CN106834699B - A kind of method of copper-contained sludge harmless treatment and higher value application - Google Patents

A kind of method of copper-contained sludge harmless treatment and higher value application Download PDF

Info

Publication number
CN106834699B
CN106834699B CN201710045860.0A CN201710045860A CN106834699B CN 106834699 B CN106834699 B CN 106834699B CN 201710045860 A CN201710045860 A CN 201710045860A CN 106834699 B CN106834699 B CN 106834699B
Authority
CN
China
Prior art keywords
copper
level
leaching
sludge
extraction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710045860.0A
Other languages
Chinese (zh)
Other versions
CN106834699A (en
Inventor
周洪波
赵邵安
周文博
陈军辉
秦荣钢
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Aige Environmental Protection Technology Co Ltd
Original Assignee
Hunan Aige Environmental Protection Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Aige Environmental Protection Technology Co Ltd filed Critical Hunan Aige Environmental Protection Technology Co Ltd
Priority to CN201710045860.0A priority Critical patent/CN106834699B/en
Publication of CN106834699A publication Critical patent/CN106834699A/en
Application granted granted Critical
Publication of CN106834699B publication Critical patent/CN106834699B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C22B7/007—Wet processes by acid leaching
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • 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
    • C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
    • 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
    • C22B3/30—Oximes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Treatment Of Sludge (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a kind of copper-contained sludge harmless treatment and the methods of higher value application, are leached by level-one, obtain copper products after two level leaching and extraction electrodeposition.Heavy iron is leached with copper-contained sludge two-stage and carries out ingenious couple by the present invention, dewatering is good, improve strainability, reduce influence of the impurity to copper extractant, conducive to the stability contorting of copper extraction process, it solves the problems, such as in high ferro copper-contained sludge leachate that iron concentration is far above copper ion concentration, makes lower by impurity in the copper rich solution that is obtained after extraction, it is easier to obtain high-quality tough cathode；It is leached using two-stage, depression effect of the copper ion to the sulphur iron oxidizing microorganisms in two level leaching of high concentration is greatly reduced after level-one leaching process, conducive to the copper of the form of the Various Complex for being not easy to be leached in microorganism in a short time depth extraction copper-contained sludge level-one leached mud, the higher value application of copper-contained sludge harmless treatment product is realized.

Description

A kind of method of copper-contained sludge harmless treatment and higher value application
Technical field
The invention belongs to hazardous waste harmlessness disposing and recycling field more particularly to a kind of copper-contained sludge are harmless Change the method for processing and higher value application.
Background technology
Copper-contained sludge is mainly the useless of Surface Processing Industry, printed circuit board industry, electroplating industry and wires and cables industry Final product in water treatment procedure, it is therein often to contain a large amount of heavy metal hydroxide and sulfide, it is a kind of non-steady Setting state is classified as hazardous waste if mishandling easily cause seriously to pollute to soil or underground water,《National Hazard is useless Name records (August in 2016 is implemented from 1 day)》In be classified as HW17 and HW22, collect, processing, storage, transport, transfer, disposition it is equal National Hazard waste related management regulation should be followed.Since the metallic copper content in copper-contained sludge exploits copper mine higher than existing Grade, and the attribute with hazardous waste mainly has heat treating process, chemical method and solid to copper-contained sludge method of disposal at present Change method etc., specific method are as follows：
(1) pyrolytic semlting absorption method, patent CN100506727C disclose a kind of recycling treatment process of electroplating sludge, Copper-contained sludge after drying is recycled into metallic copper with after flux, coke burden into smelting furnace.Patent CN102433437A is disclosed A kind of heavy metal-polluted mud resource and method for innocent treatment, first dehydrate sludge, be added solvent, binder into Row dispensing ball, finally recycles metal in smelting furnace.There are high energy consumptions for the two methods, and environmental pollution is big and is not suitable for low The processing of content heavy metal sewage sludge.
(2) method of chemical treatment, patent CN100402676C disclose one kind and " recycling the side of valuable metal from electroplating sludge Method ", by electroplating sludge Ore Leaching valuable metal, leachate is added the heavy copper of vulcanized sodium and obtains copper sulfide, but acid consumption is high, solid-liquid point From extremely difficult, washing effect is very poor, and the overall recovery of copper is low.Patent CN104726700A discloses a kind of " produced with copper-contained sludge The method of copper concentrate " extracts the metal in copper-contained sludge with sulfuric acid solution, vulcanized sodium is added into slurries, by the gold in solution Category is converted into sulfide, then floating cupric sulfide, scans tailings and is stored up after neutralizing and being dehydrated, filtrate standard discharge.But the method Obtained tailings of scanning does not handle the copper sulfide for equally be easy to causeing secondary pollution, and obtaining and is only capable of as industrial chemicals, into One step is converted to metallic copper or mantoquita product, and long flow path is of high cost.
(3) high-temperature calcination-acidleach combination method, patent of invention CN103979755A disclose a kind of electroplating sludge and contain with low amounts Copper Method for comprehensive treatment of sludge, joint and pyrogenic process and wet processing, first carry out 1000 DEG C or so high temperature drying and other treatments by sludge, The metal-containing solutions obtained using diluted acid leaching obtain mixed metal electrolytic zinc-coated steel sheet by electrolysis, and treated, and dry slag can be prepared Solidified unburned brick.But the technique, which has been related to high-temperature heating and polymetallic electrolysis, high energy consumption, can discharge toxic and harmful gas, And the alloy electrolytic zinc-coated steel sheet prepared is crude product, wherein metal still needs further separation and Extraction.
As it can be seen that heat treating process the problems such as there are high energy consumption and big environmental pollutions, although method of chemical treatment can recycle in sludge Copper, but the tailings discharged still possibly can not meet Leaching standard, and after solidification method processing sludge long-time stability It is difficult to ensure that existing processing mode is difficult to take into account economical and environmentally friendly both sides benefit.It is low to seek a kind of processing cost of disposal, It is adaptable, environmental-friendly, and can realize that minimizing, recycling and innoxious processing method of disposal just seem to copper-contained sludge It is particularly urgent.
Currently, having various ways about copper-contained sludge high level recycling, prepared by a kind of such as printed wiring board copper-contained sludge The method (CN103979755A) of nano cuprous oxide, it is a kind of produced using copper-gold ore in copper-contained sludge prepare High Purity Gold and The method (CN103397190A) of copper sulphate, a kind of method (CN103422119A) producing tough cathode using copper-contained sludge, with And a kind of etching waste liquor prepares method (CN104692447A) of copper sulphate etc. with the processing simultaneously of wiring board sludge.But these methods The features such as there are of high cost, leached mud stability is poor, product quality is difficult to control, added value is low, large-scale application difficulty is larger, and Heavy metal in leached mud easily flows into environment and makes in the case of the environment for encountering acute variation or extreme acidophilic microorganism At serious pollution.
