CN100428989C - Method for preparing loading type nano Pd/C catalyst from colloidal solution - Google Patents
Method for preparing loading type nano Pd/C catalyst from colloidal solution Download PDFInfo
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Abstract
The invention relates to a method for using colloid solution to prepare carrier nanometer Pd/C catalyst, wherein said method comprises that using chemical reduction to process palladium salt to prepare the nanometer palladium colloid solution with stable surface activity, then using some carrier to absorb it to obtain the palladium colloid, to obtain the nanometer palladium catalyst with different loaded amounts. The inventive catalyst can be used in hydrogenation.
Description
Technical field
The invention belongs to catalysis technical field, be specifically related to a kind of preparation method of loaded nano noble metal catalyst of hydrogenation process of all kinds of organic compounds that are used for industries such as petrochemical industry, pharmacy, dyestuff, agricultural chemicals and rubber chemicals, be specially adapted to nitro, aromatic ring, alkynes, alkene, ketone, the selective hydrogenation of aldehyde etc.
Background technology
Nano metal has and is different from metallic atom and the body special physics and the chemical property of metal mutually, thereby is widely used in fields such as optical material, microelectrode reaction, bioengineering and medicine, microelectronics industry and catalysis industry.Nano metal has big specific area and specific activity because of it, and in catalytic field, caused very big concern, especially carried noble metal catalyst system and catalyzing, can control activity of such catalysts by the size of modulation nano-metal particle, therefore, nano metal is catalyzed in order to study focus.But when the process of preparation nano-noble metal catalyst, how making nano particle be scattered in the surface of carrier equably, reduce the generation of agglomeration, is a very big difficult point.In order to address this problem, domestic and international many scholars have carried out extensive studies, and the most representative method is to go out to send preparation loaded nano noble metal catalyst from colloidal solution.
The character of metal micelle is not only relevant with the size of particle, also is subjected to the influence of its shape reunion situation and oxidation state.Therefore the preparation of the controlled colloidal particle of particle diameter and shape is a challenging subject in the nanometer material science always.In recent years, the scientific worker adopts diverse ways to prepare the metallic colloid of high stability, narrow distribution, and such as the thermal decomposition method of metallo-organic compound in organic solvent, surfactant or natural and synthetic high polymer are as protectant chemical reduction method etc.
Surfactant or natural and synthetic high polymer can be by changing concentration of metal ions as protectant chemical reduction method; the kind of reducing agent and consumption, surfactant or high molecular concentration, preparation parameters such as temperature and PH are controlled particle diameter; the preparation method is simple, good reproducibility.Macromolecule commonly used is polyvinylpyrrolidone (PVP), polymine (PEI), polyvinyl alcohol (PVA) etc.Nineteen forty-one, LOUIS D.RAMPIN and Nord take the lead in studying the Pt family metallic colloid of synthetic macromolecular compound PVA protection, and its catalytic activity obviously is better than traditional noble metal catalyst.The mid-1970s, it is that reducing agent, synthetic macromolecular compound are the system research of protectant preparation precious metal colloid that the horizontal well English history of Japan has been carried out with alcohol, has determined that PVP obviously is better than the effect of PVA.Employing sodium citrate salt reducing metal salt such as Miner have synthesized Au/Pt and Pd/Pt alloy.Liu Hanfan
[1]The series metal colloid stable etc. broad research PVP, as the PVP-Pd of alcohol reduction, PVP-Pt, PVP-Pd/Pt, the PVP-Ru of sodium borohydride reduction, PVP-Ru/Pt, PVP-Ru/Pd, the metallic colloid that they studied all adopt the first alcohol and water as decentralized photo.PVP is the stable metal colloid effectively, but reaction there is certain inhibitory action, as the coordination that the C=O among Pd atom and the PVP produces, PVP has not just played stabilization to metallic colloid, also the effective absorption of reactant and the desorption of product has been played reaction.Therefore, be badly in need of new surfactant of exploitation or natural and synthetic high polymer stabilizing agent as metallic colloid.
