CN108570557A - The separation method of iron, chromium, nickel, copper, zinc in a kind of high chromium electroplating sludge leachate of high ferro - Google Patents
The separation method of iron, chromium, nickel, copper, zinc in a kind of high chromium electroplating sludge leachate of high ferro Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B15/00—Other processes for the manufacture of iron from iron compounds
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
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- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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Abstract
The present invention provides the separation methods of iron, chromium, nickel, copper, zinc in a kind of high chromium electroplating sludge leachate of high ferro, include the following steps：（1）Iron powder is added into leachate, obtains copper powder product and displaced liquid；（2）Iron powder is added into displaced liquid, obtains reducing solution；（3）Heavy chromium agent is added into reducing solution, liquid and chromium precipitation after heavy chromium is obtained by filtration；（4）Activator antimonic salt is added in liquid after to heavy chromium and zinc powder is reacted, nickel powder and solution after nickel removal are obtained after filtering；（5）Acid phosphatase esters extractant extracting zinc is added into solution after nickel removal, is stripped with dilute sulfuric acid, the concentrated crystallization of zinc-rich solution prepares zinc salt product, and zinc raffinate then enters subsequent processing；（6）Zinc raffinate condensing crystallizing is prepared into green vitriol, distilled water, which returns, to be leached.The separation method flow of the present invention is short, efficient, can effectively solve chromium, iron, nickel, copper, zinc metal in the high chromium electroplating sludge leachate of high ferro and be separately separated difficult problem.
Description
Technical field
The invention belongs to more metals resourcesization in electroplating sludge to utilize field more particularly to a kind of high chromium electroplating sludge of high ferro
The separation method of iron, chromium, nickel, copper, zinc in leachate.
Background technology
Currently, electroplating sludge processing method of disposal mainly has：Solidification and stabilization technology, heat chemistry incineration disposal, wet method are returned
Receive recycling treatment disposition.Cement kiln synergic processing waste principle is to utilize the height generated in cement burning process in burning method
Temperature handles the various residue waste liquids in urban waste, the raw material as cement.The technology is by Waste disposal and cement industry
Sustainable development combines, and is that the innoxious, minimizing of one kind and disposal of resources are dangerous pollution emission control to minimizing
Waste important technology approach and the cost effective important measures for disposing above-mentioned waste on a large scale.But it from circular economy and can hold
Supervention is opened up angle and is considered, wet processing processing disposition more meets electroplating sludge minimizing, recycling, innoxious principle, has and throws
The features such as money is less, low energy consumption, simple for process, quality controllable, scale is changeable and pollution is small, it has also become at electroplating sludge processing
Set the hot spot and developing direction of research.
From the nineties in last century, the newly-built electroplating sludge treatment in China mostly uses greatly acidleach-calcium carbonate and removes iron-extraction
Electrodeposition tough cathode-sodium carbonate precipitation raw nickel matte technique, the main higher cupro-nickel of recovery value are taken, and chromium and iron are neutralized precipitation
Enter slag, the quantity of slag is caused to increase, and there are problems that the secondary pollution of chromium, electroplating sludge harmlessness disposing rate is low.Recycling for zinc,
Substantially based on sulfide precipitation, zinc is recycled in the form of zinc sulphide, and added value is low, and there are wastewater treatments for the solution after precipitation
Problem.Then, and there are some using the methods of ammonia leaching, solvent extraction, the metal salt product of various cuprics, zinc, nickel can be obtained, but
The key technology of supporting industry is not yet broken through, and there are no the reports of scale application achievement.
For electroplating sludge wet-treating disposition correlative study it is more, be mainly concerned with displacement reaction, sulfide precipitation,
The methods of metal electrodeposition, solvent extraction.The more more typical processes of metal segregation ratio of electroplating sludge leachate have：（1）With sulphur
Technique based on compound precipitation：Patent CN101058436 is leached using dilute sulfuric acid, and leached mud curing process, leachate is successively
By iron powder replacement, the heavy zinc of sulfide, the heavy nickel of sulfide, heavy ferrochrome, alkaline solution return leaching are neutralized, ferrochrome hydroxide is again
Fired processing, finally obtained product are respectively copper ingot, zinc sulphide, nickel sulfide, ferrochrome oxide product, which solves electricity
The metals resources problem of copper, zinc, nickel, chromium, iron in plating sludge, but only by pH value difference, with sulphide precipitation point
From zinc-nickel, roasting obtains ferrochrome oxide, and not only technological process is long, and obtained by-product impurity content is high, quality is low, each production
Product still need the advanced treating of long flow；（2）Technique based on metal electrodeposition method：Patent CN101786775 is provided
A method of the selective recovery copper and mickel from electroplating sludge, the solution after acidleach are directly over eddy flow electrodeposition and prepare cathode
Copper, liquid removes chromium by adjusting pH value to 4.4-5.0 after electrodeposition, and filtrate prepares electro deposited nickel using eddy flow electrodeposition again, realizes metal
The recycling of copper and mickel, but the impurity such as iron, chromium in leachate cause to seriously affect to electrolytic deposition process, it is more difficult to realize that comprehensive plating is dirty
Mud leachate recycling；（3）Technique based on solvent extraction：Patent CN104060097 provides a kind of for plating
The separation and recovery method of nickel, cobalt, copper, manganese, zinc in sludge, the method remove iron to leachate first, then P507 wide spectrums are used to extract
Agent extracts other metal ions, is then stripped successively with the hydrochloric acid of various concentration, then by different strip liquors after
Continuous extraction-precipitation separation copper and manganese, the method use full extraction process, and operating process and equipment are more complex, metal stripping process
Controlling condition the degradation for requiring high and complicated infusion solution that can accelerate extractant and grease, frequently contact is easy to form third
Phase, maintenance cost is higher, and technique is up for advanced optimizing.Particularly, patent CN104593598 discloses a kind of electroplating sludge
The method that middle copper, chromium, iron, zinc, nickel resources utilize, it is therefore an objective to solve the abundant money of the chromium in more metal plating sludge leachates
Source problem, specifically include sulfuric acid leaching, copper extraction electrodeposition, heavy chromium, neutralize sink ferrochrome, vulcanized sodium sink zinc, sodium carbonate sink nickel and
Liquid, which returns, after heavy nickel leaches, it can be achieved that all kinds of metal ions efficiently separate in leachate, but the added value that the method obtains is low
Scum and zinc enrichment material, and often there is metals content impurity height, quality problem rambunctious is contained using method processing zinc, iron
High material is measured, supplementary product onsumption is big.