And at the innoxious aspect of sludge containing heavy metal, mainly there is Agricultural University Of Nanjing Zhou Lixiang etc. to invent in a kind of sludge The biological leaching-solvent extraction-electrodeposition recovering method (CN101497942) of heavy metal copper, to Jiangsu municipal sludge acidophilus Microorganism Acidithiobacillus thiooxidans TS6 and Acidithiobacillus ferrooxidans LX5 leachings Go out 5 days, final ph 2.4, heavy metal removing rate only 90%；Jiangsu University of Technology (former Jiangsu Teachers University of Technology) Cheng Jiehong etc. It has invented a kind of dirty with Acidithiobacillus ferrooxidans, Thiobacillus thioxidans and the extraction plating of heterotroph mixed microorganism solution The method of copper and mickel in mud, the method metal leaching rate is higher, but leaching process needs 2.5 days or more, and leaching cycle is longer；Nie Yuan Etc. a kind of recoverying and utilizing method (CN103451437A) of the body refuse of valuable metal containing Cu, Ni and Co has been invented, mainly helped using microorganism Leaching method, but pH value control 1.5~3.0 in leaching process, bacterium auxiliary leaching agent is additionally added, if existed in sludge a large amount of Iron ion then easily forms colloid, causes to be separated by solid-liquid separation difficulty, innoxious degree is unsatisfactory.The present inventor seminar once invented A kind of composite bacteria agent (CN104877933A) leached for electroplating sludge, and further invented bioanalysis to leach plating dirty The condition control method (CN104862474A) of heavy metal in mud, with operating cost is low, secondary pollution is small, innoxious degree is high The features such as, there is incomparable advantage with simple wet-treating, have a extensive future.But above-mentioned patent is in harmless treatment In the process, there is also the problems that organic matter suppresses growth of microorganism.
Invention content
It suppresses growth of microorganism etc. and asks for raffinate organic substance residues in the high heavy metal copper-contained sludge of grade and its technique Topic, the technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, providing a kind of will contain The process of metallic copper in copper sewage sludge harmlessness, minimizing and high efficiente callback sludge, specially a kind of copper-contained sludge The method of harmless treatment and higher value application.
In order to solve the above technical problems, technical solution proposed by the present invention is：
A kind of method of copper-contained sludge harmless treatment and higher value application, includes the following steps：
Step A：Leaching agent is added in being homogenized to copper-contained sludge and carries out level-one leaching, obtains level-one leachate and level-one leaches Slag after the level-one leached mud removes the metal ion of its entrainment, is added complex microorganism culture solution and carries out two as leaching agent Grade leaches, and obtained two level leachate returns to level-one leaching stage and repeats next round, and obtained two level leached mud removes it The metal ion of entrainment；
Step B：Extractant is added in the level-one leachate obtained after to step A and diluent carries out copper extraction, obtains copper Additive is added in the copper rich solution in raffinate and copper rich solution, handles to obtain tough cathode through electrodeposition, then obtain after washing and drying Obtain copper products.
Above-mentioned method, it is preferred that the step A specifically comprises the following steps：
(1) level-one leaches：Homogenate sludge is obtained after copper-contained sludge is pre-processed, and is added into the homogenate sludge dilute As leaching agent, it is (4~10) to make the liquid-solid ratio of Leaching Systems for sulfuric acid and/or two level leachate:1, sulphur acid for adjusting pH value is added To 2.5~3.5, stirring carries out level-one leaching, and the level-one leachate obtained after separation of solid and liquid is directly entered extraction stages, obtains Enter two level leaching stage after the metal ion of the washed removal entrainment of level-one leached mud；
(2) two level leaches：After the level-one leached mud obtained after step (1) is quantified, complex microorganism culture solution is added and makees For leaching agent, it is (4~10) to make the liquid-solid ratio of Leaching Systems:1, sulphur acid for adjusting pH value is added to 1.0~1.5, stirring carries out two Grade leaches, and obtained two level leachate returns to level-one leaching stage and repeats next round, and obtained two level leached mud is washed Remove the metal ion of entrainment；Copper content can be reduced to 400mg/kg hereinafter, a huge sum of money in washed treated two level leached mud Belong to content and meets the general solid waste requirements of hazardous waste judging standard GB5085.3-2007 and standard of soil environment quality GB15618- 1995 grade III Standards.
Above-mentioned copper-contained sludge is the waste of waste water treatment plant's discharge, and moisture content differs greatly, including from sewage disposal Wet mud of the moisture content that factory has just been separated by solid-liquid separation 75% or more, the short-term moisture content for stacking two weeks or so are 40~75% Sludge, and long-term stockpiling moisture content are less than 40% sludge.
Above-mentioned method, it is preferred that in the step (1), in the step (1), pretreated concrete operations include such as Lower step：To moisture content less than 40% copper-contained sludge removal bulky grain foreign matter after, through dry ball be ground to -200 mesh with Under, the dilution heat of sulfuric acid that the pH value of 1~2 times of copper-contained sludge quality is 2.0~3.0 is added, carries out homogenized；Exist to moisture content After 55%~75% copper-contained sludge removes bulky grain foreign matter, the pH value that copper-contained sludge quality 15%~25% is added is 2.0~3.0 Dilution heat of sulfuric acid, carry out homogenized；Copper-contained sludge to moisture content more than 75% directly carries out homogenized.
Preferably, in the step (1), the temperature control that level-one leaches is 60~90 DEG C, stirs the impeller linear speed of use Degree is 1~5m/s, and mixing time is 2~4h.
Preferably, in the step (2), the temperature control that two level leaches is 30~45 DEG C, stirs the impeller linear speed of use Degree is 1~5m/s, and mixing time is 4~6h.
Preferably, in the step B, extractant is hydroximic species of extractants, and the hydroximic species of extractants includes973N、In 984N, Acorga M5640, N902 and Mextral 5640H it is one or more (more preferably984N or Acorga M5640), the volumetric concentration of the extractant is 10%~20% (more preferably 15%)；The diluent is sulfonation Kerosene (preferably 260#Sulfonated kerosene).
Preferably, in the step B, additive includes 250~300mg/L of cobaltous sulfate, 0.1~2mg/L of guar gum and sulphur 0.5~5mg/L of urea.
Preferably, in the step B, electrodeposition processing includes tablet electrodeposition, eddy flow electrodeposition, parallel jet electrodeposition or diaphragm electricity The current density of product, electrodeposition is 180~300A/m2。
Preferably, in the complex microorganism culture solution mainly include acidophilia iron sulfur oxidizing bacterium, acidophilia heterotroph and Nutrient solution, the acidophilia iron sulfur oxidizing bacterium include Thiobacillus (Acidithiobacillus spp.), hook end pylori Belong to (Leptospirillum spp.), iron Ureaplasma (Ferroplasma spp.), vulcanization bacillus One or more of (Sulfobacillus spp.), the acidophilia heterotroph include acidophilus Pseudomonas (Acidiphilium Spp.) and/or one or more of acidophilus candida albicans (Candida spp.), the acidophilia iron sulfur oxidizing bacterium and acidophilia The inoculum concentration ratio of heterotroph is (5~30):1；In the complex microorganism culture solution, microculture mode is to be extracted using copper Extraction raffinate is continuously cultivated, and microorganism concn is (0.5~10) × 108A/mL, Fe2+Yangization Su Shuai≤0.6g/ (Lh).