The prepared colloid of the above method all is dispersed in the mixed liquor of organic solvent and water, has caused the waste water that contains organic pollution in a large number; And the life-span of the stable colloid catalyst of this high polymer is undesirable, can not recycle for a long time, is not suitable for suitability for industrialized production.The noble metal colloidal sol of polymer protection is loaded on the inorganic carrier; realize the immobilized of metal-sol catalyst; solved not only that the colloidal sol catalyst is difficult for separating with product and problem such as repeated use; and kept the particle diameter similar to distribute and particle size to the colloidal sol catalyst; avoided the colloidal sol catalyst easily to assemble again; difficult shortcoming of separating with product is up-and-coming method.Helmut
[2,3]Deng study in recent years in tetrahydrofuran solution always, by NR
4 +(as N (Octyl) 4Cl, SB12) particle diameter of stable colloidal solution preparation is at the Pd/CaCO of 1-10m size for cationic surfactant
3, Pt/C, Pd/C, catalyst series such as Pt-Ru/C are used for the catalysis cyclohexanol, cyclohexene, reactions such as methanol oxidation, its result will be far above traditional catalyst.Srividhya Kidambi
[4]Be carried on aluminium and the activated carbon Deng having prepared PAA/PEI-Pd (0), the TEM image shows that average grain diameter is 1.5nm, uses it for pentenol, has obtained higher conversion frequency in the selective catalytic hydrogenation of 3-pentenol and 3-methyl-3-pentenol.V.Kratky etc. make in the acetone and the aqueous solution that the Pd/D catalyst is used for ortho position, a position and to being the selective hydrogenation of nitro-chlorobenzene, and compare research with the catalytic result of Pd/C, have studied kinetics mechanism.John Turkevich etc. make Pd/Al with the Pd particle of the alumina rod of 10-50nm absorption 5.5-45nm in the aqueous solution
3O
2Catalyst has been realized the immobilized of metallic colloid, and it is used and the ethylene hydrogenation reaction, and activity is commercially available 5%Pd/Al
3O
2100 times.But present preparation technology is still very complicated, and the loaded nano palladium catalyst stability that obtains is bad, and service life is shorter.
Summary of the invention
The objective of the invention is to improve the preparation method of loaded nano palladium catalyst, obtain the loaded nano palladium catalyst of high degree of dispersion.Another purpose provides that a kind of preparation method is simple, and cost is low, good reproducibility, green non-pollution, the method for preparing catalyst that the life-span is long.In the hydrogenation process of all kinds of organic compounds of catalysis, improve activity of such catalysts and selectivity.
Technical scheme of the present invention is, a kind of method for preparing loading type nano Pd/C catalyst by colloidal solution, this method step is: the stable, aqueous solution of preparing surfactant earlier, add the good palladium salting liquid of dissolving in advance then, stirring mixes it, then, add reducing agent at leisure, solution colour becomes brownish black from dark-brown, becomes dark solution at last, forms surfactant stabilized nano palladium colloidal solution, adsorb the palladium colloid that makes with inert carrier then, after adsorption process finishes, filter, washing catalyst does not have Cl to filtrate
-Exist, obtain the loaded nano palladium catalyst, wherein: surfactant concentration is 1-500 a times of critical micelle concentration, the concentration of palladium ion is 0.001-0.1mol/L, the concentration of reducing agent is 0.01-1mol/L, the needed temperature of reduction reaction is 0-90 ℃, and the needed recovery time is 3min-3h, and the adsorption time behind the adding carrier is 0.1h-12h.Described surfactant is a tween type, polyoxyethylene-type, the mixture of one or more of sapn type and polyethylene glycols macromolecular compound, its mean molecule quantity is between the 500-5000, and reducing agent is one or several the mixture in methyl alcohol, formaldehyde, hydrazine hydrate, hydrogen, sodium borohydride, lithium aluminium hydride reduction, the natrium citricum.Described palladium salt comprises palladium bichloride, palladium nitrate, and a kind of in the inorganic salts of palladiums such as palladium also can be several mixtures.When reducing agent was hydrogen, the flow of hydrogen was 0.1-50ml/min.Described carrier is an activated carbon, alundum (Al, silica, molecular sieve, zeolite, calcium carbonate, zinc oxide, zirconium dioxide, magnesia, tin ash, titanium dioxide.The load capacity of palladium is 0.2wt%-20wt%.
