CN101671009B - Method for preparing Ni2P by reducing nickel oxide precursor through thermal treatment at low temperature - Google Patents
Method for preparing Ni2P by reducing nickel oxide precursor through thermal treatment at low temperature Download PDFInfo
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- CN101671009B CN101671009B CN2009100705660A CN200910070566A CN101671009B CN 101671009 B CN101671009 B CN 101671009B CN 2009100705660 A CN2009100705660 A CN 2009100705660A CN 200910070566 A CN200910070566 A CN 200910070566A CN 101671009 B CN101671009 B CN 101671009B
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- nickel oxide
- nickel
- sodium hypophosphite
- ni2p
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Abstract
The invention provides a novel method for preparing nickel phosphide (Ni2P) by utilizing phosphine produced by thermal decomposition of sodium hypophosphite to reduce nickel oxide precursor. In the method, nickel nitrate is adopted as a nickel source and then roasted to obtain nickel oxide, and the obtained nickel oxide is dipped into sodium hypophosphite solution to obtain the nickel oxide precursor, and simple low temperature thermal treatment of the nickel oxide precursor is carried out so as to synthesize supported and unsupported Ni2P. The invention has the characteristics of simple process, low Ni2P preparation temperature, short production period, without the complex steps of temperature programming, and the like as well as just simple thermal treatment at normal temperature. Raw materials used in the method are low in price and safety, and devices used in the method are low in cost. The catalyst can be widely used for hydrogenation treatment of oils due to higher hydrodesulfurization and hydrodenitrogenation activities.
Description
Technical field
The present invention proposes a kind of phosphuret-(t)ed hydrogen reduction-oxidation nickel precursor that utilizes the sodium hypophosphite thermolysis to produce and prepares nickel phosphide (Ni
2P) novel method.It is to obtain nickel oxide after the roasting of nickel source that this method adopts nickelous nitrate, with obtaining precursor after the gained nickel oxide dipping sodium hypophosphite solution, synthesizes loading type and non-loading type Ni through precursor being carried out simple low temperature thermal treatment
2P.Characteristics of the present invention are that the technology that is adopted is simple, Ni
2The P preparation temperature is low, and is with short production cycle, do not need complicated steps such as temperature programming, only needs brief heat treating under the normal pressure.Raw materials used low price, safety, the required equipment cost is low.Such catalyzer can be widely used in the hydrotreatment of oil product because of having very high hydrogenating desulfurization and hydrodenitrogenationactivity activity.
Background technology
The energy and environment are not only the much-talked-about topic of universe's survival and development, also are our stern challenges of being faced of 21 century.Day by day the strictness of the continuous decline of crude quality and environmental regulation makes various countries improve the oil refining degree of depth one after another and the development of new catalyzer is produced clean fuel.In numerous new catalytic materials, transition metal phosphide is because of its unique physics and chemical property, and in many hydrogen-involved reactions, has excellent catalytic performance and caused that people pay close attention to widely.In numerous transition metal phosphides, Ni
2The hydrogenating desulfurization of P catalyzer and hydrodenitrogenationactivity activity have become the focus in the transition metal phosphide catalyst research field all considerably beyond commercial NiMoS catalyzer.
Loading type and non-loading type Ni
2The preparation method of P has a lot.Wherein most widely used is the temperature programmed reduction(TPR) of phosphoric acid salt in hydrogen atmosphere.Although this method is traditional method for preparing phosphide catalyst, this kind method is unfavorable for carrying out on thermodynamics.Since the steam partial pressure that this reaction needed is very low, the P-O key in the phosphoric acid salt that also need rupture, thereby need bigger hydrogen flow rate and higher preparation temperature (generally more than 550 ℃) in the preparation process.And temperature programmed reduction(TPR) also is difficult to realize in scale operation.The phosphuret-(t)ed hydrogen reduction-oxidation nickel precursor of mentioning among the present invention that utilizes the sodium hypophosphite thermolysis to produce prepares nickel phosphide (Ni
2P) novel method has solved an above difficult problem.The technology that it adopted is simple, Ni
2The P preparation temperature is low, and is with short production cycle, need not use flowing protective gas in the preparation process, do not need complicated steps such as temperature programming, only needs brief heat treating under the normal pressure.Raw materials used low price, safety, the required equipment cost is low.