In Environmental Protection Department publication《Prevention and cure of pollution best practicable technology guide is electroplated（It is tentative）》（2013）Middle plating
The comprehensive utilization best practicable technology of sludge includes：Melting law technology, ammonium hydroxide leach law technology and sulfuric acid（Ferric sulfate）Leach skill
Art.Melting technique needs sludge treatment first to carry out drying and processing, then is mixed in stove with ore, coal, reducing substances etc., also
Metal is produced in original reaction, and the method processing cost is often higher, is suitable only for the high one-component recycling sludge of tenor and is utilized,
And the clinker generated also needs to carry out harmlessness disposing；Although ammonium hydroxide lixiviation process can leach cupro-nickel selection of activated sludge and directly obtain
To Kocide SD raw material, but it is relatively low to sewage sludge harmlessness degree, and other toxic metals can not almost leach, and ammonium hydroxide leaching pair is set
Standby seal requires high；Sulfuric acid（Ferric sulfate）Lixiviation process does not generate secondary pollution, leached mud substantially although technical process is simple
Innoxious degree is higher, but for more metal plating sludge, and metal component is complex in leachate, and higher value application cost is logical
It is often higher.Iron ion in prior art technology is often removed as impurity, but the process can cause largely to neutralize slag
It is formed, and neutralizes that slag detoxification difficulty is often larger, especially for the sludge leachate containing chromium, ferrochrome will enter together to be neutralized
Slag causes electroplating sludge poisonous component more difficult to control in the Life cycle of disposing technique, the dangerous quantitation risk of waste.
In order to further increase the detoxification efficiency of leached mud, harmlessness disposing is carried out to electroplating sludge using biological extraction
With broader practice foreground, as patent CN104862250, CN104862250 and CN104862474 have been disclosed it is a kind of heavy
The microbial bacterial agent of metal sludge high-efficiency detoxicating and its efficiently the regulation and control method of extraction heavy metal, what is mainly utilized is microorganism life
Continue existing Fe in long metabolism2+Biological oxidation, organic acid synthesis, free acid the processes such as release effectively improve in sludge
Metal dissolving efficiency.The method solves the problems, such as that heavy metal sewage sludge leaching slag harmlessness is halfway, but the separation of downstream metal
There are higher iron concentrations, generally 5-20 g/L, and 20 g/L are even more than for the high sludge iron concentration of iron content.
In addition, for be more than containing chromium 10g/L high ferro electroplating sludge leachate, not only detach the complex procedures of iron, and containing in production
Chromium impurity content is even higher often beyond 1% in iron byproduct, even if using biological harmless disposition and recycling,
Its environmental benefit and economic benefit will all have a greatly reduced quality greatly.
Invention content
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
The separation method of valuable metal in the high chromium electricity sludge leachate of high ferro kind simple for process, that flow is short, efficient, this method can be with
It effectively solves chromium, iron, nickel, copper, zinc metal in the high chromium electroplating sludge leachate of high ferro and is separately separated difficult problem, improve in sludge
The recovery value of iron is particularly suitable for the metal separation process of the high chromium electroplating sludge biochemical lixivium of high ferro.