Preferably, the specific preparation method of the nutrient solution includes the following steps：
Addition 0.5~3.5g/L of ammonium sulfate in the dilution heat of sulfuric acid of pH value 1.0~2.0, bitter salt 0.3~ 0.6g/L, 0.3~0.6g/L of dipotassium hydrogen phosphate, 0.05~0.15g/L of potassium chloride, 0.01~0.02g/L of calcium nitrate, seven hydration sulphur Acid 40~50g/L of ferrous iron is to get the culture solution；Or
The copper raffinate is adsorbed with activated carbon Filter column and carries out oil removal treatment, COD in the copper raffinate is made to reduce To 100mg/L hereinafter, every liter of copper raffinate obtains the battalion after 0.5~5g of ammonium sulfate and 0.15~1g of dipotassium hydrogen phosphate is added Nutrient solution.Technical scheme of the present invention is based primarily upon following technical principle：
1, Microorganism Leaching mechanism：The present invention uses leaching agent of the complex microorganism culture solution as two level leaching stage, Certain special microorganisms in complex microorganism culture solution, can accelerate low-valent metal, simple substance and the alloy in copper-contained sludge The oxidation dissolution of equal metal components, convenient for recycling.In the present invention, the Microorganism Leaching of copper-contained sludge is by under acid condition Two kinds of approach of Chemical Leaching and microbial action realize：Chemical Leaching, that is, elemental copper is in acid aerobic environment directly by oxygen Change；Microbial action is microorganism by the Fe in system2+It is oxidized to Fe3+, the Fe of generation3+It is reacted with metallic copper, forms ionic state Copper and dissolve out.The process can be reduced to following reaction equation：
2Cu+4H++O2→2Cu2++2H2O (1)
CuO+H2SO4→CuSO4+H2O (2)
Cu(OH)2+2H+→Cu2++2H2O (3)
Cu0+2Fe3+→Cu2++2Fe2+ (5)
Fe2+It is the energy source of microorganism, one to utilize Fe in the incubation of microorganism2+Growth and breeding supplements two level The biomass of leachate, two, which carry out microorganism, obtains Fe after energy2+It is oxidized to Fe3+, it is then returned to level-one leaching, Fe3+Precipitate into Enter level-one leached mud, and due to by Fe in solution in two level leaching process3+Influence, cause iron leaching rate be suppressed, most Eventually the few scum of residual copper (harmless slugging) has been obtained after two level leaching.
Complex microorganism culture solution is compounded using heterotroph and sulphur iron oxidizing microorganisms, reduces organic matter to sulphur iron-oxidizing bacteria Growth and the inhibition of oxidation activity, iron sulfur-oxidizing microorganisms are autotrophic microbe, carbon source CO2, energy substance is for ferrous iron and also Ortho states sulphur, activity are affected by organic matter, and for the iron sulfur oxidizing bacterium of the stringent autotrophy in part, the organic matter in solution is unsuitable It is lower for the organic concentration requirement of toxicity bigger more than 200mg/L, and research shows that using oxyphilous heterotroph and very Bacterium can effectively in degraded solutions toxic organic matter and extractant, organic matter can be effectively reduced and lived to iron sulfur oxidizing bacterium The influence of property.In addition, microbial cultivation process takes full advantage of remaining Fe in copper raffinate2+Ion as growth energy, Ferrous ion concentration in printed wiring board copper-contained sludge is usually higher, and the ferrous ion of level-one leaching process remnants still remains in In copper raffinate, and the Tie Tong of reduction-state often can be as the energy substance of iron sulfur oxidizing bacterium, but due to often being pressed from both sides in raffinate Band organic matter, organic matter is sometimes even higher in 200mg/L~1000mg/L ranges under normal circumstances, can pass through activated carbon COD COD in solution is reduced to 200mg/L or less by absorption method.Remaining organic matter can pass through selection and breeding in flora Acidophilia heterotroph acidophilus Pseudomonas (Acidiphilium spp.) and acidophilus candida albicans (Candida spp.) decompose, release Inhibition of the organic matter to other autotrophic bacteriums.
Currently, Microorganism Leaching effect mainly has immediate reaction mechanism, indirect mechanism and electrochemical action mechanism：① Immediate reaction mechanism：Directly effect refers to directly being in close contact between microbial cell and metal sulfide solid, passes through micro- life Distinctive Ferroxidase and sulphur oxidizing ferment directed oxidation metal sulfide in object and release metal；2. indirect mechanism： Indirectly-acting refers to that in acid condition, microorganism is by the ferrous sulfate rapid oxidation generated in direct mechanism at sulfuric acid height Iron, and ferric sulphate is a kind of common strong oxidizer in hydrometallurgy, and redox reaction can be played with metal sulfide, instead Ferric sulphate is reduced to ferrous sulfate or elementary sulfur after answering, and metal is then dissolved in the form of sulfate, and ferrous sulfate quilt Be oxidized to ferric sulphate, elementary sulfur by microbiological oxidation at sulfuric acid, so as to form a redox circulating leaching system, 3. electrochemical mechanism：Two kinds of different sulfide being immersed in same electrolyte solution, current potential is mostly unequal, and the two is one It rises and then forms primary battery, galvanic interaction occurs, current potential is high to occur reduction reaction for anode, and current potential is low to occur oxygen for cathode Change reaction, bacterium is firmly attached to sulfide surface, can form many small primary batteries.
2, it leaches and is coupled with heavy iron：Level-one leaching process and heavy iron PROCESS COUPLING are being ensured most copper leaching by the present invention While going out, Fe in system is effectively controlled3+Ion concentration, according to Fe2O3-H2O systems balance chart, in Fe3+The very low item of concentration Under part, Fe3+Alpha-feooh crystal settling will be formed, ferric hydroxide colloid is avoided to be formed, dewatering is good.In the present invention, heavy iron It does not need to reach the completely heavy iron in traditional handicraft, in order to reduce complicated procedures of forming, the heavy iron process of traditional five slots need not be used, But in such a way that single slot sinks iron two-stage leaching, two level leachate is back to level-one leaching, utilizes the alkaline matter in mud Neutralize two level leachate to corresponding pH value, and a small amount of crystal seed also contained in sludge be conducive to from crystallize, by ferric ion with Alpha-feooh crystal form settles, the Fe in final solution3+0.1g/L is reduced to hereinafter, Fe2+9g/L is reduced to hereinafter, to meet Level-one leachate carries out the basic demand of copper extraction.