Summary of the invention
The present invention proposes a kind of phosphuret-(t)ed hydrogen reduction-oxidation nickel precursor that utilizes the sodium hypophosphite thermolysis to produce and prepares nickel phosphide (Ni
2P) novel method.It is to obtain nickel oxide after the roasting of nickel source that this method adopts nickelous nitrate, with obtaining precursor after the gained nickel oxide dipping sodium hypophosphite solution, synthesizes loading type and non-loading type Ni through precursor being carried out simple low temperature thermal treatment
2P.
Characteristics of the present invention are that the technology that is adopted is simple, Ni
2The P preparation temperature is low, and is with short production cycle, do not need complicated steps such as temperature programming, only needs brief heat treating under the normal pressure.Raw materials used low price, safety, the required equipment cost is low.
Ni
2The P synthesis step is following:
Take by weighing the roasting under 550 ℃ of air atmospheres of a certain amount of nickelous nitrate and can obtain nickel oxide in 2 hours.Under stirring at room, according to stoichiometric relation, the sodium hypophosphite of aequum is dissolved in the deionized water, after the stirring and dissolving nickel oxide of aequum joined in the solution and flood, fully stir after 2 hours gained solution is dried at a certain temperature.Pack into after precursor powder after will drying is then ground in the reactor drum, in the nitrogen protection atmosphere of static state with precursor thermal treatment at a certain temperature more than 10 minutes.Then the products therefrom dried after being washed is promptly obtained required Ni
2P.Loading type Ni
2Two step of the preparation process need dipping of P realizes that the first step dipping is with drying behind the carrier impregnation nickel nitrate solution, can obtain the loading type nickel oxide in 2 hours 550 ℃ of roastings then, all the other steps and non-loading type Ni
2The preparation process of P is identical.
Stoichiometric relation described in the synthesis step is NiO: NaH
2PO
2Equal 1: 2.75; Described nickelous nitrate is the analytical pure nickelous nitrate; Described sodium hypophosphite is the analytical pure sodium hypophosphite; The bake out temperature of precursor solution is 40～80 ℃; The precursor thermal treatment temp is 250～350 ℃.
Description of drawings
Accompanying drawing 1 is the synthetic non-loading type Ni of institute
2The x-ray diffractogram of powder of P sample A.
Accompanying drawing 2 is the synthetic loading type Ni of institute
2The x-ray diffractogram of powder of P/MCM-41 sample B.
Embodiment
The present invention can specify through embodiment, but they are not that the present invention is done any restriction.In these embodiment, XRD spectra is measured by Japan's D/MAX-2500 type of science x-ray diffractometer, and pipe is pressed 40kV, pipe stream 100mA, 8 °/min of sweep velocity.
These embodiment have explained Ni
2P and Ni
2The building-up process of P/MCM-41.
Embodiment 1
At first under the stirring at room state with the sodium hypophosphite (NaH of 5.89g
2PO
2.H
2O) join in the 18mL deionized water, add the NiO of 1.49g after the dissolving 10min.Continue to stir after 2 hours, the solution of gained is put into 80 ℃ of oven dry of petridish.Precursor powder after will drying is then packed in the reactor drum, 250 ℃ of thermal treatment 10min in the nitrogen protection of static state, and then with the products therefrom dried after being washed, the gained sample is named as A, and A has the characteristic of accompanying drawing 1.
Embodiment 2
At first under the stirring at room state with the nickelous nitrate (Ni (NO of 5.93g
3)
2.6H
2O) join in the 18mL deionized water, add the MCM-41 molecular sieve of 3.91g after the dissolving 10min.Continue to stir after 2 hours, the solution of gained is put into 100 ℃ of oven dry of petridish.Precursor powder after will drying is then put into retort furnace, and roasting obtained loading type nickel oxide (NiO/MCM-41) in 2 hours under 550 ℃ of air atmospheres.Under the stirring at room state with the NaH of 5.89g
2PO
2.H
2O joins in the 18mL deionized water, adds loading type nickel oxide (NiO/MCM-41) after the dissolving 10min.Continue to stir after 2 hours, the solution of gained is put into 80 ℃ of oven dry of petridish.Precursor powder after will drying is then packed in the reactor drum, 250 ℃ of thermal treatment 10min in the nitrogen protection of static state, and then with the products therefrom dried after being washed, the gained sample is named as B, and B has the characteristic of accompanying drawing 2.
