CN106315731A - Method for producing nickel oxide from nickel-plating wastewater - Google Patents
Method for producing nickel oxide from nickel-plating wastewater Download PDFInfo
- Publication number
- CN106315731A CN106315731A CN201610819350.XA CN201610819350A CN106315731A CN 106315731 A CN106315731 A CN 106315731A CN 201610819350 A CN201610819350 A CN 201610819350A CN 106315731 A CN106315731 A CN 106315731A
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- Prior art keywords
- nickel
- waste water
- extraction
- plating waste
- nickel oxide
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Abstract
The invention discloses a method for producing nickel oxide from nickel-plating wastewater. The method includes the steps of 1), based on the extraction technology, extracting the nickel-plating wastewater to extract organ matter; 2), subjecting the organic matter to reverse extraction; 3), subjecting reverse extraction liquid to sediment by the aid of oxalic acid to obtain nickel oxalate intermediates; 4), calcining the nickel oxalate intermediates to obtain nickel oxide products with purity larger than 99.5%. With the method for producing the nickel oxide from the nickel-plating wastewater, cost in recycling nickel is reduced, value of the nickel is increased, and meanwhile, new technical strategies for disposal of hazardous waste of the nickel-plating wastewater and the like are put forward.
Description
Technical field
The present invention relates to the recycling of heavy metal wastewater thereby valuable metal, produce oxygen particularly to one from nickel-plating waste water
The method changing nickel.
Background technology
Nickel plating industry produces substantial amounts of nickel-containing waste water, and nickel therein and compound thereof are that the environment of China must priority treatment
Heavy metal contaminants, nickel accumulation in water body environment, the water plant of water body, aquatic animal system can be produced serious danger
Evil, and affect human health by the biological concentration of food chain.Nickel content in strictly controlled environment, for ensureing ecological environment
It is significant with the safety of health.
Nickel-plating waste water mainly includes pre-treatment waste water, nickel-plating rinsing waste water, nickel plating post processing waste water and nickel-plating waste liquid.Nickel plating
Wastewater processing technology includes chemical precipitation method, ion exchange, membrane separation process, bioanalysis, emulsion liquid membrane and extraction etc..
Chemical precipitation method is that nickel-plating liquid puts into suitable precipitant, under certain pH value condition, and precipitant and waste liquid
In harmful substance carry out chemical reaction, generate insoluble precipitate, thus remove the noxious pollutant in waste water.Chemical precipitation
The advantage of method is that technics comparing is ripe, and operating cost is relatively low.Its shortcoming is to produce a large amount of electroplating sludge in processing procedure,
China specifies it is danger wastes equally, it is necessary to have qualification could to process or comprehensively utilize.Ion exchange processes nickel-containing waste water
Principle be that on nickel ion and ion-exchanger, the counter ion of active group carries out place-exchange, when exchange reaches balance, use
Certain density regenerative agent drip washing exchanger makes it regenerate, and puts into next round circulation.The subject matter that ion exchange exists is
The regeneration issues of ion-exchanger.Just can be continuing with after must regenerating after ion-exchanger absorption is saturated；Additionally this method equipment
Complexity, runs operating technology and requires height, add the lasting use of regenerative agent, and operating cost is the highest.Membrance separation is to utilize film
Difference to the selective osmosis of component each in mixture, with outside energy or chemical potential difference for motive force to different component
Gas or the liquid of mixing carry out separating, classification, the method that purifies and be enriched with.Membrane technology is used to process nickel-containing waste water, although excellent
Point is many, but also faces a lot of problem, limits membrane technology and is more widely applied.One be film relatively costly (particularly
NF membrane and reverse osmosis), not only cost is high, and operating cost is the biggest；Two is that fouling membrane is now still without good solution；Three
It is that the regeneration issues of film does not has corresponding disposal technology yet.Biochemical method heavy metal wastewater thereby is used mainly to include three aspects: first
Microorganism before this produces the physiologically substances such as pheron in metabolic processes and changes heavy metal valence state, reduces and even eliminates its poison
Property；It is the extracellular polymeric such as glycoprotein of the functional group of microorganism wall itself and secretion again, it is possible to occur with heavy metal
Electrostatic Absorption, complexation etc. are reacted, and heavy metal ion is fixed on cell surface；Metal transport agent in last microbial body will
Heavy metal is transported intracellular from antimicrobial surface, makes heavy metal be enriched with at cell cylinder accumulation.Bioanalysis is the most thorough
Method of wastewater treatment, and it is low to have processing cost, and simple to operate in running, non-secondary pollution, comprehensive treatment capability is strong