3, two-stage leaches：Copper-contained sludge have passed through level-one and leach, and 90% or so metallic copper is transferred to level-one leaching in sludge Go out in liquid, the content of metallic copper is relatively low in level-one leached mud, but also needs to carry out further depth leaching to meet nothing The requirement of evilization；In two level leaching stage, mainly use Bioleaching method, a step section acidity of going forward side by side optimum to microorganism PH value ﹤ 2.0, controlled at 30 DEG C, under the action of bacterium, what the complicated oxide morphology copper in sludge was effectively leached It avoids ferric hydroxide colloid simultaneously to be formed, filtering is easy, and dewatering is good, the Bioleaching within the scope of rational leaching cycle By sewage sludge harmlessness.In addition, two sections of leachings have the further advantage that, high concentration is greatly reduced after level-one leaching process Copper ion to two level leach in sulphur iron oxidizing microorganisms depression effect, conducive to microorganism in a short time depth extraction contain The copper of the form of the Various Complex for being not easy to be leached in copper sludge level-one leached mud.
4, extraction electrodeposition：In the present invention, the extraction electrodeposition of leachate is similar to the hydrometallurgical processes of traditional copper, tradition Copper hydrometallurgical processes flow is as shown in Figure 1.The abstraction technique of the present invention is extracted with organic solvent, frequently referred to liquid-liquid extraction, Refer to being mixed with the aqueous solution being extracted with the immiscible organic solvent (extractant) with extracting power of water with a kind of, passes through After being sufficiently stirred, since the two relative density is different, it is divided by clarification two layers, one layer is organic phase (extraction phase), another Kind it is water phase (raffinate phase), in biphase equilibrium, is extracted substance and is allocated in two-phase by certain concentration ratio, to reaches point From, purification or enrichment purpose.The electrodeposition technology of the present invention is that anode and cathode is placed in slowly flowing or the groove body stagnated, Under the action of electric field, anion is to anode displacement, and cation is to cathode displacement, by controlling certain technology item Part, the metal cation to be obtained obtains electronic deposition in cathode and is precipitated, to obtain electrodeposition product.The present invention relates to the moon Pole and anode reaction are as follows：
Cathode reaction：
Me+(aq)+e-→Me(s)；
Anode reaction：
2H2O→O2(g)↑+4H++4e-。
Compared with prior art, beneficial effects of the present invention are：
Heavy iron and copper-contained sludge two-stage, are leached that progress is ingenious to be coupled by 1, process of the invention, and dewatering is good, carries High filtration performance reduces influence of the impurity to copper extractant, is conducive to the stability contorting of copper extraction process, it is dirty to solve high ferro cupric Iron concentration is far above the problem of copper ion concentration in mud leachate, makes through impurity in the copper rich solution that is obtained after extraction more It is low, it is easier to obtain high-quality tough cathode；Copper raffinate is after removing organic matter oil removing, after adding the nutrients such as a small amount of N P and K As the culture solution that microorganism growth continuous flow adds, reduce water consumption；It is leached using two-stage, it is big after level-one leaching process The big copper ion for reducing high concentration is conducive to microorganism in short-term to the depression effect of the sulphur iron oxidizing microorganisms in two level leaching The copper of the form of the Various Complex for being not easy to be leached in interior depth extraction copper-contained sludge level-one leached mud, realizes cupric Sewage sludge harmlessness handles the higher value application of product.
2, process of the invention, in level-one leaching stage, the Fe in copper-contained sludge3+Effective control, iron are obtained Ion conversion avoids Fe (OH) for alpha-feooh crystal3It is formed, leaching slurry is easy to be separated by solid-liquid separation, and obtained level-one leaches The influence that liquid enters after copper extraction stages to extractant is smaller, and 2.5~3.5 pH value is more advantageous to the extraction effect for improving copper Rate.
3, process of the invention, in two level leaching stage, addition complex microorganism culture solution is compound as leaching agent Certain special microorganisms in microbial culture medium, can accelerate the gold such as low-valent metal, simple substance and the alloy in copper-contained sludge The oxidation dissolution for belonging to component forms microorganism continuous extraction, realizes the depth of copper containing sulfurized ore in sludge convenient for recycling Degree leaches and sewage sludge harmlessness processing, and leaching cycle is shorter compared with traditional biological metallurgical technology, and due to pH value 1.0~ Between 1.5, the copper dissolution in leached mud is more thorough, and part ferro element is still present in alpha-feooh crystal form in leached mud, Filterability is good, and the copper residual quantity in leached mud is lower, innoxious degree higher.
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 traditional copper hydrometallurgical processes flow chart.
Fig. 2 is the process flow chart of the present invention.
Specific implementation mode
To facilitate the understanding of the present invention, the present invention is done below in conjunction with Figure of description and preferred embodiment more complete 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.
Embodiment 1：
The copper-contained sludge generated in the sewage disposal process of Hunan printed circuit board enterprise, the moisture content after press filtration are 75%, main component include copper, iron, the hydroxide of calcium and sulfate form of mixtures exist, also contain a small amount of quartz, The sulfide of copper, the sulfide of iron, copper-contained sludge essential element analysis result are shown in Table shown in 1-1.
Table 1-1：Butt copper-contained sludge essential element analysis result in embodiment 1
Element Cu Fe Ca Si Al Ni Zn Mn Cr Pb Sn
Content (%) 9.45 25.33 8.42 0.5 0.02 0.003 0.044 0.07 0.015 0.001 0.037
The copper-contained sludge harmless treatment of the present invention as shown in Figure 2 a kind of and the method for higher value application, including walk as follows Suddenly：
(1) pretreatment of copper-contained sludge：It takes 1kg copper-contained sludges to be placed in the polypropylene containers of 5L, sludge quality is added The dilution heat of sulfuric acid of 20% pH value 3.0 is transferred to the level-one leaching tanks of 15L after carrying out homogenized；
(2) level-one leaches：It is slowly added to dilute sulfuric acid in the homogenate sludge obtained after being pre-processed to step (1) or two level leaches For liquid as leaching agent, it is 6 to make the liquid-solid ratio of Leaching Systems:1, sulphur acid for adjusting pH value is added to 2.5, controls 85 DEG C of temperature, stirring Level-one leaching is carried out, agitator arm linear velocity 4m/s, leaching time 4h are separated by solid-liquid separation using vacuum filtration system, Obtained level-one leachate is directly entered copper extraction stages, after the metal ion of the washed removal entrainment of obtained level-one leached mud Into two level leaching stage；Concentration of metal ions is shown in Table shown in 1-2 in level-one leachate；