The invention has the beneficial effects as follows:
1. surfactant is the nonionic surface active agent of one or more mixtures.
2. the metallic colloid decentralized photo of surfactant protection is a water, does not need other organic solvent, avoids causing organic contamination, has reduced production cost simultaneously.
3. the metallic colloid of surfactant protection is easy to be adsorbed onto on the carrier, and carrier does not need any preliminary treatment, and the catalyst noble metal after the load is difficult for running off, the catalytic activity height, and the life-span is long.
4. method for preparing catalyst is simple, good reproducibility, and the nano-metal particle high degree of dispersion is on carrier.
5. filtrate filtered can be recycled, repeatedly load of the catalyst behind the inactivation.
Description of drawings
The present invention is further described below in conjunction with the drawings and specific embodiments.
Fig. 1 is a Pd/C catalyst X-ray diffractogram of the present invention.
Fig. 2 is a Pd/C transmission electron microscope picture of the present invention.
The specific embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1
0.1673gPdCl
2Add again in the 0.6178g concentrated hydrochloric acid after adding 10ml water, under 50 ℃ of water-baths are ultrasonic it is dissolved fully, after the dissolving its adding is contained in 0.0534gBrij35 and the 0.0601g Tween20 150mL water, dropwise add 1.5g/LNaBH
4Aqueous solution 75mL, orange-yellow solution becomes black rapidly, obtains palladium colloidal solution, and the active carbon that adds 2g then stirs 1h, and filtration, fully washing, THF rinse make 5%Pd/C.
Embodiment 2
Take by weighing the catalyst 0.25g that makes among the embodiment 1, join in the autoclave of 70ml, add the reaction substrate o-nitrochlorobenzene more respectively, m-chloronitrobenzene and paranitrochlorobenzene 3.0g, solvent THF30ml, the envelope still, test leakage, inflated with nitrogen displaced air 3 times, use hydrogen exchange nitrogen again 3 times, begin heating, when temperature reached 80 ℃, pressurising power was to 2.5MPa, reaction time is 1 hour, repeat this operation, reaction result is from beginning for the second time o-nitrochlorobenzene, m-chloronitrobenzene and paranitrochlorobenzene equal 100% transforms ortho-nitraniline, the selectivity of meta nitro aniline and paranitroanilinum is more than 99.7%, and after this catalyst circulation was used 40 times, active nothing obviously descended.
Embodiment 3
Take by weighing the catalyst 0.2g that makes among the embodiment 1, join in the autoclave of 70ml, add reaction substrate alpha-olefine polymers 8g, solvent cyclohexane 15ml, solution colour are pale brown look, the envelope still, test leakage, inflated with nitrogen displaced air 3 times is used hydrogen exchange nitrogen 3 times again, begin heating, when temperature reached 160 ℃, pressurising power was reacted after 2 hours to 3.0MPa, the pale brown look of solution colour takes off, and forms water white.
Embodiment 4
Take by weighing the catalyst 1.5g that makes among the embodiment 1, join in the autoclave of 70ml, add reaction substrate quinoline 3ml, solvent decahydronaphthalenes 20ml, the envelope still is tested leakage, inflated with nitrogen displaced air 3 times is used hydrogen exchange nitrogen 3 times again, begins heating, when temperature reached 120 ℃, pressurising power was reacted after 3 hours to 3.0MPa, the conversion ratio of quinoline reaches 100%, and its hydrogenation principal product is 1,2,3, the 4-tetrahydroquinoline, productive rate reaches 98.1%.
Embodiment 5
Take by weighing the catalyst 1.0g that makes among the embodiment 1, join in the autoclave of 70ml, add reaction substrate 4-xenol 1.5g, solvent THF20ml, the envelope still is tested leakage, inflated with nitrogen displaced air 3 times, use hydrogen exchange nitrogen again 3 times, begin heating, when temperature reaches 150 ℃, pressurising power is to 4.0MPa, reacted 33 hours, 4-xenol 100% transforms, and the selectivity of 4-cyclohexylphenol is more than 92.6%.
