CN102631924A - Preparation method of o-phenylenediamine catalyst-nano nickel by hydrogenation - Google Patents
Preparation method of o-phenylenediamine catalyst-nano nickel by hydrogenation Download PDFInfo
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- CN102631924A CN102631924A CN201110059900XA CN201110059900A CN102631924A CN 102631924 A CN102631924 A CN 102631924A CN 201110059900X A CN201110059900X A CN 201110059900XA CN 201110059900 A CN201110059900 A CN 201110059900A CN 102631924 A CN102631924 A CN 102631924A
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Abstract
The invention mainly discloses a preparation method of an o-phenylenediamine catalyst-nano nickel by hydrogenation. The preparation method is characterized by comprising the following steps: (1) preparing a solution from a metal nickel salt and an organic solvent, wherein the metal nickel salt comprises nickel nitrate, nickel oxide, nickel acetate and the like, and the organic solvent comprises ethylene glycol and propylene glycol; (2) adding hydrazine hydrate into the solution obtained in the step 1 for reduction, and regulating the pH value of the solution to 9-11 with sodium hydroxide; (3) rapidly stirring a solution obtained in the step 2 for 6 hours in a water bath of 40-80 DEG C to obtain a black solution; and (4) cooling the solution obtained in the step 3, filtering, washing three times, and then adding a little amount of acetone for dispersion so as to obtain a black high-dispersion spherical nano nickel catalyst. The preparation method has the advantages that the self-prepared nano nickel catalyst has the advantages of high dispersion degree, controllable particle size, high catalytic activity, low cost and the like, and is beneficial to large-scale production; and the nano nickel catalyst can be used for a reaction for producing o-phenylenediamine by hydrogenation, so that reaction time is shortened to 1 hour, and yield reaches up to 99.9%.
Description
Technical field
The present invention relates to a kind of preparation method that the ortho-nitraniline catalytic hydrogenation prepares the new catalyst nanometer nickel of o-phenylenediamine that is used for.
Background technology
Nanometer nickel because of its crystallite dimension at nanoscale, be positioned in the crystal crystal boundary with the surface atom accounted for sizable ratio, so all different with non-nano nickel from mechanical property to electricity, magnetic, optical property.Nanometer nickel has unique surface characteristic, adsorptivity and ferromagnetism etc.; Being widely used as many fields such as effective catalyst, lubricant, light absorbing material, nano-coating material, sensor, electrocondution slurry, high density magnetic recording material, high performance electrode material, activated sintering additive, is one of domestic and international novel capabilities developing material focus.
In recent years, the method for preparing nanometer nickel both at home and abroad is a lot, but can be divided into physics method and chemical reaction method two big classes generally.Physics method and chemical method respectively have advantage: the physics method mainly comprises mechanical ball milling method, gas phase coacervation, sputtering method, discharge-induced explosion silk method, plasma method etc.; Generally higher to equipment requirements; But simple to operate: though and solution chemical reduction method technical process is more; But output is big, and product particle diameter, pattern are controlled easily, are easy to accomplish scale production.Compare with traditional skeletal nickel catalyst, the nano-nickel powder catalyst improves nitro compound hydrogenation reaction speed greatly.
Summary of the invention
The present invention provides a kind of preparation method who is used for new catalyst-nanometer nickel that the ortho-nitraniline catalytic hydrogenation prepares o-phenylenediamine, specifically is a kind of preparation method that can make new catalyst-nanometer nickel that the o-phenylenediamine preparation efficiency improves, yield improves.
In order to solve above technical problem, a kind of hydrogenation of the present invention is produced the preparation method of o-phenylenediamine catalyst-nanometer nickel, it is characterized in that adopting the solution chemical reduction method, and concrete technical scheme is following:
(1) with the slaine and the organic solvent wiring solution-forming of nickel.The slaine of nickel such as nickel nitrate, nickel chloride, nickel acetate etc., organic solvent such as ethylene glycol, propane diols etc.;
(2) hydrazine hydrate is added in the step 1 gained solution reduce, use sodium hydroxide solution to transfer the solution pH value to be 9-11; The pH value of said solution is preferably 10;
(3) with step 2 gained solution under water-bath 40-80 ℃, stir 6 h fast, dark solution;
(4) with the cooling cooling of step 3 gained solution, filter, add small amount of acetone after the washing three times and disperse, the spherical nano nickel catalyst of black high dispersive.
