CN101502797A - Platinum-based selective hydrogenation catalyst as well as preparation method and use thereof - Google Patents
Platinum-based selective hydrogenation catalyst as well as preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to a platinum-based selective hydrogenation catalyst. The catalyst uses active carbon as a carrier; and based on the total mass of the catalyst, in terms of mass content, the content of active component platinum metal is 0.5 to 5 percent, and the grain diameter of the platinum metal is less than 30 nanometers. The invention also relates to a preparation method for the catalyst: after the active carbon is subjected to ultrasonic treatment by nitric acid solution with a certain concentration, the active carbon is repeatedly washed by deionized water to be neutral and then added into PtCl2 aqueous solution with a certain pH value to carry out ultrasonic immersion, the solution is filtered, a filer cake is pulped and then reduced by using a chemical reduction method and filtered and washed until no chloride ion exist, and the filter cake is transferred into an oven to be dried to form a nano Pt/active carbon catalyst. The invention further relates to application of the catalyst. The catalytic hydrogenation activity of the catalyst is good, the selectivity is high, the catalyst can effectively inhibit dechlorination without adding dehalogenation inhibitor, the preparation process is simple to operate, and the platinum metal is easy to recover.
Description
Technical field
The present invention relates to selective hydrocatalyst and its production and application; Particularly relate to a kind of platinum-based selective hydrogenation catalyst and its production and application.
Background technology
3,3-dichloro-benzidine (DCB) is the important intermediate of synthesizing yellow, orange organic pigment, with it is the multiple organic pigment of the seriation function admirable made of main body, is widely used in the production of printing ink, paint, rubber, plastics, painted and textile printing pigment and pigment dyeing slurry such as wax yellow.Use 3 in the world at present, all kinds of pigment of 3-dichloro-benzidine manufacturing account for more than 25% of whole organic pigment output, have more than 600 kind of 23 classes, and have irreplaceability.In recent years along with the fast development of related industries such as China's printing ink, paint, rubber, plastics, the demand of organic yellow color system pigment is rapidly increased, and driven its key intermediate 3, the rush of demand of 3-dichloro-benzidine.Present industrial production 3, the 3-dichloro-benzidine mainly contains two kinds of methods: 1, formaldehyde-hydrazine hydrate method, yield only is 49% when independent use formaldehyde reduces, after domestic researcher improves this method, yield can bring up to 76%, use formaldehyde-hydrazine hydrate joint operation can reach about 89%, but produce a large amount of waste water in process of production, intermediate product need separate purification, complicated operation, labour intensity is bigger, and the price of hydrazine hydrate is higher, toxicity is bigger, is listed in limited technology in " the chemical 10th Five-Year Plan " of issue in 2002; 2, catalytic hydrogenation method, this method need not to isolate intermediate product, reaction can one the step finish, have simple to operate, characteristics such as catalyst can be repeatedly used, the wastewater flow rate that produces in the production process is few, environmentally friendly, yield height.Become the main flow of suitability for industrialized production at present.But the specification requirement height of catalytic hydrogenation method need to use noble metal catalyst, this technology to be mainly developed country such as America and Europe and grasps.
U.S. Pat 3156742 (1964) is introduced the earliest and is used 5%Pd/C to be catalyst, adds 2 simultaneously, 3-two chloro-1, and the 4-naphthoquinones is made co-catalyst, by the direct catalytic hydrogenating reduction preparation 3 of o-chloronitrobenzene, the technology of 3-dichloro-benzidine.But this patent needs principal product and catalyst to carry out the liquid phase separation operation, has increased Operating Complexity, the technology preparation 3 of this patent employing simultaneously, and the yield of 3-dichloro-benzidine (80-90%) is not high.
