfonic acid product, content 99.9%, production capacity 950kg/h.
Embodiment 2
(1) methanol 5000kg, 1- sulfonic group 5- nitronaphthalenes 1250kg is put into material kettle, subsequently fed intake according to the ratio
Example, stirs evenly, is squeezed into pump in level-one hydrogenation reaction kettle, adds in ReneyNi catalyst 125kg, the grain size of catalyst is 500
μm；It is passed through nitrogen displacement system three times, then is passed through hydrogen exchange system three times, open stirring, be warming up to 80-90 DEG C, with
The flow of 5000L/h is hydrogenated with the material liquid that 1- sulfonic group 5- nitronaphthalenes are pumped into kettle to level-one, is passed through H2, the hydrogen in control system
Atmospheric pressure is 3.0MPa, and is added at interval of 3h into level-one hydrogenation reaction kettle into ReneyNi catalyst 2.5kg, level-one hydrogenation
It after material in kettle gradually increases, is flowed by overflow port in secondary hydrogenation kettle, material residence time about 2-3h in hydrogenation kettle,
After reaction qualified (with 1- sulfonic group 5- nitronaphthalenes 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 in hydrogenation kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by cycle in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed by the catalyst feed liquid pumped concentration in catalyst shot tank, 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 1-naphthylamine-5-sulfonic acid product, content 99.8%, production capacity 790kg/h.
Embodiment 3
(1) methanol 12500kg, 1- sulfonic groups 5- nitronaphthalenes 1250kg is put into material kettle, is subsequently fed intake according to the ratio
It stirs evenly, stirs evenly, squeezed into pump in level-one hydrogenation reaction kettle, add in ReneyNi catalyst 125kg, the grain of catalyst
Footpath is 10nm；It is passed through nitrogen displacement system three times, then is passed through hydrogen exchange system three times, open stirring, be warming up to 90-100 DEG C,
The material liquid that 1- sulfonic group 5- nitronaphthalenes are pumped into kettle is hydrogenated with to level-one with the flow of 6000L/h, is passed through H2, in control system
Hydrogen Vapor Pressure is 3.0MPa, and is added at interval of 3h into level-one hydrogenation reaction kettle into ReneyNi catalyst 2.5kg, and level-one adds
It after material in hydrogen kettle gradually increases, is flowed by overflow port in secondary hydrogenation kettle, material residence time about 2- in hydrogenation kettle
3h, after reacting qualified (with 1- sulfonic group 5- nitronaphthalenes 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 in hydrogenation kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by cycle in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed by the catalyst feed liquid pumped concentration in catalyst shot tank, 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 1-naphthylamine-5-sulfonic acid product, content 99.2%, production capacity 430kg/h.
Embodiment 4
(1) methanol 5000kg, 1- sulfonic groups 5- nitronaphthalenes 1250kg is put into material kettle, is subsequently fed intake according to the ratio,
It stirs evenly, is squeezed into pump in level-one hydrogenation reaction kettle, add in ReneyNi catalyst 125kg, the grain size of catalyst is 100 μm；
It is passed through nitrogen displacement system three times, then is passed through hydrogen exchange system three times, open stirring, 80-90 DEG C is warming up to, with 5000L/h
Flow be hydrogenated with to level-one in kettle and be pumped into the material liquids of 1- sulfonic group 5- nitronaphthalenes, be passed through H2, the Hydrogen Vapor Pressure in control system
It for 2.0MPa, and adds into level-one hydrogenation reaction kettle at interval of 3h into ReneyNi catalyst 2.5kg, in level-one hydrogenation kettle
It after material gradually increases, is flowed by overflow port in secondary hydrogenation kettle, material residence time about 2-3h, reaction in hydrogenation kettle are closed
After lattice (with 1- sulfonic group 5- nitronaphthalenes 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 in hydrogenation kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by cycle in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed by the catalyst feed liquid pumped concentration in catalyst shot tank, 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 1-naphthylamine-5-sulfonic acid product, content 99.0%, production capacity 790kg/h.
