CN105152388A - Advanced treatment and recovery method of nickel and cobalt production enterprise extraction raffinate wastewater - Google Patents
Advanced treatment and recovery method of nickel and cobalt production enterprise extraction raffinate wastewater Download PDFInfo
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- CN105152388A CN105152388A CN201510406950.9A CN201510406950A CN105152388A CN 105152388 A CN105152388 A CN 105152388A CN 201510406950 A CN201510406950 A CN 201510406950A CN 105152388 A CN105152388 A CN 105152388A
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- nickel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention provides an advanced treatment and recovery method of nickel and cobalt production enterprise extraction raffinate wastewater. The method comprises the following steps: 1, primarily settling extraction raffinate sewage, wherein the residual nickel and cobalt concentration is 1.0-5.0mg/l, and the residual organic matter concentration OiL is not greater than 20mg/l; 2, allowing the primarily settled extraction raffinate sewage to go through an adsorption column filled with active manganese dioxide or carrying out an adsorption reaction in a single-tank quantified intermittent manner or a multiple-groove parallel continuous stirring manner at a temperature of 25-50DEG C under a pH value of 6.0-8.5 for 20-40min according to a liquid (extraction raffinate sewage): solid (active manganese dioxide) ratio of 500:(1-5), and filtering after the adsorption ends to obtain filtrate water which is industrial sewage meeting standard reaching emission requirements; and 3, washing nickel and cobalt supported manganese dioxide slag powder filtered in step 2 by using 8.0-12.0% of an ammonia solution, eluting a nickel and cobalt backwash solution to recover nickel and cobalt, and rinsing eluted manganese dioxide to regenerate.
Description
Technical field
The present invention relates to a kind of chemical wastewater treatment technology, be a kind of method utilizing sorbing material, advanced treatment to reclaim raffinate sewage in nickel cobalt hydrometallurgy industry specifically, belong to the technical field of environmental improvement and resource recovery project.
Background technology
In nickel, cobalt hydrometallurgy production process, with P
507after extraction agent extracting and separating nickel cobalt in its raffinate water body still containing a small amount of nickel cobalt ion, if to this not in addition efficient recovery, not only cause the waste of the limited resources inevitable environment polluting periphery simultaneously after discharge; For this reason, the common process recovery method of relevant enterprise filters after nickel cobalt ion being precipitated as oxyhydroxide or sulfide precipitation with liquid caustic soda, lime or Sodium Sulphide, though this technique is simple, reliable, easy, nickel cobalt still containing about 1.0 ~ 5.0mg/l in the sewage so leached is difficult to thoroughly precipitate recovery, for reaching the pollution exhaust criteria of national regulation, most enterprise has to by other fresh water body additional for dilution, thus causes the waste of fresh water and the expansion of the industrial sewage water yield.
Summary of the invention
The invention provides and a kind ofly utilize physical adsorption principle, reclaim first heavy nickel cobalt with active material advanced treatment after raffinate sewage, the waste water treatment process of the complete qualified discharge of water quality that reprocessing is crossed, this technological operation is easy, flow process is simple and direct, efficiency is high, effective.
The technical solution used in the present invention is: a kind of nickel, the advanced treatment recovery method of cobalt manufacturing enterprise raffinate waste water, it is characterized in that: adopt device to comprise first, two adsorbing agitation tanks, ammonia solution dosing vessel, type washing trough, filtration pump and filtration unit, first, agitator is equipped with in two adsorbing agitation tanks, first, between two adsorbing agitation tanks, the catheter of band drain control valve is communicated with, first adsorbing agitation tank is provided with sewage fluid inlet and solid material adds entrance, steam heating tube is connected on first adsorbing agitation tank, second adsorbing agitation tank is communicated with filtration unit through filter pump, described ammonia solution dosing vessel, type washing trough are communicated with filtration unit through control valve respectively, recycling step:
Raffinate sewage primary sedimentation: residual nickel cobalt concentration 1.0 ~ 5.0mg/l, organic concentration OiL≤20mg/l after raffinate sewage primary sedimentation;
Nickel cobalt adsorbs: just heavy rear raffinate Sewage water temp 25 DEG C ~ 50 DEG C, pH value 6.0 ~ 8.5 times, by be filled with activated manganese dioxide adsorption column or with the quantitative intermittent type of single groove or with the absorption reaction of multiple-grooved continuously stirring mode arranged side by side, the liquid-solid ratio of raffinate sewage and active manganese dioxide powder is 500:(1 ~ 5), adsorption time 20 ~ 40min, absorption terminates rear filtration, and filtrate water is can the industrial sewage of qualified discharge;
Nickel and cobalt recovery: the ammonia solution washing step (2) with 8.0 ~ 12.0% filters the Manganse Dioxide granulated slag that back loading has nickel cobalt, the backwash liquor of eluting nickel cobalt reclaims nickel cobalt, the Manganse Dioxide rinsing regeneration after wash-out.
Further, the water body nickel cobalt of described filtrate water remains Ni≤0.5mg/l, Co≤1.0mg/l.
Further, described second adsorbing agitation tank is provided with thief hole.