It is major catalyst that another piece U.S. Pat 4217307 (1979) then adopts Pd/C, 2-hydroxy-anthraquione or 2,6-dihydroxy anthraquinone are co-catalyst, are under the condition of solvent at benzene, toluene or dimethylbenzene, in alkaline medium, one step of o-chloronitrobenzene is reduced to 3, the 3-dichloro-benzidine.But there be separating of product and co-catalyst in this technology, and product yield is lower, only is 84%.
European patent EP 391606 (1990) proposes to use tetrahydronaphthalene to be solvent, utilizes its hydrogen atom that discharges in reaction to carry out hydrogenation, in the reduction later stage alkali concn in the medium is adjusted to about 25%, and 3, the yield of 3-dichloro-benzidine is 92%.
German patent DE 2733741 (1990) adopts the 2-hydroxy-anthraquione as co-catalyst catalyst repeated use activity is not reduced, and yield is 84%.
637979 propositions of Swiss Patent SWISS add proper amount of surfactant such as neopelex etc. in reaction system, help the separation of product after reaction finishes.
Domestic researcher Song Dongming (Dalian University of Technology's journal, 1995,35 (3): 330-332) adopt homemade 0.8%Pd/C catalyst, with toluene is solvent, in reaction system, add proper amount of surfactant and co-catalyst simultaneously, under 0.6MPa, 55-75 ℃ with the direct hydrogenation of o-chloronitrobenzene 3 hours, 3, the yield of 3-dichloro-benzidine reaches 93%.
Summary of the invention
Technical problem to be solved by this invention is at catalyst activity in the prior art and selectivity is not high, catalytic efficiency is low deficiency, a kind of platinum-based selective hydrogenation catalyst is provided, its carrier and active component are used, make the catalyst to catalyzing hydrogenating activity good, the selectivity height, good stability, long service life, catalytic efficiency improves greatly.
For this reason, the invention provides a kind of platinum-based selective hydrogenation catalyst, it is characterized in that, this catalyst is carrier with the active carbon, is benchmark with the gross mass of catalyst, in mass content, comprise the active component platinum, its content is 0.5%-5%, and the particle diameter of described platinum is less than 30nm.
The present invention also provides a kind of preparation method of platinum-based selective hydrogenation catalyst, it is characterized in that, comprises the steps:
The preliminary treatment of step 1, active carbon: active carbon powder is joined the HNO that concentration is 1-5mol/L
3Soak in the solution, and place the ultrasonic processing of ultrasonic generator 5-12 hour, spend the deionised water active carbon then, obtain the good active carbon filter cake of preliminary treatment to neutral and filtration, standby;
Step 2, the preparation of nanometer Pt/ activated-carbon catalyst: the active carbon filter cake of step (1) joined with alkaline aqueous solution regulate in the metal platinum compound water solution that the pH value is 1-5, under temperature 45-90 ℃, stirred dipping also ultrasonic 0.5-3 hour, filter, after the active carbon filter cake adds the deionized water making beating, adopting chemical reduction method to add reducing agent reduces, activity component metal platinum is evenly distributed on the carried by active carbon surface with the nano-scale particle of high dispersive type, then cake filtration is also washed to there not being chlorion, be transferred in the baking oven, descended dry 1-5 hour at temperature 80-120 ℃, promptly obtain nanometer Pt/ activated-carbon catalyst.
The present invention provides the above-mentioned catalyst of a kind of use to carry out selective hydrogenation preparation 3 again, the method of 3-dichloro-benzidine, it is characterized in that, this method is to be raw material with the o-chloronitrobenzene, under nanometer Pt/ activated-carbon catalyst and hydrogen effect, in solvent toluene, in 50-100 ℃ reaction temperature, 0.5-1.0MPa reaction pressure under carry out hydrogenation reaction and generate 3, the 3-dichloro-benzidine; The mass ratio of described o-chloronitrobenzene and solvent toluene is 1: 3-5, described nanometer Pt/ activated-carbon catalyst consumption is the 0.1-1% of described o-chloronitrobenzene quality.