Embodiment 5
(1) methanol 5000kg, 1- sulfonic groups 5- nitronaphthalenes 1250kg is put into material kettle, is subsequently fed intake according to the ratio,
It stirs evenly, is squeezed into pump in level-one hydrogenation reaction kettle, add in ReneyNi catalyst 125kg, the grain size of catalyst is 250 μm；
It is passed through nitrogen displacement system three times, then is passed through hydrogen exchange system three times, open stirring, 80-90 DEG C is warming up to, with 5750L/h
Flow be hydrogenated with to level-one in kettle and be pumped into the material liquids of 1- sulfonic group 5- nitronaphthalenes, be passed through H2, the Hydrogen Vapor Pressure in control system
It for 0.8MPa, and adds into level-one hydrogenation reaction kettle at interval of 3h into ReneyNi catalyst 2.5kg, in level-one hydrogenation kettle
It after material gradually increases, is flowed by overflow port in secondary hydrogenation kettle, material residence time about 2-3h, reaction in hydrogenation kettle are closed
After lattice (with 1- sulfonic group 5- nitronaphthalenes 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 in hydrogenation kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by cycle in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed by the catalyst feed liquid pumped concentration in catalyst shot tank, 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 1-naphthylamine-5-sulfonic acid product, content 94.6%, production capacity 900kg/h.
Embodiment 6
(1) methanol 5000kg, 1- sulfonic groups 5- nitronaphthalenes 1250kg is put into material kettle, is subsequently fed intake according to the ratio,
It stirring evenly, is squeezed into pump in level-one hydrogenation reaction kettle, add in ReneyNi catalyst 125kg, the grain size of catalyst is 10nm,
It is passed through nitrogen displacement system three times, then is passed through hydrogen exchange system three times, open stirring, 80-90 DEG C is warming up to, with 5750L/h
Flow be hydrogenated with to level-one in kettle and be pumped into the material liquids of 1- sulfonic group 5- nitronaphthalenes, be passed through H2, the Hydrogen Vapor Pressure in control system
It for 2.5MPa, and adds into level-one hydrogenation reaction kettle at interval of 3h into ReneyNi catalyst 2.5kg, in level-one hydrogenation kettle
It after material gradually increases, is flowed by overflow port in secondary hydrogenation kettle, material residence time about 2-3h, reaction in hydrogenation kettle are closed
After lattice (with 1- sulfonic group 5- nitronaphthalenes 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 in hydrogenation kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by cycle in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed by the catalyst feed liquid pumped concentration in catalyst shot tank, 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 1-naphthylamine-5-sulfonic acid product, content 98.9%, production capacity 900kg/h.
Embodiment 7
(1) methanol 5000kg, 1- sulfonic groups 5- nitronaphthalenes 1250kg is put into material kettle, is subsequently fed intake according to the ratio,
It stirs evenly, is squeezed into pump in level-one hydrogenation reaction kettle, add in ReneyNi catalyst 125kg, the grain size of catalyst is 30nm；
It is passed through nitrogen displacement system three times, then is passed through hydrogen exchange system three times, open stirring, 90-100 DEG C is warming up to, with 6250L/h
Flow be hydrogenated with to level-one in kettle and be pumped into the material liquids of 1- sulfonic group 5- nitronaphthalenes, be passed through H2, the Hydrogen Vapor Pressure in control system
It for 2.5MPa, and adds into level-one hydrogenation reaction kettle at interval of 3h into ReneyNi catalyst 2.5kg, in level-one hydrogenation kettle
It after material gradually increases, is flowed by overflow port in secondary hydrogenation kettle, material residence time about 2-3h, reaction in hydrogenation kettle are closed
After lattice (with 1- sulfonic group 5- nitronaphthalenes 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 in hydrogenation kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by cycle in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed by the catalyst feed liquid pumped concentration in catalyst shot tank, 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 1-naphthylamine-5-sulfonic acid product, content 99.6%, production capacity 980kg/h.
