CN103962574A - Method for preparing porous nickel particles through nickel ions in hydrothermal hydrogen gas reduction waste water - Google Patents
Method for preparing porous nickel particles through nickel ions in hydrothermal hydrogen gas reduction waste water Download PDFInfo
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- CN103962574A CN103962574A CN201410182662.5A CN201410182662A CN103962574A CN 103962574 A CN103962574 A CN 103962574A CN 201410182662 A CN201410182662 A CN 201410182662A CN 103962574 A CN103962574 A CN 103962574A
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- nickel
- waste water
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Abstract
The invention discloses a method for preparing porous nickel particles through nickel ions in hydrothermal hydrogen gas reduction waste water. The method comprises the following steps that the waste water containing the nickel ions, ammonium sulfate, a nickel specie and ammonia water are added into a reaction kettle at room temperature, the reaction kettle is sealed and heated to the temperature ranging frame 80 DEG C to 180 DEG C, hydrogen gas with the pressure ranging frame 2.5 MPa to 5.5 MPa is led into the reaction kettle, the mixture is stirred, the reaction is carried out for 20 min to 120 min, the product is washed with alcohol and water, filtered and dried, and the porous nickel particles are obtained. According to the method for preparing the porous nickel particles through the nickel ions in the hydrothermal hydrogen gas reduction waste water, the hydrothermal hydrogen gas reduction technology is adopted, the nickel ions in the waste water are converted into the porous nickel particles, the reaction temperature is low, the conversion rate is high, and the reaction process is simple, economical and easy to control; the obtained nickel particles have the advantages of being porous, good in appearance and the like, the diameter of the particles ranges from 10 micrometers to 80 micrometers, and the size of the nickel nano-particles ranges from 500 nanometers to 900 nanometers.
Description
Technical field
The present invention relates to a kind of recovery and treatment method of heavy metal ions in wastewater, be specifically related to the method that nickel ion in a kind of hydro-thermal hydrogen reducing waste water is prepared nickel porous particulate.
Background technology
Along with economical and social fast development, many heavy-metal pollution things that suitability for industrialized production produces are discharged in the middle of rivers and soil, cause environmental pollution more and more serious.Wherein, nickeliferous ion waste water is the industrial wastewater that a kind of harm is larger, and it mainly comes from the enterprise of mineral industry, colored metallurgical industrial, metal processing, instrument and meter, plating, printing and dyeing, process hides and various application of nickel compounds.Research shows, heavy metal ion is difficult to natural degradation, can hide for a long time in soil and water, and enter human body with food chain, thus harm humans health.Therefore, the removal of heavy metals in industrial wastewater ion seems particularly important.
At present, the method for removing heavy metal ions in sewage mainly contains coprecipitation, ion-exchange, absorption method etc., and these methods exist treatment effect poor, and expense is higher, easily causes secondary pollution problems, is restricted in actual applications.In recent years, some new sorbing materials were applied to the processing of nickel-containing waste water, and as CNT, Graphene, biomembrane etc., but these material costs are higher.In short supply along with resource, not only require that effluent containing heavy metal ions treatment effect is good, cost is low, non-secondary pollution, also require heavy metal ion to recycle, in heavy metal wastewater thereby, contain more valuable heavy metal element, if the heavy metal in waste water is reclaimed, not only solve heavy metal wastewater thereby pollution problem, and also had certain economic benefit.Zhang Yongfeng etc. adopt complexing-ultrafiltration-electrolysis integrated technology to process heavy metal wastewater thereby, and the concentrate of ultrafiltration can pass through electrolytic recovery heavy metal, thereby realize the dual purpose of waste water recycling and heavy metal recovery.Reducing process is by add reducing agent in waste water, makes metal ion be reduced to metal, then adopts certain method to separate, and reducing process can be used for the recovery of metal ion.It is not high that existing recovery method reclaims transformation efficiency, and the control of course of reaction complicated difficult, so how nickel ion in waste water is reclaimed and obtained valuable heavy metal element by a kind of efficient method of simple economy, remains the problem of being badly in need of solution.