Compare with existing patented technology, the present invention has the following advantages:
1. new catalyst preparation process.Preparation technology of the present invention joins active carbon in the aqueous solution of active component platinum compounds, under 45-90 ℃, stirs dipping, and adopts the power ultrasonic technology to carry out ultrasonic processing.Hyperacoustic wave-length coverage is greatly about (10
-3～10) cm, much larger than molecular scale, therefore ultrasonic chemical action is not direct and material effect, but mainly finishes by the cavitation of liquid.So-called cavitation is meant liquid under high-intensity ultrasonication, and the micro-bubble nuclear in the liquid produces vibration under the ultrasonic wave effect, and when acoustic pressure reaches certain value, bubble will expand rapidly, and is closed suddenly then, produces shock wave when bubble is closed.A series of dynamic processes such as this expansion, closure and vibration claim ultrasonic cavitation.The focus of cavitation more than the instantaneous generation 5000K in part, pressure is up to up to a hundred MPa simultaneously.Ultrasonication helps eliminating the coalescent of particle, and active noble metals platinum is improved at the decentralization of carried by active carbon surface, has increased the number in activated centre greatly, has greatly improved activity of such catalysts.The preparation of this new applicable loaded catalyst of catalyst preparation process obtains high nano metal decentralization, realizes high activity and high selectivity.
2. the activity of noble metal catalyst is low to the particle size dependence of carrier active carbon.The ultrasonic immersing that the present invention adopts, the nano noble metal particles of acquisition high dispersive, bigger serface, activity of such catalysts is directly by the decentralization height, and the size of the nano-noble metal that specific area is big determines.And the catalyst activity of traditional handicraft preparation mainly is subjected to influence as the granule size of the active carbon of catalyst carrier.Therefore adopt preparation technology of the present invention to reduce the dependence of catalyst activity to the carrier granularity.
3. precious metals pt/the activated-carbon catalyst of the present invention's preparation generates 3 at the o-chloronitrobenzene hydrogenation, 3-dichloro-benzidine reaction table reveals high activity and high selectivity, under the situation that need not add the dehalogenation inhibitor, suppressed the dechlorination phenomenon effectively, and preparation process is simple to operate.For 3, the large-scale industrial production of 3-dichloro-benzidine has huge application potential.
The nanometer Pt/ activated-carbon catalyst of the present invention's preparation is applied to the reaction of formation of o-chloronitrobenzene hydrogenation and has obtained to be higher than 95% high product selectivity.
Below by example technical scheme of the present invention is described in further detail.
The specific embodiment
Embodiment 1
Place pulverizer to be ground into powder active carbon, sieving out 100-300 order active carbon, to join concentration be the 3mol/L salpeter solution, and placed the ultrasonic generator ultrasonic immersing 8 hours, and spend the deionised water active carbon then to neutral and filtration, obtain the good active carbon filter cake of preliminary treatment.With 30mL concentration is the platinum acid chloride solution of 0.01g/mL, is the K of 0.5mol/L with concentration
2CO
3It is 2.5 that the aqueous solution is adjusted to the pH value, as the maceration extract of Preparation of Catalyst.Then the active carbon filter cake is joined in the above-mentioned maceration extract, under 75 ℃, stirred dipping also ultrasonic 2.5 hours, filter, it is 100mL that filter cake adds deionized water making beating volume, adopts chemical reduction method to be added dropwise to formic acid and reduces, and filters then and washs to there not being chlorion, filter cake is transferred in the baking oven to descend dry 3 hours at 90 ℃, promptly obtains nanometer Pt/ activated-carbon catalyst.The most platinum particles particle diameter of this nanometer Pt/ activated-carbon catalyst is less than 30nm.