Etc. plurality of advantages.But bacterium solution is because of the highest with heavy metal reaction efficiency, need bacterium solution amount very big in actual mechanical process, and
The cultivation Reproduction Conditions of heavy metal adsorption bacterium is high, speed is also slow, and cost of investment is high.It addition, the heavy metal wastewater thereby of Biochemical method
Although water outlet tenor can be up to standard, but also can remain some microorganisms and plankton in water, can only flush the toilet or cultivate bacterium
Kind etc., limit the reuse of waste water.Liquid membrane emulsion technology extracts nickel and is all confined to laboratory research, but along with pending feed liquid
From simple nickel solution, to simulation actual waste water, then to actual waste water, liquid membrane emulsion technology extracts nickel and the most progressively reduces merely
Theoretical research and actual application between gap.Industrial applications to be realized, liquid membrane emulsion technology also needs to overcome a lot of difficulty
Topic, such as the stability of liquid film, effective demulsification technology and oil phase recycle, developing of liquid membrane emulsion technology relevant device
Deng, it is desirable to have the scholar of will constantly makes great efforts to explore.Research shows to use abstraction technique can reclaim the nickel in nickel-plating waste liquid, and three is pungent
Methyl ammonium reaches 99% as extractant nickel extraction yield, but requires that pH value, more than 10, uses benzene to have as solvent simultaneously
Certain toxicity, tri-n-octyl methyl ammonium chloride price is 15-20 ten thousand yuan/ton, uneconomical on cost.The most industrially should
With.
In the recent period, Tsing-Hua University, on the basis of technological accumulation for many years, develops the special compounding extractant of nickel-plating waste water, at pH
Value more than 5 nickel extraction yield reaches more than 99.5%.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, it is an object of the invention to provide a kind of production from nickel-plating waste water and aoxidize
The method of nickel, on the basis of extraction process, uses sulphuric acid back extraction, then obtains nickel organogenous sediment and displacement by organic acid precipitation
Going out sulphuric acid, the sulphuric acid of displacement carries out being back to back extraction operation, and the calcining of nickel organogenous sediment obtains nickel oxide product, reduces sulphuric acid
Consume and few discharge is caused secondary pollution, the value that reclaims product being greatly improved simultaneously, there are good popularization and application
Prospect.
To achieve these goals, the technical solution used in the present invention is:
A kind of method producing nickel oxide from nickel-plating waste water, comprises the steps:
1) based on extraction process, extraction nickel-plating waste liquid is extracted Organic substance；
2) extraction Organic substance is carried out back extraction；
3) utilize oxalic acid, strip liquor is precipitated, obtains nickel oxalate intermediate；
4) calcining of nickel oxalate intermediate is obtained nickel oxide product.
Described step 1) in, use phosphoric acid class to compound extractant or tri-n-octyl methyl ammonium chloride extractant, to nickel-plating waste liquid
Extract.
Phosphoric acid class compounds extractant according to phosphoric acid kind of extractants (such as, P507 or P204): synergic reagent: sulfonated kerosene=1:
The volume ratio of 1:2 is compounding to be obtained, and compounds extractant according to phosphoric acid class: the volume ratio of nickel-plating waste water=1:1 uses.
When using described phosphoric acid class to compound extractant extraction, aqueous phase is adjusted to pH=4-5.Use described tricaprylmethyl chlorine
When changing the extraction of ammonium extractant, aqueous phase is adjusted to pH=10.
Extraction time 3-5 minute, can be extracted Organic substance after split-phase.
Described step 2) in, back extraction first use sulphuric acid, back extraction condition is: sulfuric acid concentration is 1-3mol/L, organic facies with
Water is in a ratio of O/W=3-8:1, and optimal back extraction condition is: sulfuric acid concentration is 3mol/L, and organic facies and water are in a ratio of O/W=6:1；
Subsequent process uses precipitation tail washings back extraction.
Described step 3) in, consumption of oxalic acid is 0.8 to 1.4 times of theoretical amount, and optimum amount is the 0.8 of theoretical amount
Times, the rate of deposition of nickel is more than 90%.Theoretical amount refers to often precipitate the mole of the oxalic acid needed for 1 mole of nickel ion.
Described step 4) in, first that nickel oxalate intermediate is dried, calcine 1-3 hour at 300-500 DEG C, obtain purity
Nickel oxide product more than 99.5%.
Compared with prior art, the present invention obtain for technical grade nickel oxide product, can with direct marketing, stripping process without
Sulfuric acid consumption, product nickel oxide is higher than metallic nickel valency, reduces cost, makes value-added content of product be improved.Technique is not only
Reducing the cost that nickel reclaims, improve the value of nickel, the process for this kind of danger wastes of nickel-plating waste water simultaneously proposes new
Technology path.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet of the present invention.
