CN101811973A - Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent - Google Patents
Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent Download PDFInfo
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Abstract
The invention discloses a method for synthesizing halogen aromatic amines by halogen aromatic nitro compounds through liquid phase hydrogenation, which is characterized in that: the reaction for synthesizing the halogen aromatic amines by the halogen aromatic nitro compounds through liquid phase hydrogenation is carried out in the presence of a Pd/C catalyst under the condition of no solvent; and the method for preparing the Pd/C catalyst comprises the following steps of: performing impregnation pretreatment on active carbon by using aqueous solution of potassium halide, and filtering and washing until the filter liquor does not contain halide ions; preparing the pretreated active carbon into slurry by using de-ionized water, adding aqueous solution of HaPdCl4 dropwise for impregnation treatment, adjusting the pH value to alkali, and filtering and washing until the filter liquor is neutral; and preparing the obtained filter cakes into slurry by using de-ionized water, reducing in aqueous solution of reducing agent by a wet method, and filtering and washing until the filter liquor is neutral to obtain the Pd/C catalyst. The catalyst is adopted to prepare the halogen aromatic amines under the condition of no solvent, the selectivity is over 99.9 percent, the product quality meets the medical requirements, the production process is simplified, the production cost and energy consumption are reduced, the production efficiency is improved, and adverse factors such as solvent and product steam severely harming human bodies and polluting environment are improved.
Description
(1) technical field
The present invention relates to a kind of method of halogenated aromatic nitro-compound liquid phase catalytic hydrogenation synthesizing halogen aromatic amines.
(2) background technology
Halo aniline is important basic chemical industry raw material and organic chemical industry's intermediate, is widely used in the synthetic of fine chemicals such as medicine, agricultural chemicals, dyestuff.Its production method is mainly produced by corresponding halogenated aromatic nitro-compound reduction, comprises chemical reduction method (iron powder reducing method, sodium sulfide reducing method and hydrazine hydrate reduction method etc.), electrolytic reduction and catalytic hydrogenating reduction method etc.Chemical reduction method has advantages such as operational path is simple, easy and simple to handle, investment is little, and is comparatively ripe technically.Defectives such as but this method ubiquity, and environmental pollution is big, product yield is low, product quality difference and energy consumption height and being eliminated gradually.Electrolytic reduction is difficult to realize industrialization owing to be subjected to the restriction of factors such as electrode materials, electrolyzer, cost to rest on the laboratory study stage always.It is simple that the catalytic hydrogenating reduction method has operating process, the product yield height, and advantage such as superior product quality and energy consumption are low and receiving much concern is an eco-friendly friendly process.But in the practical application, under Raney-Ni or the effect of charcoal supported noble metal catalyst, halogenated aromatic nitro-compound hydrogenating reduction generates in the halogen aromatic amines process and exists optionally huge challenge.In theory, because the strong electrophilic effect of nitro, C-X (X halogen) bonding electron cloud density reduces, and C-X key stability strengthens, and the nitro activity is far above the C-X key, and therefore, halogenated aromatic nitro-compound hydrogenation reduction is easy to carry out towards the main reaction direction.But after nitro was reduced and generates amino, because the amino sub-effect of power supply increases the X cloud density on the C-X key, the C-X bonding strength reduced, and activity strengthens.If catalyst activity is higher or there is stronger acid active centre in catalyst surface, chemisorption very easily takes place with the catalyst activity surface in the C-X key on the aminocompound, the C-X key is further activated, and the hydrogenolysis-dehalogenation side reaction takes place cause product selectivity to descend.Therefore, the shortening technology synthesizing halogen aromatic amines of exploitation highly selective is very urgent.