Embodiment 2
Place pulverizer to be ground into powder active carbon, sieving out 100-300 order active carbon, to join concentration be the 3mol/L salpeter solution, and placed the ultrasonic generator ultrasonic immersing 8 hours, and spend the deionised water active carbon then to neutral and filtration, obtain the good active carbon filter cake of preliminary treatment.With 30mL concentration is the platinum acid chloride solution of 0.01g/mL, with concentration be the KOH aqueous solution of 0.5mol/L to be adjusted to the pH value be 2.5, as the maceration extract of Preparation of Catalyst.Then the active carbon filter cake is joined in the above-mentioned maceration extract, under 75 ℃, stirred dipping also ultrasonic 2.5 hours, filter, it is 100mL that filter cake adds deionized water making beating volume, adopts chemical reduction method to be added dropwise to formic acid and reduces, and filters then and washs to there not being chlorion, filter cake is transferred in the baking oven to descend dry 3 hours at 90 ℃, promptly obtains nanometer Pt/ activated-carbon catalyst.The most platinum particles particle diameter of this nanometer Pt/ activated-carbon catalyst is less than 30nm.
Embodiment 3
Place pulverizer to be ground into powder active carbon, sieving out 100-300 order active carbon, to join concentration be the 3mol/L salpeter solution, and placed the ultrasonic generator ultrasonic immersing 8 hours, and spend the deionised water active carbon then to neutral and filtration, obtain the good active carbon filter cake of preliminary treatment.With 30mL concentration is the platinum acid chloride solution of 0.01g/mL, is the Na of 0.5mol/L with concentration
2CO
3It is 2.5 that the aqueous solution is adjusted to the pH value, as the maceration extract of Preparation of Catalyst.Then the active carbon filter cake is joined in the above-mentioned maceration extract, under 75 ℃, stirred dipping also ultrasonic 2.5 hours, filter, it is 100mL that filter cake adds deionized water making beating volume, adopts chemical reduction method to be added dropwise to formic acid and reduces, and filters then and washs to there not being chlorion, filter cake is transferred in the baking oven to descend dry 3 hours at 90 ℃, promptly obtains nanometer Pt/ activated-carbon catalyst.The most platinum particles particle diameter of this nanometer Pt/ activated-carbon catalyst is less than 30nm.
Embodiment 4
Place pulverizer to be ground into powder active carbon, sieving out 100-300 order active carbon, to join concentration be the 3mol/L salpeter solution, and placed the ultrasonic generator ultrasonic immersing 8 hours, and spend the deionised water active carbon then to neutral and filtration, obtain the good active carbon filter cake of preliminary treatment.With 30mL concentration is the platinum acid chloride solution of 0.01g/mL, with concentration be the NaOH aqueous solution of 0.5mol/L to be adjusted to the pH value be 2.5, as the maceration extract of Preparation of Catalyst.Then the active carbon filter cake is joined in the above-mentioned maceration extract, under 75 ℃, stirred dipping also ultrasonic 2.5 hours, filter, it is 100mL that filter cake adds deionized water making beating volume, adopts chemical reduction method to be added dropwise to formic acid and reduces, and filters then and washs to there not being chlorion, filter cake is transferred in the baking oven to descend dry 3 hours at 90 ℃, promptly obtains nanometer Pt/ activated-carbon catalyst.The most platinum particles particle diameter of this nanometer Pt/ activated-carbon catalyst is less than 30nm.
Embodiment 5
Place pulverizer to be ground into powder active carbon, sieving out 100-300 order active carbon, to join concentration be the 3mol/L salpeter solution, and placed the ultrasonic generator ultrasonic immersing 8 hours, and spend the deionised water active carbon then to neutral and filtration, obtain the good active carbon filter cake of preliminary treatment.With 30mL concentration is the platinum acid chloride solution of 0.01g/mL, is the K of 0.5mol/L with concentration
2CO
3It is 2.5 that the aqueous solution is adjusted to the pH value, as the maceration extract of Preparation of Catalyst.Then the active carbon filter cake is joined in the above-mentioned maceration extract, under 75 ℃, stirred dipping also ultrasonic 2.5 hours, filter, it is 100mL that filter cake adds deionized water making beating volume, adopts chemical reduction method to be added dropwise to hydrazine hydrate and reduces, and filters then and washs to there not being chlorion, filter cake is transferred in the baking oven to descend dry 3 hours at 90 ℃, promptly obtains nanometer Pt/ activated-carbon catalyst.The most platinum particles particle diameter of this nanometer Pt/ activated-carbon catalyst is less than 30nm.
