CN103273074B - Process method of continuously producing ultra-fine nickel powder - Google Patents
Process method of continuously producing ultra-fine nickel powder Download PDFInfo
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- CN103273074B CN103273074B CN201310101754.1A CN201310101754A CN103273074B CN 103273074 B CN103273074 B CN 103273074B CN 201310101754 A CN201310101754 A CN 201310101754A CN 103273074 B CN103273074 B CN 103273074B
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Abstract
The invention provides a process method of continuously producing ultra-fine nickel powder. The process method comprises the working procedures of preparation of raw materials, material conveying, ultrasound enhancement tubular reaction, rapid cleaning of pipelines, ultrasonic agitation stabilizing treatment, continuous cleaning and collection of the powder, vacuum drying, ball-milling dispersion and the like. By means of the technologies, in a preparation course, the process method has the advantages that continuous industrial production can be achieved, equipment investment is small, product quality is stable, and the shapes and the particle sizes of products are controllable.
Description
Technical field
The present invention relates to a kind of method of producing extra-fine nickel powder, relate in particular to a kind of pipe reaction of being convenient to pipeline-cleaning and product-collecting and produce continuously extra-fine nickel powder method.
Background technology
Granularity is tiny owing to having for extra-fine nickel powder, specific area large, surface energy advantages of higher, and have broad application prospects in fields such as electronics, electric power, metallurgy, chemical industry, can be used as the different field such as electrocondution slurry, secondary cell, catalyst, carbide alloy, electrical alloy.
The industrialized preparing process that domestic extra-fine nickel powder is relatively commonly used mainly contains carbonyl nickel thermal decomposition method, using vaporization condensation process, electrolysis, argon shield machinery ball-milling method, liquid phase reduction; adopt diverse ways can make sub-micron and the micron-class superfine nickel powder from 0.1 micron to 3 microns, but product prepared by different processes present different powder morphology feature and particle size distribution.The present invention generally speaking should belong to the one improvement to existing liquid phase reduction, has solved some practical problems that exist in existing technique.
Existing extra-fine nickel powder industrialized preparing process has the following problem defect in other words: such as: 1. carbonyl nickel thermal decomposition method: there is strong toxicity, therefore production process is high to equipment requirement, industrialization investment is very large, and domestic production line is unstable, also there is security incident in the production of relevant producer; 2. using vaporization condensation process: domestic industry is done and to be obtained preferably extra-fine nickel powder production technology, but due to more than nickel will being heated to boiling point, therefore to equipment require highly, production cost is also difficult to reduce; 3. electrolysis: energy consumption is large, and the powder size of preparation is bigger than normal.Argon shield machinery ball-milling method: size distribution is inhomogeneous, and powder shape is irregular; 4. traditional liquid phase reduction: generally adopt still reaction, powder size lack of homogeneity, and be difficult to realize serialization production, between product batches, otherness is large.
The main technique method of domestic production sub-micron and nano level superfine nickel powder is plasma or laser atomization process at present, and high but this technique requires production equipment, equipment investment is large, thereby production cost is very high.Adopt liquid chemical method to prepare extra-fine nickel powder because production equipment is general, technical process is simple, is a process that can effectively reduce extra-fine nickel powder production cost.But adopt conventional reaction still reaction, again due to problems such as concentration gradients, have the shortcomings such as resultants in reaction process granularity is difficult to control evenly, the inconvenient dispersion of product.
Summary of the invention
In order to solve above technical problem, the present invention adopts pipe reaction, mainly to have made improved technology method for the production of popular response autoclave, adopting the method powder to be created in pipeline completes fast, follow-up under dispersant and ultrasonic compound action, reduce the powder particle tendency of growing up of reuniting.Activity due to superfines in pipe reaction process is very high, has the possibility of gathering at reacting pipe wall, even may occur the phenomenon of pipeline blockage when serious.