(3) two level leaches：After the level-one leached mud obtained after step (2) is quantified, complex microorganism culture solution is added and makees For leaching agent, cell concentration 1.2 × 108A/mL, it is 6 to make the liquid-solid ratio of Leaching Systems:1, addition sulphur acid for adjusting pH value to 1.5, Temperature 45 C, agitator arm linear velocity 1.6.m/s, leaching time 4h are controlled, stirring carries out two level leaching；Obtained two level Contain copper and iron in leachate, it is added in the homogenate sludge of level-one leaching stage at a slow speed, the sludge of next round is repeated It leaches, concentration of metal ions is shown in Table shown in 1-2 in two level leachate；Obtained two level leached mud is through 6:The clear water of 1 liquid-solid ratio is washed The metal ion for removing entrainment afterwards twice is washed, metallic element analysis result such as table 1-3 institutes in the two level leached mud obtained after washing Show；
It is described mainly including acidophilia iron sulfur oxidizing bacterium, acidophilia heterotroph and nutrient solution in complex microorganism culture solution Acidophilia iron sulfur oxidizing bacterium is Acidithiobacillus ferrooxidans (Acidithiobacillus ferrooxidans ATCC 23270, culture presevation number：ATCC 23270 is purchased from American Type Culture Collection, the typical micro- life in the U.S. Object Culture Collection Center), the acidophilia heterotroph is that Acidiphilium acidophilum ATCC 27807 (protect by strain Tibetan number：ATCC 23270 is purchased from American Type Culture Collection, in American Type Culture preservation The heart), the inoculum concentration ratio of the acidophilia iron sulfur oxidizing bacterium and acidophilia heterotroph is 5:1, by the copper ion of gradient concentration Domestication is cultivated, and continuous passage culture is above three times under the conditions of each gradient copper ion concentration improves to next concentration, copper ion Concentration is followed successively by 0.5g/L, 1g/L, 3g/L, 6g/L, 9g/L, 12g/L, 15g/L and 20g/L, and raising terminates to tame to 25g/L, Fe2+Oxidation rate be 1.0g/ (Lh) when be enlarged culture, initial nutrient solution key component is：(NH4)2SO4 3g/L、 MgSO4·7H2O 0.5g/L、K2HPO4 0.5g/L、KCl 0.1g/L、Ca(NO3)20.01g/L and FeSO4·7H2O 44.70g/L, nutrient solution sulphur acid for adjusting pH value 1.0~2.0 control 35 DEG C of cultivation temperature；Cycle stage nutrient solution is from step Suddenly the copper raffinate obtained after (4), copper raffinate activated carbon Filter column adsorb oil removal treatment, can COD be reduced to 100mg/L Hereinafter, microculture is continuously to be cultivated using raffinate, (NH is periodically added in culture of continuous cultivation into raffinate4)2SO4 0.5g/L and K2HPO40.15g/L, the leaching agent that cultured microbial solution is leached as two level；
(4) extraction of copper：The level-one leachate obtained after step (1) is entered before extraction and first passes through the removal of coarse filtration system Grain object adds extractant and diluent and carries out copper extraction, extractant use volumetric concentration for 15% hydroximic species of extractants Mextral5640H, diluent 260#Sulfonated kerosene, extraction carry out in taper stirred tanks of the 2L with temperature control, temperature control 30 DEG C of system, extraction phase ratio O/A are 1:1, extraction series is 3 grades, and extraction stirring 10min, split-phase 3min wash 1 grade of series, washing It is 2 compared to O/A:1, copper rich solution is obtained, back extraction is 2 compared to O/A:1, obtain back extraction copper-rich liquid；Each GOLD FROM PLATING SOLUTION category of extraction stages Ion concentration is shown in Table shown in 1-2；
(5) electrodeposition of copper：Additive, including cobaltous sulfate 250mg/L, Gu are added in the copper rich solution obtained after step (4) You are glue 2mg/L and thiocarbamide 1mg/L, and the back extraction copper-rich liquid of the 10L of multigroup experiment is taken to be powered in batches in the small-sized eddy flow electrowinning plants of 4L Product tough cathode, cathode area 0.04m2, current density 200A/m2, the tough cathode that electrodeposition obtains, through washing and drying obtain copper products, The analysis result of contained element is as shown in table 1-4 in tough cathode.
Table 1-2：1 each solution metal ion concentration analysis result of embodiment
Table 1-3：Metallic element analysis result in the two level leached mud that embodiment 1 obtains after washing
Table 1-4：The analysis result of contained element in 1 tough cathode of embodiment
Using this technique it can be seen from table 1-2, table 1-3 and table 1-4, the copper in sludge is gradually in level-one leachate Enrichment, and the iron ion (predominantly ferric iron) in solution is controlled well in lower level, further by extracting electricity Product can prepare 1# cathode copper products, and the filter residue after level-one leaches is extracted further through microorganism further by the copper in solid phase Content be reduced to 375mg/kg, the copper content in detoxification leached mud is close to Soil standard.
Embodiment 2：
The copper-contained sludge generated in the sewage disposal process of Jiangsu surface treatment enterprise, the moisture content 68% after press filtration, Main component is shown in Table shown in 2-1, and copper object distributed mutually is as shown in table 2-2.
Table 2-1：Butt copper-contained sludge essential element analysis result in embodiment 2
Element Cu Fe Ca Si Al Mg Mn Na Ni Pb Zn Cr
Content (%) 14 19.05 12.16 0.026 0.227 1.578 0.21 0.235 0.089 0.002 0.001 0.001
Table 2-2：The object distributed mutually of butt copper in embodiment 2
Object phase Free copper oxide In conjunction with copper oxide Chalcopyrite Secondary copper sulfide Total copper
Content (%) 8.94 5 0.01 0.05 14
Ratio (%) 63.86 35.71 0.07 0.36 100
The copper-contained sludge harmless treatment of the present invention as shown in Figure 2 a kind of and the method for higher value application, including walk as follows Suddenly：
(1) pretreatment of copper-contained sludge：It takes 40kg copper-contained sludges to be placed in the polypropylene containers of 500L, sludge quality is added The dilution heat of sulfuric acid of 20% pH value 3.0 carries out homogenized and obtains homogenate sludge；
(2) level-one leaches：It is slowly added to dilute sulfuric acid in the homogenate sludge obtained after being pre-processed to step (1) or two level leaches For liquid as leaching agent, it is 10 to make the liquid-solid ratio of Leaching Systems:1, sulphur acid for adjusting pH value is added to 2.5, controls 85 DEG C of temperature, stirring Impeller linear velocity 2m/s, leaching time 2h, stirring carries out level-one leaching, using 1m2The vacuum filtration system of filter area It is separated by solid-liquid separation, obtained level-one leachate is directly entered copper extraction stages, the washed removal folder of obtained level-one leached mud Enter two level leaching stage after the metal ion of band；Concentration of metal ions is shown in Table shown in 2-3 in level-one leachate；
(3) two level leaches：After the level-one leached mud obtained after step (2) is quantified, complex microorganism culture solution is added and makees For leaching agent, cell concentration 1 × 108A/mL, it is 10 to make the liquid-solid ratio of Leaching Systems:1, addition sulphur acid for adjusting pH value to 1.5., 40 DEG C of temperature, agitator arm linear velocity 2m/s, leaching time 4h are controlled, stirring carries out two level leaching；Obtained two level leaching Go out and contain copper and iron in liquid, it is added in the homogenate sludge of level-one leaching stage at a slow speed, repeats the sludge leaching of next round Go out, concentration of metal ions is shown in Table shown in 2-3 in two level leachate；Obtained two level leached mud is through 6:The clear water of 1 liquid-solid ratio washs The metal ion for removing entrainment afterwards twice, metallic element analysis result is as shown in Table 2-4 in the two level leached mud obtained after washing；