Embodiment 6
Place pulverizer to be ground into powder active carbon, sieving out 100-300 order active carbon, to join concentration be the 3mol/L salpeter solution, and placed the ultrasonic generator ultrasonic immersing 8 hours, and spend the deionised water active carbon then to neutral and filtration, obtain the good active carbon filter cake of preliminary treatment.With 30mL concentration is the platinum acid chloride solution of 0.01g/mL, is the K of 0.5mol/L with concentration
2CO
3It is 2.5 that the aqueous solution is adjusted to the pH value, as the maceration extract of Preparation of Catalyst.Then the active carbon filter cake is joined in the above-mentioned maceration extract, under 75 ℃, stirred dipping also ultrasonic 2.5 hours, filter, it is 100mL that filter cake adds deionized water making beating volume, adopts chemical reduction method to be added dropwise to formaldehyde and reduces, and filters then and washs to there not being chlorion, filter cake is transferred in the baking oven to descend dry 3 hours at 90 ℃, promptly obtains nanometer Pt/ activated-carbon catalyst.The most platinum particles particle diameter of this nanometer Pt/ activated-carbon catalyst is less than 30nm.
Embodiment 7
Place pulverizer to be ground into powder active carbon, sieving out 100-300 order active carbon, to join concentration be the 3mol/L salpeter solution, and placed the ultrasonic generator ultrasonic immersing 8 hours, and spend the deionised water active carbon then to neutral and filtration, obtain the good active carbon filter cake of preliminary treatment.With 30mL concentration is the platinum acid chloride solution of 0.01g/mL, is the K of 0.5mol/L with concentration
2CO
3It is 2.5 that the aqueous solution is adjusted to the pH value, as the maceration extract of Preparation of Catalyst.Then the active carbon filter cake is joined in the above-mentioned maceration extract, under 75 ℃, stirred dipping also ultrasonic 2.5 hours, filter, it is 100mL that filter cake adds deionized water making beating volume, and the sodium formate solution that adopts chemical reduction method to be added dropwise to 0.5mol/L is reduced, and filters then and washs to there not being chlorion, filter cake is transferred in the baking oven to descend dry 3 hours at 90 ℃, promptly obtains nanometer Pt/ activated-carbon catalyst.The most platinum particles particle diameter of this nanometer Pt/ activated-carbon catalyst is less than 30nm.
Embodiment 8
Place pulverizer to be ground into powder active carbon, sieving out 100-300 order active carbon, to join concentration be the 3mol/L salpeter solution, and placed the ultrasonic generator ultrasonic immersing 5 hours, and spend the deionised water active carbon then to neutral and filtration, obtain the good active carbon filter cake of preliminary treatment.With 30mL concentration is the platinum acid chloride solution of 0.01g/mL, is the K of 0.5mol/L with concentration
2CO
3It is 2.5 that the aqueous solution is adjusted to the pH value, as the maceration extract of Preparation of Catalyst.Then the active carbon filter cake is joined in the above-mentioned maceration extract, under 75 ℃, stirred dipping also ultrasonic 2.5 hours, filter, it is 100mL that filter cake adds deionized water making beating volume, adopts chemical reduction method to be added dropwise to formic acid and reduces, and filters then and washs to there not being chlorion, filter cake is transferred in the baking oven to descend dry 3 hours at 90 ℃, promptly obtains nanometer Pt/ activated-carbon catalyst.The most platinum particles particle diameter of this nanometer Pt/ activated-carbon catalyst is less than 30nm.
