CN103071486A - Preparation method of palladium-platinum bimetallic catalyst - Google Patents
Preparation method of palladium-platinum bimetallic catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of a palladium-platinum bimetallic catalyst. The preparation method is characterized by using active carbon as a carrier, pretreating the active carbon respectively by hydrochloric acid and nitric acid before preparation, then simultaneously loading palladium and platinum on the pretreated active carbon, and adding an activating agent into the active carbon with palladium and platinum for reduction to finally obtain the palladium-platinum bimetallic catalyst. According to the invention, the preparation method is simple; and the obtained palladium-platinum bimetallic catalyst disclosed herein has the advantages of high activity, long life, etc, and is especially suitable for preparing o-phenylenediamine by solvent-free hydrogenation.
Description
Technical field
The present invention relates to a kind of preparation method of palladium platinum bimetallic catalyst, particularly a kind of for the preparation method of ortho-nitraniline Hydrogenation for the palladium platinum bimetallic catalyst of o-phenylenediamine.
Background technology
O-phenylenediamine is a kind of important chemical intermediate, can be used for producing benzimidazole germicide, such as carbendazim, thiophanate-methyl etc.Traditional o-phenylenediamine production technology is sodium sulfide reducing, and this technology is ripe, flow process is simple, but its " three wastes " seriously polluted and waste water is difficult to process.Along with the pay attention to day by day of country to environmental issue, Preparation of O-Phenylenediamine by Catalytic Hydrogenation technique has obtained faster development in recent years, namely under the catalyst existence condition ortho-nitraniline catalytic hydrogenating reduction is obtained o-phenylenediamine.Catalyst is important influence factor in catalytic hydrogenating reduction technique, and now widely used is Raney nickel, and its shortcoming is that poor product quality behind the hydrogenation, yield are low, and Raney nickel very easily spontaneous combustion in air, greatly reduces the security of production.
For above-mentioned existing problems, adopting in recent years the charcoal supported noble metal catalyst of high activity, high selectivity to prepare o-phenylenediamine more and more comes into one's own, as use Pd/carbon catalyst as hydrogenation catalyst, many pieces of bibliographical informations are arranged both at home and abroad, Chinese patent CN102070464 A discloses a kind of method that dinitro benzene palladium catalyst hydrogenating reduction is produced phenylenediamine of mixing, this patent is take dinitro benzene as raw material, alcohols is as solvent, palladium/carbon of 5% carries out hydrogenation reduction as catalyst under 40 ~ 60 ℃ of reaction temperatures, reaction pressure 0.25 ~ 0.6MPa condition.Explain plain beautiful [chemical industry in Jiangsu Province such as grade, 1999,27:22 ~ 24] report use 5% palladium/charcoal is as catalyst, and water is as solvent, sodium phosphate is as auxiliary agent, is that 100 ~ 120 ℃, reaction pressure are to be o-phenylenediamine with the ortho-nitraniline hydrogenating reduction under 0.5 ~ 0.6MPa condition in reaction temperature.[the dye industry such as Song Dongming, 1994,6:16 ~ 18] adopt homemade 0.8% palladium/charcoal as catalyst, with water as solvent, regulate PH 〉=9 by the sodium carbonate that adds 15wt%, hydrogenation 5h obtains o-phenylenediamine under 80 ℃ of reaction temperatures, reaction pressure 0.7MPa condition.US Patent No. 3230259 discloses a kind of preparation method of o-phenylenediamine, and as catalyst, NaOH is as auxiliary agent with 5% palladium/carbon for the method, and water is as solvent, at 70 ~ 100 ℃ of reaction temperatures, reaction pressure 15 ~ 60 pound/inch
2React 5h under the condition, the o-phenylenediamine yield can reach more than 95%.