Embodiment 8
(1) methanol 5000kg, 1- sulfonic groups 5- nitronaphthalenes 1250kg is put into material kettle, is subsequently fed intake according to the ratio,
It stirs evenly, is squeezed into pump in level-one hydrogenation reaction kettle, add in ReneyNi catalyst 125kg, the grain size of catalyst is 100nm；
It is passed through nitrogen displacement system three times, then is passed through hydrogen exchange system three times, open stirring, 90-100 DEG C is warming up to, with 6250L/h
Flow be hydrogenated with to level-one in kettle and be pumped into the material liquids of 1- sulfonic group 5- nitronaphthalenes, be passed through H2, the Hydrogen Vapor Pressure in control system
It for 0.8MPa, and adds into level-one hydrogenation reaction kettle at interval of 3h into ReneyNi catalyst 2.5kg, in level-one hydrogenation kettle
It after material gradually increases, is flowed by overflow port in secondary hydrogenation kettle, material residence time about 2-3h, reaction in hydrogenation kettle are closed
After lattice (with 1- sulfonic group 5- nitronaphthalenes 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 in hydrogenation kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by cycle in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed by the catalyst feed liquid pumped concentration in catalyst shot tank, 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 1-naphthylamine-5-sulfonic acid product, content 99.2%, production capacity 970kg/h.
Comparative example 1
(1) methanol 5000kg, 1- sulfonic groups 5- nitronaphthalenes 1250kg is put into material kettle, is subsequently fed intake according to the ratio,
It stirs evenly, is squeezed into pump in level-one hydrogenation reaction kettle, add in ReneyNi catalyst 125kg, the grain size of catalyst is 10nm；
It is passed through nitrogen displacement system three times, then is passed through hydrogen exchange system three times, open stirring, 80-90 DEG C is warming up to, with 5000L/h
Flow be hydrogenated with to level-one in kettle and be pumped into the material liquids of 1- sulfonic group 5- nitronaphthalenes, be passed through H2, the Hydrogen Vapor Pressure in control system
It for 1.0MPa, and adds into level-one hydrogenation reaction kettle at interval of 3h into ReneyNi catalyst 2.5kg, in level-one hydrogenation kettle
It after material gradually increases, is flowed by overflow port in secondary hydrogenation kettle, material residence time about 3-5h, raw material in hydrogenation kettle is residual
The reaction of surplus >=5.6% 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 in hydrogenation kettle, and upper strata reducing solution is driven by pumping
In membrane filtration system, two membrane filter series connection, by cycle in pump realization, the catalyst in reducing solution is gradually concentrated into 10-
30%, it is squeezed by the catalyst feed liquid pumped concentration in catalyst shot tank, 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 1-naphthylamine-5-sulfonic 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, and cat easy in inactivation is, it is necessary to which the cat dosages that increase 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 a hydrogenation 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, and kettle, well below two autoclave serial hydrogenation kettles of unit interval production capacity are hydrogenated with using level-one.
Claims (10)
1. a kind of preparation method of 1-naphthylamine-5-sulfonic acid, which is characterized in that comprise the steps of：In methanol, in the work of catalyst
Under, 1- sulfonic group 5- nitronaphthalenes 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 ReneyNi；
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 enters the thermopnore for the material liquid that 1- sulfonic group 5- nitronaphthalenes and methanol are formed
Flow during reactor.
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. 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；
It is preferred that 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 be connected in series, and be to connect 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 are hydrogenated with for two or more hydrogenation kettles, such as level-one
Kettle, secondary hydrogenation kettle, three-level hydrogenation kettle, until N grades of hydrogenation kettles.
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；It is preferred that the film is to be connected in series；
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 catalyst and the 1- sulfonic groups 5- nitronaphthalenes
Weight ratio is 0.05:1-0.15:1, such as 0.1:1；
And/or the mass ratio of the 1- sulfonic groups 5- nitronaphthalenes 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 1- sulfonic group 5- nitronaphthalenes is pumped into the flowing bed reactor, then the catalyst is added in the stream
In dynamic bed reactor, and with inert gas replacement reaction system, then hydrogen displacement reaction system is passed through, 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 solution of the 1- sulfonic groups 5- nitronaphthalenes is pumped into flowing bed reactor, while the continuous hydrogen that is passed through controls hydrogen pressure
Power.
