CN104117372B

CN104117372B - A kind of nanometer red phosphorus is the hydrothermal preparing process of the support type catalyst of phosphatizing nickel of phosphorus source

Info

Publication number: CN104117372B
Application number: CN201310149267.2A
Authority: CN
Inventors: 黄翔; 甄冠胜
Original assignee: Ocean University of China; China Petroleum and Natural Gas Co Ltd
Current assignee: Ocean University of China; China Petroleum and Natural Gas Co Ltd
Priority date: 2013-04-26
Filing date: 2013-04-26
Publication date: 2016-08-03
Anticipated expiration: 2033-04-26
Also published as: CN104117372A

Abstract

The present invention relates to the hydrothermal preparing process of the support type catalyst of phosphatizing nickel that a kind of nanometer red phosphorus is phosphorus source, pure bulky grain red phosphorus is not had with water logging, mechanical lapping, adding strong base solution regulation is 9～14 to pH value, it is incubated at 150～300 DEG C, it is cooled to room temperature, filters, be vacuum dried to obtain nanoscale red phosphorus；By nanoscale red phosphorus, Nickel dichloride. and carrier according to mol ratio P:Ni=15～30, the loading of nickel phosphide 30～50% ratio add water mixing, add strong base solution and adjust pH value to be 9～14, it is incubated at 150～300 DEG C, being cooled to room temperature, filter, vacuum drying obtains support type catalyst of phosphatizing nickel；This method improves the surface activity of red phosphorus, avoid solvent and other additive and the introducing of hypertoxic and inflammable and explosive reactant of costliness, reduce the temperature of preparation, provide cost savings, shorten the cycle of production, improve the performance of catalyst article and the speed of production and safety.

Description

A kind of nanometer red phosphorus is the hydrothermal preparing process of the support type catalyst of phosphatizing nickel of phosphorus source

Technical field

The present invention relates to the treatment technology of a kind of catalyst of phosphatizing nickel with nanometer red phosphorus as phosphorus source, particularly relate to the preparation method of a kind of support type catalyst of phosphatizing nickel with nanometer red phosphorus as phosphorus source under hydrothermal conditions.

Background technology

Nickel phosphide has multiple phase, such as Ni₂P、Ni₃P、Ni₅P₂、Ni₈P₃And Ni₁₂P₅Deng, have a wide range of applications in catalytic field.At present, the Ni used as catalyst₂P is generally by 600～650 DEG C, and in hydrogen atmosphere prepared by the temperature-programmed reduction method of ammonium phosphate nickel salt presoma.Meanwhile, the liquid phase synthesis of nickel phosphide have also been obtained development.Such as, 2005, Hyeon et al. used TOP (to include Ni as phosphorus source, the anisotropic nanostructured being prepared for magnetic phosphide₂P).Henkes and Schaak is less than at 370 DEG C, by the metal nanoparticle being freshly formed and the direct reaction of TOP, it is thus achieved that metal phosphide (includes Ni₂P).Additionally, Wang Xinjun et al. uses white phosphorus as P^3-Source, has developed Ni₂The solvent-thermal process route of P nanocrystal.But in the above methods, it usually needs the solvent of costliness, the temperature of hypertoxic reactant or higher.

Hydro-thermal method (HydrothermalSynthesis), is on the basis of geologist simulates the exploration of nature mineralization, the scientists of 20 beginnings of the century develops rapidly after establishing blending theory.This method is in special closed reactor (autoclave), use aqueous solution as reaction system, by reaction system being heated, pressurizeing (or spontaneous vapour pressure), create relatively-high temperature, a reaction environment for high pressure, usual indissoluble or insoluble material are dissolved, and recrystallization and carry out a kind of effective ways that Inorganic synthese processes with material.If the advantage of hydro-thermal method is to add morphology control agent in reaction system to synthesize the nano-particle with given shape, such as polyhedron, spherical etc.；Nucleation rate can be changed by regulating reaction condition, adding suitable additive or control the change etc. of reactant concentration, thus the particle size distribution of product grain controlled in narrower scope；Its environmental pollution is few simultaneously, cost is relatively low, be prone to commercialization, it is thus also avoided that the impurity pollution to product in synthesis.At present, the research preparing support type catalyst of phosphatizing nickel by hydro-thermal method has focused largely on solvent thermal, adds the method such as dispersant and surfactant, but by directly using the approach of hydro-thermal to process red phosphorus, and the research of support type catalyst of phosphatizing nickel, the rarest report is prepared with this nanometer red phosphorus prepared for phosphorus source.

Summary of the invention

It is an object of the invention to provide a kind of technology preparing support type catalyst of phosphatizing nickel under hydrothermal conditions with nanometer red phosphorus for phosphorus source, it reduces production cost greatly, shortens the production cycle, improves quality and the performance of catalyst article.

The hydrothermal preparing process of a kind of support type catalyst of phosphatizing nickel with nanometer red phosphorus as phosphorus source of the present invention, it is characterised in that

(1) pretreatment red phosphorus: do not have pure bulky grain red phosphorus with water logging, then mechanical lapping is to can't see obvious large grained red phosphorus, adding strong base solution regulation is 9～14 to its pH value, pours into the most rapidly in reactor, is allowed at 150～300 DEG C insulation 2～24 hours, after stopping insulation, it is allowed to cool to room temperature, then the suspension generated is filtered, proceed in vacuum drying oven after filter cake is repeatedly washed, it is dried under vacuum, obtains nano level red phosphorus；

(2) catalyst is prepared: nanoscale red phosphorus, Nickel dichloride. and the carrier of gained will be processed according to mol ratio P:Ni=15～30, the loading of nickel phosphide be 30～50% ratio add water mixing, being subsequently adding strong base solution regulation is 9～14 to its pH value, pour into the most rapidly in reactor, it is allowed at 150～300 DEG C insulation 2～24 hours, after stopping insulation, it is allowed to cool to room temperature, then the suspension generated is filtered, proceed to after filter cake is repeatedly washed in vacuum drying oven, it is dried under vacuum, obtains support type catalyst of phosphatizing nickel.