But the Pd/carbon catalyst of above-mentioned use all needs to add entry or alcohols as solvent in the standby o-phenylenediamine technique of Hydrogenation, and the use of solvent can increase the postprocessing working procedures such as the separation of product and solvent recovery.In addition, be conversion ratio after above-mentioned catalyst is being applied mechanically or decline selectively all occurred, cause the production cost of o-phenylenediamine to increase.Therefore, adopt the hydrogenation catalyst of a kind of high activity, high selectivity, life-span length and production safety to have larger Social benefit and economic benefit.
Summary of the invention
The object of the invention provides a kind of preparation method of palladium platinum bimetallic catalyst, and the catalyst that makes is applicable to the solvent-free Preparation of O-Phenylenediamine by Catalytic Hydrogenation of ortho-nitraniline.Catalyst preparation process of the present invention is simple, has in higher hydrogenation conversion and selective and the catalytic hydrogenation process to need not to add any solvent.
The present invention is by the control to the preliminary treatment of the quality control of carrier active carbon, active carbon and palladium, platinum ratio, so that palladium, two kinds of metals of platinum distribute more even at active carbon, decentralization is further improved, the bimetallic cooperative effect of palladium-platinum is enhanced, and then improved the activity, selective of catalyst, prolonged the service life of catalyst.
Palladium platinum bimetallic catalyst preparation method of the present invention may further comprise the steps:
1) with concentration being the hydrochloric acid of 5wt% ~ 15wt%, is 1:1 ~ 1:5 by active carbon and hydrochloric acid weight ratio, to charcoal treatment 3 ~ 4h, filters rear washing, drying under 50 ~ 100 ℃;
2) with concentration being the nitric acid of 10wt% ~ 20wt%, is 1:1 ~ 1:5 by active carbon and nitric acid weight ratio, and the active carbon after step 1) is processed is at 50 ~ 100 ℃ of lower 3 ~ 4h of processing, and washing after filtering, drying add suitable quantity of water with filter cake to be mixed with the charcoal slurries;
3) palladium salt and platinum salt are dissolved in respectively in the hydrochloric acid that concentration is 5wt% ~ 20wt%, obtain the slaine mixed liquor after again two kinds of metal salt solutions being mixed;
4) the slaine mixed liquor that step 3) is obtained drops to step 2) in the described charcoal slurries, fully stir and be heated to 30 ~ 40 ℃, add simultaneously alkali and regulate pH value to 9 ~ 10, obtain palladium platinum/charcoal mixed liquor;
5) in the described palladium platinum of step 4)/charcoal mixed liquor, pass into hydrogen, under 30 ~ 40 ℃ of conditions, reduce and process 6 ~ 8h, more after filtration, washing obtains described palladium platinum bimetallic catalyst.
Among the preparation method provided by the invention, active carbon can be powdery carbo lignius or shell class charcoal, preferred powdery shell class charcoal.The active carbon that is made by plant has the characteristics such as porous, specific area are large, and general specific area can be greater than 800 m
2/ g.Described powdery shell class charcoal is selected from coconut husk, apricot shell or peach shell, and its specific area can be 800 ~ 2000m
2/ g, granularity≤75 μ m, ash content≤2%.
Among the preparation method provided by the invention, by the processing of hydrochloric acid to active carbon, removed the inorganic impurity in the active carbon, oxidation processes by nitric acid can make the oxidation of impurities in the active carbon on the one hand, forms soluble-salt and removes, on the other hand, make the catalyst carrier functionalisation of surfaces, destroy the reproducibility group of activated carbon surface, avoided precious metal ion to carry out direct-reduction, and then make noble metal be easier to evenly distribute and the effective increase that suppresses the noble metal crystallite size at activated carbon surface.
Among the preparation method provided by the invention, the preferred palladium bichloride of described palladium salt or palladium nitrate, the preferred chloroplatinic acid of platinum salt or potassium chloroplatinate.
Among the preparation method provided by the invention, preferred 0.1 wt% of palladium and the platinum content in described catalyst ~ 5wt%.
Among the preparation method provided by the invention, the weight ratio of palladium and platinum preferred 0.1 ~ 5 in the described catalyst.