In order to solve the above technical problems, technical solution proposed by the present invention is：
The separation method of iron, chromium, nickel, copper, zinc in a kind of high chromium electroplating sludge leachate of high ferro, siderochrome content in the leachate
It is above 10g/L, is included the following steps：
（1）Iron powder is added in leaching liquid thereto, replaces the copper ion in leachate, and further in reducing leaching liquid
Fe3+To Fe2+, solid-liquid is then detached, copper powder product and displaced liquid are obtained；
（2）Iron powder is added into displaced liquid, by the Fe in solution3+It is fully converted to Fe2+, obtain reducing solution；
（3）Heavy chromium agent is added into reducing solution, is filtered after sedimentation to be precipitated, obtains liquid and chromium precipitation after heavy chromium；
（4）The nickel in activator antimonic salt and zinc dust precipitation solution is added after to heavy chromium in liquid, nickel powder is obtained after filtering and except after nickel
Liquid；
（5）The zinc in acid phosphatase esters extractant extraction solution after nickel removal is added into solution after nickel removal, is stripped with dilute sulfuric acid
It takes, after multistage back extraction enrichment（It is preferred that when zinc concentration reaches 150 g/L in zinc-rich solution）, condensing crystallizing prepare zinc salt production
Product, zinc raffinate then enter step（6）；
（6）After zinc raffinate is removed organic matter with activated carbon, condensing crystallizing prepares green vitriol, can be used as at waste water
Agent is managed, distilled water then returns to leaching.
Above-mentioned separation method, it is preferred that the iron powder derives from Industrial iron powder, waste iron filing, waste iron wire, iron scrap, gives up
At least one of ferroaluminium, reduced iron powder are ground to -200 mesh or less；The step（1）Middle iron powder addition is to leach
1.5-2.0 times of theoretical amount needed for copper ion displacement in liquid；The step（2）Middle iron powder dosage is by Fe3+Restore All is Fe2 +1.5-2.0 times of theoretical amount.
Above-mentioned separation method, it is preferred that the step（3）In to sink chromium agent be one kind in phosphoric acid and soluble phosphate
Or it is a variety of, additive amount is 1.1 ~ 1.2 times of theoretical amount needed for chromium ion sedimentation, and the pH of reaction process is 1.5-2.0, and temperature is
80-90 DEG C, the reaction time is 0.5-2.0 hours, and further purification obtains crude chromic salts to the chromium phosphate after sedimentation.
Above-mentioned separation method, it is preferred that the step（4）Middle that antimonic salt activator is first added, additive amount is total nickel mole
The 2%-9% of amount, is then added -200 mesh thin zinc powder below, and additive amount is 1.5-3.0 times of total nickel mole.
Above-mentioned separation method, it is preferred that the step（5）Middle extraction and back extraction carry out at room temperature, settling time
For 1-30 min；The acid phosphatase esters extractant of the extraction process is at least one in P204, P507 and Cyanex272
Kind, diluent is sulfonated kerosene, and extractant concentration 15%-25%, extraction phase ratio O/A are 1/1-5/1；The back extraction process
Strippant is the sulfuric acid of 150-200 g/L, and back extraction is 1/1-5/1 compared to O/A.
Above-mentioned separation method, it is preferred that the step（5）Middle solution after nickel removal adds acid after need to being cooled to 25-35 DEG C
Property phosphoric acid ester extractant is extracted.
Above-mentioned separation method, it is preferred that the step（6）Middle zinc raffinate is concentrated into ferrous ion content and is less than 20g/
When L, leaching can be directly returned after oil removing.
Above-mentioned separation method, it is preferred that 10-30 containing chromium g/L in the electroplating sludge leachate, iron 10-50 g/L,
Copper 1-15 g/L, nickel 1-15 g/L, zinc 1-15 g/L.
Above-mentioned separation method, it is preferred that the electroplating sludge leachate derives from Bioleaching, the Bioleaching
The microorganism used for acidophilus irony bacterium, thiobacillus ferrooxidans, thermophilic iron hook end pylori, Sulfobacillus acidophilus in it is a kind of or
It is a variety of.
Above-mentioned separation method, it is preferred that the step（1）Middle stirring is that leachate is placed in stirred reactor, with
2-8 m/s linear velocities quickly stir, and the reaction time that iron powder and leachate is added is 0.5-2.0 hours；The step（2）In plus
The reaction time for entering iron powder and displaced liquid is 0.5-1.0 hours.
Compared with the prior art, the advantages of the present invention are as follows：
（1）The present invention to the high chromium electroplating sludge leachate of high ferro using iron replacement method handle, iron powder can not only preferential substitution it is molten
Copper in liquid, and excessive iron powder can also be by the Fe in solution3+It is reduced to Fe2+, reduce the dosage of downstream reducing agent, subtract
Few foreign ion is brought into, and Fe in solution is also improved2+Ferrous sulfate yield and quality can be improved in the concentration of ion.
（2）In the present invention reduction treatment of leachate under the premise of ensureing not to be introduced into impurity by the Fe in solution3+Fully
It is reduced into Fe2+, then selection acid phosphate sinks chromium at the low ph, in solution chromium concn can be reduced to 0.05g/L with
Under, obtain the entrainment of chromium phosphate sediment less, the total metal contents such as zinc, nickel, iron are controlled 1% hereinafter, can be used as chromic salts after appropriate washing
Process raw material.
（3）The present invention will be molten while obtaining nickel powder using nickel of the zinc replacement before zinc extraction in removing solution
Nickel content in liquid is reduced to 20 mg/L hereinafter, also improving zinc ion concentration in solution.