Embodiment 9
Place pulverizer to be ground into powder active carbon, sieving out 100-300 order active carbon, to join concentration be the 3mol/L salpeter solution, and placed the ultrasonic generator ultrasonic immersing 8 hours, and spend the deionised water active carbon then to neutral and filtration, obtain the good active carbon filter cake of preliminary treatment.With 30mL concentration is the platinum acid chloride solution of 0.01g/mL, is the K of 0.5mol/L with concentration
2CO
3It is 2.5 that the aqueous solution is adjusted to the pH value, as the maceration extract of Preparation of Catalyst.Then the active carbon filter cake is joined in the above-mentioned maceration extract, under 75 ℃, stirred dipping also ultrasonic 1 hour, filter, it is 100mL that filter cake adds deionized water making beating volume, adopts chemical reduction method to be added dropwise to formic acid and reduces, and filters then and washs to there not being chlorion, filter cake is transferred in the baking oven to descend dry 3 hours at 90 ℃, promptly obtains nanometer Pt/ activated-carbon catalyst.The most platinum particles particle diameter of this nanometer Pt/ activated-carbon catalyst is less than 30nm.
Embodiment 10
The Pt/C catalyst of embodiment 1 to embodiment 9 described method preparation is used for catalytic hydrogenation o-chloronitrobenzene hydrogenation preparing 3, the method of 3-dichloro-benzidine is: add o-chloronitrobenzene in autoclave according to a certain percentage successively, toluene, the NaOH aqueous solution and catalyst, neopelex and naphthoquinones, in o-chloronitrobenzene weight, catalyst amount is the 0.1-1% of o-chloronitrobenzene weight, the toluene consumption is the 300-500% of o-chloronitrobenzene weight, sodium hydroxide concentration is the 50-100% of o-chloronitrobenzene weight, the neopelex consumption is the 0.5-1% of o-chloronitrobenzene weight, and the naphthoquinones consumption is the 0.5-1% of o-chloronitrobenzene weight.With behind the air in nitrogen replacement autoclave 2-3 time, use hydrogen exchange nitrogen again before the hydrogenation, logical then hydrogen carries out hydrogenation reaction at the pressure of 0.5-1.0MPa, and 50-100 ℃ of control reaction temperature after the system for the treatment of is no longer inhaled hydrogen, shows that reaction finishes.Get a certain amount of oil phase product, in the volumetric flask of 10mL, ultrasonic degas is got 5 μ L sample introductions after handling through the dilute filtration constant volume.Various organic chromatographic peak and peak area in chromatograph test back computer demonstration oil phase, the size by calculating each simple spike and the content of various material compositions.
The catalyst activity testing procedure:
In autoclave, add the 30mL o-chloronitrobenzene successively, 100mL toluene, 25%NaOH aqueous solution 90g and 50mg (being accurate to 0.1mg) catalyst, 0.2g neopelex and 0.2g naphthoquinones.Use hydrogen exchange nitrogen twice again with behind the air in the nitrogen replacement still three times before the hydrogenation, get rid of hydrogen in the still then rapidly, under pressure-fired, be warmed up to 75 ℃, lead to the pressure of hydrogen at last, close the hydrogen intake valve then to 0.8MPa.Be warmed up to 80 ± 2 ℃ again, turn on agitator picks up counting.Stir speed (S.S.) is controlled at 900r/min, in the observation course of reaction hydrogen-pressure over time, single batch of sample is every pressure of 5min record, to 20min.Like this under catalyst action along with catalyst is inhaled hydrogen and hydrogen and raw material reaction, consume the Hydrogen Vapor Pressure that hydrogen causes and descend, by measuring the Hydrogen Vapor Pressure of (20min) behind the certain hour, just can calculate the hydrogen of unit mass catalyst by gas equation.Pressure descends many, and then hydrogen is many, and the catalyst activity height is described.Emit material, separate organic facies, carry out liquid-phase chromatographic analysis after the sampling, detect 3, the relative amount of 3-dichloro-benzidine is determined the conversion ratio and the selectivity of reactant.Get a certain amount of oil phase product, in the volumetric flask of 10mL, ultrasonic degas is got 5 μ L sample introductions after handling through the dilute filtration constant volume.Sample needs through 0.45 μ m filtering with microporous membrane.
