CN109897955A - A kind of method of nickel sulfate solution deep purifying - Google Patents
A kind of method of nickel sulfate solution deep purifying Download PDFInfo
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- CN109897955A CN109897955A CN201910310382.0A CN201910310382A CN109897955A CN 109897955 A CN109897955 A CN 109897955A CN 201910310382 A CN201910310382 A CN 201910310382A CN 109897955 A CN109897955 A CN 109897955A
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- nickel sulfate
- sulfate solution
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Abstract
The invention belongs to nonferrous metallurgy complicated ingredient solution deep purification removing impurities and purification technique fields, are related to a kind of method of nickel sulfate solution deep purifying, comprising the following steps: S1) nickel sulfate solution vulcanization removing impurities；S2 liquid Strong oxdiative removing impurities after) vulcanizing；S3) oxidated solution removes zinc.It has selected hydrogen sulfide and ozone is deep impurity-removing reagent, and the removing process of iron, cobalt, calcium, magnesium addition is merged into a step by three steps, process flow is simplified, admirably realize the deep removal of copper in nickel sulfate solution, arsenic, antimony, bismuth, zinc, iron, cobalt, lead, calcium, magnesium addition element, traditional handicraft deficiency present in deep purifying complicated ingredient nickel sulfate solution is compensated for, the mass ratio M of nickel and impurity in the purified nickel sulfate solution of gainedNickel: m > 10000:1 creates necessary condition therefrom to extract and preparing high purity nickel salt product.
Description
Technical field
The invention belongs to nonferrous metallurgy complicated ingredient solution deep purification removing impurities and purification technique fields, and in particular to a kind of
The method of nickel sulfate solution deep purifying.
Background technique
In the purification and purifying industrial work of nickel salt, usually using the nickel sulfate solution of complicated component as raw material, nickel sulfate solution
In common impurity metallic elements include copper, arsenic, antimony, bismuth, zinc, iron, cobalt, lead, calcium, magnesium etc., so the purification and purification of nickel salt
Technology involved in industry is mainly the deep removal technology of Determination of Multi-Impurities in nickel salt solution；
The researcher of metallurgy industry had more exploration, more classical process route to nickel sulfate solution purification and impurity removal technique
For " air oxidation is except iron-→ black nickel oxidation except cobalt-→ sodium fluoride removing calcium and magnesium-→ P507 extracts copper removal zinc ", which can not
Arsenic, antimony, bismuth in nickel sulfate solution is removed in depth, and it divides the removing of iron, cobalt, calcium, magnesium in solution to three Duan Jinhang, technique stream
Journey is long, and it is strong oxidizer that black nickel, which selects black nickel except cobalt, and the self-sufficiency of black nickel is only applicable to smelting enterprise larger, that technique is complete
Industry is not optimal selection to small business；
Therefore, for prior art in nickel sulfate solution is removed in depth existing deficiency during plurality of impurities, develop one kind
The method of nickel sulfate solution deep purifying novel, suitable for complicated component is meaningful.
Summary of the invention
For the deficiency for making up existing nickel sulfate solution deep purifying impurity removal process, the purpose of the present invention is to provide a kind of sulphur
The method of sour nickel solution deep purifying, this method process flow is short, good impurity removing effect, be able to achieve copper in nickel sulfate solution, arsenic,
The deep removal of the impurity elements such as antimony, bismuth, zinc, iron, cobalt, lead, calcium, magnesium obtains clean nickel sulfate solution, therefrom to extract system
Standby high purity nickel salt product creates necessary condition.
To achieve the above object, of the present invention the specific scheme is that a kind of method of nickel sulfate solution deep purifying,
The following steps are included:
1) nickel sulfate solution vulcanizes removing impurities: using hydrogen sulfide gas as vulcanizing agent, carrying out sulphur to nickel sulfate solution under an increased pressure
Change removing impurities, copper therein, arsenic, bismuth and part antimony, lead etc. is removed in depth in prime element, filtering, liquid and vulcanized slag after being vulcanized；
2) liquid Strong oxdiative removing impurities after vulcanizing: sodium hydroxide solution is added in liquid after to vulcanization obtained by step 1), controls to adjust pH value, presses
NaF is added in ratio, is passed through ozone after being heated to certain temperature, and iron therein, cobalt, antimony, lead, calcium, magnesium is removed in depth, and reaction terminates
After filter, obtain oxidated solution and oxidizing slag；
3) oxidated solution removes zinc: using D2EHPA as extractant, using centrifugal extracting process processing step 2) gained oxidated solution, it is deep
Degree removes zinc therein, obtains the nickel sulfate solution of deep purifying；
According to the embodiment of the present disclosure, the S1) described in nickel sulfate solution be that concentration is greater than 90g/L, and in solution nickel concentration with
The ratio between the total concentration of other impurities metal M(nickel g/L): m(impurity g/L)>=6:1.