（4）Phosphoric acid extraction agent direct extracting zinc under the conditions of low ph value (pH value 2.0 ~ 3.5) is used in the present invention, is reduced
Complicated saponifying process is washed by multitple extraction and is stripped, the zinc concentration being stripped in zinc-rich liquid can be improved to 150 g/L with
On, then the zinc salt product of high quality, distilled water reuse obtained by condensing crystallizing.
（5）Liquid progress condensing crystallizing prepares ferrous sulfate after the present invention will extract zinc, partly contains ferrous mother liquor and distilled water can
Microculture is returned, microculture cost is reduced.
（6）The method of the present invention in reduced levels, not only solves the more metal separation process solution ph controls of electroplating sludge
Electroplating sludge is innoxious and recycling problem, and reduces acid-base neutralization process, and wash water acid reclamation rate is high, meets cleaning life
The theory of production.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the separating technology flow of iron, chromium, nickel, copper, zinc in a kind of high chromium electroplating sludge leachate of high ferro of the present invention
Figure.
Specific implementation mode
To facilitate the understanding of the present invention, it is done more entirely below in conjunction with Figure of description and preferred embodiment to inventing herein
Face meticulously describes, but protection scope of the present invention is not limited to following specific examples.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention's
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Reagent explanation：
The entitled di-(2-ethylhexyl)phosphoric acid ester of P204 Chinese, alias have：Bis- (2- ethylhexyls) phosphates；Di(2-ethylhexyl)phosphate is different pungent
Ester；Dioctylphosphoric acid ester；D2EHPA, national CAS accession number：298-07-7 is a kind of liquid that water white transparency is more sticky.Solidification
- 60 DEG C of point, relative density 0.973（25/25℃）, index of refraction 1.4420（25℃）, 209 DEG C of (1.33kPa of boiling point）.
The entitled 2- ethylhexyl phosphoric acids -2- ethylhexyls of P507 Chinese, national CAS accession number：14802-03-0, molecule
Formula: (C8H17)2HPO3, for colourless or yellowish oily transparency liquid, the organic solvents such as alcohol, benzene, ketone are dissolved in, not soluble in water, combustion
228 DEG C of point, 209 DEG C of boiling point（10 mmHg）, 196 DEG C of flash-point, low toxicity.
Cyanex272 Chinese entitled two（2,4,4- tri-methyl-amyls）Hypophosphorous acid, appearance by colourless to light amber liquid,
Proportion（24℃）It is 0.92, viscosity（25℃）For 422cP, 108 DEG C of lightning.
Sulfonated kerosene, i.e., 260#Solvent naphtha, appearance colorless is transparent, and initial boiling point is not less than 195 DEG C, does not higher than 260 DEG C,
Aromatic hydrocarbon content is not more than 10%, flash-point（Opening）Not less than 65 DEG C, kinematic viscosity（20℃）No more than 2.4 mm2/ s, density
（20℃）No more than 820 kg/m3, evaporation rate is uniform and slow, and aromatic hydrocarbon content is less, and smell is small, and matter is pure, evaporates nothing
Residue, not oxidizable, toxicity very little of being heated, safety are higher.
Embodiment 1：
The sludge that the present embodiment is selected comes from the waste water treatment plant of Wuxi surface treatment garden, and moisture content about 65%, butt contains
Chromium 5.74%, iron 7.7%, copper 0.54%, nickel 0.54%, zinc 3.87% weigh 1 kg wet muds as 5 L polypropylene stirred reactors
It is interior, control liquid-solid ratio 5:1, sulphur acid for adjusting pH value to 1.8,500 rpm of speed of agitator is stirred and is completed within 2.0 hours to leach, leachate
In containing 11.3 g/L of chromium, 10.56 g/L of iron, copper 1.06g/L, nickel 1.12g/L, zinc 7.65g/L.