Further, described filtration unit is filter-pressing device.
Again further, discharge outlet is provided with bottom first and second adsorbing agitation tank described.
the present invention has the following advantages:
1. technique is simple, and operating process is easy, processing efficiency is high, labor strength is little, and the cost that puts into operation is low;
2. adopt physical adsorption principle at the first adsorbing agitation tank, other assistant medicament need not be added in treating processes, avoid the secondary pollution that water body and environment are caused; The oxidation characteristic of activated manganese dioxide has synergistic function to COD, BOD of reducing water quality while Adsorption of Heavy Metal Ions; Sewage nickel concentration after process can be less than 0.5mg/l, cobalt concentration can be less than 1.0mg/l, meets discharging standards, good waste water treatment effect; Reclaimed by the backwash liquor of ammonia solution eluting nickel cobalt and obtain comparatively pure, the nickel of high-quality, cobalt metal-salt, metal recovery degree is high.Adopt physical adsorption principle, other assistant medicament need not be added in treating processes, avoid the secondary pollution that water body and environment are caused; The oxidation characteristic of activated manganese dioxide has synergistic function to COD, BOD of reducing water quality while Adsorption of Heavy Metal Ions;
3. process after sewage nickel concentration can be less than 0.5mg/l, cobalt concentration can be less than 1.0mg/l, meet discharging standards, good waste water treatment effect.
Accompanying drawing explanation
fig. 1 is that the present invention adopts apparatus structure schematic diagram.
in figure:first adsorbing agitation tank 1, second adsorbing agitation tank 2, steam heating tube 3, sewage fluid inlet 4, Gu material adds entrance 5, catheter 6, ammonia solution dosing vessel 7, type washing trough 8, filtration pump 9, filtration unit 10, drain control valve 11, agitator 12.
concrete case study on implementation
shown in Fig. 1:the advanced treatment retrieving arrangement of a kind of nickel, cobalt manufacturing enterprise raffinate waste water comprise first and second adsorbing agitation tank 1,2, ammonia solution dosing vessel 7, type washing trough 8, filtration pump 9 and filtration unit 10, agitator 12 is equipped with in first and second adsorbing agitation tank, between first and second adsorbing agitation tank, the catheter 6 of band drain control valve 11 is communicated with, first adsorbing agitation tank 1 is provided with sewage fluid inlet 4 and solid material adds entrance 5, connect steam heating tube 3, second adsorbing agitation tank 2 on first adsorbing agitation tank 1 and be communicated with filtration unit 10 through filter pump 9; Ammonia solution dosing vessel 7, type washing trough 8 are communicated with filtration unit 10 through control valve respectively.
The further improvement of above-described embodiment, the second adsorbing agitation tank is provided with thief hole.
The further improvement of above-described embodiment, filtration unit is filter-pressing device.
The further improvement of above-described embodiment, is provided with discharge outlet bottom first and second adsorbing agitation tank.
Recovery method of the present invention is as follows:
embodiment 1
Raffinate sewage containing Ni1.6mg/l, Co3.4mg/l, pH6.25 after first heavy nickel cobalt is added in adsorbing agitation tank, adding when being heated to 26 DEG C with sorbing material mass ratio is the active manganese dioxide powder body of 450:1 ratio, whip attachment is after 20 minutes, and filtration records residue in water nickel cobalt and is respectively: Ni-0.31mg/l, Co-0.78mg/l;
embodiment 2
Raffinate sewage containing Ni2.3mg/l, Co3.7mg/l, pH7.19 after first heavy nickel cobalt is added in adsorbing agitation tank, adding when being heated to 48 DEG C with sorbing material mass ratio is the active manganese dioxide powder body of 200:1 ratio, whip attachment is after 30 minutes, and filtration records residue in water nickel cobalt and is respectively: Ni-0.16mg/l, Co-0.62mg/l;
embodiment 3
Raffinate sewage containing Ni5.2mg/l, Co6.9mg/l, pH7.83 after first heavy nickel cobalt is added in adsorbing agitation tank, adding when being heated to 31 DEG C with sorbing material mass ratio is the active manganese dioxide powder body of 500:1 ratio, whip attachment is after 22 minutes, and filtration records residue in water nickel cobalt and is respectively: Ni-0.44mg/l, Co-0.93mg/l;
embodiment 4
Raffinate sewage containing Ni4.6mg/l, Co6.1mg/l, pH8.37 after first heavy nickel cobalt is added in adsorbing agitation tank, adding when being heated to 29 DEG C with sorbing material mass ratio is the active manganese dioxide powder body of 150:1 ratio, whip attachment is after 25 minutes, and filtration records residue in water nickel cobalt and is respectively: Ni-0.27mg/l, Co-0.59mg/l;
embodiment 5
Raffinate sewage containing Ni3.7mg/l, Co5.2mg/l, pH6.92 after first heavy nickel cobalt is added in adsorbing agitation tank, adding when being heated to 25 DEG C with sorbing material mass ratio is the active manganese dioxide powder body of 500:1 ratio, whip attachment is after 18 minutes, and filtration records residue in water nickel cobalt and is respectively: Ni-0.41mg/l, Co-0.76mg/l;
the filter residue of above-described embodimentload have the Manganse Dioxide granulated slag of nickel cobalt with 8.0 ~ 12.0% ammonia solution washing, the backwash liquor of eluting nickel cobalt reclaims nickel cobalt, the Manganse Dioxide rinsing regeneration after wash-out.