According to the embodiment of the present disclosure, the S1) in nickel sulfate solution vulcanization removing impurities using hydrogen sulfide gas as vulcanizing agent, normal
It is carried out under temperature, pressurized conditions, 0.10~0.14kg/m of concentration of hydrogen sulfide-3, 10 ± 1Kpa of reaction pressure, the reaction time 10~
30min。
According to the embodiment of the present disclosure, oxidant described in the S2 is ozone；The auxiliary additive is sodium fluoride.
According to the embodiment of the present disclosure, it is 4.5~6.0 that reaction process, which controls PH, and sodium fluoride is by molar ratio (Ca in solution2++
Mg2+): NaF=1:3 addition, 80~90 DEG C of reaction temperature, the reaction time 6~8 hours；10~15mg/L of ozone concentration used, often
It is 1:6 that minute ozone, which is passed through volume and reaction solution volume ratio, and after being passed through ozone 30min, solution oxide current potential is greater than 300mV.
According to the embodiment of the present disclosure, the S3) in extractant used be D2EHPA, control extractant concentration 15~20%,
Saponification rate 65~70% compares O/A=1:4, three stage countercurrents.
According to the embodiment of the present disclosure, in step s 2, filter type is secondary filter, filter sizes≤3 μm.
The beneficial effects of the present invention are: the present invention is using " hydrogen sulfide vulcanization removal of impurities --- ozone oxidation removal of impurities --- extraction
Remove zinc " be trunk process flow processes composition complexity nickel sulfate solution, selected hydrogen sulfide and ozone for deep impurity-removing
Reagent, and the removing process of iron, cobalt, calcium, magnesium addition is merged into a step by three steps, process flow has been simplified, has admirably been realized
The deep removal of copper, arsenic, antimony, bismuth, zinc, iron, cobalt, lead, calcium, magnesium addition element, compensates for traditional handicraft in nickel sulfate solution
The deficiency present in deep purifying complicated ingredient nickel sulfate solution, the matter of nickel and impurity in the purified nickel sulfate solution of gained
Amount compares MNickel: m > 10000:1 creates necessary condition therefrom to extract and preparing high purity nickel salt product.
Detailed description of the invention
Fig. 1 is a kind of process flow chart of the method for nickel sulfate solution deep purifying of the present invention.
Specific embodiment
Technical scheme is described further combined with specific embodiments below.
As shown in Figure 1, a kind of method of nickel sulfate solution deep purifying of the present invention, comprising the following steps:
S1) nickel sulfate solution vulcanize removing impurities: by vulcanizing agent be added nickel sulfate solution in, under an increased pressure to nickel sulfate solution into
Row vulcanization removing impurities, is removed in depth copper, arsenic, bismuth and part antimony therein, lead impurity element, filtering, liquid and vulcanization after being vulcanized
Slag；
S2 liquid Strong oxdiative removing impurities after) vulcanizing: sodium hydroxide solution is added in liquid after to vulcanization obtained by S1), adjusts pH value, leads to after heating
Enter oxidant and auxiliary additive, control oxidation reaction current potential, iron therein, cobalt, antimony, lead, calcium, magnesium, reaction knot is removed in depth
It is filtered after beam, obtains oxidated solution and oxidizing slag；
S3) oxidated solution removes zinc: extractant is added, using oxidated solution obtained by centrifugal extracting process processing step S2, depth is de-
Except zinc therein, the nickel sulfate solution of deep purifying is obtained.
According to the embodiment of the present disclosure, the S1) described in nickel sulfate solution be that concentration is greater than 90g/L, and nickel is dense in solution
The ratio between degree and the total concentration of other impurities metal M(nickel g/L): m(impurity g/L)>=6:1.
According to the embodiment of the present disclosure, the S1) in nickel sulfate solution vulcanization removing impurities using hydrogen sulfide gas as vulcanizing agent, normal
It is carried out under temperature, pressurized conditions, 0.10~0.14kg/m of concentration of hydrogen sulfide-3, reaction pressure 10Kpa, reaction time 10min.