The separation method of iron, chromium, nickel, copper, zinc is to above-mentioned in the high chromium electroplating sludge leachate of high ferro according to the invention
Copper, chromium, nickel, zinc, iron in sludge leachate are detached successively, are included the following steps, as shown in Figure 1：（1）1 L is taken to leach
Liquid stirs 2 m/s of linear velocity as in corresponding stirred tank, wherein following 1.8 g of waste iron filing powder of -100 mesh is added, to replace institute
It is 0.5 hour to have 2.0 times of iron powder amount needed for copper ion, reaction time, replaces the copper ion in leachate, and further restore
Fe in leachate3+To Fe2+, copper powder product and displaced liquid are obtained after separation of solid and liquid；（2）Iron powder is added into displaced liquid
3.5 g, to restore all Fe3+1.5 times of required iron powder amount, the reaction time is 1.0 hours, by the Fe in solution3+Conversion completely
For Fe2+, obtain reducing solution；（3）Heavy chromium agent is added into reducing solution, chromium agent of sinking is sodium phosphate, is added doubly by the 1.2 of total chromium mole
Add, control pH value in reaction is 2.0, and temperature is 85 DEG C, and the reaction time is 2.0 hours, and the chromium precipitation obtained after filtering enters next
Purifying technique is walked, chromium 22.46%, iron 0.2%, nickel 0.11%, zinc 0.19%, using further purification are contained in obtained chromium phosphate
After corresponding chromic salts product can be obtained, liquid 0.045g/L containing chromium after obtained heavy chromium, 13.46 g/L of iron, 0.008 g/L of copper, nickel
1.16 g/L, 7.86 g/L of zinc；（4）Liquid after heavy chromium is kept the temperature 80 DEG C, pH value is adjusted to 3.0, and activator potassium antimony tartrate is added
With the nickel in -200 mesh zinc dust precipitation solution, zinc powder additive amount is 2.6 g, is 2 times of total nickel mole, activator additive amount is
The 3% of total nickel mole, 1.0 hours reaction time obtain 1.2 g of nickel powder and solution after nickel removal that nickel content is more than 90%；（5）It waits removing
After liquid is cooled to 30 DEG C after nickel, the zinc in acid phosphatase esters extractant extraction solution after nickel removal is added, extractant uses P204, dilute
It is sulfonated kerosene to release agent, and extractant concentration 15%, extraction, back extraction are compared to being O/A=1/1, using two level extraction level-one washing
Two level is stripped, and is stripped with 180 g/L dilute sulfuric acids, and zinc concentration reaches in the zinc-containing solution after multitple extraction back extraction enrichment
When 150 g/L, condensing crystallizing obtains zinc salt product, zinc raffinate 13.22 g/L containing ferrous iron, 3.4 mg/L of chromium, 78 mg/L of zinc,
10 mg/L of nickel, 0.8 mg/L of copper, zinc raffinate enter subsequent processing；（6）After zinc raffinate is removed organic matter with activated carbon,
Ferrous sulfate acid solution is obtained, condensing crystallizing prepares green vitriol（Iron-holder is more than 18%, FeSO4˖7H2O content is big
In 90%）, as waste water treating agent, distilled water returns to be leached product.
Embodiment 2：
The sludge that the present embodiment is selected comes from the waste water treatment plant of Zhejiang surface treatment garden, and moisture content about 58%, butt contains
Chromium 6.7%, iron 18%, copper 2.1%, nickel 1.6%, zinc 5.7% weigh 1 kg wet basis sludge as in 5 L polypropylene stirred reactors,
Acidophilia mixed bacteria liquid is added（ContainAcidithiobacillus ferrooxidans23270 Hes of ATCCAcidiphiliumacidophilumATCC 27807, respectively accounts for 50%）It sizes mixing, sulphur acid for adjusting pH value to 1.5, speed of agitator 500
Rpm is stirred and is completed within 8.0 hours to leach, containing 13.27 g/L of chromium, 34.20 g/L of iron, 4.12 g/L of copper, nickel 3.17 in leachate
G/L, 11.29 g/L of zinc obtain innoxious leached mud after leached mud washing, moisture content about 60%, main component is gypsum after drying
And iron hydroxide, quality account for 82 % and 17% respectively.
The separation method of iron, chromium, nickel, copper, zinc is to above-mentioned in the high chromium electroplating sludge leachate of high ferro according to the invention
Copper, chromium, nickel, zinc, iron in sludge organism leachate are detached successively, are included the following steps：（1）Leachate is placed in 3 L
Stirred tank in, stir 5 m/s of linear velocity, into leachate be added the following waste iron filing powder 17.2g of -200 mesh, the iron powder amount be will
Copper ion thoroughly replaces the desired amount of 1.57 times, and the reaction time is 0.5 hour, replaces the copper ion in leachate, and further
Fe in reducing leaching liquid3+To Fe2+, copper powder product and displaced liquid are obtained after separation of solid and liquid；（2）It is added into displaced liquid
20 g of iron powder, to restore Fe3+1.7 times of theoretical amount, the reaction time is 1.0 hours, by the Fe in solution3+It is fully converted to Fe2 +, obtain reducing solution；（3）Heavy chromium agent is added into reducing solution, chromium agent of sinking is ten phosphate dihydrate sodium, by 1.2 times of total chromium mole
Addition, control pH value in reaction are 2.0, and temperature is 85 DEG C, and the reaction time is 2.0 hours, under the chromium precipitation obtained after filtering enters
One step purifying technique, contains chromium 25.6% in obtained chromium phosphate, iron 0.1%, nickel 0.12%, and zinc 0.08% is purified into next step
Corresponding chromic salts product can be obtained in technique, liquid after obtained heavy chromium, and liquid is containing 30 mg/L of chromium, 32.20 g/L of iron, copper 47 after heavy chromium
Mg/L, 3.01 g/L of nickel, 11.53 g/L of zinc；（4）Liquid after heavy chromium is kept the temperature 80 DEG C, pH value is adjusted to 3.0, and activator wine is added
Nickel in the zinc dust precipitation solution of stone acid antimony potassium and -200 mesh, zinc powder additive amount are 16.5 g, are 1.6 times of total nickel mole,
Activator additive amount is the 3% of total nickel mole, and the reaction time is 1.0 hours, obtains nickeliferous 97% 8.9 g of nickel powder and except after nickel
Liquid；（5）After solution after nickel removal is cooled to 30 DEG C, the zinc in acid phosphatase esters extractant extraction solution after nickel removal, extractant is added
Using Cyanex272, diluent is sulfonated kerosene, and extractant concentration 15%, extraction back extraction is compared to being O/A=2/1, using three
Grade extraction level-one washing two level back extraction, is stripped, the zinc-containing solution after multitple extraction back extraction enrichment with 200 g/L dilute sulfuric acids
When middle zinc concentration reaches 150 g/L, condensing crystallizing obtains zinc salt product, zinc raffinate 39.4 g/L containing ferrous iron, 3 mg/L of chromium,
201 mg/L of zinc, 16 mg/L of nickel, 15 mg/L of copper, zinc raffinate enter subsequent processing；（6）Zinc raffinate is removed with activated carbon
After organic matter, green vitriol is prepared in condensing crystallizing（Iron-holder is more than 18%, FeSO4˖7H2O content is more than 90%）,
Product returns to microculture or leaching as waste water treating agent, distilled water.