The process that the invention provides a kind of continuous production extra-fine nickel powder, is characterized in that, comprises following step:
Steps A: nickel sulfate hexahydrate is dissolved in deionized water, then adds dispersant, fully after stirring and dissolving, heating is preserved, and obtains solution A, is stored in the first storage tank and the 3rd storage tank; Dissolution of sodium hydroxide, in deionized water, is heated and is incubated after fully stirring, then adding hydrazine hydrate and NaBH
4, fully after stirring and dissolving, heat, obtain mixed solution B and be stored in the second storage tank and the 4th storage tank.
Step B: adopt flow pump respectively solution A and solution B to be delivered to ultrasonic intensified response entrance, open supersonic generator, by hybrid reaction in reaction raw materials input channel mixing reactor, reacted rear mixed solution and outputed in agitator.
Step C: the solution that contains nickel powder that has reacted rear generation flows in buffer storge vat, starts ultrasonic and opens and stir, and adds lauryl sodium sulfate, stabilization processes.
Step D: the mixed solution that completes ultrasonic stabilization processes is flow through to the conveyer belt with magnetic-adsorption effect, complete collection, the powder of collecting is dried to processing in vacuum drying chamber, then carry out ball milling dispersion treatment, obtain extra-fine nickel powder product.
Wherein, the first storage tank, the second storage tank, the 3rd storage tank and the 4th storage tank are the identical storage tanks of same capacity, and two cover aggregate-storing systems are used alternatingly, and ensure the continuity of producing.Conveyer belt with magnetic-adsorption effect adopts belt magnetic separator.
The serialization that the present invention adopts a kind of improved liquid phase reduction to realize extra-fine nickel powder is produced, and main process comprises the operations such as the continuous wash collection, vacuum drying, ball milling dispersion of raw material preparation, mass transport, ultrasonic enhancing pipe reaction, pipeline Rapid Cleaning, ultrasonic agitation stabilization processes, powder.Its advantage is, realizes the control to final products pattern, granularity by the adjusting of the proportioning to material composition and mass transport speed.Adopt ultrasonically enhanced pipe reaction to complete the reduction of nickel powder, and ensure the uniformity consistency of powder size.Adopt the method for pipeline Rapid Cleaning to carry out the unimpeded of realization response pipeline, ensure the industrial efficiency of serialization.Ultrasonically enhanced rapid stirring and appropriate adding of dispersant can effectively prevent the reunion between powder particle.Magnetic conveyor type continuous wash is collected the production efficiency that can improve product, and reduces powder in water and the dew of air is put the time, reduces the degree of oxidation of superfine powder.Finally adopt vacuum drying and ball milling to disperse to realize dehydration completely and the dispersion of product, reach the quality control requirement of corresponding product.
Preferably, in described steps A, nickel sulfate hexahydrate is dissolved in deionized water, then adds dispersant, fully after stirring and dissolving, be heated to 60-90 DEG C of preservation, obtain solution A, be stored in the first storage tank and the 3rd storage tank; Dissolution of sodium hydroxide, in deionized water, is heated to 60-90 DEG C of insulation after fully stirring, adds hydrazine hydrate and NaBH4, fully after stirring and dissolving, be heated to 60 DEG C-90 DEG C, obtain mixed solution B and be stored in the second storage tank and the 4th storage tank.
Preferably, in described steps A, the mass ratio of described hydrazine hydrate and NaBH4 is 1:5-5:1, and described dispersant adopts PVP.
Preferably, in described step B, the supersonic frequency of described supersonic generator is 30-50KHz, and power is 550-650W.
Preferably, in described step B, the environment temperature of pipeline is 60-90 DEG C.
Preferably, in described step B, the flow velocity of solution A and solution B is 0.5-5.0L/min.
Preferably, in described step C, ultrasonic frequency is 25-30KHz, and mixing speed is 200-1000 rev/min, and the time of stabilization processes is 1-3 hour.
Preferably, before described step C, when pipeline blockage or flow velocity reduce if occur, adopt acid solution and deionized water to carry out circulation flushing to pipeline.