Adsorption activation how to avoid C-X key on the aminocompound is the key that suppresses hydrogenolysis-dehalogenation.On catalyst preparation technology, suppress the dehalogenation side reaction and mainly contain three approach:
1) modified catalyst method.This method is many to be active ingredient with the precious metal, and iron, copper etc. is auxiliary agent, loads on the carriers such as gac, aluminum oxide.A kind of technological process that is used to prepare the chloro arylamine is disclosed as U.S. patent of invention US5120875A1.This process is a catalyzer with Pt-Ni (Cr)/C, is solvent with Virahol (moisture 15%), catalytic hydrogenating reduction chloronitrobenzene under 120～160 ℃ and 5.0～25.0MPa condition, and dechlorination rate is 1.0%; U.S. patent of invention US5512529A1 discloses a kind of catalyzer and preparation process thereof that is used for halogenated nitrobenzene selective hydrogenation system halogen aromatic amines.This process in heat-insulating high pressure batch reactor, with Pt-Cu/AC (Pt: Cu=10: being catalyzer 1), is solvent with toluene, catalytic hydrogenating reduction 3 under 40 ℃ of reaction pressure 6.0MPa of starting temperature, 4-dichloronitrobenzene, dechlorination rate are 0.7%.After this catalyst recirculation is used 3 times, 3,4-dichlorphenamide bulk powder yield is reduced to 91.4% from 100%; It is a kind of 3 that Chinese patent CN200510050594 discloses, the production method of 4-dichlorphenamide bulk powder.This process is with Ru-Fe/Al
2O
3Being catalyzer, is solvent with the aqueous ethanolic solution, in 130～180 ℃ of following catalytic hydrogenating reductions 3, and the 4-dichloronitrobenzene, the dehalogenation rate is minimum to be reached about 0.3%, but this catalyst preparation process complexity, and owing to use Al
2O
3As carrier, cause the precious metal cost recovery to improve; Chinese patent CN101658788A discloses a kind of Catalysts and its preparation method that is used for the green synthesizing halogen aromatic amines of halogenated aromatic nitro-compound efficient catalytic hydrogenation.It is active ingredient that this method adopts two precious metals (as Au-Pt), is that carrier is (as TiO with the oxide compound
2), be solvent with alcohol, catalytic hydrogenating reduction o-chloronitrobenzene under the normal temperature, the Ortho-Chloro aniline selectivity is near 100%.But after catalyzer was applied mechanically 3 times, the o-chloronitrobenzene transformation efficiency reduced to 97.0%.Chinese patent CN02148509.7 discloses a kind of production method of halogenated nitrobenzene shortening synthesizing halogen aromatic amines.This method is a catalyzer with nano-carbon tube load Pt, is solvent with ethanol, catalysis o-chloronitrobenzene or parachloronitrobenzene or 3, and 4-dichloronitrobenzene or the corresponding halo aniline of 3-chloro-4-fluoronitrobenzene hydrogenation system, the dehalogenation rate is below 1.0%.But the CNT (carbon nano-tube) carrier costs an arm and a leg, reusable edible not, and therefore, this patented technology will depend on the cost of carbon pipe in industrial application prospect.
2) add dehalogenation inhibitor method.Promptly the dehalogenation inhibitor is joined and carry out hydrogenation reaction in the reaction solution with catalyzer, raw material, solvent etc.Add-on is generally the 0.1-5% of material quantity.Dehalogenation inhibitor normally some organic basess or other contains the compound of electron-donating group.As organic amine (JP 73-49728), thanomins/2-methoxyethyl amine (US 4990663A1) etc. such as morpholine/piperazine or corresponding N-methyl, N-ethyl derivative (US 3361819A1), triphenyl phosphite/triphenylphosphate (US 3474144), trialkyl phosphite (GB 1498722), ammoniacal liquor (US 4230637A1), sulfone compound (US 5126485), alkylamine/hydramine/heterocyclic amines.The adding of dehalogenation inhibitor has suppressed the generation of dehalogenation side reaction effectively, and the dehalogenation rate is dropped to below 0.5～1%, has improved reaction preference and product yield greatly.But the adding of dechlorination inhibitor brings inhibitor separation difficulty, production cost to increase, influence a series of problems such as product quality thereupon.
3) modulation carried noble metal size of particles.Cop etc. [J.Mol.Catal., 1991,68 (3): 331-345] are at research Pt/Al
2O
3Find during catalyzer that in the hydrogenation of parachloronitrobenzene, the selectivity of p-Chlorobenzoic acid amide depends on the size of Pt particle.Under comparable conditions, the p-Chlorobenzoic acid amide selectivity on the big Pt particle is far above the p-Chlorobenzoic acid amide selectivity on the little Pt particle.Therefore, it is an ideal method that regulation and control carried noble metal size of particles suppresses dehalogenation, but how according to halogenated aromatic nitro-compound constructional feature guiding regulation and control metallics size and form the size homogeneous and distribute and become the technical bottleneck of this type of catalyzer of preparation, this has higher requirement to preparation method and preparation process.
In the technology of existing patent and open report, solved the problem that halogenated aromatic catalytic hydrogenation of nitro compound reduction reaction selectivity is on the low side, product quality is relatively poor to a certain extent by modification and methods such as technology of preparing improvement or interpolation dehalogenation inhibitor, become a kind of environmental friendliness friendly process of the comparatively widespread use of halogenated aromatic nitro-compound reduction synthesizing halogen aromatic amines in the present industry catalyzer.But, in the existing shortening technology, still there is modified catalyst preparation process complexity, precious metal reclaims difficulty, adds the problem that the dehalogenation inhibitor influences purifying products.And the dehalogenation rate generally is higher than 0.2%, can't one-step synthesis goes out to satisfy that single foreign matter content requirement is lower than 0.1% ultrahigh quality halogen aromatic amines in the medicine intermediate.In addition, the hydrogenating reduction process need add a large amount of volatile organic solvents usually, and (raw material and solvent ratio are about 1: 1.2-2 (Kg/L)) in order to dissolving raw material or product, contact probability between augmenting response thing, hydrogen and the catalyzer three-phase, strengthen mass transfer and heat-transfer effect, accelerate speed of reaction; But use solvent then can increase last handling processes such as product separation and solvent recuperation, thereby cause a series of problems such as cost of investment increase, energy consumption increase, safety coefficient reduction, work situation variation.