Embodiment 3：
The present embodiment selects Shenzhen electroplating sludge ferric sulphate leachate（15.28g/L containing chromium, 23.7 g/L of iron, copper 3.51
G/L, 11.5 g/L of nickel, 10.3 g/L of zinc）, innoxious leached mud is obtained after leached mud washing, moisture content about 62% is main after drying
It is gypsum to want ingredient, and content accounts for about 88.9%, other heavy metal total contents are less than 1%.
The separation method of iron, chromium, nickel, copper, zinc is to above-mentioned in the high chromium electroplating sludge leachate of high ferro according to the invention
Copper, chromium, nickel, zinc, iron in sludge leachate are detached successively, are included the following steps：（1）100 L leachates are poured into and are stirred
Slot is mixed, 5 m/s of linear velocity is stirred, -100 mesh 650 g of Industrial iron powder below is added into the leachate quickly stirred, for displacement
The desired amount of 2 times of all copper ions, reaction time are 0.5 hour, replace the copper ion in leachate, and further reducing leaching
Fe in liquid3+To Fe2+, copper powder product and displaced liquid are obtained after press filtration, displaced liquid is transferred to heavy chromium slot；（2）To after displacement
1 kg of iron powder is added in liquid, to restore all Fe3+1.8 times of required iron powder amount, reaction time are 1.0 hours, will be in solution
Fe3+It is fully converted to Fe2+, obtain reducing solution；（3）Heavy chromium agent is added into reducing solution, chromium agent of sinking is sodium phosphate, is rubbed by total chromium
1.2 times of additions of your amount, control pH value in reaction are 1.8, and temperature is 80 DEG C, and the reaction time is 2.0 hours, the chromium obtained after filtering
Precipitation enters next step purifying technique, contains chromium 23.5%, iron 0.13%, nickel 0.11%, zinc 0.05% in obtained chromium phosphate, then pass through
Corresponding chromic salts product can be obtained after crossing further purification, liquid 20 mg/L containing chromium, 31 g/L of iron, 5 mg/ of copper after obtained heavy chromium
L, 11.1 g/L of nickel, 10.2 g/L of zinc；（4）Liquid after the heavy chromium of 50 L is kept the temperature 80 DEG C, pH value is adjusted to 3.0, and activator three is added
The nickel in the zinc dust precipitation solution of two antimony and -300 mesh is aoxidized, 1.27 kg of zinc powder additive amount is 2 times of total nickel mole, activator
Additive amount is the 2% of total nickel mole, and the reaction time is 1.0 hours, obtains nickeliferous 96.1% 0.577 kg of nickel powder and except after nickel
Liquid；（5）After solution after nickel removal is cooled to 30 DEG C, acid phosphatase esters extractant is added and is extracted in solution after nickel removal in extraction tank
Zinc, it is sulfonated kerosene that extractant, which uses P507, diluent, and extractant concentration 15%, it is O/A=3/1 that extraction, back extraction, which are compared,
Using three-level extraction level-one washing two level back extraction, it is stripped with 180 g/L dilute sulfuric acids, containing after multitple extraction back extraction enrichment
When zinc concentration reaches 150 g/L in zinc solution, condensing crystallizing obtains zinc salt product, zinc raffinate 30 g/L containing ferrous iron, chromium 4
Mg/L, 151 mg/L of zinc, 18 mg/L of nickel, 1.2 mg/L of copper, zinc raffinate enter subsequent processing；（6）By zinc raffinate activity
After charcoal removes organic matter, green vitriol is prepared in condensing crystallizing（Iron-holder is more than 18%, FeSO4˖7H2O content is big
In 90%）, as waste water treating agent, distilled water returns to be leached product.
Comparative example 1：
Using traditional sulfuric acid leaching ,-copper extracts-removes Wuxi sludge in the heavy zinc-nickel Processing Example 1 of iron-sulfide, the technique pair
The leaching rate of each metal is up to 97%, and leached mud decrement 30%, obtained product includes tough cathode, iron dross removing, zinc sulphide and sulphur
Change nickel mixture, which can obtain 99.97% tough cathode, but the formation of iron dross removing causes the full technique quantity of slag to increase, and contain
Chromium content reaches 2%, and Zn content can be improved to 15% or more in obtained zinc-nickel slag, but wherein nickeliferous 1.1%, contain chromium 3.2%, together
Sample also belongs to intractable hazardous waste, and filtration difficulty.