It is described mainly including acidophilia iron sulfur oxidizing bacterium, acidophilia heterotroph and nutrient solution in complex microorganism culture solution Acidophilia iron sulfur oxidizing bacterium is Thiobacillus ferrooxidans (Acidithiobacillus ferrooxidans ATCC 23270, bacterium Kind preserving number：ATCC 23270, is purchased from American Type Culture Collection, and American Type Culture is protected Tibetan center), leptospirillum ferriphilum (Leptospirillum ferriphilum CS13, culture presevation number：M2015010 is protected Hide place：China typical culture collection center) and Sulfobacillus acidophilus (Sulfobacillus acidophilus CS5, culture presevation number：M2015006, preservation place：China typical culture collection center), the acidophilia heterotroph is 27807 (culture presevation number of Acidiphilium acidophilum ATCC：ATCC 23270 is purchased from American Type Culture Collection, American Type Culture collection), inoculum concentration ratio is 2 in the order described above:2:2: 1, it tames and cultivates by the copper ion of gradient concentration, continuous passage culture is above three times under the conditions of each gradient copper ion concentration carries Up to next concentration, copper ion concentration are followed successively by 0.5g/L, 1g/L, 3g/L, 6g/L, 9g/L, 12g/L, 15g/L and 20g/L, Raising terminates to tame to 25g/L, Fe2+Oxidation rate be enlarged culture when being 1.0g/ (Lh), the main group of initial nutrient solution It is divided into：(NH4)2SO4 3g/L、MgSO4·7H2O 0.5g/L、K2HPO4 0.5g/L、KCl 0.1g/L、Ca(NO3)2 0.01g/L And FeSO4·7H2O 44.70g/L, nutrient solution sulphur acid for adjusting pH value 1.0~2.0 control 35 DEG C of cultivation temperature；Cycle stage Nutrient solution derives from the copper raffinate obtained after step (4), and copper raffinate activated carbon Filter column adsorbs oil removal treatment, can incite somebody to action COD is reduced to 100mg/L hereinafter, microculture is continuous culture, is periodically added into raffinate in culture of continuous cultivation (NH4)2SO41.5g/L and K2HPO40.25g/L, the leaching agent that cultured microbial solution is leached as two level；
(4) extraction of copper：The level-one leachate obtained after step (1) is entered before extraction and first passes through the removal of coarse filtration system Grain object adds extractant and diluent and carries out copper extraction, extractant use volumetric concentration for 15% hydroximic species of extractants Acorga M5640, diluent 260#Sulfonated kerosene, extraction carry out in taper stirred tanks of the 2L with temperature control, temperature control 30 DEG C of system, extraction phase ratio O/A are 1:1, extraction series is 3 grades, and extraction stirring 10min, split-phase 3min wash 1 grade of series, washing It is 2 compared to O/A:1, copper rich solution is obtained, back extraction is 2 compared to O/A:1, obtain back extraction copper-rich liquid；Each GOLD FROM PLATING SOLUTION category of extraction stages Ion concentration is shown in Table shown in 2-3；
(5) electrodeposition of copper：Additive, including cobaltous sulfate 250mg/L, Gu are added in the copper rich solution obtained after step (4) You are glue 2mg/L and thiocarbamide 1mg/L, and the back extraction copper-rich liquid of the 10L of multigroup experiment is taken to be powered in batches in the small-sized eddy flow electrowinning plants of 4L Product tough cathode, cathode area 0.04m2, current density 300A/m2, the tough cathode that electrodeposition obtains, through washing and drying obtain copper products, The analysis result of contained element is as shown in table 2-5 in tough cathode.
Table 2-3：2 each solution metal ion concentration analysis result of embodiment
Table 2-4：Metallic element analysis result in the two level leached mud that embodiment 2 obtains after washing
Table 2-5：The analysis result of contained element in 2 tough cathode of embodiment
It can be seen that using this technique by table 2-3, table 2-4 and table 2-5, the copper in sludge is gradually rich in level-one leachate Collection, and the iron ion (predominantly ferric iron) in solution is controlled well in lower level, further pass through extraction electrodeposition 1# cathode copper products can be prepared, and the filter residue after level-one leaches is extracted further through microorganism further by the copper in solid phase Content is reduced to 0.028%, and the copper content in detoxification leached mud is close to Soil standard.
Embodiment 3：
The acid water of the cupric of Guangdong printed wiring board enterprise by lime precipitation by most heavy metal precipitation, Moisture content 65% after the copper-contained sludge press filtration of sedimentation, main component are shown in Table 3-1, and copper object distributed mutually is as shown in table 3-2.
Table 3-1：Butt copper-contained sludge essential element analysis result in embodiment 3
Table 3-2：The object distributed mutually of butt copper in embodiment 3
Object phase Free copper oxide In conjunction with copper oxide Chalcopyrite Secondary copper sulfide Total copper
Content (%) 5.14 3.5 0.24 3.77 12.65
Ratio (%) 40.63 27.67 1.90 29.80 100.00
The copper-contained sludge harmless treatment of the present invention as shown in Figure 2 a kind of and the method for higher value application, including walk as follows Suddenly：
(1) pretreatment of copper-contained sludge：200kg copper-contained sludges are taken to be placed in 2m3Level-one leaching tanks in, be added sludge quality The dilution heat of sulfuric acid of 20% pH value 3.0 carries out homogenized and obtains homogenate sludge；
(2) level-one leaches：It is slowly added to dilute sulfuric acid in the homogenate sludge obtained after being pre-processed to step (1) or two level leaches For liquid as leaching agent, it is 10 to make the liquid-solid ratio of Leaching Systems:1, sulphur acid for adjusting pH value is added to 2.5, controls 75 DEG C of temperature, stirring Impeller linear velocity 5m/s, leaching time 4h, stirring carries out level-one leaching, using 3m2The vacuum filtration system of filter area It is separated by solid-liquid separation, obtained level-one leachate is directly entered copper extraction stages, the washed removal folder of obtained level-one leached mud Enter two level leaching stage after the metal ion of band；Concentration of metal ions is shown in Table shown in 3-3 in level-one leachate；
(3) two level leaches：After the level-one leached mud obtained after step (2) is quantified, complex microorganism culture solution is added and makees For leaching agent, cell concentration 1 × 108A/mL, it is 10 to make the liquid-solid ratio of Leaching Systems:1, addition sulphur acid for adjusting pH value to 1.5, 40 DEG C of temperature, agitator arm linear velocity 2.3m/s, leaching time 4h are controlled, stirring carries out two level leaching；Obtained two level Contain copper and iron in leachate, it is added in the homogenate sludge of level-one leaching stage at a slow speed, the sludge of next round is repeated It leaches, concentration of metal ions is shown in Table shown in 3-3 in two level leachate；Obtained two level leached mud is through through 6:The clear water of 1 liquid-solid ratio The metal ion of entrainment is removed after washing twice, metallic element analysis result such as table 3-4 in the two level leached mud obtained after washing It is shown；