Among the preparation method provided by the invention, any one in the preferred potassium hydroxide of the described alkali of step 4), NaOH, sodium carbonate, the sodium acetate.
Catalyst provided by the invention is compared with existing Pd/carbon catalyst, especially is applied to the production of o-phenylenediamine hydrogenation, has following advantage:
1) compare with the one pack system Pd/carbon catalyst, the adding of platinum can make catalyst form the bimetallic synergy of palladium platinum, activity and the life-span of effectively having improved catalyst;
2) the present invention is applied to the production of o-phenylenediamine hydrogenation, need not to add water or organic solvent, has saved the required equipment investment of product separation and solvent recovery and energy consumption, has reduced production cost.
3) preparation process condition of the present invention is simple, and equipment requirement is low, is easy to suitability for industrialized production.
The specific embodiment
Following examples illustrate technical scheme of the present invention, but protection scope of the present invention is not limited to this:
Embodiment 1
Coconut husk charcoal take granularity as 75 μ m is as absorbent charcoal carrier, and its specific area is 1500 m
2/ g, ash content is 1.5%, takes by weighing the above-mentioned active carbon of 50g, adds the hydrochloric acid 1000ml of 10wt% to it, and 4h is boiled in heating under 80 ℃, and filtration is rear extremely neutral with the deionized water washing, and filtration is rear in 110 ℃ of oven dry.Add the nitric acid 400ml of 20wt% in the active carbon after the oven dry, boil 4h 60 ℃ of lower heating, after filtering with the deionized water washing to neutral, filter, after 110 ℃ of oven dry, filter cake is added the 200ml deionized water is mixed with the charcoal slurry.
Take by weighing the 1.67g palladium bichloride and 1.33g six hydration chloroplatinic acids are dissolved in respectively in the 20wt% watery hydrochloric acid of 50ml, obtain the uniform slaine mixed liquor of 100ml after above-mentioned two kinds of solution are mixed.It is added in the charcoal slurry in 30 ℃ stirs 2h, adding simultaneously 10% sodium carbonate, to regulate pH be 9.5, continues to pass into hydrogen in the backward mixed liquor of insulation 4h, and the time of logical hydrogen is 6.5h.With deionized water cyclic washing catalyst, until the pH of catalyst is neutral, obtain palladium platinum bimetallic catalyst 102.5g after the filtration, moisture 52% after filtering.In inductive coupling plasma emission spectrograph (ICP) detection catalyst, contain palladium 1.98%, platiniferous 0.99%.
Add the 400g ortho-nitraniline in the 1L autoclave, the above-mentioned bimetallic catalyst of 2.0g seals still, behind the pressure testing leak test, uses hydrogen exchange 5 ~ 6 times, is filled with hydrogen until pressure is 1.0MPa, and the control reaction temperature is 80 ℃, when reaction is incubated the 0.5h end after not inhaling hydrogen.Namely obtain 301.2g o-phenylenediamine finished product after hydrogenation liquid is light through taking off, the rectifying, gas spectrum normalizing content 99.7% collects rate as 96.2% take ortho-nitraniline.This catalyst carries out recovery, adds the 0.2g raw catelyst for every batch, apply mechanically 20 batches after product content, yield all normal.
Embodiment 2
Apricot shell charcoal take granularity as 75 μ m is as absorbent charcoal carrier, and its specific area is 1200 m
2/ g, ash content is 2%, takes by weighing the above-mentioned active carbon of 50g, adds the hydrochloric acid 1000ml of 10wt% to it, and 4h is boiled in heating under 80 ℃, and filtration is rear extremely neutral with the deionized water washing, and filtration is rear in 110 ℃ of oven dry.Add the nitric acid 400ml of 20wt% in the active carbon after the oven dry, boil 4h 60 ℃ of lower heating, after filtering with the deionized water washing to neutral, filter, after 110 ℃ of oven dry, filter cake is added the 200ml deionized water is mixed with the charcoal slurry.