By above example and comparative example it is found that the present invention the high chromium electroplating sludge leachate of high ferro in iron, chromium, nickel, copper,
The separation method technological process of zinc is short, easy to operate, efficient, can effectively solve in the high chromium electroplating sludge leachate of high ferro
Chromium, iron, nickel, copper, zinc metal are separately separated difficult problem.
Claims (10)
1. the separation method of iron, chromium, nickel, copper, zinc in a kind of high chromium electroplating sludge leachate of high ferro, siderochrome in the leachate
Content is above 10 g/L, which is characterized in that includes the following steps：
（1）Leaching liquid is added iron powder, then detaches solid-liquid thereto, obtains copper powder product and displaced liquid；
（2）Iron powder is added into displaced liquid, reducing solution is obtained by the reaction；
（3）Heavy chromium agent is added into reducing solution to be reacted, liquid and chromium precipitation after heavy chromium are obtained after filtering；
（4）Activator antimonic salt is added in liquid after to heavy chromium and zinc powder is reacted, nickel powder and solution after nickel removal are obtained after filtering；
（5）The zinc in acid phosphatase esters extractant extraction solution after nickel removal is added into solution after nickel removal, is stripped with dilute sulfuric acid
It takes, after multistage back extraction enrichment, condensing crystallizing prepares zinc salt product, and zinc raffinate then enters step（6）；
（6）After zinc raffinate is removed organic matter with activated carbon, condensing crystallizing prepares green vitriol, and distilled water returns to leaching
Go out.
2. separation method according to claim 1, which is characterized in that the iron powder derives from Industrial iron powder, waste iron filing, gives up
At least one of iron wire, iron scrap, scrap iron aluminium alloy, reduced iron powder, are ground to -200 mesh or less；The step（1）Middle iron
Powder addition is 1.5-2.0 times of theoretical amount needed for copper ion displacement in leachate；The step（2）Middle iron powder dosage is will
Fe3+Restore All is Fe2+1.5-2.0 times of theoretical amount.
3. separation method according to claim 1 or 2, which is characterized in that the step（3）In to sink chromium agent be phosphoric acid and can
One or more in soluble phosphoric acid salt, additive amount is 1.1 ~ 1.2 times of theoretical amount needed for chromium ion sedimentation, reaction process
PH is 1.5-2.0, and temperature is 80-90 DEG C, and the reaction time is 0.5-2.0 hours, and further purification obtains the chromium phosphate after sedimentation
Crude chromic salts.
4. separation method according to claim 1 or 2, which is characterized in that the step（4）It is middle that antimonic salt activation is first added
Agent, additive amount are the 2%-9% of total nickel mole, and -200 mesh thin zinc powder below is then added, and additive amount is total nickel mole
1.5-3.0 again.
5. separation method according to claim 1 or 2, which is characterized in that the step（5）Middle extraction and back extraction exist
It carries out at room temperature, settling time is 1-30 min；The acid phosphatase esters extractant of the extraction process be P204, P507 and
At least one of Cyanex272, diluent are sulfonated kerosene, and extractant concentration 15%-25%, extraction phase ratio O/A are 1/1-
5/1；The strippant of the back extraction process is the sulfuric acid of 150-200g/L, and back extraction is 1/1-5/1 compared to O/A.
6. separation method according to claim 5, which is characterized in that the step（5）Middle solution after nickel removal need to be cooled to 25-
Acid phosphatase esters extractant is added after 35 DEG C to be extracted.
7. separation method according to claim 1 or 2, which is characterized in that the step（6）Middle zinc raffinate is concentrated into
When ferrous ion content is less than 20 g/L, leaching can be directly returned after oil removing.
8. separation method according to claim 1 or 2, which is characterized in that 10- containing chromium in the electroplating sludge leachate
30 g/L, iron 10-50 g/L, copper 1-15 g/L, nickel 1-15 g/L, zinc 1-15 g/L.
9. separation method according to claim 1 or 2, which is characterized in that the electroplating sludge leachate is from life
Object leaches, and the microorganism that the Bioleaching uses is acidophilus irony bacterium, thiobacillus ferrooxidans, thermophilic iron hook end pylori, acidophilus
Vulcanize one or more in bacillus.