According to the embodiment of the present disclosure, liquid enhanced oxidation removing impurities oxidant is ozone after vulcanization, is auxiliary addition with sodium fluoride
Agent.
According to the embodiment of the present disclosure, reaction process control PH is 4.5~6.0 in the S2, and the oxidizing potential is greater than
300mV, 80~90 DEG C of reaction temperature, the reaction time 6~8 hours.
According to the embodiment of the present disclosure, the additional amount of the sodium fluoride is by molar ratio (Ca in reaction solution2++Mg2+): NaF
=1:3；10~15mg/L of ozone concentration used, ozone per minute is passed through volume and reaction solution volume ratio is 1:6.
According to the embodiment of the present disclosure, the S3) in extractant used be D2EHPA, control extractant mass concentration 15~
20%, saponification rate 65~70% compares O/A=1:4, three stage countercurrents.
According to the embodiment of the present disclosure, in step s 2, filter type is secondary filter, filter sizes≤3 μm.
Examples 1 to 3
Three groups of experiments are carried out according to above-mentioned steps, the corresponding experiment 1 of embodiment 1, embodiment 2 is corresponding to test 2, and embodiment 3 is corresponding real
3 are tested, every group of experiment parameter is as shown in table 1；
1 experiment parameter control table of table
It is as shown in table 2 to test nickel sulfate solution ingredient used
2 nickel sulfate solution component list g/L of table
It is as shown in table 3 to vulcanize removing impurities experimental result
Liquid component list g/L after table 3 vulcanizes
4 vulcanized slag component list % of table
5 vulcanized slag component list % of table
With hydrogen sulfide vulcanizing agent, the impurity in nickel sulfate solution is removed under 10Kpa pressure condition, copper, arsenic, bismuth can be removed to
For 0.005g/L hereinafter, antimony, lead can be removed to 0.02g/L, nickel direct yield is greater than 99.0%；
Strong oxdiative removing impurities is carried out to liquid after vulcanization, the experimental results are shown inthe following table:
6 oxidated solution component list g/L of table
7 oxidizing slag component list % of table
8 oxidizing slag component list % of table
Using ozone as strong oxidizer, while adding sodium fluoride, after vulcanization in liquid iron, cobalt, antimony, lead can be removed to 0.005g/L with
Under, removal efficiency is greater than 99.9%, and magnesium can be removed to 0.005g/L, and calcium can be removed to 0.008g/L, and removal efficiency is greater than 97%, and nickel is straight
Yield is greater than 97%；
Using D2EHPA as extractant, extraction is carried out except zinc, experimental result such as following table institute to oxidated solution using centrifugal extracting process
Show:
Nickel sulfate solution component list after table 9 purifies
Using D2EHPA as extractant, extraction is carried out except zinc to oxidated solution using centrifugal extracting process, controls extractant concentration
15%, saponification rate 70%, three stage countercurrents, zinc can be removed to 0.005g/L hereinafter, removal efficiency is greater than 99.9% in solution, and nickel is directly received
Rate is greater than 97%；
The vulcanized slag recycles copper arsenic；
The oxidizing slag recycles nickel；
Nickel sulfate solution extraction prepares high purity nickel salt product after gained purification；
Final statement, the scope of the present invention are not limited thereto, and are subject to according to the technical scheme of the invention and its inventive conception
Equivalent substitution or change should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of method of nickel sulfate solution deep purifying, which is characterized in that method includes the following steps:
S1) nickel sulfate solution vulcanize removing impurities: by vulcanizing agent be added nickel sulfate solution in, under an increased pressure to nickel sulfate solution into
Row vulcanization removing impurities, is removed in depth copper, arsenic and bismuth therein；Part antimony and lead impurity element, filtering, liquid and vulcanization after being vulcanized
Slag；
S2 liquid Strong oxdiative removing impurities after) vulcanizing: after to vulcanization obtained by S1) liquid be added sodium hydroxide solution to the pH value of liquid after vulcanization into
Row adjustment, is passed through oxidant and auxiliary additive after heating, control oxidation reaction current potential, be removed in depth iron therein, cobalt, antimony,
Calcium, magnesium and remaining lead, filter after reaction, obtain oxidated solution and oxidizing slag；
S3) oxidated solution removes zinc: extractant is added, using oxidated solution obtained by centrifugal extracting process processing step S2, depth is de-
Except zinc therein, the nickel sulfate solution of deep purifying is obtained.