8. a kind of preparation method of 1-naphthylamine-5-sulfonic acid, which is characterized in that comprise the following steps：Exist in hydrogen, catalyst
Under, it is anti-that the mixed system of 1- sulfonic group 5- nitronaphthalenes and solvent is continuously added to progress continuous catalytic hydrogenation in flowing bed reactor
It should；The flowing bed reactor is that kettle series connection is hydrogenated at least more than two-stage or two-stage；Reaction solution is successively in hydrogenation kettles at different levels
It after carrying out continuous catalytic hydrogenation, is settled into sedimentation kettle, the thermopnore is returned to by settling obtained catalyst
It is recycled in reactor, realizes continuous catalytic hydrogenation；The supernatant that sedimentation is obtained passes through two or more strings
The membrane filter of connection is filtered, and interior cycle is realized by pump between the membrane filter, and filtrate is post-treated to obtain naphthalidine -5- sulphurs
Acid, you can；Wherein, when the flow of the mixed system is 5000L/h~6000L/h, the pressure of the hydrogen for 2~
3MPa；Or the flow of the mixed system is when being 5750L/h~6250L/h, 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；The catalyst
For ReneyNi；The solvent is methanol.
9. production method as claimed in claim 8, which is characterized in that in the flowing bed reactor, the single hydrogenation
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 connected between each hydrogenation kettle in a manner that overflow pipe is set；
And/or it is connected between the sedimentation kettle and the hydrogenation kettle in a manner that overflow pipe is set；
And/or the feed postition of the hydrogen, comprise 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 afterwards and replaces nitrogen therein, displacement is once or one
More than secondary, hydrogen is then continuously passed through；
And/or the mass ratio of the 1- sulfonic groups 5- nitronaphthalenes and the solvent is 1:4~1:10；
And/or the 1- sulfonic group 5- nitronaphthalenes 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 1- sulfonic group 5- nitronaphthalenes 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 interior the cycling 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 1-naphthylamine-5-sulfonic acid；That recycles is molten
Agent recycles.
10. preparation method as claimed in claim 8 or 9, which is characterized in that comprise the following steps：
(1) by the mixed system of the 1- sulfonic group 5- nitronaphthalenes and 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 hydrogenated with kettle for two-stage, is connected by being hydrogenated with the overflow pipe set between kettle；
Hydrogen will be replaced into the flowing bed reactor；
(2) in the presence of the hydrogen and the catalyst, the mixture of the 1- sulfonic group 5- nitronaphthalenes and solvent
System is continuously added to carry out catalytic hydrogenation reaction in the level-one hydrogenation kettle of the flowing bed reactor；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 is gradual in the level-one hydrogenation kettle
It after increasing, is flowed by overflow port in secondary hydrogenation kettle, carries out continuous catalytic hydrogenation in hydrogenation kettles at different levels successively；
(3) reaction solution after catalytic hydrogenation is settled by described described in the overflow pipe entrance set between kettle and the hydrogenation kettle
It is settled in sedimentation kettle, is made by settling the obtained catalyst pump and returning in the flowing bed reactor cycle
With；The supernatant that sedimentation obtains is filtered by the membrane filter of two series connection；By in pump progress between the membrane filter
Xun Huan 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 1-naphthylamine-5-sulfonic acid；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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| CN104084206A (en) * | 2014-06-13 | 2014-10-08 | 浙江龙盛化工研究有限公司 | Aromatic amine hydrogenation catalyst recycling method |
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| US4929757A (en) * | 1987-06-17 | 1990-05-29 | Bayer Aktiengesellschaft | Process for the preparation of 3-aminophenyl 2-hydroxy-ethyl sulphone |
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