CN106238099B - The preparation method and application of 1,5- dinitronaphthalene hydrogenation catalyst - Google Patents

The preparation method and application of 1,5- dinitronaphthalene hydrogenation catalyst Download PDF

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CN106238099B
CN106238099B CN201610704781.1A CN201610704781A CN106238099B CN 106238099 B CN106238099 B CN 106238099B CN 201610704781 A CN201610704781 A CN 201610704781A CN 106238099 B CN106238099 B CN 106238099B
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catalyst
phenolic resin
diaminonaphthalene
dinitronaphthalene
reaction
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CN106238099A (en
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严生虎
李彦飞
张跃
马晓明
倪伟
刘建武
沈介发
辜顺林
陈代祥
何汶晓
倪凤超
张勇超
魏进
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Nantong Longyi New Material Technology Co ltd
Changzhou University
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LONGXIANG CHEMICAL CO Ltd NANTONG
Changzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/653—500-1000 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
    • B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes

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Abstract

The invention discloses the preparation method and applications of 1,5- dinitronaphthalene hydrogenation catalyst, are related to the synthesis technical field of 1,5-diaminonaphthalene.Method for preparing catalyst adds curing agent, one or more, the obtained phenolic resin base catalyst with nano aperture of one-step method of VIII race's metallic element of load regulation using phenolic resin as precursor.The continuous synthesis technology being related to are as follows: on the fixed bed bed for being filled with above-mentioned catalyst, with 1,5- dinitronaphthalene is reaction raw materials, using simple substance hydrogen as reducing agent, temperature be 40~110 DEG C, Hydrogen Vapor Pressure be 0.3~3 MPa, the residence time be 0.1~5 min under conditions of carry out catalytic reduction reaction, Efficient Conversion synthesizes 1,5-diaminonaphthalene product.Have the characteristics that preparation process is simple, catalytic activity is high, resistance to deactivation is strong, safe to use, economical rationality according to catalyst prepared by the method for the present invention.

Description

The preparation method and application of 1,5- dinitronaphthalene hydrogenation catalyst
Technical field
The present invention relates to the synthesis technical field of 1,5-diaminonaphthalene, specifically one kind 1,5- dinitronaphthalene adds hydrogen to urge The preparation method of agent and the technique that the catalyst is applied to continuous fixed-bed catalytic hydrogenation synthesis 1,5- diaminonaphthalene.
Background technique
Diaminonaphthalene is there are many isomer structure, and different diaminonaphthalenes is in organic synthesis, pigment, dyestuff, advanced The tradition chemical industry such as polyurethane material and chemical industry new technical field suffer from irreplaceable role.In addition 1,5- diaminonaphthalene may be used also As the excellent substitute and 1 of forbidden diphenyl amine dyestuff, the primary raw material of 5- naphthalene diisocyanate, there is wide answer Use prospect.
Currently, the synthesis route of 1,5-diaminonaphthalene mainly include the following types:
1. the iron powder reducing method using iron powder as reducing medium
The reaction equation of iron powder reducing method are as follows:
CN1100403A is proposed dinitronaphthalene, iron powder, alcohol, water, glacial acetic acid, caustic soda, sodium hydrogensulfite etc. by certain Ratio mixing, a series of method of unit operation production 1,5-diaminonaphthalenes such as agitated, reaction, post-processing.This method is mesh The main method of preceding industry production 1,5-diaminonaphthalene, has the advantages that at low cost, product quality is high.The deficiency of the method Place is: intermittently operated, labor intensity is big, and to equipment corruption candle, serious wear, Operation and Maintenance is costly, the iron cement of generation Cause very big pollution, the sedimentation of iron cement post-processing cumbersome environment.
2. electrochemical reduction prepares 1,5- diaminonaphthalene
The reaction equation of electrochemical reducing are as follows:
By potentiostatic deposition reduction reaction occurs for this method, makes 1,5- dinitronaphthalene through nitroso, azanol class intermediate, Finally it is reduced to 1,5- diaminonaphthalene.Process avoids the processing of organic spent acid and other waste materials, but this method equipment is more multiple Miscellaneous, concentration of substrate is very low in solution, and waste water yield is big, and unstable product quality is at high cost, is not easy amplification production.