Summary of the invention
The technical problem solving: for the deficiencies in the prior art, the invention provides nickel ion in a kind of hydro-thermal hydrogen reducing waste water and prepare the method for nickel porous particulate, can not only realize the secondary conversion utilization of waste water, and course of reaction simply, easily controls and clean, reclaim conversion ratio high.
Technical scheme: in hydro-thermal hydrogen reducing waste water provided by the invention, nickel ion is prepared the method for nickel porous particulate, it comprises and is prepared as follows step: at room temperature, by waste water (containing 2.5molL
-1ni
2+), ammonium sulfate, (consumption is with Ni in waste water for nickel kind
2+amount and determine) and ammoniacal liquor (mass concentration is 28～30%) add in reactor, the mass ratio of waste water, ammonium sulfate, nickel kind and ammoniacal liquor is 100:66:14:15～70, Ni in nickel kind and waste water
2+mass ratio be 1:1, by reactor put into can temperature programming electric furnace, good seal, adopt nitrogen to get rid of the air in reactor, add electrothermal stove to 80～180 DEG C, pass into hydrogen 2.5～3.5MPa, stirring reaction 20～120 minutes, grey deposit in still is collected to washing, filters, then in vacuum drying chamber in 50 DEG C dry 4 hours, obtain nickel porous particulate.
As preferred version, the mass ratio of described waste water, ammonium sulfate, nickel kind and ammoniacal liquor is 100:66:0 ~ 15:22.5～45.
As preferred version, the mass ratio of described waste water, ammonium sulfate, nickel kind and ammoniacal liquor is 100:66:0 ~ 15:30～37.5.
In hydro-thermal hydrogen reducing waste water provided by the invention, nickel ion is prepared the method for nickel porous particulate, and reaction principle is as follows:
Ni
2++ nNH
3→Ni(NH
3)
n 2+(1)
2Ni + H
2→2Ni-H (2)
Ni(NH
3)
n 2++2Ni-H→3Ni + 2NH
4 ++(n-2)NH
3(3)
Beneficial effect: (1) the present invention adopts hydro-thermal hydrogen reducing technology, in closed system, under the regulation and control of ammoniacal liquor and seed, is converted into nickel porous particulate by nickel ion in waste water, and reaction temperature is low, and conversion ratio is high, and course of reaction simple economy is easily controlled.
(2) the nickel porous particulate that method of the present invention obtains, has the advantages such as porous, pattern are good, and its mean particle dia is about 10 ~ 80 microns, and the size of nano nickel particles is about 500 ~ 900 nanometers.
Brief description of the drawings
Fig. 1 is the X-ray powder diffraction spectrogram of the nickel porous particulate prepared of embodiment 1;
Fig. 2 is the stereoscan photograph that embodiment 1 uses nickel kind;
Fig. 3 is the low power stereoscan photograph of the nickel porous particulate prepared of embodiment 1;
Fig. 4 is the stereoscan photograph of the single nickel porous particulate prepared of embodiment 1;
Fig. 5 is the high power scanned photograph of the nickel porous particulate prepared of embodiment 1;
Fig. 6 is the stereoscan photograph of the nickel porous particulate cross section prepared of embodiment 1;
Fig. 7 is the graph of pore diameter distribution of the nickel porous particulate prepared of embodiment 1;
Fig. 8 is the hydrogen adsorption performance of the nickel porous particulate prepared of embodiment 1.
Detailed description of the invention
Embodiment 1
By waste water (Ni
2+amount concentration be 2.5mol/L), ammonium sulfate, nickel kind (size is about 700 nanometers) and ammoniacal liquor (mass concentration is 28 ~ 30%) is in mass ratio for 100:66:14:35 mixes, add in the stainless steel cauldron of 160 milliliters, by reactor put into can temperature programming electric furnace, good seal, adopt nitrogen to get rid of the air in reactor, treat that furnace temperature is raised to 180 DEG C from room temperature, pass into the hydrogen that pressure is 3.5MPa, react and naturally cool to room temperature after 60 minutes.Grey deposit in still is collected with distilled water and absolute ethanol washing, filtration, then in vacuum drying chamber in 50 DEG C dry 4 hours, obtain nickel porous particulate.