(3) summary of the invention
The technical problem to be solved in the present invention is to provide the method for halogenated aromatic nitro-compound synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under a kind of condition of no solvent.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of method of halogenated aromatic nitro-compound liquid-phase hydrogenatin synthesizing halogen aromatic amines, the reaction of described halogenated aromatic nitro-compound liquid-phase hydrogenatin synthesizing halogen aromatic amines are to carry out under activated carbon supported palladium catalyst (Pd/C catalyzer) effect under condition of no solvent; Described Pd/C catalyzer is prepared as follows: gac is earlier with the pre-treatment of potassium halide aqueous solution dipping, filtration washing halogen ion to the filtrate; The gained pretreated active carbon is mixed with slurries with deionized water, drips H
2PdCl
4The aqueous solution carries out dip treating, and the back regulator solution pH value that disposes is to alkalescence, and it is neutral that filtration washing to filtrate is; The gained filter cake is mixed with slurries with deionized water again, wet reducing in the reductive agent aqueous solution, and filtration washing to filtrate is neutral once more, promptly gets the Pd/C catalyzer.
The present invention, described halogenated aromatic nitro-compound is one of following: o-chloronitrobenzene, m-chloro-nitrobenzene, parachloronitrobenzene, 3,4-dichloronitrobenzene, 3,5-dichloronitrobenzene, 6-chloro-2-nitrotoluene, 2,5-dichloronitrobenzene, o-fluoronitrobenzene, p-fluoronitrobenzene, a fluoronitrobenzene, 2,4-difluoro nitrobenzene, 2,5-difluoro nitrobenzene, 2,3-difluoro nitrobenzene, 2,6-difluoro nitrobenzene, 2,3,4-trifluoronitrobenzene, 2,4,6-trifluoronitrobenzene, 3,4,5-trifluoronitrobenzene etc.
Further, in the Pd/C catalyst preparation process of the present invention, described gac floods pretreated actual conditions with the potassium halide aqueous solution to be recommended as follows: the described potassium halide aqueous solution is potassium iodide aqueous solution, and its concentration is 0.3～8.0mol/L; The quality proportioning of described gac and potassium iodide aqueous solution is 1: 10～18, and pretreatment temperature is 20～80 ℃, and pretreatment time is 0.5～10 hour.Further, 25～75 ℃ of preferred pretreatment temperature, pretreatment time 1～8 hour, the concentration 1.0～5.0mol/L of potassium iodide aqueous solution.
Further, in the Pd/C catalyst preparation process of the present invention, recommending according to the palladium charge capacity is the ratio dropping H of 0.8～2.5wt%
2PdCl
4The aqueous solution.
Further, in the Pd/C catalyst preparation process of the present invention, pretreated active carbon and deionized water are mixed with slurries by mass ratio 1: 10～15, drip palladium compound H
2PdCl
4The aqueous solution carries out dip treating, and treatment temp is 60～90 ℃, and the treatment time is 3～6 hours.
Further, in the Pd/C catalyst preparation process of the present invention, after finishing, dip treating regulates slurry pH value to 7.5～9.5 with alkaline aqueous solution; Described alkaline aqueous solution is Na
2CO
3, NaHCO
3, NaOH, K
2CO
3, KHCO
3Or the aqueous solution of KOH, the concentration of alkaline aqueous solution is 5～15g/L.
Further, in the Pd/C catalyst preparation process of the present invention, before the catalyst reduction, earlier gained filter cake and deionized water are mixed with slurries by mass ratio 1: 15～20, then wet reducing in hydrazine hydrate aqueous solution.
Further, in the Pd/C catalyst preparation process of the present invention, the concentration of described hydrazine hydrate aqueous solution is 20～85wt%, described hydrazine hydrate (N
2H
4) with the quality proportioning of palladium be 15～20: 1, reduction temperature is 0～50 ℃, the recovery time is 15min～10 hour.Preferred reduction temperature is 25～35 ℃.
Further, the present invention is concrete to recommend described Pd/C catalyzer to be prepared as follows: take by weighing gac and impregnated in the KI aqueous solution that concentration is 1.0～5.0mol/L, the volumetric usage of the described KI aqueous solution is counted 10～18ml/g with the quality of gac, and constant temperature stirred 1～8 hour under 25～75 ℃ of conditions.Filter, mother liquor reclaims recycled, and filter cake does not have the I-ion with deionized water wash to filtrate.Again above-mentioned pretreated active carbon and deionized water are mixed with slurries according to the ratio that every g gac adds 10～15ml deionized water, are warming up to 60～90 ℃, constant temperature.By the palladium loading is that 0.8～2.5wt% slowly drips H
2PdCl
4The aqueous solution stirs.Flood after 3～6 hours, with alkaline aqueous solution regulator solution pH value to 7.5～9.5, cool the temperature to room temperature thereupon, filter, filter cake is extremely neutral with deionized water wash.Again filter cake and deionized water are mixed with slurries according to the ratio that every g filter cake adds 15～20ml deionized water, press reductive agent (N
2H
4) drip 20～85wt% hydrazine hydrate solution with the quality proportioning of palladium 15～20: 1, stir 15min～10 hour in 0～50 ℃, filter, filter cake to neutral, promptly gets described activated carbon supported palladium catalyst with deionized water wash.The palladium particle diameter with the preparation condition different distributions between 15～30nm.