3. hydrazine hydrate reduction method:
CN102070467A is proposed under normal pressure with Iron trichloride hexahydrate and carbon compositing catalyst, N, N- dimethyl formyl Amine, N-Methyl pyrrolidone, o-dichlorohenzene, chlorobenzene etc. are solvent, and 40% ~ 80% hydrazine hydrate reduction dinitronaphthalene, product is added dropwise Yield reaches as high as 95.0%.But this method operation is cumbersome, and technology stability is poor, post-processing trouble.
4. catalytic hydrogenation method:
Catalytic hydrogenation method is the 1,5- diaminonaphthalene novel green synthetic method of current most industrial prospect.Reactional equation Formula are as follows:
This method is a kind of relatively advanced production technology, and product is easily separated, and three-waste free discharge, is a kind of green, has The technique of development prospect.Patent CN101575295, CN102172528A, CN101544569A etc. propose using this method, in With stirring stainless steel autoclave in complete 1,5-diaminonaphthalene synthesis, can get satisfactory feed stock conversion and Selectivity of product.But the method use the valuable catalysts of high activity, and the reaction time is longer, and catalyst utilization is low, equipment It is required that property is high.
In concrete technology, CN101544569A, CN101575295A are proposed using 5% Pd/C as catalyst, in reaction system Middle addition metal ion is auxiliary agent, is used for synthesizing diamino naphthalene compounds, can obtain higher reaction yield.Pd/C catalyst As the most popular catalyst of current this method, higher yield can be obtained, but Pd/C catalyst itself there are easy in inactivation, Using or the defects of safety is poor, low efficiency of living again of process of living again.
CN102174528A proposes to use liquid phase catalytic hydrogenation method, using carbon nanotube as carrier, by group VIII metal element Catalyst with the preparation of 1VB race metallic element for catalytic hydrogenation synthesis 1,5- diaminonaphthalene.In the method that the patent proposes, Catalysts and solvents are reusable, technique cleanliness without any pollution.But the cost of material that this method prepares catalyst is higher, prepares Journey is complex.
RU2307120 (C2) then proposes using aluminium oxide, sulfated zirconia as carrier, load active component palladium, and passes through Innovative design is carried out to hydrogenation reaction device, simplifies operation, the final 1,5-diaminonaphthalene product for synthesizing high-quality.But it should The problems such as method that patent proposes makes there are reaction unit complexity, reaction time length, catalyst with replacement complex steps.
CN103420851A is proposed, by the way that one or more of Ni, Mn, Mo are supported on γ-Al2O3With titanium silicon molecule On sieve, the catalyst for catalyzing and synthesizing 1,5-diaminonaphthalene can be prepared.Under the catalyst, raw naphthalene material, ammonium hydroxide, dioxygen Water can one-step synthesis 1,5- diaminonaphthalene.But the yield of the program is low, and catalyst preparation is complicated, and production security is poor.
Phenolic resin is as phenol and formaldehyde or derivatives thereof through not cladding resin polymer made from polycondensation reaction.Phenolic aldehyde tree Rouge has been widely used in chemical industry since putting into production, wherein nano aperture phenolic resin is to prepare resin base The persursor material of foamy carbon.Nano aperture phenolic resin has that compact structure, large specific surface area, linear expansion coefficient be low, crushing resistance The features such as good, has wide practical use in the fields such as heat control material, catalyst carrier, high temperature insulating.And with nanometer Aperture phenolic resin load Pd prepares hydrogenating reduction catalyst, can significantly improve the service performance of heterogeneous catalysis.At present Method for preparing catalyst in relation to nano aperture phenolic resin load Pd is rarely reported, and catalyst prepared by this method is used to add Hydrogen catalysis synthesis 1,5- diaminonaphthalene is even more to have not been reported.Exploitation is corresponding easy, efficient catalyst type, preparation method and Catalyst technique for applying has significant use value.