Further, the slaine of used nickel comprises a kind of in nickel nitrate, nickel chloride, the nickel acetate in the said step (1).
Further, the organic solvent described in the said step (1) is ethylene glycol or propane diols.
Further, using sodium hydroxide solution to transfer the solution pH value described in the said step (2) is 10.
Further, used bath temperature is 60 ℃ in the said step (2).
Further, it is characterized in that: said nickel slaine: the mol ratio of hydrazine hydrate=1:1-2.
Advantage of the present invention: homemade nano nickel catalyst has the decentralization height, particle size is controlled, catalytic activity is high, cost is low, be beneficial to advantages such as large-scale production.Be used for hydrogenation and produce the o-phenylenediamine reaction, make the reaction time shorten to 1h, yield is up to 99.9%.
Description of drawings
Accompanying drawing 1 is the XRD figure spectrum of spherical nanometer nickel.
The practical implementation method
Embodiment 1
Take by weighing 290 g nickel nitrates, adding has in the there-necked flask of stirring, adds 600 mL ethylene glycol then, stirs and makes it abundant dissolving, gets green solution.20 g hydrazine hydrates are slowly dropped in the there-necked flask again, use the sodium hydroxide solution mol 1 then, transferring the solution pH value is 10, under 60 ℃ of water-baths, stirs 6 h fast, gets dark solution.Cooling cooling, filter, add 300 mL acetone after the washing three times and disperse; Get the black nano Raney nickel and be designated as A; The particle size of its catalyst A is as shown in Figure 1, and Fig. 1 is the XRD spectra data, and the size that calculates nano particle crystal grain according to the Debye-Scherrer formula is 10nm.
Embodiment 2
Said as embodiment 1, the solution pH value is 9, and made nano nickel catalyst is designated as B, shows that through the XRD spectra data particle size of its catalyst B is 9.2nm.
Embodiment 3
Said as embodiment 1, the solution pH value is 11, and made nano nickel catalyst is designated as C and shows that through the XRD spectra data particle size of its catalyst C is 14nm.
Application implementation example 1
Get ortho-nitraniline 500 g, methyl alcohol 1000 g, catalyst A 25 g, 2.0 MPa, 60 ℃ of reactions, to pressure constant (about 1 h), sampling, filtration catalizer steams and removes methyl alcohol, and the o-phenylenediamine yield is 99.9%.
Application implementation example 2
Said as application implementation example 1, catalyst B 25g, o-phenylenediamine yield are 98.7%.
Application implementation example 3
Said as application implementation example 1, catalyst C 25g, o-phenylenediamine yield are 97.6%.
Application implementation example 4
Get ortho-nitraniline 500 g, methyl alcohol 1000 g, skeletal nickel catalyst 25 g, 2.0 MPa, 60 ℃ of reactions, to pressure constant (about 5 h), filtration catalizer steams and removes methyl alcohol, and gas phase analysis o-phenylenediamine yield is 96.5%.
In sum, compare with skeletal nickel catalyst, the nano nickel catalyst particle belongs to the high dispersive system all at nanoscale, and reactivity is high, and not only the yield with o-phenylenediamine is increased to 99.9%, also makes the reaction time shorten 4h.
Claims (6)
1. a hydrogenation is produced the preparation method of o-phenylenediamine catalyst-nanometer nickel, it is characterized in that: adopt the solution chemical reduction method, may further comprise the steps:
(1) with the slaine and the organic solvent wiring solution-forming of nickel;
(2) hydrazine hydrate is added in the step 1 gained solution reduce, use sodium hydroxide solution to transfer the solution pH value to be 9-11;
(3) with step 2 gained solution under water-bath 40-80 ℃, stir 6 h fast, dark solution;
(4) with the cooling cooling of step 3 gained solution, filter, add acetone after the washing three times and disperse, the nano nickel catalyst of black high dispersive.