Claims (5)
1. the advanced treatment recovery method of a nickel, cobalt manufacturing enterprise raffinate waste water, it is characterized in that: adopt device to comprise first and second adsorbing agitation tank, ammonia solution dosing vessel, type washing trough, filtration pump and filtration unit, agitator is equipped with in first and second adsorbing agitation tank, between first and second adsorbing agitation tank, the catheter of band drain control valve is communicated with, first adsorbing agitation tank is provided with sewage fluid inlet and solid material adds entrance, connect steam heating tube on first adsorbing agitation tank, the second adsorbing agitation tank is communicated with filtration unit through filter pump; Described ammonia solution dosing vessel, type washing trough are communicated with filtration unit through control valve respectively; Recycling step:
Raffinate sewage primary sedimentation: residual nickel cobalt concentration 1.0 ~ 5.0mg/l, organic concentration OiL≤20mg/l after raffinate sewage primary sedimentation;
Nickel cobalt adsorbs: just heavy rear raffinate Sewage water temp 25 DEG C ~ 50 DEG C, pH value 6.0 ~ 8.5 times, by be filled with activated manganese dioxide adsorption column or with the quantitative intermittent type of single groove or with the absorption reaction of multiple-grooved continuously stirring mode arranged side by side, the liquid-solid ratio of raffinate sewage and active manganese dioxide powder is 500:(1 ~ 5), adsorption time 20 ~ 40min, absorption terminates rear filtration, and filtrate water is can the industrial sewage of qualified discharge;
Nickel and cobalt recovery: the ammonia solution washing step (2) with 8.0 ~ 12.0% filters the Manganse Dioxide granulated slag that back loading has nickel cobalt, the backwash liquor of eluting nickel cobalt reclaims nickel cobalt, the Manganse Dioxide rinsing regeneration after wash-out.
2. the advanced treatment recovery method of nickel according to claim 1, cobalt manufacturing enterprise raffinate waste water, is characterized in that: the water body nickel cobalt of described filtrate water remains Ni≤0.5mg/l, Co≤1.0mg/l.
3. the advanced treatment recovery method of nickel according to claim 1, cobalt manufacturing enterprise raffinate waste water, is characterized in that: described second adsorbing agitation tank is provided with thief hole.
4. the advanced treatment recovery method of nickel according to claim 1, cobalt manufacturing enterprise raffinate waste water, is characterized in that: described filtration unit is filter-pressing device.
5. the advanced treatment recovery method of nickel according to claim 1, cobalt manufacturing enterprise raffinate waste water, is characterized in that: be provided with discharge outlet bottom first and second adsorbing agitation tank described.
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| CN201510406950.9A CN105152388A (en) | 2015-07-13 | 2015-07-13 | Advanced treatment and recovery method of nickel and cobalt production enterprise extraction raffinate wastewater |
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| CN201510406950.9A CN105152388A (en) | 2015-07-13 | 2015-07-13 | Advanced treatment and recovery method of nickel and cobalt production enterprise extraction raffinate wastewater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106893874A (en) * | 2017-02-21 | 2017-06-27 | 中南大学 | A kind of method that nickel is reclaimed in the nickel-containing waste water from ammonia |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103638905A (en) * | 2013-11-28 | 2014-03-19 | 沈阳化工大学 | Method for adsorbing heavy metals with tartaric acid intercalated hydrotalcite |
| CN104692579A (en) * | 2015-02-16 | 2015-06-10 | 桂林奥尼斯特节能环保科技有限责任公司 | Advanced recycling method for wastewater generated in making acid by using smelting flue gas |
| CN104692561A (en) * | 2015-03-11 | 2015-06-10 | 北京矿冶研究总院 | Advanced treatment method of thallium-containing wastewater |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103638905A (en) * | 2013-11-28 | 2014-03-19 | 沈阳化工大学 | Method for adsorbing heavy metals with tartaric acid intercalated hydrotalcite |
| CN104692579A (en) * | 2015-02-16 | 2015-06-10 | 桂林奥尼斯特节能环保科技有限责任公司 | Advanced recycling method for wastewater generated in making acid by using smelting flue gas |
| CN104692561A (en) * | 2015-03-11 | 2015-06-10 | 北京矿冶研究总院 | Advanced treatment method of thallium-containing wastewater |
Non-Patent Citations (1)
| Title |
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| 颜妮: "GNS/MnO2吸附剂去除废水中重金属离子的实验研究", 《哈尔滨工程大学工学硕士学位论文》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106893874A (en) * | 2017-02-21 | 2017-06-27 | 中南大学 | A kind of method that nickel is reclaimed in the nickel-containing waste water from ammonia |
| CN106893874B (en) * | 2017-02-21 | 2018-01-05 | 中南大学 | A kind of method that nickel is reclaimed in the nickel-containing waste water from ammonia |
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