Summary of the invention
The invention discloses a kind of for being catalyzed the catalyst of 1,5- dinitronaphthalene hydrogenating reduction synthesis 1,5- diaminonaphthalene Preparation method, the method for preparing catalyst is with preparation process is simple, catalyst activity is high, catalyst resistance to deactivation is strong, makes The characteristics of with highly-safe, economical rationality.The invention further relates to a kind of fixed bed continuous catalytic hydrogenations to synthesize 1,5- diaminonaphthalene Technique, with fixed bed reactors replace conventional high-tension kettle reactor, can simplify operation, shorten the reaction time, mention Catalytic efficiency is risen, keeps simple process clean, product quality is high, and post-processing is simple.
The technology path that the present invention takes is: using phenolic resin as precursor, adding curing agent, VIII race's metallic element of load regulation The phenolic resin base catalyst with nano aperture is made in one or more of cobalt, nickel, palladium, platinum, one-step method；It then will be made Technique of the standby catalyst for fixed bed continuous catalytic hydrogenation synthesis 1,5- diaminonaphthalene.
The preparation method of 1,5- dinitronaphthalene hydrogenation catalyst carries out as steps described below:
(1) phenolic resin is dissolved in the methanol of 1~15 times of quality, static rear filtering and impurity removing；
(2) the group VIII metal compound for weighing certain mass in proportion, meeting active component quality is catalyst quality 0.1%~30%, add the curing agent of phenolic resin quality 1~15%, be uniformly mixed；
(3) raw material (1), (2) are mixed, nitrogen replaces the hollow gas of system, 0.1~1.0 MPa of pressurising；
(4) temperature programming solidifies 4~12 hours at 90~190 DEG C；
(5) it is filtered, washed after reaction, is dried to obtain catalyst.
In the above catalyst preparation technology scheme, the pore diameter range of the phenolic resin base catalyst of the preparation is 200 ~600 nm, density are 0.10~0.30 g/cm3。
In the above catalyst preparation technology scheme, the phenolic resin is phenol formaldehyde (PF) phenolic resin, xylenol formaldehyde One or more of resin, resorcinol formaldehyde resin.
In the above catalyst preparation technology scheme, the phenolic resin curing agent be hexa, paraformaldehyde, One or more of aniline.
In the above catalyst preparation technology scheme, the group VIII metal element be one of cobalt, nickel, palladium, platinum or It is several.
In the above catalyst preparation technology scheme, VIII race's metal consumption of load regulation be catalyst quality 0.1~ 30%.Hardener dose is the 1~15% of catalyst quality.
In the above catalyst preparation technology scheme, the group VIII metal compound is metal acetate salt, nitrate, salt One or more of phosphate compounds.
Catalyst technique for applying of the invention are as follows: synthesize prepared catalyst applied to fixed-bed catalytic continuously hydrogen adding The technique of 1,5-diaminonaphthalene carries out as steps described below:
The pressure control range of fixed bed reactors are as follows: normal pressure~10 MPa, temperature control range are as follows: 20 DEG C of (room temperature)~550 DEG C.
A kind of technique of fixed-bed catalytic continuously hydrogen adding synthesis 1,5-diaminonaphthalene, the reaction of 1,5- dinitronaphthalene Solvent be selected from one of aniline, methanol, isopropanol, tetrahydrofuran, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or Several mixtures.The mass concentration of 1,5- diaminonaphthalene is 5~20%.
A kind of technique of fixed bed continuous catalytic hydrogenation synthesis 1,5-diaminonaphthalene, reaction temperature is 40~110 DEG C, react 0.3~3 MPa of Hydrogen Vapor Pressure, 0.1~5 min of reaction time.
The advantage of method for preparing catalyst of the invention compared with existing method for preparing catalyst are as follows: one-step method is complete simultaneously At the preparation of nano aperture phenolic resin and the load of catalyst, manufacturing process is simple, safe；Nano aperture phenolic resin is excellent Architectural characteristic, the catalyst activity for assigning preparation is high, not easy in inactivation；Catalyst storage uses safe height, cost of manufacture warp Ji；In addition, its unique architectural characteristic is allowed to very properly add the catalyst of hydrogen as fixed-bed catalytic.With prior art phase Than the Catalytic processes replace conventional high-tension tank reactor using fixed bed reactors, shorten the reaction time, simplify reaction step Suddenly, simplify post-reaction treatment, reduce the mechanical damage of catalyst, technique cleaning, product quality height.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Fig. 2 is present invention process main device schematic diagram.1. reacting tubing string；2. inert filler；3. catalyst；4. temperature Meter probe；5. temperature regulating device；6. condensing unit；7. safety valve；8. device for storing liquid.