Detailed description of the invention
Embodiments of the present invention are described in detail below in conjunction with the accompanying drawings with embodiment.
As it is shown in figure 1, the invention mainly comprises four aspect technology contents:
1) extraction process extraction nickel-plating waste liquid is used to obtain extracting nickel Organic substance；Organic substance of the present invention is phosphate ester
Class compounds extractant, and compounding Organic substance is 1:1-2 with sulfonated kerosene ratio, or uses tri-n-octyl methyl ammonium chloride as extraction
Agent, at total organic matter: the condition of nickel-plating waste water 1:1 extracts 3-5 minute, is extracted Organic substance after split-phase.
2) sulphuric acid and precipitation tail washings carry out back extraction；To extract Organic substance, and use sulphuric acid back extraction, the concentration of sulphuric acid is 1-
3mol/L, organic facies and water are in a ratio of O/W=3-8:1, and optimal back extraction condition is, sulfuric acid concentration 3mol/L compares O/W=6:1；
After Er Ci, precipitation tail washings is used to carry out back extraction.
3) strip liquor precipitation, uses oxalic acid to precipitate the most at normal temperatures, is filtrated to get intermediate product nickel oxalate, tail
Liquid returns stripping process and uses；
4) intermediate product is calcined at a certain temperature and is obtained nickel oxide product.
The following is a specific embodiment:
Using the chemical nickel plating waste solution of Jiangsu enterprise, the pH:4-5 of chemical nickel plating waste solution, its main component is shown in Table 1:
The component of effluent analysis of table 1 chemical nickel plating
| Chemical composition | Ni | Hypophosphorous acid root | Orthophosphite | Malic acid with | Sulfate radical |
| Concentration (g/L) | 4.90 | 50 | 92 | 45 | 32 |
Concrete implementation process is as follows:
1) by using phosphoric acid ester extractant (P507 or P204) to compound with synergic reagent, phosphoric acid ester extractant/association's extraction
Agent/sulfonated kerosene=1/1/2 (volume ratio), obtains phosphoric acid ester and compounds extractant；The extraction nickel plating of this compounding extractant is used to give up
Nickel in water, by organic substance extraction agent/nickel-plating waste water=1/1 (volume ratio), extracts 3 minutes, is extracted Organic substance after split-phase；
May be used without tri-n-octyl methyl ammonium chloride to extract as extractant, but use tri-n-octyl methyl ammonium chloride extraction time need by
Aqueous phase (nickel-plating waste water) is adjusted to pH=10, is extracted Organic substance after same split-phase.
2) by above-mentioned extraction Organic substance, using sulphuric acid back extraction for the first time, the concentration of sulphuric acid is 3mol/L, organic facies and aqueous phase
Ratio is O/W=6:1, uses precipitation tail washings to carry out repeatedly back extraction afterwards, and repeatedly back extraction result is as follows.
Table 2 precipitates tail washings back extraction number of times and affects back extraction ratio
| Precipitation tail washings back extraction number of times | 1 | 2 | 3 |
| Back extraction ratio (%) | 96.59 | 93.30 | 93.61 |
The sulphuric acid that every time precipitation process generates, goes back extraction in the case of the most additionally supplementing sulphuric acid again, experiment continuous precipitation,
Back extraction three times, back extraction ratio change is little, all more than 90%.Failing the nickel that back extraction gets off enters extracting system with organic facies, because of
This does not cause the loss of nickel.
3) strip liquor uses oxalic acid precipitation, uses sulphuric acid back extraction to obtain strip liquor for the first time, and precipitant consumption of oxalic acid is reason
1.4 times of opinion consumption, the rate of deposition of nickel is 93.14%.Post precipitation process precipitant consumption of oxalic acid is the 0.8 of theoretical amount
Times, the rate of deposition of nickel is more than 90%.The nickel not precipitated is back to stripping process, thus without causing the loss of nickel, and
To environmental emission.
4) after drying precipitate, calcining 1 hour, obtain nickel oxide product at 400 DEG C, its purity is more than 99.5%.
Claims (10)
1. the method producing nickel oxide from nickel-plating waste water, it is characterised in that comprise the steps:
1) based on extraction process, extraction nickel-plating waste liquid is extracted Organic substance；
2) extraction Organic substance is carried out back extraction；
3) utilize oxalic acid, strip liquor is precipitated, obtains nickel oxalate intermediate；
4) calcining of nickel oxalate intermediate is obtained nickel oxide product.