Preferably, described acid solution adopts at least one in hydrochloric acid and nitric acid.
Preferably, in described step D, there is the situation of pipeline blockage for eliminating course of reaction, adopt deionized water and absolute ethyl alcohol to clean.
Preferably, in described step D, vacuum when vacuum drying is not higher than 100Pa, and temperature is 40-60 DEG C, heat preservation and dryness 10-12 hour.
The efficiency of actual that the present invention adopts special flushing of pipeline mechanism to clean to ensure this reaction pipeline to it, is conducive to the realization of the course of industrialization of this process.Simultaneously in the conveyor type mechanism of following adopted band magnetic-adsorption, powder is carried out collecting continuously the production efficiency that has also improved widely product, improved being exposed to for a long time in water or in air and the oxidation situation producing in extra-fine nickel powder wet production cleaning process.And the advantage such as the preparation process of technology that the present invention adopts can realize, and serialization industrial production, equipment investment are little, constant product quality, shape of product granularity are controlled.
Brief description of the drawings
Fig. 1 is implementing process flow chart of the present invention
Fig. 2 is globular powdered nickel ESEM picture prepared by the embodiment of the present invention 1
Fig. 3 is thorn shape nickel powder ESEM picture prepared by the embodiment of the present invention 2
Detailed description of the invention
Below in conjunction with accompanying drawing, preferably embodiment of the present invention is described in further detail:
Embodiment 1
As shown in Figure 1, this method comprises following flow process:
1) raw material is prepared: by 13Kg NiSO
4 . 6H
2o is dissolved in 100L deionized water, then adds 225g PVP, fully after stirring and dissolving, is heated to 60 DEG C, obtains solution A, is stored in the first storage tank and the 3rd storage tank; 5.2KgNaOH is dissolved in 96L deionized water, heating after fully stirring, in the time of 60 DEG C of water temperatures, adding 4L concentration is 50% hydrazine hydrate and 1.85Kg NaBH
4, fully after stirring and dissolving, be heated to 60 DEG C, obtain mixed solution B and be stored in the second storage tank and the 4th storage tank.
2) mass transport: by measuring pump, A and B two solution are pumped in reacting pipe, control respectively the flow velocity of two solution at 0.5L/min.
3) ultrasonic enhancing pipeline hybrid reaction: before reaction, reacting pipe environment temperature is warmed up to 60 DEG C, keeps constant temperature, before reaction starts, open ultrasonic wave, control ultrasonic frequency is 40KHz, and power is 600W, makes the fully reaction in pipeline of A and B two solution.
4) not timing pipeline is got express developed: observe the situation of change of flow pump, in the time that pipeline blockage or flow obviously reduce, switch in time pipe valve, stop mass transport, with circulation acid solution and deionized water rinsing pipeline, guarantee the unimpeded of pipeline.
5) ultrasonic agitation stabilization processes: the solution that contains nickel powder that has reacted rear generation flows in buffer storge vat, start ultrasonic and open and stir, control ultrasonic frequency is 28KHz, and mixing speed is 300 revs/min, add lauryl sodium sulfate (SDS) 100g, stabilization processes 2 hours.
6) the attached powder cleaning of the continuous magnetic of conveyor type and collection: the mixing material that completes stabilization processes is slowly imported on belt magnetic separator, nickel powder is drawn and upwards departs from deionized water solution by conveyer belt under magnetic-adsorption effect, deionized water, under Action of Gravity Field, enters in waste liquid pool.Then by receive nickel powder again deionized water for stirring clean, magnetic-adsorption, so in triplicate, to the pH value of mixed solution be 7.And then by receive nickel powder stirring and washing, magnetic-adsorption in absolute ethyl alcohol again, so in triplicate.
7) vacuum drying: will collect to such an extent that nickel powder carries out vacuum drying in vacuum drying chamber, vacuum is 100Pa, and temperature is 50 DEG C, heat preservation and dryness 12 hours.