Adopt Japanese Rigaku D/max-
γa type x-ray powder diffraction instrument (XRD) carries out material phase analysis to the nickel particle obtaining.Fig. 1 is the X-ray powder diffraction spectrogram of the nickel porous particulate prepared of the present embodiment, and as seen from Figure 1, in x-ray diffraction spectra, 2 θ are at 10-80
othere are 3 stronger diffraction maximums, be positioned at 44.5 °, 51.8 ° and 76.4 °, correspond respectively to (111), (200) and (220) three crystal faces,, there is not other impurity peaks in the nickel (JCPDS card JCPDS 04-850) that is demarcated as face-centered cubic phase.
Fig. 2 is the stereoscan photograph that the present embodiment uses nickel kind, and result shows, nickel kind is the particle that size is about 700 nanometers.Fig. 3 is the low power stereoscan photograph of the nickel porous particulate prepared of the present embodiment, as seen from Figure 3, the nickel product that adopts the inventive method to obtain, its productive rate is higher, and pattern is even; Fig. 4 is the stereoscan photograph of the single nickel porous particulate prepared of embodiment 1, and as seen from Figure 4, it is cellular that nickel particle is, and its diameter is about 72 microns; Fig. 5 is the high power scanned photograph of the nickel porous particulate prepared of embodiment 1, and as seen from Figure 5, nickel particle is to be assembled by nano particle, and its nano particle diameter is about 570 nanometers.
Sample thin slice, by JEOL SM-09010 type cross section polishing instrument, uses argon ion laser to form sample treatment.Then, observe pattern, the particle size in sample cross section with ESEM (FESEM, JEOL JSM-6360).Fig. 6 is the stereoscan photograph of the nickel porous particulate cross section prepared of embodiment 1, and further visible nickel particle is assembled by a lot of nano particles, and has higher porosity, and the size of nano particle is consistent with Fig. 5.
By high-pressure mercury porosimeter (Micromeritics Autopore IV 9500), the hole information of nickel porous particulate is measured, measurement category is 0.1 to 60000psia.Test result shows always to enter mercury volume, total hole area and average cell size and is respectively 0.9561mL/g, 1.011m
2/ g and 3.7839 μ m.Fig. 7 is the graph of pore diameter distribution of the nickel porous particulate prepared of embodiment 1, and Fig. 7 shows, aperture mainly concentrates near 1.5 μ m and 26 μ m.
Under 398K and 0.1-10MPa, adopt the absorption property of the specially designed western water static capacity technical testing hydrogen of equipment.Fig. 8 is the hydrogen adsorption amount of the nickel porous particulate prepared of embodiment 1, and Fig. 7 shows, under 298K and 10MPa condition, the maximal absorptive capacity of nickel porous particle is about 0.46wt%.
Above result shows, by nickel ion in hydro-thermal hydrogen reducing technical finesse waste water, can not only process the nickel ion in waste water completely, can also obtain the nickel porous particulate of consistent appearance, size uniform and productive rate nearly 100%, and have good hydrogen adsorption performance.
Embodiment 2
Except waste water (Ni
2+amount concentration be 2.5mol/L), ammonium sulfate, nickel kind and ammoniacal liquor is in mass ratio for outside 100:66:14:15, preparation process is identical with embodiment 1.The Average Particle Diameters of the present embodiment gained nickel porous particulate is about 10 microns, nano nickel particles diameter and is about 500 nanometers, and productive rate is about 30%.
Embodiment 3
Except waste water (Ni
2+amount concentration be 2.5 mol/L), ammonium sulfate, nickel kind and ammoniacal liquor is in mass ratio for outside 100:66:14:22.5, preparation process is identical with embodiment 1.The Average Particle Diameters of the present embodiment gained nickel porous particulate is about 45 microns, nano nickel particles diameter and is about 540 nanometers, and productive rate is about 60%.
Embodiment 4
Except waste water (Ni
2+amount concentration be 2.5 mol/L), ammonium sulfate, nickel kind and ammoniacal liquor is in mass ratio for outside 100:66:14:70, preparation process is identical with embodiment 1.The Average Particle Diameters of the present embodiment gained nickel porous particulate is about 80 microns, nano nickel particles diameter and is about 620 nanometers, and productive rate is about 100%.