It is described mainly including acidophilia iron sulfur oxidizing bacterium, acidophilia heterotroph and nutrient solution in complex microorganism culture solution Acidophilia iron sulfur oxidizing bacterium is leptospirillum ferriphilum (Leptospirillum ferriphilum CS13, culture presevation number： M2015010, preservation place：China typical culture collection center) and Sulfobacillus acidophilus (Sulfobacillus Acidophilus CS5, culture presevation number：M2015006, preservation place：China typical culture collection center), the acidophilus Property heterotroph be 27807 (culture presevation number of Acidiphilium acidophilum ATCC：ATCC 23270, is purchased from American Type Culture Collection, American Type Culture collection) and acidophilus candida albicans (Candida digboiensis MTCC 4731T, culture presevation number：MTCC 4731T, it is purchased from Microbial Type Culture Collection and Gene Bank, India's representative microbial and gene preservation library), it is inoculated in the order described above Ratio is 5:5:1:1, it tames and cultivates by the copper ion of gradient concentration, continuous passage training under the conditions of each gradient copper ion concentration Support it is above three times improve to next concentration, copper ion concentration be followed successively by 0.5g/L, 1g/L, 3g/L, 6g/L, 9g/L, 12g/L, 15g/L and 20g/L, raising terminate to tame to 25g/L, Fe2+Oxidation rate be 1.0g/ (Lh) when be enlarged culture, just Beginning nutrient solution key component is：(NH4)2SO4 3g/L、MgSO4·7H2O 0.5g/L、K2HPO4 0.5g/L、KCl 0.1g/L、 Ca(NO3)20.01g/L and FeSO4·7H2O 44.70g/L, nutrient solution sulphur acid for adjusting pH value 1.5 control cultivation temperature 45 ℃；Cycle stage nutrient solution derives from the copper raffinate obtained after step (4), and copper raffinate activated carbon Filter column adsorbs oil removing COD can be reduced to 100mg/L hereinafter, microculture is continuous culture, periodically to raffinate in culture of continuous cultivation by processing In add (NH4)2SO42.5g/L and K2HPO40.35g/L, the leaching agent that cultured microbial solution is leached as two level；
(4) extraction of copper：The level-one leachate obtained after step (1) is entered before extraction and first passes through the removal of coarse filtration system Grain object adds extractant and diluent and carries out copper extraction, extractant use volumetric concentration for 15% hydroximic species of extractants973N, diluent 260#Sulfonated kerosene, extraction carry out in taper stirred tanks of the 2L with temperature control, temperature control 30 DEG C, extraction phase ratio O/A is 1:1, extraction series is 2 grades, and extraction stirring 10min, split-phase 3min wash 1 grade of series, wash phase It is 2 than O/A:1, copper rich solution is obtained, back extraction is 2 compared to O/A:1, obtain back extraction copper-rich liquid；Each GOLD FROM PLATING SOLUTION category of extraction stages from Sub- concentration is shown in Table shown in 3-3；
(5) electrodeposition of copper：Additive, including cobaltous sulfate 250mg/L, Gu are added in the copper rich solution obtained after step (4) You are glue 2mg/L and thiocarbamide 1mg/L, using small-sized slot type electrolytic cell electrodeposition, cathode plate effective area 1.6m2, current density 250A/ m2The 8.5kg tough cathodes that electrodeposition obtains obtain copper products through washing and drying, the analysis result such as table 3- of contained element in tough cathode Shown in 5.
Table 3-3：3 each solution metal ion concentration analysis result of embodiment
Table 3-4：Metallic element analysis result in the two level leached mud that embodiment 3 obtains after washing
Table 3-5：The analysis result of contained element in 3 tough cathode of embodiment
Using this technique it can be seen from table 3-3, table 3-4 and table 3-5, the copper in sludge is gradually in level-one leachate Enrichment, and the iron ion (predominantly ferric iron) in solution is controlled well in lower level, further by extracting electricity Product can prepare 1# cathode copper products, and the filter residue after level-one leaches is extracted further through microorganism further by the copper in solid phase Content be reduced to 390mg/kg, the copper content in detoxification leached mud is close to Soil standard.
Embodiment 4：
The copper-contained sludge generated in the sewage disposal process of Zhejiang printed wiring board enterprise, the moisture content after direct press filtration 58%, main component is shown in Table 4-1.
Table 4-1：Butt copper-contained sludge essential element analysis result in embodiment 4
Element Cu Fe Ca Si Al Mg Mn Na Ni Pb Zn Cr
Content (%) 8.99 5.81 20.6 1.8 0.79 0.44 0.18 0.01 0.07 0.09 0.14 0.001
The copper-contained sludge harmless treatment of the present invention as shown in Figure 2 a kind of and the method for higher value application, including walk as follows Suddenly：
(1) pretreatment of copper-contained sludge：It takes 40kg copper-contained sludges to be placed in the level-one leaching tanks of 500L, sludge quality is added The dilution heat of sulfuric acid of 20% pH value 3.0 carries out homogenized and obtains homogenate sludge；
(2) level-one leaches：It is slowly added to dilute sulfuric acid in the homogenate sludge obtained after being pre-processed to step (1) or two level leaches For liquid as leaching agent, it is 10 to make the liquid-solid ratio of Leaching Systems:1, sulphur acid for adjusting pH value is added to 2.8, controls 85 DEG C of temperature, stirring Impeller linear velocity 2m/s, leaching time 4h, stirring carries out level-one leaching, using 1m2The vacuum filtration system of filter area It is separated by solid-liquid separation, obtained level-one leachate is directly entered copper extraction stages, the washed removal folder of obtained level-one leached mud Enter two level leaching stage after the metal ion of band；Concentration of metal ions is shown in Table shown in 4-2 in level-one leachate；
(3) two level leaches：After the level-one leached mud obtained after step (2) is quantified, complex microorganism culture solution is added and makees For leaching agent, cell concentration 3.9 × 108A/mL, it is 8 to make the liquid-solid ratio of Leaching Systems:1, addition sulphur acid for adjusting pH value to 1.5, 30 DEG C of temperature, agitator arm linear velocity .1.44m/s, leaching time 4h are controlled, stirring carries out two level leaching；Two obtained Contain copper and iron in grade leachate, it is added in the homogenate sludge of level-one leaching stage at a slow speed, the dirt of next round is repeated Mud leaches, and concentration of metal ions is shown in Table shown in 4-2 in two level leachate；Obtained two level leached mud is through through 6:1 liquid-solid ratio it is clear Water washing removes the metal ion of entrainment afterwards twice, metallic element analysis result such as table 4- in the two level leached mud obtained after washing Shown in 3；