Among the present invention, the method of described halogenated aromatic nitro-compound liquid-phase hydrogenatin synthesizing halogen aromatic amines is specifically carried out according to following: raw material halogenated aromatic nitro-compound is poured in the reactor, slowly being warming up to fusion, is that 1: 100～500 ratio adds described Pd/C catalyzer in catalyzer and raw materials quality ratio then; The off-response still, use the nitrogen replacement air, use hydrogen exchange nitrogen again, fill hydrogen to 0.2～1.5MPa after displacement finishes, control hydrogenation reaction temperature is fully reacted the postcooling cooling at 75～180 ℃ of stirring reactions, take out still internal reaction liquid, the filtering separation catalyzer, gained filtrate is utilized the branch water outlet that is separated, and promptly gets halogen aromatic amines.
Further, the hydrogenation reaction temperature is preferably 75～150 ℃.
The present invention under condition of no solvent under the Pd/C catalyst action highly selective synthesized halogen aromatic amines, its reason may be: the present invention uses the potassiumiodide of different concns that gac is modified and makes its surface functional functional group of the equally distributed iodide ion of formation, utilize itself and Pd ionic group complexing action mechanism again, the generation and the speed of growth in conjunction with the constructional feature of different halogenated aromatic nitro-compounds guiding control Pd crystal particles reach suitable different halogen aromatic amines shortening synthetic palladium particle distribution of orderly regulation and control and size.The low dispersity of the low charge capacity of this catalyzer has effectively reduced catalyst active center, has reduced the reaction probability of C-X key absorption hydrogenolysis.Simultaneously, the relative stronger electron rich characteristic that bigger palladium particle diameter active centre may exist has also suppressed the chemisorption of C-X key effectively.In addition, under the condition of no solvent, the higher halogenated aromatic nitro-compound of relative viscosity becomes the gas-liquid-solid phase reaction medium, therefore, have under the solvent state, the rate of mass transfer of hydrogen in reaction system reduces, ADSORPTION STATE hydrogen quantity minimizing in the heart in the unit catalyst surface active, ADSORPTION STATE-NO
2Increase with ADSORPTION STATE-H relative concentration, promote that molecular balance carries out towards the main reaction direction, the side reaction of C-X key hydrogenolysis is effectively suppressed.This also may be one of reason of halogen aromatic amines highly selective of the present invention.
The present invention compared with prior art, its advantage is embodied in:
1) to suppress the dehalogenation effect obvious in the present invention, and the halogen aromatic amines selectivity is greater than 99.9%, and the dehalogenation rate is lower than 0.1%, and product quality reaches the pharmaceutical grade requirement.The present invention need not to add organic solvent in addition, therefore, delete solvent recuperation and product purification process in the catalytic hydrogenation process, reduced cost of investment and energy expenditure, improved production efficiency, improved solvent, product steam person murder by poisoning and the bigger unfavorable factor of environmental pollution.
2) the present invention need not in reaction solution to add the dehalogenation inhibitor, has solved a series of problems such as the separation and purification of products that occurs in the present industrial application, etching apparatus.
3) catalyst preparation process of the present invention's employing is simple, and pretreating reagent is capable of circulation to be applied mechanically, and has reduced the Catalyst Production cost.
4) to suppress the dehalogenation effect obvious in the present invention, and the dehalogenation by product is few, therefore reduced its poisoning effect to catalyzer.Catalyzer can repeat to apply mechanically, and has improved the effective rate of utilization of catalyzer, has reduced the catalyzer use cost.Also reduced in the catalyst recovery regenerative process and polluted and energy consumption.
(4) description of drawings
The TEM collection of illustrative plates of the Pd/C catalyzer that Fig. 1 makes for embodiment two;
The palladium particle statistics of the Pd/C catalyzer that Fig. 2 makes for embodiment two.
(5) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment one
Take by weighing the 10g cocoanut active charcoal and impregnated in the KI aqueous solution that 170ml concentration is 2.5mol/L, 50 ℃ of constant temperature stirred 6 hours, filtered, and did not have iodide ion with deionized water wash to filtrate.With deionized water above-mentioned gac is mixed with the 150ml slurries then, is warming up to 80 ℃, constant temperature.By the palladium charge capacity is that 2.0wt% slowly drips H
2PdCl
4Solution (Pd content 0.05g/ml) stirs.Behind the dipping 5h, with 10wt%NaOH solution regulator solution pH value to 8.5, cool the temperature to room temperature thereupon, filter, filter cake is neutral with deionized water wash to filtrate.Again filter cake is configured to the 200ml slurries under 30 ℃, slowly drips 4ml 85wt% hydrazine hydrate solution, stirred 2 hours, filter, filter cake is neutral with deionized water wash to filtrate, promptly gets described activated carbon supported palladium catalyst.Through high power transmissioning electric mirror determining palladium average crystal grain size is 22nm.