Claims (9)
1. a platinum-based selective hydrogenation catalyst is characterized in that, this catalyst is carrier with the active carbon, gross mass with catalyst is a benchmark, in mass content, comprises the active component platinum, its content is 0.5%-5%, and the particle diameter of described platinum is less than 30nm.
2. a Preparation of catalysts method according to claim 1 is characterized in that, comprises the steps:
The preliminary treatment of step 1, active carbon: active carbon powder is joined the HNO that concentration is 1-5mol/L
3Soak in the solution, and place the ultrasonic processing of ultrasonic generator 5-12 hour, spend the deionised water active carbon then, obtain the good active carbon filter cake of preliminary treatment to neutral and filtration, standby;
Step 2, the preparation of nanometer Pt/ activated-carbon catalyst: the active carbon filter cake of step (1) joined with alkaline aqueous solution regulate in the metal platinum compound water solution that the pH value is 1-5, under temperature 45-90 ℃, stirred dipping also ultrasonic 0.5-3 hour, filter, after the active carbon filter cake adds the deionized water making beating, adopting chemical reduction method to add reducing agent reduces, activity component metal platinum is evenly distributed on the carried by active carbon surface with the nano-scale particle of high dispersive type, then cake filtration is also washed to there not being chlorion, filter cake is transferred in the baking oven, descended dry 1-5 hour at temperature 80-120 ℃, promptly obtain nanometer Pt/ activated-carbon catalyst.
3. the preparation method of a kind of platinum-based selective hydrogenation catalyst according to claim 2, the volume ratio that it is characterized in that compound water solution of metal platinum described in the step 2 and active carbon filter cake is 1-100: 1.
4. the preparation method of a kind of platinum-based selective hydrogenation catalyst according to claim 2 is characterized in that alkaline aqueous solution described in the step 2 is NaOH, Na
2CO
3, KOH or K
2CO
3The aqueous solution.
5. the preparation method of a kind of platinum-based selective hydrogenation catalyst according to claim 4 is characterized in that described alkaline aqueous solution concentration is 0.1-1mol/L.
6. the preparation method of a kind of platinum-based selective hydrogenation catalyst according to claim 2 is characterized in that reducing agent described in the step 2 is water-soluble reducing agent HCOONa, HCHO, HCOOH or hydrazine hydrate.
7. the preparation method of a kind of platinum-based selective hydrogenation catalyst according to claim 6, the mol ratio that it is characterized in that described reducing agent and metal platinum is 5-100: 1.
8. the preparation method of a kind of platinum-based selective hydrogenation catalyst according to claim 2, the granularity that it is characterized in that active carbon described in the step 1 is the 100-300 order.
9. an application catalyst as claimed in claim 1 carries out selective hydrogenation preparation 3, the method of 3-dichloro-benzidine, it is characterized in that, this method is to be raw material with the o-chloronitrobenzene, under nanometer Pt/ activated-carbon catalyst and hydrogen effect, in solvent toluene, in 50-100 ℃ reaction temperature, 0.5-1.0MPa reaction pressure under carry out hydrogenation reaction and generate 3, the 3-dichloro-benzidine; The mass ratio of described o-chloronitrobenzene and solvent toluene is 1: 3-5, described nanometer Pt/ activated-carbon catalyst consumption is the 0.1-1% of described o-chloronitrobenzene quality.
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