Specific embodiment
Example is implemented by fixed bed reaction equipment.Fixed bed reactors are also known as packed bed reactor, such as Fig. 2 institute Show, reacts filling solid catalyst 3 in tubing string in element 1, reaction raw materials (including gas and liquid two phases) are pumped into tubing string in proportion, pass through Under 5 temperature control function of element, reaction raw materials are reacted on bed by catalyst bed, it is cold at element 6 to obtain product It is solidifying, crude product is obtained at element 8, subsequent processing operation can be collected at product exit or directly be carried out to crude product.
Embodiment 1
5.0 g of phenol formaldehyde (PF) phenolic resin, 2.4 g of cobalt acetate, 0.56 g of hexa are taken, 5.0 g methanol are added Sufficiently dissolution, is placed in autoclave.It is filled with the nitrogen of 1.0 MPa, solidifies 4 h at 90 DEG C, is filtered, washed, dried Obtain cobalt/phenolic resin catalyst of the content 10% of grey black.560 ± 35nm of catalyst aperture, density 0.10g/cm3。
Prepare mass fraction 10% 1,5- dinitronaphthalene aniline solution, in fixed bed reactors, insert 10% cobalt/ 5.0 g of phenolic resin catalyst, catalyst upper and lower level is filled with quartz sand in reaction tube, with the replacement fixed bed interior air 5 of nitrogen It is secondary.1.0 MPa of fixed bed reaction area pressure is controlled, 70 DEG C of temperature, is pumped into 1,5- dinitronaphthalene reaction solution, by adjusting flow velocity, The control residence time is 3.0 min.Reaction obtains colourless liquid, reddens rapidly in air.Product is through chromatography, 1,5- dinitro The conversion ratio of base naphthalene is 99.6%, and the selectivity of 1,5-diaminonaphthalene is 91.2%.
Embodiment 2
5.0 g of phenol formaldehyde (PF) phenolic resin, 0.043 g of platinum nitrate, 0.36 g of paraformaldehyde are taken, 75.0 g methanol are added and fill Divide dissolution, is placed in autoclave.It is filled with the nitrogen of 0.5 MPa, solidifies 8 h at 140 DEG C, is filtered, washed, dried Obtain platinum/phenolic resin catalyst of canescence content about 0.5%.420 ± 30nm of catalyst aperture, density 0.18g/cm3。
Prepare mass fraction 5% 1,5- dinitronaphthalene methanol solution, in fixed bed reactors, filling about 5% platinum/ 5.0 g of phenolic resin catalyst, catalyst upper and lower level is filled with quartz sand in reaction tube, with the replacement fixed bed interior air 5 of nitrogen It is secondary.3.0 MPa of fixed bed reaction area pressure is controlled, 90 DEG C of temperature, is pumped into 1,5- dinitronaphthalene reaction solution, by adjusting flow velocity, The control residence time is 0.8 min, obtains aubergine liquid, red intensification in air.Product is through chromatography, 1,5- dinitro The conversion ratio of naphthalene is 92.4%, and the selectivity of 1,5-diaminonaphthalene is 61.7%.
Embodiment 3
10.0 g of phenol formaldehyde (PF) phenolic resin, 16.5 g of nickel nitrate, 1.65 g of hexa are taken, 120.0 g are added Methanol sufficiently dissolves, and is placed in autoclave.It is filled with the nitrogen of 0.1 MPa, solidifies 12 h at 170 DEG C, filtered, washed Wash, be dried to obtain nickel/phenolic resin catalyst of canescence content about 30%.230 ± 25nm of catalyst aperture, density 0.24g/ cm3。
The n,N-dimethylacetamide solution for preparing 1, the 5- dinitronaphthalene of mass fraction 20%, in fixed bed reactors, About 30% nickel/10.0 g of phenolic resin catalyst is inserted, catalyst upper and lower level is filled in reaction tube with quartz sand.It is set with nitrogen Change air 5 times in fixed bed.1.5 MPa of fixed bed reaction area pressure is controlled, 110 DEG C of temperature, is pumped into the reaction of 1,5- dinitronaphthalene Liquid, by adjusting flow velocity, the control residence time is 2.0 min.Colourless liquid is obtained, is reddened rapidly in air.Product is through chromatography Analysis, the conversion ratio of 1,5- dinitronaphthalene are 100%, and the selectivity of 1,5-diaminonaphthalene is 98.3%.