Take by weighing the 1.67g palladium bichloride and 1.33g six hydration chloroplatinic acids are dissolved in respectively in the 20wt% watery hydrochloric acid of 50ml, obtain the uniform slaine mixed liquor of 100ml after above-mentioned two kinds of solution are mixed.It is added in the charcoal slurry in 30 ℃ stirs 2h, adding simultaneously 10% NaOH, to regulate pH be 9.6, continues to stir in the backward mixed liquor of insulation 4h to pass into hydrogen, and the time of logical hydrogen is 7.0h.With deionized water cyclic washing catalyst, until the pH of catalyst is neutral, obtain palladium platinum bimetallic catalyst 107g after the filtration, moisture 54% after filtering.In inductive coupling plasma emission spectrograph detection catalyst, contain palladium 1.97%, platiniferous 0.99%.
Get above-mentioned catalyst 2.0g and carry out the o-phenylenediamine hydrogenation, other operates with example 1, obtains 300g o-phenylenediamine finished product, and gas spectrum normalizing content is 99.5%, collects rate as 95.8% take ortho-nitraniline.This catalyst carries out recovery, adds the 0.2g raw catelyst for every batch, apply mechanically 15 batches after product content, yield all normal.
Embodiment 3
Coconut husk charcoal take granularity as 106 μ m is as absorbent charcoal carrier, and its specific area is 1200 m
2/ g, ash content is 1.5%, takes by weighing the above-mentioned active carbon of 50g, adds the hydrochloric acid 1000ml of 10wt% to it, and 4h is boiled in heating under 80 ℃, and filtration is rear extremely neutral with the deionized water washing, and filtration is rear in 110 ℃ of oven dry.Add the nitric acid 400ml of 20wt% in the active carbon after the oven dry, boil 4h 60 ℃ of lower heating, after filtering with the deionized water washing to neutral, filter, after 110 ℃ of oven dry, add the 200ml deionized water and be mixed with the charcoal slurry.
Take by weighing the 3.34g palladium bichloride and 1.33g six hydration chloroplatinic acids are dissolved in respectively in the 20wt% watery hydrochloric acid of 50ml, obtain the uniform slaine mixed liquor of 100ml after above-mentioned two kinds of solution are mixed.It is added in the charcoal slurry in 30 ℃ stirs 2h, adding simultaneously 10% NaOH, to regulate pH be 9.3, continues to stir in the backward mixed liquor of insulation 4h to pass into hydrogen, and the time of logical hydrogen is 6.5h.With deionized water cyclic washing catalyst, until the pH of catalyst is neutral, obtain palladium platinum bimetallic catalyst 107g after the filtration, moisture 54% after filtering.In inductive coupling plasma emission spectrograph detection catalyst, contain palladium 3.98%, platiniferous 0.98%.
Get above-mentioned catalyst 1.0g and carry out the o-phenylenediamine hydrogenation, other operates with example 1, obtains 298.5g o-phenylenediamine finished product, and gas spectrum normalizing content is 99.6%, collects rate as 95.4% take ortho-nitraniline.This catalyst carries out recovery, adds the 0.1g raw catelyst for every batch, apply mechanically 15 batches after product content, yield all normal.
Embodiment 4
Coconut husk charcoal take granularity as 75 μ m is as absorbent charcoal carrier, and its specific area is 1500 m
2/ g, ash content is 1.5%, takes by weighing the above-mentioned active carbon of 50g, adds the hydrochloric acid 1000ml of 10wt% to it, and 4h is boiled in heating under 80 ℃, and filtration is rear extremely neutral with the deionized water washing, and filtration is rear in 110 ℃ of oven dry.Add the nitric acid 400ml of 20wt% in the active carbon after the oven dry, boil 4h 60 ℃ of lower heating, after filtering with the deionized water washing to neutral, filter, after 110 ℃ of oven dry, add the 200ml deionized water and be mixed with the charcoal slurry.