The method producing nickel oxide from nickel-plating waste water the most according to claim 1, it is characterised in that described step 1) in, adopt
Compound extractant or tri-n-octyl methyl ammonium chloride extractant by phosphoric acid class, nickel-plating waste liquid is extracted.
The method producing nickel oxide from nickel-plating waste water the most according to claim 2, it is characterised in that the compounding extraction of described phosphoric acid class
Take agent according to phosphoric acid kind of extractants: synergic reagent: the volume ratio of sulfonated kerosene=1:1:2 is compounding to be obtained, according to the compounding extraction of phosphoric acid class
Take agent: the volume ratio of nickel-plating waste water=1:1 uses.
The method producing nickel oxide from nickel-plating waste water the most according to claim 3, it is characterised in that described phosphoric acid kind of extractants
For P507 or P204.
The method producing nickel oxide from nickel-plating waste water the most according to claim 2, it is characterised in that use described phosphoric acid class multiple
When joining extractant extraction, aqueous phase is adjusted to pH=4-5；When using described tri-n-octyl methyl ammonium chloride extractant to extract, by aqueous phase
It is adjusted to pH=10.
6. according to the method producing nickel oxide from nickel-plating waste water described in Claims 2 or 3 or 4 or 5, it is characterised in that described extraction
Take the time 3-5 minute, after split-phase, be extracted Organic substance.
The method producing nickel oxide from nickel-plating waste water the most according to claim 1, it is characterised in that described step 2) in, first
Secondary back extraction uses sulphuric acid, and back extraction condition is: sulfuric acid concentration is 1-3mol/L, and organic facies and water are in a ratio of O/W=3-8:1；Follow-up
Process uses precipitation tail washings back extraction.
The method producing nickel oxide from nickel-plating waste water the most according to claim 6, it is characterised in that described back extraction condition is:
Sulfuric acid concentration is 3mol/L, and organic facies and water are in a ratio of O/W=6:1.
The method producing nickel oxide from nickel-plating waste water the most according to claim 1, it is characterised in that described step 3) in, grass
Acid consumption is 0.8 to 1.4 times of theoretical amount, and the rate of deposition of nickel is more than 90%.
The method producing nickel oxide from nickel-plating waste water the most according to claim 1, it is characterised in that described step 4) in, first
Nickel oxalate intermediate is dried, calcine 1-3 hour at 300-500 DEG C, obtain the purity nickel oxide product more than 99.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610819350.XA CN106315731A (en) | 2016-09-13 | 2016-09-13 | Method for producing nickel oxide from nickel-plating wastewater |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610819350.XA CN106315731A (en) | 2016-09-13 | 2016-09-13 | Method for producing nickel oxide from nickel-plating wastewater |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170527A (en) * | 2020-02-11 | 2020-05-19 | 中冶一局环境科技有限公司 | Treatment method of chemical nickel plating waste liquid |
| CN112607813A (en) * | 2021-01-04 | 2021-04-06 | 南昌航空大学 | Method for synergistically extracting nickel from nickel plating wastewater |
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| CN1651584A (en) * | 2005-02-06 | 2005-08-10 | 金川集团有限公司 | Production method of dentritic morphology nickel powder |
| CN104561552A (en) * | 2013-10-21 | 2015-04-29 | 王珂 | Nickel waste recycling technology |
| CN104745821A (en) * | 2015-02-12 | 2015-07-01 | 江苏恒嘉再生资源有限公司 | Method for recovering nickel and copper metals in acid pickling sludge |
| CN105369036A (en) * | 2015-11-20 | 2016-03-02 | 中国科学院过程工程研究所 | Method for extracting vanadium from vanadium-containing high-concentration hydrochloric acid solution |
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2016
- 2016-09-13 CN CN201610819350.XA patent/CN106315731A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1651584A (en) * | 2005-02-06 | 2005-08-10 | 金川集团有限公司 | Production method of dentritic morphology nickel powder |
| CN104561552A (en) * | 2013-10-21 | 2015-04-29 | 王珂 | Nickel waste recycling technology |
| CN104745821A (en) * | 2015-02-12 | 2015-07-01 | 江苏恒嘉再生资源有限公司 | Method for recovering nickel and copper metals in acid pickling sludge |
| CN105369036A (en) * | 2015-11-20 | 2016-03-02 | 中国科学院过程工程研究所 | Method for extracting vanadium from vanadium-containing high-concentration hydrochloric acid solution |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170527A (en) * | 2020-02-11 | 2020-05-19 | 中冶一局环境科技有限公司 | Treatment method of chemical nickel plating waste liquid |
| CN112607813A (en) * | 2021-01-04 | 2021-04-06 | 南昌航空大学 | Method for synergistically extracting nickel from nickel plating wastewater |
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