Embodiment 6
0.1670gPdCl
2Add again in the 0.7346g concentrated hydrochloric acid after adding 10ml water, under 50 ℃ of water-baths are ultrasonic it is dissolved fully, after the dissolving its adding is contained in 0.7319gBrij35 and the 0.5986g Tween20 743mL water, dropwise add 1.5g/LNaBH
4Aqueous solution 300mL, orange-yellow solution becomes black rapidly, obtains palladium colloidal solution, and the active carbon that adds 0.5g then stirs 1h, filters washing, and the THF rinse makes 20%Pd/C.
Embodiment 7
Take by weighing the catalyst 1.0g that makes among the embodiment 6, join in the autoclave of 70ml, add reaction substrate 4-xenol 1.5g, solvent THF20ml, the envelope still is tested leakage, inflated with nitrogen displaced air 3 times, use hydrogen exchange nitrogen again 3 times, begin heating, when temperature reaches 150 ℃, pressurising power is to 4.0MPa, reacted 8 hours, 4-xenol 100% transforms, and the selectivity of 4-cyclohexylphenol is more than 92.4%.
Embodiment 8
0.0668gPdCl
2Add the 0.37g concentrated hydrochloric acid after adding 10ml water, under 50 ℃ of water-baths are ultrasonic it is dissolved fully, its adding is contained in the 83mL water of 0.0454gTween20 after the dissolving, dropwise add 0.2588mol/LNaBH
4Aqueous solution 33.9mL, orange-yellow solution becomes black rapidly, obtains palladium colloidal solution, adds then with salt acid treatment silica later to carry 0.8g body stirring 1h, filters washing, and the THF rinse makes 5%Pd/SiO
2
Embodiment 9
Take by weighing the catalyst 1.0g that makes among the embodiment 8, join in the autoclave of 70ml, add reaction substrate 4-xenol 1.5g, solvent THF20ml, the envelope still is tested leakage, inflated with nitrogen displaced air 3 times, use hydrogen exchange nitrogen again 3 times, begin heating, when temperature reaches 150 ℃, pressurising power is to 4.0MPa, reacted 30 hours, 4-xenol 100% transforms, and the selectivity of 4-cyclohexylphenol is more than 90.4%.
0.0668gPdCl
2Add the 0.37g concentrated hydrochloric acid after adding 10ml water, under 50 ℃ of water-baths are ultrasonic it is dissolved fully, its adding is contained in the 83mL water of 0.0454gTween20 after the dissolving, dropwise add 0.2588mol/LNaBH
4Aqueous solution 33.9mL, orange-yellow solution becomes black rapidly, obtains palladium colloidal solution, adds then with salt acid treatment silica later to carry 4g body stirring 1h, filters washing, and the THF rinse makes 1%Pd/SiO
2
Embodiment 11
Take by weighing the catalyst 1.5g that makes among the embodiment 10, join in the autoclave of 70ml, add reaction substrate paranitrochlorobenzene 3.0g again, solvent THF30ml, the envelope still is tested leakage, inflated with nitrogen displaced air 3 times is used hydrogen exchange nitrogen 3 times again, begins heating, when temperature reaches 80 ℃, pressurising power is to 2.5MPa, and the reaction time is 1 hour, repeats this operation, reaction result transforms from beginning for the second time paranitrochlorobenzene 100%, and the selectivity of parachloroanilinum is more than 99.7%.
Claims (4)
1, a kind of method for preparing loading type nano Pd/C catalyst by colloidal solution, it is characterized in that, this method comprises the following steps: at first to prepare the stable, aqueous solution of surfactant, add the good palladium salting liquid of dissolving in advance then, stirring mixes it, then, add reducing agent at leisure, solution colour becomes brownish black from dark-brown, becomes dark solution at last, forms surfactant stabilized nano palladium colloidal solution, the palladium colloidal solution that makes with the inert carrier active carbon adsorption then, after adsorption process finishes, filter, washing catalyst does not have Cl to filtrate
-Exist, obtain loading type nano Pd/C catalyst, wherein: surfactant concentration is 1-500 a times of critical micelle concentration, the concentration of palladium ion is 0.001-0.1mol/L, the concentration of reducing agent is 0.01-1mol/L, the needed temperature of reduction reaction is 0-90 ℃, and the needed recovery time is 3min-3h, and the adsorption time behind the adding inert carrier is 0.1h-12h; Wherein:
Described surfactant is a tween type, polyoxyethylene-type, and the mixture of one or more of sapn type and polyethylene glycols macromolecular compound, its mean molecule quantity are between the 500-5000.