10. separation method according to claim 1 or 2, which is characterized in that the step（1）Middle stirring is by leachate
It is placed in stirred reactor, is quickly stirred with 2-8 m/s linear velocities, the reaction time that iron powder and leachate is added is 0.5-2.0
Hour；The step（2）The middle iron powder and the reaction time of displaced liquid of being added is 0.5-1.0 hours.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109085031A (en) * | 2018-07-10 | 2018-12-25 | 济南裕兴化工有限责任公司 | A kind of foundation and its application of the measuring method and its quality testing system of titanium powder industry reduced iron powder Van der Waals absorption organic matter |
| CN110373544A (en) * | 2019-07-25 | 2019-10-25 | 中国科学院过程工程研究所 | A kind of Deep-Sea Microorganisms gradient handles the device and method of metal ion in heavy metal sewage sludge |
| CN110512082A (en) * | 2019-09-20 | 2019-11-29 | 常州工学院 | A kind of recovery method of discarded metal sludge |
| CN111254292A (en) * | 2020-01-20 | 2020-06-09 | 昆明瀚创科技有限公司 | Method for removing nickel, cobalt and germanium by zinc sulfate aqueous solution purification |
| CN113403486A (en) * | 2021-06-18 | 2021-09-17 | 国家电投集团黄河上游水电开发有限责任公司 | Process for removing iron from nickel sulfide concentrate leachate by goethite method |
| CN113403477A (en) * | 2021-06-18 | 2021-09-17 | 国家电投集团黄河上游水电开发有限责任公司 | Comprehensive utilization method of nickel sulfide concentrate |
| CN113416855A (en) * | 2021-06-18 | 2021-09-21 | 国家电投集团黄河上游水电开发有限责任公司 | Method for preparing nickel sulfate from nickel sulfide concentrate leaching solution |
| CN114752766A (en) * | 2021-07-30 | 2022-07-15 | 中南大学 | Method for selectively separating zinc, chromium and iron and recovering multiple metals in electroplating sludge |
| CN114933291A (en) * | 2022-04-08 | 2022-08-23 | 四川顺应动力电池材料有限公司 | Method for preparing high-purity lithium iron phosphate by using nickel-iron alloy |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014337A (en) * | 2013-01-10 | 2013-04-03 | 北京矿冶研究总院 | Method for separating copper, chromium and zinc in acid leaching solution |
| CN105200239A (en) * | 2015-09-29 | 2015-12-30 | 广西银亿再生资源有限公司 | Method of separating and recovering zinc from electroplating sludge |
| CN105648218A (en) * | 2015-12-31 | 2016-06-08 | 南京工业大学 | Method for recovering zinc and iron from electroplating sludge with high iron content |
| CN105734294A (en) * | 2016-02-05 | 2016-07-06 | 湖南埃格环保科技有限公司 | Harmless disposal and resource utilization method for electroplating sludge |
-
2017
- 2017-03-14 CN CN201710150999.1A patent/CN108570557B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014337A (en) * | 2013-01-10 | 2013-04-03 | 北京矿冶研究总院 | Method for separating copper, chromium and zinc in acid leaching solution |
| CN105200239A (en) * | 2015-09-29 | 2015-12-30 | 广西银亿再生资源有限公司 | Method of separating and recovering zinc from electroplating sludge |
| CN105648218A (en) * | 2015-12-31 | 2016-06-08 | 南京工业大学 | Method for recovering zinc and iron from electroplating sludge with high iron content |
| CN105734294A (en) * | 2016-02-05 | 2016-07-06 | 湖南埃格环保科技有限公司 | Harmless disposal and resource utilization method for electroplating sludge |
Non-Patent Citations (2)
| Title |
|---|
| 徐志峰 等: ""由混合电镀污泥硫酸浸出液选择性沉淀分离铬的研究"", 《有色金属科学与工程》 * |
| 雷霆 等编著: "《锌冶金》", 31 January 2013, 冶金工业出版社 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109085031A (en) * | 2018-07-10 | 2018-12-25 | 济南裕兴化工有限责任公司 | A kind of foundation and its application of the measuring method and its quality testing system of titanium powder industry reduced iron powder Van der Waals absorption organic matter |
| CN110373544A (en) * | 2019-07-25 | 2019-10-25 | 中国科学院过程工程研究所 | A kind of Deep-Sea Microorganisms gradient handles the device and method of metal ion in heavy metal sewage sludge |
| CN110512082A (en) * | 2019-09-20 | 2019-11-29 | 常州工学院 | A kind of recovery method of discarded metal sludge |
| CN110512082B (en) * | 2019-09-20 | 2020-11-03 | 常州工学院 | Recovery method of waste metal sludge |
| CN111254292A (en) * | 2020-01-20 | 2020-06-09 | 昆明瀚创科技有限公司 | Method for removing nickel, cobalt and germanium by zinc sulfate aqueous solution purification |
| CN113403486A (en) * | 2021-06-18 | 2021-09-17 | 国家电投集团黄河上游水电开发有限责任公司 | Process for removing iron from nickel sulfide concentrate leachate by goethite method |
| CN113403477A (en) * | 2021-06-18 | 2021-09-17 | 国家电投集团黄河上游水电开发有限责任公司 | Comprehensive utilization method of nickel sulfide concentrate |
| CN113416855A (en) * | 2021-06-18 | 2021-09-21 | 国家电投集团黄河上游水电开发有限责任公司 | Method for preparing nickel sulfate from nickel sulfide concentrate leaching solution |
| CN113403477B (en) * | 2021-06-18 | 2023-02-28 | 国家电投集团黄河上游水电开发有限责任公司 | Comprehensive utilization method of nickel sulfide concentrate |
| CN114752766A (en) * | 2021-07-30 | 2022-07-15 | 中南大学 | Method for selectively separating zinc, chromium and iron and recovering multiple metals in electroplating sludge |
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