2. the method for nickel sulfate solution deep purifying according to claim 1, which is characterized in that the S1) described in sulphur
The concentration of sour nickel solution is greater than 90g/L, and the ratio between total concentration of nickel concentration and foreign metal M in solution(nickel g/L): m(impurity g/L)>=6:
1。
3. the method for nickel sulfate solution deep purifying according to claim 1, which is characterized in that the S1) in nickel sulfate
Solution vulcanizes removing impurities using hydrogen sulfide as vulcanizing agent, carries out under room temperature, pressurized conditions, 10 ± 1Kpa of reaction pressure, the reaction time
10~30min.
4. the method for nickel sulfate solution deep purifying according to claim 1, which is characterized in that reaction process in the S2
Control PH be 4.5~6.0, the oxidizing potential be greater than 300mV, 80~90 DEG C of reaction temperature, the reaction time 6~8 hours.
5. the method for nickel sulfate solution deep purifying according to claim 1, which is characterized in that the oxidant is smelly
Oxygen；The auxiliary additive is sodium fluoride.
6. the method for nickel sulfate solution deep purifying according to claim 5, which is characterized in that the addition of the sodium fluoride
Amount is by molar ratio (Ca in reaction solution2++Mg2+): NaF=1:3；10~15mg/L of ozone concentration used, ozone per minute are logical
Enter volume and reaction solution volume ratio is 1:6.
7. the method for nickel sulfate solution deep purifying according to claim 1, which is characterized in that the S3) in extraction used
Taking agent is D2EHPA, and control extractant mass concentration is 15~20%, and saponification rate 65~70% compares O/A=1:4, and three-level is inverse
Stream.
8. the method for nickel sulfate solution deep purifying according to claim 1, which is characterized in that in the step S2, mistake
Filter mode is secondary filter, filter sizes≤3 μm.
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Cited By (5)
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| CN112481501A (en) * | 2020-11-12 | 2021-03-12 | 阳谷祥光铜业有限公司 | Method for preparing nickel powder by using decoppering final solution |
| CN113512649A (en) * | 2021-05-27 | 2021-10-19 | 金川集团股份有限公司 | Production method for realizing nickel-cobalt separation by utilizing ozone under mixed acid system |
| CN113528818A (en) * | 2021-06-22 | 2021-10-22 | 江门市长优实业有限公司 | Method for removing impurities from nickel sulfate solution |
| CN114737222A (en) * | 2022-04-27 | 2022-07-12 | 金川集团股份有限公司 | Process for deeply removing copper, arsenic and lead in nickel electrolysis mixed acid system anolyte |
| CN114752782A (en) * | 2022-04-29 | 2022-07-15 | 紫金铜业有限公司 | Process suitable for refining and impurity removing of low-calcium magnesium crude nickel sulfate |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112481501A (en) * | 2020-11-12 | 2021-03-12 | 阳谷祥光铜业有限公司 | Method for preparing nickel powder by using decoppering final solution |
| CN112481501B (en) * | 2020-11-12 | 2022-09-27 | 阳谷祥光铜业有限公司 | Method for preparing nickel powder by using decoppering final solution |
| CN113512649A (en) * | 2021-05-27 | 2021-10-19 | 金川集团股份有限公司 | Production method for realizing nickel-cobalt separation by utilizing ozone under mixed acid system |
| CN113528818A (en) * | 2021-06-22 | 2021-10-22 | 江门市长优实业有限公司 | Method for removing impurities from nickel sulfate solution |
| CN113528818B (en) * | 2021-06-22 | 2022-11-29 | 江门市长优实业有限公司 | Method for removing impurities from nickel sulfate solution |
| CN114737222A (en) * | 2022-04-27 | 2022-07-12 | 金川集团股份有限公司 | Process for deeply removing copper, arsenic and lead in nickel electrolysis mixed acid system anolyte |
| CN114752782A (en) * | 2022-04-29 | 2022-07-15 | 紫金铜业有限公司 | Process suitable for refining and impurity removing of low-calcium magnesium crude nickel sulfate |
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Address after: 330096 No. 15 Metallurgical Avenue, Guixi City, Yingtan City, Jiangxi Province Applicant after: Jiangxi Copper Co., Ltd. Address before: No. 7666 high tech Zone Chang East Road 330096 Jiangxi city of Nanchang Province Applicant before: Jiangxi Copper Co., Ltd. |
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