8) ball milling disperses: adopt low speed ball milling after vacuum drying, to present powder fragmentation, the dispersion of slight reunion, prepare corresponding superfine spherical nickel powder.
Embodiment 2
1) raw material is prepared: by 13Kg NiSO
4 . 6H
2o is dissolved in 100L deionized water, then adds 225g PVP, fully after stirring and dissolving, is heated to 80 DEG C, obtain solution A, is stored in the first storage tank and the 3rd storage tank; 5.2Kg NaOH is dissolved in 77.5L deionized water, heating after fully stirring, in the time that water temperature approaches 80 DEG C soon, adding 22.5L concentration is 50% hydrazine hydrate, fully after stirring and dissolving, be heated to 80 DEG C, obtain mixed solution B and be stored in the second storage tank and the 4th storage tank.
2) mass transport: by measuring pump, A and B two solution are pumped in reacting pipe, control respectively the flow velocity of two solution at 1.5L/min.
3) ultrasonic enhancing pipeline hybrid reaction: before reaction, reacting pipe environment temperature is warmed up to 80 DEG C, keeps constant temperature, before reaction starts, open ultrasonic wave, control ultrasonic frequency is 50KHz, and power is 650W, makes the fully reaction in pipeline of A and B two solution.
4) not timing pipeline is got express developed: observe the situation of change of flow pump, in the time that pipeline blockage or flow obviously reduce, switch in time pipe valve, stop mass transport, with circulation acid solution and deionized water rinsing pipeline, guarantee the unimpeded of pipeline.
5) ultrasonic agitation stabilization processes: the solution that contains nickel powder that has reacted rear generation flows in buffer storge vat, start ultrasonic and open and stir, control ultrasonic frequency is 30KHz, and mixing speed is 250 revs/min, add lauryl sodium sulfate (SDS) 100g, stabilization processes 3 hours.
6) the attached powder cleaning of the continuous magnetic of conveyor type and collection: the mixing material that completes stabilization processes is slowly imported on belt magnetic separator, nickel powder is drawn and upwards departs from deionized water solution by conveyer belt at magneticaction, deionized water, under Action of Gravity Field, enters in waste liquid pool.Then by receive nickel powder again deionized water for stirring clean, magnetic-adsorption, so in triplicate, to the pH value of mixed solution be 7.And then by receive nickel powder stirring and washing, magnetic-adsorption in absolute ethyl alcohol again, so in triplicate.
7) vacuum drying: will collect to such an extent that nickel powder carries out vacuum drying in vacuum drying chamber, vacuum 80Pa, temperature is 60 DEG C, heat preservation and dryness 10 hours.
8) ball milling disperses: adopt low speed ball milling after vacuum drying, to present powder fragmentation, the dispersion of slight reunion, prepare corresponding ultra-fine thorn shape nickel powder.
The particle diameter of the nickel powder being obtained from Fig. 2 and 3, embodiment 1 and embodiment 2 is respectively 150 nanometers and 500 nanometers, and particle diameter is little, can reach even particle size distribution, and powder shape rule.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. a process of producing continuously extra-fine nickel powder, is characterized in that, comprises following step:
Steps A: nickel sulfate hexahydrate is dissolved in deionized water, then adds dispersant, fully after stirring and dissolving, heating is preserved, and obtains solution A, is stored in the first storage tank and the 3rd storage tank; Dissolution of sodium hydroxide, in deionized water, is heated and is incubated after fully stirring, then adding hydrazine hydrate or/and NaBH
4, fully after stirring and dissolving, heat, obtain mixed solution B and be stored in the second storage tank and the 4th storage tank;
Step B: adopt flow pump respectively solution A and solution B to be delivered to ultrasonic intensified response entrance, open supersonic generator, by hybrid reaction in reaction raw materials input channel mixing reactor, reacted rear mixed solution and outputed in agitator;
Step C: the solution that contains nickel powder that has reacted rear generation flows in buffer storge vat, starts ultrasonic and opens and stir, and adds stabilizing agent, carries out stabilization processes;
Step D: the mixed solution that completes ultrasonic stabilization processes is flow through to the conveyer belt with magnetic-adsorption effect, complete collection, carry out ball milling dispersion treatment after the powder of collecting is dried in vacuum drying chamber, obtain extra-fine nickel powder product.