Embodiment 5
Except waste water (Ni
2+amount concentration be 2.5 mol/L), ammonium sulfate, nickel kind and ammoniacal liquor is in mass ratio for outside 100:66:14:30, preparation process is identical with embodiment 1.The Average Particle Diameters of the present embodiment gained nickel porous particulate is about 65 microns, nano nickel particles diameter and is about 560 nanometers, and productive rate is about 89%.
Embodiment 6
Except waste water (Ni
2+amount concentration be 2.5 mol/L), ammonium sulfate, nickel kind and ammoniacal liquor is in mass ratio for outside 100:66:14:37.5, preparation process is identical with embodiment 1.The Average Particle Diameters of the present embodiment gained nickel porous particulate is about 76 microns, nano nickel particles diameter and is about 570 nanometers, and productive rate is about 100%.
Embodiment 7
Except waste water (Ni
2+amount concentration be 2.5 mol/L), ammonium sulfate, nickel kind and ammoniacal liquor is in mass ratio for outside 100:66:14:45, preparation process is identical with embodiment 1.The Average Particle Diameters of the present embodiment gained multilevel hierarchy nickel particle is about 80 microns, nano nickel particles diameter and is about 580 nanometers, and productive rate is about 100%.
Embodiment 8
Except waste water (Ni
2+amount concentration be 2.5 mol/L), ammonium sulfate, nickel kind and ammoniacal liquor is 100:66:14:35 in mass ratio, the reaction time is outside 80 DEG C, preparation process is identical with embodiment 1.The Average Particle Diameters of the present embodiment gained nickel porous particulate is about 30 microns, nano nickel particles diameter and is about 900 nanometers, and productive rate is about 100%.
Embodiment 9
Except waste water (Ni
2+amount concentration be 2.5 mol/L), ammonium sulfate, nickel kind and ammoniacal liquor is 100:66:14:35 in mass ratio, the reaction time is outside 120 DEG C, preparation process is identical with embodiment 1.The Average Particle Diameters of the present embodiment gained nickel porous particulate is about 30 or 75 microns, nano nickel particles diameter and is about 600 or 900 nanometers, and productive rate is about 100%.
Embodiment 10
Except waste water (Ni
2+amount concentration be 2.5 mol/L), ammonium sulfate, nickel kind and ammoniacal liquor is 100:66:14:35 in mass ratio, the reaction time is outside 160 DEG C, preparation process is identical with embodiment 1.The Average Particle Diameters of the present embodiment gained nickel porous particulate is about 75 microns, nano nickel particles diameter and is about 600 nanometers, and productive rate is about 100%.
Claims (4)
1. in hydro-thermal hydrogen reducing waste water, nickel ion is prepared the method for nickel porous particulate, it is characterized in that preparation process is as follows: at room temperature, will contain 2.5molL
-1ni
2+waste water, ammonium sulfate, nickel kind and mass concentration be 28～30% ammoniacal liquor adds in reactor, the mass ratio of waste water, ammonium sulfate, nickel kind and ammoniacal liquor is 100:66:14:15～70, reactor is put into the electric furnace of temperature programming, good seal, adopt nitrogen to get rid of the air in reactor, add electrothermal stove to 80～180 DEG C, passing into pressure is 2.5～5.5MPa hydrogen, stirring reaction 20～120 minutes, grey deposit in still is collected to washing, filters, then in vacuum drying chamber in 50 DEG C dry 4 hours, obtain nickel porous particulate.
2. in hydro-thermal hydrogen reducing waste water according to claim 1, nickel ion is prepared the method for nickel porous particulate, it is characterized in that Ni in described nickel kind and waste water
2+mass ratio be 1:1.
3. in hydro-thermal hydrogen reducing waste water according to claim 1, nickel ion is prepared the method for nickel porous particulate, and the mass ratio that it is characterized in that described waste water, ammonium sulfate, nickel kind and ammoniacal liquor is 100:66:1 ~ 15:22.5～45.