Embodiment two
Take by weighing the 10g cocoanut active charcoal and impregnated in the KI aqueous solution that 120ml concentration is 4.0mol/L, 50 ℃ of constant temperature stirred 6 hours, filtered, and did not have iodide ion with deionized water wash to filtrate.With deionized water above-mentioned gac is mixed with the 150ml slurries then, is warming up to 80 ℃, constant temperature.By the palladium charge capacity is that 2.0wt% slowly drips H
2PdCl
4Solution (Pd content 0.05g/ml) stirs.Behind the dipping 5h, with 10wt%NaOH solution regulator solution pH value to 8.5, cool the temperature to room temperature thereupon, filter, filter cake is neutral with deionized water wash to filtrate.Again filter cake is configured to the 200ml slurries under 30 ℃, slowly drips 4ml 85wt% hydrazine hydrate solution, stirred 2 hours, filter, filter cake is neutral with deionized water wash to filtrate, promptly gets described activated carbon supported palladium catalyst.Through high power transmissioning electric mirror determining palladium average crystal grain size is 28nm.
Embodiment three
Take by weighing the 10g cocoanut active charcoal and impregnated in the KI aqueous solution that 150ml concentration is 3.5mol/L, 40 ℃ of constant temperature stirred 6 hours, filtered, and did not have iodide ion with deionized water wash to filtrate.With deionized water above-mentioned gac is mixed with the 150ml slurries then, is warming up to 80 ℃, constant temperature.By the palladium charge capacity is that 2.0wt% slowly drips H
2PdCl
4Solution (Pd content 0.05g/ml) stirs.Behind the dipping 5h, with 10wt%NaOH solution regulator solution pH value to 8.5, cool the temperature to room temperature thereupon, filter, filter cake is neutral with deionized water wash to filtrate.Again filter cake is configured to the 200ml slurries under 30 ℃, slowly drips 4ml 85wt% hydrazine hydrate solution, stirred 2 hours, filter, filter cake is neutral with deionized water wash to filtrate, promptly gets described activated carbon supported palladium catalyst.Through high power transmissioning electric mirror determining palladium average crystal grain size is 26nm.
Embodiment four
Take by weighing the 10g cocoanut active charcoal and impregnated in the KI aqueous solution that 170ml concentration is 2.5mol/L, 30 ℃ of constant temperature stirred 3 hours, filtered, and did not have iodide ion with deionized water wash to filtrate.With deionized water above-mentioned gac is mixed with the 150ml slurries then, is warming up to 80 ℃, constant temperature.By the palladium charge capacity is that 2.0wt% slowly drips H
2PdCl
4Solution (Pd content 0.05g/ml) stirs.Behind the dipping 5h, with 10wt%NaOH solution regulator solution pH value to 8.5, cool the temperature to room temperature thereupon, filter, filter cake is neutral with deionized water wash to filtrate.Again filter cake is configured to the 200ml slurries under 30 ℃, slowly drips 4ml 85wt% hydrazine hydrate solution, stirred 2 hours, filter, filter cake is neutral with deionized water wash to filtrate, promptly gets described activated carbon supported palladium catalyst.Through high power transmissioning electric mirror determining palladium average crystal grain size is 24nm.
Embodiment five
Take by weighing the 10g cocoanut active charcoal and impregnated in the KI aqueous solution that 170ml concentration is 2.5mol/L, 50 ℃ of constant temperature stirred 6 hours, filtered, and did not have iodide ion with deionized water wash to filtrate.With deionized water above-mentioned gac is mixed with the 150ml slurries then, is warming up to 80 ℃, constant temperature.By the palladium charge capacity is that 1.5wt% slowly drips H
2PdCl
4Solution (Pd content 0.05g/ml) stirs.Behind the dipping 5h, with 10wt%NaOH solution regulator solution pH value to 8.5, cool the temperature to room temperature thereupon, filter, filter cake is neutral with deionized water wash to filtrate.Again filter cake is configured to the 200ml slurries under 30 ℃, slowly drips 3.5ml 85wt% hydrazine hydrate solution, stirred 2 hours, filter, filter cake is neutral with deionized water wash to filtrate, promptly gets described activated carbon supported palladium catalyst.Through high power transmissioning electric mirror determining palladium average crystal grain size is 20nm.
Embodiment six
Take by weighing the 10g cocoanut active charcoal and impregnated in the KI aqueous solution that 170ml concentration is 2.5mol/L, 50 ℃ of constant temperature stirred 6 hours, filtered, and did not have iodide ion with deionized water wash to filtrate.With deionized water above-mentioned gac is mixed with the 120ml slurries then, is warming up to 70 ℃, constant temperature.By the palladium charge capacity is that 2.0wt% slowly drips H
2PdCl
4Solution (Pd content 0.05g/ml) stirs.Behind the dipping 5h, with 10wt%NaOH solution regulator solution pH value to 8.5, cool the temperature to room temperature thereupon, filter, filter cake is neutral with deionized water wash to filtrate.Again filter cake is configured to the 200ml slurries under 30 ℃, slowly drips 4ml 85wt% hydrazine hydrate solution, stirred 2 hours, filter, filter cake is neutral with deionized water wash to filtrate, promptly gets described activated carbon supported palladium catalyst.Through high power transmissioning electric mirror determining palladium average crystal grain size is 25nm.