Described red phosphorus is 1:1～20 with the mass ratio of water,

Described strong base solution is NaOH, KOH or ammonia,

Described carrier is ZSM-5, M41S, SiO₂Or γ-Al₂O₃。

Milling apparatus used by the present invention does not has special requirement, and the device being mostly used in grinding is all suitable for；The hydro-thermal method used avoids solvent and other additives and the introducing of hypertoxic and inflammable and explosive reactant of costliness, reduces again temperature prepared by catalyst simultaneously, provides cost savings, improve the performance of catalyst article.

Accompanying drawing explanation

Fig. 1, the flow chart of the hydrothermal preparing process of the support type catalyst of phosphatizing nickel with nanometer red phosphorus as phosphorus source.

Fig. 2, pretreated red phosphorus photo under transmission electron microscope.

Fig. 3, carrier ZSM-5 photo under transmission electron microscope.

The catalyst of phosphatizing nickel of Fig. 4, ZSM-5 load photo under transmission electron microscope.

Detailed description of the invention

Present invention water logging does not has pure bulky grain red phosphorus, then mechanical lapping；Configuration strong base solution, joins in red phosphorus suspension, pours into the most rapidly in reactor, be incubated it, obtain nano level red phosphorus；Add water in proportion mixing by the nanoscale red phosphorus, Nickel dichloride. and the carrier that process gained, it is subsequently adding strong base solution, pour into the most rapidly in reactor, it is incubated, after stopping insulation, it is allowed to cool to room temperature, then the suspension generated is filtered, it is dried after filter cake is repeatedly washed, obtains support type catalyst of phosphatizing nickel.

Mechanical lapping of the present invention does not has particular/special requirement to milling apparatus, to can't see obvious large grained red phosphorus；Described strong base solution is NaOH, KOH or ammonia, and the pH scope of regulation is 9～14；Described reactor insulation, holding temperature scope is 150～300 DEG C, and temperature retention time scope is 2～24 hours；Reactant and carrier are according to mol ratio P:Ni=15～30, and the loading of nickel phosphide is the ratio mixing of 30～50%；Described carrier includes ZSM-5, M41S, SiO₂Or γ-Al₂O₃Deng described filtration cakes torrefaction, it is being dried under vacuum.

Described red phosphorus is 1:1～20 with the mass ratio of water.

The key problem in technology of the present invention: first, selects suitable strong basicity environment, and this strong basicity environment uses strong base solution NaOH, KOH or ammonia to regulate, and the pH regulated is 9～14.Secondly, will select suitable holding temperature and temperature retention time, this holding temperature scope is 150～300 DEG C, and temperature retention time scope is 2～24 hours；Finally, the mixing of reactant and carrier to select suitable ratio, and for mol ratio P:Ni=15～30, the loading of nickel phosphide is 30～50%.

Embodiment 1

Do not have bulky grain red phosphorus pure for 6kg, then mechanical lapping with 10L water logging, to can't see obvious large grained red phosphorus, add 60L water and obtain grinding the suspension of red phosphorus；Configuration concentration is the potassium hydroxide solution of 1.0mol/L, and joins in red phosphorus suspension, and regulation is 13 to its pH value, pours into the most rapidly in reactor；After assembling reactor, it is allowed at 200 DEG C insulation 10 hours；After stopping insulation, it is allowed to cool to room temperature, then the suspension of generation is filtered, proceed in vacuum drying oven by after Cake Wash 3 times, be vacuum dried 5 hours at 40 DEG C, obtain nano level red phosphorus.The ZSM-5 that 62Kg processes the nanoscale red phosphorus of gained, 19Kg six water Nickel dichloride. and 9Kg is added in 100L water mixing, it is subsequently adding the potassium hydroxide solution of 1.0mol/L, regulation to its pH value is 13, then pours into rapidly in reactor, is allowed at 200 DEG C insulation 10 hours, after stopping insulation, it is allowed to cool to room temperature, then the suspension of generation is filtered, proceed in vacuum drying oven by after Cake Wash 3 times, it is vacuum dried 5 hours at 40 DEG C, obtains support type catalyst of phosphatizing nickel.

Claims

1. a nanometer red phosphorus is the hydrothermal preparing process of support type catalyst of phosphatizing nickel of phosphorus source, it is characterised in that:

(2) catalyst is prepared: nanoscale red phosphorus, Nickel dichloride. and the carrier of gained will be processed according to mol ratio P:Ni=15～30, the loading of nickel phosphide be 30～50% ratio add water mixing, being subsequently adding strong base solution regulation is 9～14 to its pH value, pour into the most rapidly in reactor, it is allowed at 150～300 DEG C insulation 2～24 hours, after stopping insulation, it is allowed to cool to room temperature, then the suspension generated is filtered, proceed to after filter cake is repeatedly washed in vacuum drying oven, it is dried under vacuum, obtains support type catalyst of phosphatizing nickel；

Described red phosphorus is 1:1～20 with the mass ratio of water,

Described strong base solution is NaOH, KOH or ammonia,

Described carrier is ZSM-5, M41S, SiO₂Or γ-Al₂O₃。