Embodiment 4
10.0 g of resorcinol formaldehyde resin, 0.43 g of palladium acetate, 1.1 g of aniline are taken, it is sufficiently molten that 45.0 g methanol are added Solution, is placed in autoclave.It is filled with the nitrogen of 0.4 MPa, solidifies 10 h at 190 DEG C, is filtered, washed, is dried to obtain The palladium of canescence content about 2%/phenolic resin catalyst.210 ± 15nm of catalyst aperture, density 0.30g/cm3。
The tetrahydrofuran solution for preparing 1, the 5- dinitronaphthalene of mass fraction 20%, in fixed bed reactors, filling about 2% Palladium/10.0 g of phenolic resin catalyst, catalyst upper and lower level is filled with quartz sand in reaction tube.It is replacement fixed bed interior with nitrogen Air 5 times.Fixed bed reaction area pressure 0.3MPa is controlled, 40 DEG C of temperature, 1,5- dinitronaphthalene reaction solution is pumped into, passes through adjusting Flow velocity, control residence time are 0.1 min.Obtain aubergine liquid, red intensification in air.Product is through chromatography, and 1,5- The conversion ratio of dinitronaphthalene is 98.1%, and the selectivity of 1,5-diaminonaphthalene is 58.8%.
Embodiment 5
10.0 g of resorcinol formaldehyde resin, 1.08 g of palladium acetate, 1.1 g of aniline are taken, it is sufficiently molten that 70.0 g methanol are added Solution, is placed in autoclave.It is filled with the nitrogen of 0.5 MPa, solidifies 4 h at 170 DEG C, is filtered, washed, is dried to obtain The palladium of canescence content about 5%/phenolic resin catalyst.230 ± 15nm of catalyst aperture, density 0.26g/cm3。
The n,N-Dimethylformamide solution for preparing 1, the 5- dinitronaphthalene of mass fraction 20%, in fixed bed reactors, About 5% palladium/10.0 g of phenolic resin catalyst is inserted, catalyst upper and lower level is filled in reaction tube with quartz sand.It is replaced with nitrogen Air 5 times in fixed bed.0.8 MPa of fixed bed reaction area pressure is controlled, 75 DEG C of temperature, is pumped into 1,5- dinitronaphthalene reaction solution, By adjusting flow velocity, the control residence time is 0.5min.Obtain aubergine liquid, red intensification in air.Product is through chromatography point Analysis, the conversion ratio of 1,5- dinitronaphthalene are 93.3%, and the selectivity of 1,5-diaminonaphthalene is 75.8%.
Embodiment 6
10.0 g of phenol formaldehyde (PF) phenolic resin, 0.91 g of nickel nitrate, 0.72 g of paraformaldehyde are taken, 40.0 g methanol are added and fill Divide dissolution, is placed in autoclave.It is filled with the nitrogen of 0.1 MPa, solidifies 12 h at 90 DEG C, is filtered, washed, dried Obtain nickel/phenolic resin catalyst of canescence content about 2.5%.540 ± 30nm of catalyst aperture, density 0.11g/cm3。
The methanol solution for preparing 1, the 5- dinitronaphthalene of mass fraction 10%, in fixed bed reactors, filling about 2.5% Nickel/5.0 g of phenolic resin catalyst, catalyst upper and lower level is filled with quartz sand in reaction tube.It is replacement fixed bed interior with nitrogen gas Air 5 times.2.5 MPa of fixed bed reaction area pressure is controlled, 110 DEG C of temperature, 1,5- dinitronaphthalene reaction solution is pumped into, passes through tune Throttling speed, control residence time are 5.0 min.Colourless liquid is obtained, is gradually reddened in air.Product is through chromatography, and 1,5- The conversion ratio of dinitronaphthalene is 99.8%, and the selectivity of 1,5-diaminonaphthalene is 98.0%.