2. hydrogenation according to claim 1 is produced the preparation method of o-phenylenediamine catalyst-nanometer nickel, it is characterized in that: the slaine of used nickel comprises a kind of in nickel nitrate, nickel chloride, the nickel acetate in the step (1).
3. hydrogenation according to claim 1 is produced the preparation method of o-phenylenediamine catalyst-nanometer nickel, and it is characterized in that: the organic solvent described in the step (1) is ethylene glycol or propane diols.
4. hydrogenation according to claim 1 is produced the preparation method of o-phenylenediamine catalyst-nanometer nickel, it is characterized in that: using sodium hydroxide solution to transfer the solution pH value described in the step (2) is 10.
5. hydrogenation according to claim 1 is produced the preparation method of o-phenylenediamine catalyst-nanometer nickel, and it is characterized in that: used bath temperature is 60 ℃ in the step (2).
6. hydrogenation according to claim 1 is produced the preparation method of o-phenylenediamine catalyst-nanometer nickel, it is characterized in that: said nickel slaine: the mol ratio of hydrazine hydrate=1:1-2.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107224976A (en) * | 2016-03-25 | 2017-10-03 | 中国石化扬子石油化工有限公司 | A kind of nanocatalyst and preparation method thereof |
| CN107684909A (en) * | 2017-09-30 | 2018-02-13 | 陕西科技大学 | A kind of preparation method of the flower-shaped nickel nano catalytic material of high activity |
| CN109503386A (en) * | 2018-12-19 | 2019-03-22 | 南京杰科丰环保技术装备研究院有限公司 | A kind of paranitroanilinum catalytic hydrogenation prepares the preparation method of p-phenylenediamine |
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| CN1261565A (en) * | 1999-01-21 | 2000-08-02 | 中国科学技术大学 | Method for preparing nanometre metal cobalt powder or nickel powder |
| CN101028653A (en) * | 2007-04-10 | 2007-09-05 | 北京科技大学 | Chemical production of metal nickel nano-line |
| CN101342598A (en) * | 2008-08-28 | 2009-01-14 | 上海交通大学 | Method for preparing metallic nickel nano-wire |
| CN101486102A (en) * | 2009-01-05 | 2009-07-22 | 江苏科技大学 | Method for preparing metallic nickel nano-wire |
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2011
- 2011-03-14 CN CN201110059900XA patent/CN102631924A/en active Pending
Patent Citations (4)
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| CN1261565A (en) * | 1999-01-21 | 2000-08-02 | 中国科学技术大学 | Method for preparing nanometre metal cobalt powder or nickel powder |
| CN101028653A (en) * | 2007-04-10 | 2007-09-05 | 北京科技大学 | Chemical production of metal nickel nano-line |
| CN101342598A (en) * | 2008-08-28 | 2009-01-14 | 上海交通大学 | Method for preparing metallic nickel nano-wire |
| CN101486102A (en) * | 2009-01-05 | 2009-07-22 | 江苏科技大学 | Method for preparing metallic nickel nano-wire |
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| 李忠平等: "制备条件对纳米镍粉电化学性能的影响", 《中国有色金属学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107224976A (en) * | 2016-03-25 | 2017-10-03 | 中国石化扬子石油化工有限公司 | A kind of nanocatalyst and preparation method thereof |
| CN107224976B (en) * | 2016-03-25 | 2021-04-27 | 中国石化扬子石油化工有限公司 | Nano catalyst and preparation method thereof |
| CN107684909A (en) * | 2017-09-30 | 2018-02-13 | 陕西科技大学 | A kind of preparation method of the flower-shaped nickel nano catalytic material of high activity |
| CN109503386A (en) * | 2018-12-19 | 2019-03-22 | 南京杰科丰环保技术装备研究院有限公司 | A kind of paranitroanilinum catalytic hydrogenation prepares the preparation method of p-phenylenediamine |
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Application publication date: 20120815 |