4. in hydro-thermal hydrogen reducing waste water according to claim 1, nickel ion is prepared the method for nickel porous particulate, and the mass ratio that it is characterized in that described waste water, ammonium sulfate, nickel kind and ammoniacal liquor is 100:66:1 ~ 15:30～37.5.
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| CN201410182662.5A CN103962574B (en) | 2014-04-30 | 2014-04-30 | In hydro-thermal hydrogen reducing waste water, nickel ion prepares the method for nickel porous particulate |
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| CN201410182662.5A CN103962574B (en) | 2014-04-30 | 2014-04-30 | In hydro-thermal hydrogen reducing waste water, nickel ion prepares the method for nickel porous particulate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105618034A (en) * | 2014-11-24 | 2016-06-01 | 北京大学 | Supported ruthenium nanocluster based catalyst as well as preparation and application thereof |
| CN110743555A (en) * | 2019-10-08 | 2020-02-04 | 中国科学院兰州化学物理研究所 | Preparation method of nano porous metal nickel catalyst |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101209876A (en) * | 2007-12-25 | 2008-07-02 | 金川集团有限公司 | Method for processing wastewater containing carbonyl nickel |
| CN101381816A (en) * | 2008-01-25 | 2009-03-11 | 佛山市邦普镍钴技术有限公司 | Method and equipment for recovering cadmium and nickel from waste and old nickel-cadmium battery and preparing metal cadmium ingot and superfine nickel powder |
| CN101549920A (en) * | 2008-03-31 | 2009-10-07 | 邵琳 | Method for recovering nickel salts in nickel-electroplating waste water |
| CN101805831A (en) * | 2010-03-24 | 2010-08-18 | 埃梯星(厦门)电子科技有限公司 | Method for directly extracting nickel in alkaline chemical nickel-plating waste liquid |
| CN102134120A (en) * | 2011-02-25 | 2011-07-27 | 深圳市科之泉水处理科技有限公司 | Method for recovering precious metals in acidic waste liquid |
| JP2012197473A (en) * | 2011-03-18 | 2012-10-18 | Tohoku Univ | Method for synthesizing metal or alloy nanoparticle by supercritical hydrothermal reaction under reductive atmosphere |
-
2014
- 2014-04-30 CN CN201410182662.5A patent/CN103962574B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101209876A (en) * | 2007-12-25 | 2008-07-02 | 金川集团有限公司 | Method for processing wastewater containing carbonyl nickel |
| CN101381816A (en) * | 2008-01-25 | 2009-03-11 | 佛山市邦普镍钴技术有限公司 | Method and equipment for recovering cadmium and nickel from waste and old nickel-cadmium battery and preparing metal cadmium ingot and superfine nickel powder |
| CN101549920A (en) * | 2008-03-31 | 2009-10-07 | 邵琳 | Method for recovering nickel salts in nickel-electroplating waste water |
| CN101805831A (en) * | 2010-03-24 | 2010-08-18 | 埃梯星(厦门)电子科技有限公司 | Method for directly extracting nickel in alkaline chemical nickel-plating waste liquid |
| CN102134120A (en) * | 2011-02-25 | 2011-07-27 | 深圳市科之泉水处理科技有限公司 | Method for recovering precious metals in acidic waste liquid |
| JP2012197473A (en) * | 2011-03-18 | 2012-10-18 | Tohoku Univ | Method for synthesizing metal or alloy nanoparticle by supercritical hydrothermal reaction under reductive atmosphere |
Non-Patent Citations (2)
| Title |
|---|
| 李钒等: ""水热氢还原制备镍粉的动力学研究"", 《中国稀土学报》 * |
| 赵立新等: ""自催化还原法回收化学镀镍废液"", 《电镀与精饰》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105618034A (en) * | 2014-11-24 | 2016-06-01 | 北京大学 | Supported ruthenium nanocluster based catalyst as well as preparation and application thereof |
| CN110743555A (en) * | 2019-10-08 | 2020-02-04 | 中国科学院兰州化学物理研究所 | Preparation method of nano porous metal nickel catalyst |
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| CN103962574B (en) | 2016-04-13 |
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