Embodiment 7
10.0 g of diformazan fluosite, 0.017 g of palladium chloride, 0.55 g of hexa are taken, 100.0g first is added Alcohol sufficiently dissolves, and is placed in autoclave.It is filled with the nitrogen of 0.2 MPa, solidifies 7 h at 110 DEG C, be filtered, washed, It is dried to obtain palladium/phenolic resin catalyst of canescence content about 0.1%.460 ± 30nm of catalyst aperture, density 0.14g/cm3
The aqueous isopropanol for preparing 1, the 5- dinitronaphthalene of mass fraction 20%, in fixed bed reactors, filling about 0.1% Nickel/10.0 g of phenolic resin catalyst, catalyst upper and lower level is filled with quartz sand in reaction tube.It is replacement fixed bed interior with nitrogen Air 5 times.1.0 MPa of fixed bed reaction area pressure is controlled, 80 DEG C of temperature, 1,5- dinitronaphthalene reaction solution is pumped into, passes through adjusting Flow velocity, control residence time are 3.5 min.Aubergine liquid is obtained, redden intensification in air.Product is through chromatography, and 1,5- The conversion ratio of dinitronaphthalene is 98.3%, and the selectivity of 1,5-diaminonaphthalene is 66.4%.

Claims (2)

1. one kind 1,5- catalytic hydrogenation of dinitronaphthalene synthesizes the method for preparing catalyst of 1,5-diaminonaphthalene, it is characterised in that: presses It is carried out according to following step:
(1) phenolic resin is dissolved in the methanol of 1~15 times of quality, static rear filtering and impurity removing；
(2) the group VIII metal compound for weighing certain mass in proportion, meeting active component quality is catalyst quality 0.1%~30%, the curing agent of phenolic resin quality 1~15% is added, is uniformly mixed；
(3) raw material (1), (2) are mixed, nitrogen replaces the hollow gas of system, 0.1~1.0 MPa of pressurising；
(4) temperature programming solidifies 4~12 hours at 90~190 DEG C；
(5) it is filtered, washed after reaction, is dried to obtain catalyst；
The pore diameter range of the phenolic resin base catalyst wherein prepared is 200~600 nm, and density is 0.10~0.30 g/cm3；
Wherein the phenolic resin carrier is phenol formaldehyde (PF) phenolic resin, diformazan fluosite, resorcinol formaldehyde resin One or more of；
Wherein the curing agent of the phenolic resin is one or more of hexa, paraformaldehyde, aniline；
Wherein the group VIII metal element is one or more of cobalt, nickel, palladium, platinum；
Wherein the group VIII metal compound is one of acetate, nitrate, hydrochloride compound of respective metal Or it is several.
2. a kind of method for preparing catalyst of 1,5- catalytic hydrogenation of dinitronaphthalene synthesis 1,5- diaminonaphthalene described in claim 1 The application of the catalyst of preparation, it is characterised in that: prepared phenolic resin base catalyst is applied to fixed bed continuous catalysis The technique of hydrogenation synthesis 1,5- diaminonaphthalene；The fixed bed reactors pressure control range are as follows: normal pressure~10 MPa, temperature control range Are as follows: 20 DEG C~550 DEG C；The reaction dissolvent of 1,5- dinitronaphthalene is selected from aniline, methanol, isopropanol, tetrahydrofuran, N, N- diformazan The mixture of one or more of base formamide, DMAC N,N' dimethyl acetamide；The mass concentration of 1,5- diaminonaphthalene be 5%~ 20%；
React 0.3~3 MPa of Hydrogen Vapor Pressure, 0.1~5 min of reaction time；Wherein reaction temperature is 40 DEG C~110 DEG C.
CN201610704781.1A 2016-08-22 2016-08-22 The preparation method and application of 1,5- dinitronaphthalene hydrogenation catalyst Active CN106238099B (en)

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