2. the process of continuous production extra-fine nickel powder as claimed in claim 1, it is characterized in that, in described steps A, nickel sulfate hexahydrate is dissolved in deionized water, add again dispersant, fully after stirring and dissolving, be heated to 60-90 DEG C of preservation, obtain solution A, be stored in the first storage tank and the 3rd storage tank; Dissolution of sodium hydroxide, in deionized water, is heated to 60-90 DEG C of insulation after fully stirring, adds hydrazine hydrate and NaBH
4, fully after stirring and dissolving, be heated to 60 DEG C-90 DEG C, obtain mixed solution B and be stored in the second storage tank and the 4th storage tank.
3. the process of continuous production extra-fine nickel powder as claimed in claim 1, is characterized in that, in described steps A, described dispersant adopts PVP.
4. the process of continuous production extra-fine nickel powder as claimed in claim 1, is characterized in that, in described step D, described stabilizing agent adopts lauryl sodium sulfate.
5. the process of continuous production extra-fine nickel powder as claimed in claim 1, is characterized in that, in described step B, the supersonic frequency of described supersonic generator is 30-50KHz, and power is 550-650W.
6. the process of continuous production extra-fine nickel powder as claimed in claim 1, is characterized in that, in described step B, the environment temperature of pipeline is 60-90 DEG C.
7. the process of continuous production extra-fine nickel powder as claimed in claim 1, is characterized in that, in described step B, the flow velocity of solution A and solution B is 0.5-5.0L/min.
8. the process of continuous production extra-fine nickel powder as claimed in claim 1, is characterized in that, in described step C, ultrasonic frequency is 25-30KHz, and mixing speed is 200-1000 rev/min, and the time of stabilization processes is 1-3 hour.
9. the process of continuous production extra-fine nickel powder as claimed in claim 1, is characterized in that, before described step C, when pipeline blockage or flow velocity reduce if occur, adopts acid solution and deionized water to carry out circulation flushing to pipeline.
10. the process of continuous production extra-fine nickel powder as claimed in claim 1, is characterized in that, in described step D, vacuum when vacuum drying is not higher than 100Pa, and temperature is 40-60 DEG C, heat preservation and dryness 10-12 hour.
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| CN103894623B (en) * | 2014-03-19 | 2016-08-17 | 深圳航天科技创新研究院 | A kind of preparation method of antioxidant ultrafine nickel powder |
| JP6641632B2 (en) * | 2016-03-04 | 2020-02-05 | 住友金属鉱山株式会社 | Nickel powder manufacturing method |
| JP6819087B2 (en) * | 2016-06-21 | 2021-01-27 | 住友金属鉱山株式会社 | Nickel powder manufacturing method, nickel powder manufacturing equipment |
| CN108247077B (en) * | 2018-01-25 | 2021-01-08 | 深圳市中金岭南科技有限公司 | Method for preparing copper powder by micro-reaction |
| CN109663929B (en) * | 2019-01-24 | 2021-07-23 | 兰州石化职业技术学院 | Preparation method of regular nano gold particles |
| CN112358737B (en) * | 2020-11-05 | 2021-09-21 | 浙江迪邦化工有限公司 | Continuous production process of azo disperse dye with ester group |
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| US20060090601A1 (en) * | 2004-11-03 | 2006-05-04 | Goia Dan V | Polyol-based method for producing ultra-fine nickel powders |
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| CN101081364A (en) * | 2007-07-13 | 2007-12-05 | 北京工业大学 | Method for preparation of load type metallic catalyst and equipment thereof |
| CN101332515A (en) * | 2008-08-05 | 2008-12-31 | 中南大学 | Preparation method of fibrous iron-nickel alloy powder |
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