Take by weighing the 2.0g palladium bichloride and 0.8g six hydration chloroplatinic acids are dissolved in respectively in the 20wt% watery hydrochloric acid of 50ml, obtain the uniform slaine mixed liquor of 100ml after above-mentioned two kinds of solution are mixed.It is added in the charcoal slurry in 30 ℃ stirs 2h, adding simultaneously 10% sodium carbonate, to regulate pH be 9.5, continues to pass into hydrogen in the backward mixed liquor of insulation 4h, and the time of logical hydrogen is 7.0h.With deionized water cyclic washing catalyst, until the pH of catalyst is neutral, obtain palladium platinum bimetallic catalyst 102.5g after the filtration, moisture 52% after filtering.In inductive coupling plasma emission spectrograph detection catalyst, contain palladium 2.38%, platiniferous 0.59%.
Get above-mentioned catalyst 2.0g and carry out the o-phenylenediamine hydrogenation, other operates with example 1, obtains 298g o-phenylenediamine finished product, and gas spectrum normalizing content is 99.7%, collects rate as 95.2% take ortho-nitraniline.This catalyst carries out recovery, adds the 0.2g raw catelyst for every batch, apply mechanically 15 batches after product content, yield all normal.
Claims (8)
1. the preparation method of a palladium platinum bimetallic catalyst is characterized in that, may further comprise the steps:
1) with concentration being the hydrochloric acid of 5wt% ~ 15wt%, is 1:1 ~ 1:5 by active carbon and hydrochloric acid weight ratio, to charcoal treatment 3 ~ 4h, filters rear washing, drying under 50 ~ 100 ℃;
2) with concentration being the nitric acid of 10wt% ~ 20wt%, is 1:1 ~ 1:5 by active carbon and nitric acid weight ratio, and the active carbon after step 1) is processed is at 50 ~ 100 ℃ of lower 3 ~ 4h of processing, and washing after filtering, drying add suitable quantity of water with filter cake to be mixed with the charcoal slurries;
3) palladium salt and platinum salt are dissolved in respectively in the hydrochloric acid that concentration is 5wt% ~ 20wt%, obtain the slaine mixed liquor after again two kinds of metal salt solutions being mixed;
4) the slaine mixed liquor that step 3) is obtained drops to step 2) in the described charcoal slurries, fully stir and be heated to 30 ~ 40 ℃, add simultaneously alkali and regulate pH value to 9 ~ 10, obtain palladium platinum/charcoal mixed liquor;
5) in the described palladium platinum of step 4)/charcoal mixed liquor, pass into hydrogen, under 30 ~ 40 ℃ of conditions, reduce and process 6 ~ 8h, more after filtration, washing obtains described palladium platinum bimetallic catalyst.
2. the preparation method of palladium platinum bimetallic catalyst according to claim 1 is characterized in that, the described active carbon of step 1) is powdery carbo lignius or powdery shell class charcoal, preferred powdery shell class charcoal.
3. the preparation method of palladium platinum bimetallic catalyst according to claim 2 is characterized in that, described powdery shell class charcoal is selected from coconut husk, apricot shell or peach shell.
4. the preparation method of palladium platinum bimetallic catalyst according to claim 2 is characterized in that, the specific area of described powdery shell class charcoal is 800 ~ 2000m
2/ g, granularity≤75 μ m, ash content≤2%.
5. the preparation method of palladium platinum bimetallic catalyst according to claim 1 is characterized in that, the described palladium salt of step 3) is palladium bichloride or palladium nitrate, and platinum salt is chloroplatinic acid or potassium chloroplatinate.
6. the preparation method of palladium platinum bimetallic catalyst according to claim 1 is characterized in that, the total content of palladium and platinum is 0.1wt% ~ 5wt% in the described catalyst, and the weight ratio of palladium and platinum is 0.1 ~ 5.
7. the preparation method of palladium platinum bimetallic catalyst according to claim 1 is characterized in that, the described alkali of step 4) is any one in potassium hydroxide, NaOH, sodium carbonate, the sodium acetate.