Embodiment seven
Take by weighing the 10g cocoanut active charcoal and impregnated in the KI aqueous solution that 170ml concentration is 2.5mol/L, 50 ℃ of constant temperature stirred 6 hours, filtered, and did not have iodide ion with deionized water wash to filtrate.With deionized water above-mentioned gac is mixed with the 150ml slurries then, is warming up to 80 ℃, constant temperature.By the palladium charge capacity is that 1.0wt% slowly drips H
2PdCl
4Solution (Pd content 0.05g/ml) stirs.Behind the dipping 3h, with 10wt%NaOH solution regulator solution pH value to 8.0, cool the temperature to room temperature thereupon, filter, filter cake is neutral with deionized water wash to filtrate.Again filter cake is configured to the 200ml slurries under 30 ℃, slowly drips 1.8ml 85wt% hydrazine hydrate solution, stirred 2 hours, filter, filter cake is neutral with deionized water wash to filtrate, promptly gets described activated carbon supported palladium catalyst.Through high power transmissioning electric mirror determining palladium average crystal grain size is 18nm.
Embodiment eight
Take by weighing the 10g cocoanut active charcoal and impregnated in the KI aqueous solution that 170ml concentration is 2.5mol/L, 50 ℃ of constant temperature stirred 6 hours, filtered, and did not have iodide ion with deionized water wash to filtrate.With deionized water above-mentioned gac is mixed with the 150ml slurries then, is warming up to 80 ℃, constant temperature.By the palladium charge capacity is that 2.0wt% slowly drips H
2PdCl
4Solution (Pd content 0.05g/ml) stirs.Behind the dipping 5h, with 10wt%NaOH solution regulator solution pH value to 8.5, cool the temperature to room temperature thereupon, filter, filter cake is neutral with deionized water wash to filtrate.Again filter cake is configured to the 200ml slurries under 30 ℃, slowly drips 4ml 85wt% hydrazine hydrate solution, stirred 3 hours, filter, filter cake is neutral with deionized water wash to filtrate, promptly gets described activated carbon supported palladium catalyst.Through high power transmissioning electric mirror determining palladium average crystal grain size is 23nm.
Embodiment nine
Take by weighing the 10g cocoanut active charcoal and impregnated in the KI aqueous solution that 170ml concentration is 2.5mol/L, 50 ℃ of constant temperature stirred 6 hours, filtered, and did not have iodide ion with deionized water wash to filtrate.With deionized water above-mentioned gac is mixed with the 150ml slurries then, is warming up to 80 ℃, constant temperature.By the palladium charge capacity is that 2.0wt% slowly drips H
2PdCl
4Solution (Pd content 0.05g/ml) stirs.Behind the dipping 5h, with 10wt%NaOH solution regulator solution pH value to 8.5, cool the temperature to room temperature thereupon, filter, filter cake is neutral with deionized water wash to filtrate.Again filter cake is configured to the 150ml slurries under 30 ℃, slowly Dropwise 5 ml 65wt% hydrazine hydrate solution stirred 2 hours, filtered, and filter cake is neutral with deionized water wash to filtrate, promptly gets described activated carbon supported palladium catalyst.Through high power transmissioning electric mirror determining palladium average crystal grain size is 20nm.
Embodiment ten
Take by weighing the 10g cocoanut active charcoal and impregnated in the KI aqueous solution that 170ml concentration is 2.5mol/L, 50 ℃ of constant temperature stirred 6 hours, filtered, and did not have iodide ion with deionized water wash to filtrate.With deionized water above-mentioned gac is mixed with the 150ml slurries then, is warming up to 80 ℃, constant temperature.By the palladium charge capacity is that 2.0wt% slowly drips H
2PdCl
4Solution (Pd content 0.05g/ml) stirs.Behind the dipping 5h, with 10wt%NaOH solution regulator solution pH value to 8.5, cool the temperature to room temperature thereupon, filter, filter cake is neutral with deionized water wash to filtrate.Again filter cake is configured to the 200ml slurries under 30 ℃, slowly drips 8ml 45wt% hydrazine hydrate solution, stirred 5 hours, filter, filter cake is neutral with deionized water wash to filtrate, promptly gets described activated carbon supported palladium catalyst.Through high power transmissioning electric mirror determining palladium average crystal grain size is 27nm.
Embodiment 11 to 27
The Pd/C catalyzer that adopts above-mentioned preparation method to make is applied to the example of halo virtue catalytic hydrogenation of nitro compound synthesizing halogen aromatic amines.Solvent-free hydrogenation process operation is as follows: take by weighing 200g halo virtue nitro-compound and pour in the 500ml reactor, slowly heating up makes it to be molten state, adds a certain amount of Pd/C catalyzer then immediately, the off-response still.With nitrogen replacement air three times, each inflated with nitrogen is used hydrogen exchange nitrogen three times again to 0.5MPa, fills hydrogen to 0.5MPa at every turn.Fill hydrogen to 1.0MPa after displacement finishes, open and stir, being provided with and stirring revolution is 900r/min.Finish until reaction at 75～180 ℃ by the cooling water control temperature of reaction.Cool, take out hydrogenation liquid in the still, the filtering separation catalyzer utilizes to be separated moisture is gone out, and promptly gets halogen aromatic amines.Selectivity of product is analyzed through GC, and area normalization is obtained.Reaction conditions and reaction result see Table 1.