2, a kind of method for preparing loading type nano Pd/C catalyst by colloidal solution according to claim 1, it is characterized in that described reducing agent is one or several the mixture in methyl alcohol, formaldehyde, hydrazine hydrate, sodium borohydride, lithium aluminium hydride reduction, the natrium citricum.
3, according to claim 1ly a kind ofly prepare the method for loading type nano Pd/C catalyst, it is characterized in that described palladium salt comprises palladium bichloride, palladium nitrate, a kind of in the palladium by colloidal solution.
4, according to claim 1ly a kind ofly prepare the method for loading type nano Pd/C catalyst, it is characterized in that the load capacity of described palladium is 0.2wt%-20wt% by colloidal solution.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4507507A (en) * | 1982-04-12 | 1985-03-26 | Phillips Petroleum Company | Catalysts |
| US5679614A (en) * | 1994-02-04 | 1997-10-21 | University Of Sherbrooke | Steam reforming catalyst and method of preparation |
| CN1559686A (en) * | 2004-03-04 | 2005-01-05 | 厦门大学 | Method of depositing high density loading metal platinum on carbon nanometer pipe surface using oriented chemistry |
| CN1663679A (en) * | 2004-12-24 | 2005-09-07 | 南化集团研究院 | Carbon-supported noble metal catalyst and preparation method thereof |
| CN1672787A (en) * | 2005-01-07 | 2005-09-28 | 贵研铂业股份有限公司 | Rosin-disproportionating high activity Pd/C catalyst preparing process |
| CN1698962A (en) * | 2005-04-08 | 2005-11-23 | 浙江大学 | Preparation method for loading platinum nanoparticles on carbon carrier |
| CN1709571A (en) * | 2004-06-18 | 2005-12-21 | 中国石油化工股份有限公司 | Method for preparing load type palladium/carbon catalyst |
| CN1775361A (en) * | 2005-07-28 | 2006-05-24 | 大连理工大学 | Method for preparing nano noble metal hydrogenation catalyst by substitution method and its use |
-
2006
- 2006-09-06 CN CNB2006100477020A patent/CN100428989C/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4507507A (en) * | 1982-04-12 | 1985-03-26 | Phillips Petroleum Company | Catalysts |
| US5679614A (en) * | 1994-02-04 | 1997-10-21 | University Of Sherbrooke | Steam reforming catalyst and method of preparation |
| CN1559686A (en) * | 2004-03-04 | 2005-01-05 | 厦门大学 | Method of depositing high density loading metal platinum on carbon nanometer pipe surface using oriented chemistry |
| CN1709571A (en) * | 2004-06-18 | 2005-12-21 | 中国石油化工股份有限公司 | Method for preparing load type palladium/carbon catalyst |
| CN1663679A (en) * | 2004-12-24 | 2005-09-07 | 南化集团研究院 | Carbon-supported noble metal catalyst and preparation method thereof |
| CN1672787A (en) * | 2005-01-07 | 2005-09-28 | 贵研铂业股份有限公司 | Rosin-disproportionating high activity Pd/C catalyst preparing process |
| CN1698962A (en) * | 2005-04-08 | 2005-11-23 | 浙江大学 | Preparation method for loading platinum nanoparticles on carbon carrier |
| CN1775361A (en) * | 2005-07-28 | 2006-05-24 | 大连理工大学 | Method for preparing nano noble metal hydrogenation catalyst by substitution method and its use |
Non-Patent Citations (2)
| Title |
|---|
| Pd/C催化剂的表征及其制备条件对脂肪腈加氢催化的影响. 张建远等.皮革化工，第23卷第2期. 2006 |
| Pd/C催化剂的表征及其制备条件对脂肪腈加氢催化的影响. 张建远等. 皮革化工，第23卷第2期. 2006 * |
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