Claims (4)
1. one kind prepares Ni
2The method of P; It is characterized in that comprising following steps: (1) takes by weighing the roasting under 550 ℃ of air atmospheres of a certain amount of nickelous nitrate and obtained nickel oxide in 2 hours; Under stirring at room, according to stoichiometric relation, the sodium hypophosphite of aequum is dissolved in the deionized water, after the stirring and dissolving nickel oxide of aequum joined in the solution and flood, fully stir after 2 hours gained solution is dried at a certain temperature; Pack into after precursor powder after will drying is then ground in the reactor drum, in the nitrogen protection atmosphere of static state with precursor 250～350 ℃ of following thermal treatments more than 10 minutes; Then the products therefrom dried after being washed is promptly obtained required Ni
2P; (2) loading type Ni
2Two step of the preparation process need dipping of P realizes that the first step dipping is with drying behind the carrier impregnation nickel nitrate solution, obtained the loading type nickel oxide in 2 hours 550 ℃ of roastings then, all the other steps and non-loading type Ni
2The preparation process of P is identical; Described stoichiometric relation is NiO: NaH
2PO
2Mol ratio equal 1: 2.75.
2. preparation method according to claim 1 is characterized in that described nickelous nitrate is the analytical pure nickelous nitrate.
3. preparation method according to claim 1 is characterized in that described sodium hypophosphite is the analytical pure sodium hypophosphite.
4. preparation method according to claim 1, the bake out temperature that it is characterized in that described solution is 40～80 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105926021A (en) * | 2016-03-24 | 2016-09-07 | 西北师范大学 | Preparation method and application of nickel phosphide nano film |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030317B (en) * | 2010-11-08 | 2013-04-17 | 南开大学 | Method for controllably preparing supported and non-supported Ni2P under mild conditions |
| CN102994141A (en) * | 2011-09-15 | 2013-03-27 | 中国石油天然气股份有限公司 | Poor quality aviation kerosene hydrotreatment method |
| CN104383948A (en) * | 2014-10-31 | 2015-03-04 | 常州大学 | Preparation method of siliceous mesocellular foams (MCFs) loaded nano Ni2P hydrogenation catalyst |
| CN105126884A (en) * | 2015-09-22 | 2015-12-09 | 云南师范大学 | Ammonia borane or hydrazine hydrate catalytic hydrolysis hydrogen release system containing nano-metal phosphide MxPy catalyst and application of catalytic hydrolysis hydrogen release system |
| CN108620117B (en) * | 2018-05-03 | 2020-12-11 | 常州大学 | Low-temperature reduction preparation of high-dispersion load type Ni2Method for preparing P catalyst |
| CN109647459B (en) * | 2019-01-17 | 2021-07-30 | 淮北师范大学 | Preparation method of nickel-based phosphide with controllable composition |
| CN116196930A (en) * | 2021-08-03 | 2023-06-02 | 中国科学院青岛生物能源与过程研究所 | Phosphorus doped nickel aluminum oxide and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327439A (en) * | 2008-08-01 | 2008-12-24 | 南开大学 | Hypophosphite precursor heat decomposition method for preparing Ni2P catalyst |
| CN101376108A (en) * | 2007-08-29 | 2009-03-04 | 中国科学院大连化学物理研究所 | Nickel phosphide catalyst as well as preparation method and application |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376108A (en) * | 2007-08-29 | 2009-03-04 | 中国科学院大连化学物理研究所 | Nickel phosphide catalyst as well as preparation method and application |
| CN101327439A (en) * | 2008-08-01 | 2008-12-24 | 南开大学 | Hypophosphite precursor heat decomposition method for preparing Ni2P catalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105926021A (en) * | 2016-03-24 | 2016-09-07 | 西北师范大学 | Preparation method and application of nickel phosphide nano film |
| CN105926021B (en) * | 2016-03-24 | 2018-02-27 | 西北师范大学 | A kind of nickel phosphide nano thin-film and its preparation method and application |
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