8. a method for preparing o-phenylenediamine wherein in the presence of the palladium platinum bimetallic catalyst of requirement 1 ~ 7 preparation of having the right, prepares o-phenylenediamine by the ortho-nitraniline hydrogenation reduction.
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Cited By (9)
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| CN104549243A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Supported catalyst and preparation method and application of supported catalyst and method for preparing 5,6-diamino benzimidazolone |
| CN106732557A (en) * | 2016-12-01 | 2017-05-31 | 西安凯立新材料股份有限公司 | A kind of preparation method of HPO methods synthesizing azanol phosphate noble metal catalyst |
| CN106807365A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of preparation method of core shell structure elctro-catalyst |
| CN107970967A (en) * | 2017-11-21 | 2018-05-01 | 江苏扬农化工集团有限公司 | A kind of preparation method that chloro arylamine catalyst is prepared for catalytic hydrogenation |
| CN108031469A (en) * | 2017-12-11 | 2018-05-15 | 赣南师范大学 | Charcoal-palladium carbon catalyst mixture and preparation method thereof |
| CN109317139A (en) * | 2018-08-28 | 2019-02-12 | 浙江工业大学 | A kind of preparation of the activated carbon supported noble metal catalyst of sulfur doping and its application in halogenated aromatic nitro compound hydrogenation reaction |
| CN110227448A (en) * | 2019-07-17 | 2019-09-13 | 江西省汉高新材料有限公司 | Platinum palladium bimetallic catalyst and preparation method thereof |
| CN111036266A (en) * | 2019-12-05 | 2020-04-21 | 武汉热解无限能源科技有限公司 | Preparation method of nitrogen-doped carbon catalyst and application of nitrogen-doped carbon catalyst in biological oil hydrogenation |
| CN113813957A (en) * | 2020-06-19 | 2021-12-21 | 台州学院 | Bimetal composite catalyst, preparation method and application thereof, working electrode and battery system |
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| CN104549243A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Supported catalyst and preparation method and application of supported catalyst and method for preparing 5,6-diamino benzimidazolone |
| CN106807365A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of preparation method of core shell structure elctro-catalyst |
| CN106732557B (en) * | 2016-12-01 | 2019-11-08 | 西安凯立新材料股份有限公司 | A kind of preparation method of HPO method synthesizing azanol phosphate noble metal catalyst |
| CN106732557A (en) * | 2016-12-01 | 2017-05-31 | 西安凯立新材料股份有限公司 | A kind of preparation method of HPO methods synthesizing azanol phosphate noble metal catalyst |
| CN107970967A (en) * | 2017-11-21 | 2018-05-01 | 江苏扬农化工集团有限公司 | A kind of preparation method that chloro arylamine catalyst is prepared for catalytic hydrogenation |
| CN107970967B (en) * | 2017-11-21 | 2020-07-14 | 江苏扬农化工集团有限公司 | Preparation method of catalyst for preparing chloroarylamine by catalytic hydrogenation |
| CN108031469A (en) * | 2017-12-11 | 2018-05-15 | 赣南师范大学 | Charcoal-palladium carbon catalyst mixture and preparation method thereof |
| CN108031469B (en) * | 2017-12-11 | 2021-04-16 | 赣南师范大学 | Carbon-palladium-carbon catalyst mixture and preparation method thereof |
| CN109317139A (en) * | 2018-08-28 | 2019-02-12 | 浙江工业大学 | A kind of preparation of the activated carbon supported noble metal catalyst of sulfur doping and its application in halogenated aromatic nitro compound hydrogenation reaction |
| CN109317139B (en) * | 2018-08-28 | 2022-03-18 | 浙江工业大学 | Preparation of sulfur-doped activated carbon-supported noble metal catalyst and application of sulfur-doped activated carbon-supported noble metal catalyst in hydrogenation reaction of halogenated aromatic nitro compound |
| CN110227448A (en) * | 2019-07-17 | 2019-09-13 | 江西省汉高新材料有限公司 | Platinum palladium bimetallic catalyst and preparation method thereof |
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Application publication date: 20130501 |