Shortening synthesizing halogen aromatic amines example under the table 1. halo virtue nitro-compound condition of no solvent
| Embodiment | Reactant | Catalyzer | Catalyst levels g | Reaction conditions | Transformation efficiency % | Selectivity % |
| 11 | O-chloronitrobenzene | Embodiment five | ??0.8 | ??0.5～1.0MPa，75-100℃ | ??100 | ??99.95 |
| 12 | M-chloro-nitrobenzene | Embodiment five | ??0.8 | ??0.5～1.0MPa，75-100℃ | ??100 | ??99.90 |
| 13 | Parachloronitrobenzene | Embodiment five | ??0.8 | ??0.5～1.0MPa，75-100℃ | ??100 | ??99.92 |
| 14 | 3, the 4-dichloronitrobenzene | Embodiment two | ??1.0 | ??0.5～1.0MPa，75-115℃ | ??100 | ??99.91 |
| 15 | 3, the 5-dichloronitrobenzene | Embodiment two | ??1.0 | ??0.5～1.0MPa，75-115℃ | ??100 | ??99.93 |
| 16 | 6-chloro-2-nitrotoluene | Embodiment two | ??0.8 | ??0.5～1.0MPa，75-110℃ | ??100 | ??99.95 |
| 17 | 2, the 5-dichloronitrobenzene | Embodiment two | ??0.8 | ??0.5～1.0MPa，75-110℃ | ??100 | ??99.90 |
| 18 | O-fluoronitrobenzene | Embodiment three | ??1.5 | ??0.5～1.0MPa，85-100℃ | ??100 | ??99.96 |
| 19 | P-fluoronitrobenzene | Embodiment three | ??1.5 | ??0.5～1.0MPa，85-100℃ | ??100 | ??99.94 |
| 20 | Between fluoronitrobenzene | Embodiment three | ??1.5 | ??0.5～1.0MPa，85-100℃ | ??100 | ??99.92 |
| 21 | 2, the 4-difluoro nitrobenzene | Embodiment six | ??1.2 | ??0.5～1.0MPa，85-100℃ | ??100 | ??99.94 |
| 22 | 2, the 5-difluoro nitrobenzene | Embodiment six | ??1.2 | ??0.5～1.0MPa，90-100℃ | ??100 | ??99.96 |
| Embodiment | Reactant | Catalyzer | Catalyst levels g | Reaction conditions | Transformation efficiency % | Selectivity % |
| 23 | 2, the 3-difluoro nitrobenzene | Embodiment six | ??1.2 | ??0.5～1.0MPa，90-100℃ | ??100 | ??99.94 |
| 24 | 2, the 6-difluoro nitrobenzene | Embodiment six | ??1.2 | ??0.5～1.0MPa，90-100℃ | ??100 | ??99.95 |
| 25 | 2,3, the 4-trifluoronitrobenzene | Embodiment ten | ??1.5 | ??0.5～1.0MPa，85-95℃ | ??100 | ??99.92 |
| 26 | 2,4, the 6-trifluoronitrobenzene | Embodiment ten | ??1.5 | ??0.5～1.0MPa，85-95℃ | ??100 | ??99.93 |
| 27 | 3,4, the 5-trifluoronitrobenzene | Embodiment ten | ??1.5 | ??0.5～1.0MPa，85-95℃ | ??100 | ??99.95 |
Embodiment 28
Take by weighing 200g 6-chloro-2-nitrotoluene and pour in the 500ml reactor, slowly heating up makes it to be molten state, adds a certain amount of Pd/C catalyzer then immediately, the off-response still.With nitrogen replacement air three times, each inflated with nitrogen is used hydrogen exchange nitrogen three times again to 0.5MPa, fills hydrogen to 0.5MPa at every turn.Fill hydrogen to 1.0MPa after displacement finishes, open and stir, being provided with and stirring revolution is 900r/min.Finish until reaction at 0.5～1.0MPa at 75-110 ℃, control hydrogen pressure by the cooling water control temperature of reaction.Cool, take out hydrogenation liquid in the still, the filtering separation catalyzer utilizes to be separated moisture is gone out, and promptly gets 3-chloro-2-aminotoluene.Selectivity of product is analyzed through GC, and area normalization is obtained.Isolated catalyzer repeats to apply mechanically, and it is as shown in table 2 to apply mechanically the result:
Table 2. catalyzer is applied mechanically situation
Claims (10)
1. the method for a halogenated aromatic nitro-compound liquid-phase hydrogenatin synthesizing halogen aromatic amines is characterized in that the reaction of described halogenated aromatic nitro-compound liquid-phase hydrogenatin synthesizing halogen aromatic amines is to carry out under the Pd/C catalyst action under condition of no solvent; Described Pd/C catalyzer is prepared as follows: gac is earlier with the pre-treatment of potassium halide aqueous solution dipping, filtration washing halogen ion to the filtrate; The gained pretreated active carbon is mixed with slurries with deionized water, drips H
2PdCl
4The aqueous solution carries out dip treating, and the back regulator solution pH value that disposes is to alkalescence, and it is neutral that filtration washing to filtrate is; The gained filter cake is mixed with slurries with deionized water again, wet reducing in the reductive agent aqueous solution, and filtration washing to filtrate is neutral once more, promptly gets the Pd/C catalyzer.
2. the method for halogenated aromatic nitro-compound liquid-phase hydrogenatin synthesizing halogen aromatic amines as claimed in claim 1, it is as follows to it is characterized in that described gac floods pretreated actual conditions with the potassium halide aqueous solution: the described potassium halide aqueous solution is potassium iodide aqueous solution, and its concentration is 0.3～8.0mol/L; The quality proportioning of described gac and potassium iodide aqueous solution is 1: 10～18, and pretreatment temperature is 20～80 ℃, and pretreatment time is 0.5～10 hour.
3. the method for halogenated aromatic nitro-compound liquid-phase hydrogenatin synthesizing halogen aromatic amines as claimed in claim 1 is characterized in that according to the palladium charge capacity being the ratio dropping H of 0.8～2.5wt%
2PdCl
4The aqueous solution.
4. the method for halogenated aromatic nitro-compound liquid-phase hydrogenatin synthesizing halogen aromatic amines as claimed in claim 3 is characterized in that pretreated active carbon and deionized water are mixed with slurries by mass ratio 1: 10～15, drips H
2PdCl
4The aqueous solution carries out dip treating, and treatment temp is 60～90 ℃, and the treatment time is 3～6 hours.
5. the method for halogenated aromatic nitro-compound liquid-phase hydrogenatin synthesizing halogen aromatic amines as claimed in claim 1 is characterized in that regulating slurry pH value to 7.5～9.5 with alkaline aqueous solution after dip treating finishes; Described alkaline aqueous solution is Na
2CO
3, NaHCO
3, NaOH, K
2CO
3, KHCO
3Or the aqueous solution of KOH, the concentration of alkaline aqueous solution is 5～15g/L.
6. the method for halogenated aromatic nitro-compound liquid-phase hydrogenatin synthesizing halogen aromatic amines as claimed in claim 1 is characterized in that gained filter cake and deionized water are mixed with slurries by mass ratio 1: 15～20, then wet reducing in hydrazine hydrate aqueous solution.
7. the method for halogenated aromatic nitro-compound liquid-phase hydrogenatin synthesizing halogen aromatic amines as claimed in claim 6, the concentration that it is characterized in that described hydrazine hydrate aqueous solution is 20～85wt%, the quality proportioning of described hydrazine hydrate and palladium is 15～20: 1, reduction temperature is 0～50 ℃, and the recovery time is 15min～10 hour.
8. the method for halogenated aromatic nitro-compound liquid-phase hydrogenatin synthesizing halogen aromatic amines as claimed in claim 7 is characterized in that reduction temperature is 25～35 ℃.
9. as the method for the described halogenated aromatic nitro-compound of one of claim 1～8 liquid-phase hydrogenatin synthesizing halogen aromatic amines, the method that it is characterized in that described halogenated aromatic nitro-compound liquid-phase hydrogenatin synthesizing halogen aromatic amines is specifically carried out according to following: raw material halogenated aromatic nitro-compound is poured in the reactor, slowly being warming up to fusion, is that 1: 100～500 ratio adds described Pd/C catalyzer in catalyzer and raw materials quality ratio then; The off-response still, use the nitrogen replacement air, use hydrogen exchange nitrogen again, fill hydrogen to 0.2～1.5MPa after displacement finishes, control hydrogenation reaction temperature is fully reacted the postcooling cooling at 75～180 ℃ of stirring reactions, take out still internal reaction liquid, the filtering separation catalyzer, gained filtrate is utilized the branch water outlet that is separated, and promptly gets halogen aromatic amines.
10. as the method for the described halogenated aromatic nitro-compound of one of claim 1～8 liquid-phase hydrogenatin synthesizing halogen aromatic amines, it is characterized in that described halogenated aromatic nitro-compound is one of following: o-chloronitrobenzene, m-chloro-nitrobenzene, parachloronitrobenzene, 3, the 4-dichloronitrobenzene, 3, the 5-dichloronitrobenzene, 6-chloro-2-nitrotoluene, 2, the 5-dichloronitrobenzene, o-fluoronitrobenzene, p-fluoronitrobenzene, between fluoronitrobenzene, 2, the 4-difluoro nitrobenzene, 2, the 5-difluoro nitrobenzene, 2, the 3-difluoro nitrobenzene, 2, the 6-difluoro nitrobenzene, 2,3, the 4-trifluoronitrobenzene, 2,4, the 6-trifluoronitrobenzene, 3,4, the 5-trifluoronitrobenzene.
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