Include mainly acidophilia iron sulfur oxidizing bacterium, acidophilia heterotroph and nutrient solution, acidophilus in complex microorganism culture solution Property iron sulfur oxidizing bacterium be Acidithiobacillus ferrivorans CS12 (culture presevation number：M2015009, preservation Point：China typical culture collection center), leptospirillum ferriphilum (Leptospirillum ferriphilum CS13, bacterium Kind preserving number：M2015010, preservation place：China typical culture collection center) and Sulfobacillus acidophilus (Sulfobacillus acidophilus CS5, culture presevation number：M2015006, preservation place：Chinese Typical Representative culture is protected Tibetan center), the acidophilia heterotroph is 27807 (culture presevation number of Acidiphilium acidophilum ATCC：ATCC 23270, it is purchased from American Type Culture Collection, American Type Culture collection), according to upper It is 2 to state sequence inoculum concentration ratio:2:2:1, tame culture, each gradient copper ion concentration condition by the copper ion of gradient concentration Lower continuous passage culture is above three times to improve to next concentration, copper ion concentration be followed successively by 0.5g/L, 1g/L, 3g/L, 6g/L, 9g/L, 12g/L, 15g/L and 20g/L, raising terminate to tame to 25g/L, Fe2+Oxidation rate be 1.0g/ (Lh) when carry out Expand culture, initial nutrient solution key component is：(NH4)2SO4 3g/L、MgSO4·7H2O 0.5g/L、K2HPO4 0.5g/L、 KCl 0.1g/L、Ca(NO3)20.01g/L and FeSO47H2O 44.70g/L, nutrient solution with sulphur acid for adjusting pH value 1.0~ 2.0 controlling 30 DEG C of cultivation temperature；Cycle stage nutrient solution derives from the copper raffinate obtained after step (4), and copper raffinate is lived Property charcoal Filter column adsorb oil removal treatment, COD can be reduced to 100mg/L hereinafter, microculture be using copper raffinate it is continuous It cultivates, periodically (NH is added into copper raffinate in culture of continuous cultivation4)2SO40.5g/L and K2HPO40.15g/L is cultivated The leaching agent that is leached as two level of microbial solution；
(4) extraction of copper：The level-one leachate obtained after step (1) is entered before extraction and first passes through coarse filtration removal particle Object adds extractant and diluent and carries out copper extraction, extractant use volumetric concentration for 20% hydroximic species of extractants Acorga M5640 andThe one of 984N is than first-class volume mixture object, diluent 260#Sulfonated kerosene, extraction is in 2L band temperature It is carried out in the taper stirred tank of control, temperature controls 30 DEG C, and extraction phase ratio O/A is 1:1, extraction series is 3 grades, extraction stirring 10min, split-phase 3min, wash 1 grade of series, and washing is 2 compared to O/A:1, copper rich solution is obtained, back extraction is 2 compared to O/A:1, it obtains It is stripped copper-rich liquid；Each metal ion in solution concentration of extraction stages is shown in Table shown in 4-2；
(5) electrodeposition of copper：Additive, including cobaltous sulfate 250mg/L, Gu are added in the copper rich solution obtained after step (4) You are glue 2mg/L and thiocarbamide 1mg/L, and the back extraction copper-rich liquid of the 10L of multigroup experiment is taken to be powered in batches in the small-sized eddy flow electrowinning plants of 4L Product tough cathode, cathode area 0.04m2, current density 200A/m2, electrodeposition obtains tough cathode, copper products is obtained through washing and drying, cloudy The analysis result of contained element is as shown in table 4-4 in the copper of pole.
Table 4-2：4 each solution metal ion concentration analysis result of embodiment
Table 4-3：Metallic element analysis result in the two level leached mud that embodiment 4 obtains after washing
Table 4-4：The analysis result of contained element in 4 tough cathode of embodiment
Using this technique it can be seen from table 4-2, table 4-3 and table 4-4, the copper in sludge is gradually in level-one leachate Enrichment, and the iron ion (predominantly ferric iron) in solution is controlled well in lower level, further pass through extraction-electricity Product can prepare 1# cathode copper products, and the filter residue after level-one leaches is extracted further through microorganism further by the copper in solid phase Content be reduced to 390mg/kg, the copper content in detoxification leached mud is close to Soil standard.
Comparative example 1：
The leachate 1L of Example 1~4 respectively, in the Buchner funnel (Buchner funnel specification 150mm) that internal diameter is 135mm On filtered with double-layer filter paper, it is (each to compare a step leaching using traditional acidleach under the same conditions by limiting pressure 0.06Pa Control group condition is：Liquid-solid ratio, extraction temperature, stirring extent are identical as each group embodiment, pH value 2.0, and mixing time is 2 small When) and the present invention in two-stage leach filter until filter cake crack, record filter the time, filter effect comparison be shown in Table 5-1.
Table 5-1：The leachate strainability of comparative example 1 compares
Title Level-one leachate filters the time (min) Two level leachate filters the time (min) Acidleach control filters the time (min)
Embodiment 1 10 15 325
Embodiment 2 8 10 250
Embodiment 3 15 20 275
Embodiment 4 14 17 300
Iron in sludge is can effectively avoid it can be seen from table 5-1 using this technique to form in dissolving out equilibrium process Colloid, strainability significantly improves compared with conventional method.
Comparative example 2：
Using conventional wet leaching as control group, each collating condition is：Liquid-solid ratio, extraction temperature, stirring extent and each group are real It is identical to apply example, pH value 2.0, mixing time is 2 hours, the leached mud and leachate that solid-liquid obtains, and it is molten that extraction back extraction obtains copper-rich Liquid.The leaching effect of copper in analysis Examples 1 to 4 and the copper and iron distribution situation in leachate are shown in Table 6-1.
Table 6-1：The copper and iron leaching effect of comparative example 2 compares
Compared with the prior art, the present invention is cleverly combined biological extraction with two level leaching, is ensureing metallic copper In the case of high-recovery, not only effectively the iron in sludge can be inhibited in leached mud, it is fully sharp to be conducive to downstream process With the metallic iron in sludge, while ensuring being carried out continuously for Bacteria Culture so that copper-contained sludge effectively obtains cleaning harmless Change disposition and higher value application.
Only several embodiments of the present invention are expressed for embodiment described above, the description thereof is more specific and detailed, but Can not the limitation of the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that coming for member of ordinary skill in the art It says, without departing from the inventive concept of the premise, several deformations or change can also be made, these belong to the protection of the present invention Range.Therefore, scope of patent protection of the present invention should be determined by the appended claims.

Claims (9)

1. a kind of method of copper-contained sludge harmless treatment and higher value application, includes the following steps：
Step A：Level-one leaches, and homogenate sludge is obtained after copper-contained sludge is pre-processed, is added into the homogenate sludge dilute As leaching agent, it is (4~10) to make the liquid-solid ratio of Leaching Systems for sulfuric acid and/or two level leachate:1, sulphur acid for adjusting pH value is added To 2.5~3.5, stirring carries out level-one leaching, and obtaining level-one leachate after separation of solid and liquid is directly entered extraction stages, obtains Enter two level leaching stage after the metal ion of the washed removal entrainment of level-one leached mud；
Two level leaches, and after the level-one leached mud obtained after level-one is leached is quantitative, complex microorganism culture solution is added as leaching Agent, it is (4~10) to make the liquid-solid ratio of Leaching Systems:1, sulphur acid for adjusting pH value is added to 1.0~1.5, stirring carries out two level leaching, Obtained two level leachate returns to level-one leaching stage and repeats next round, the washed removal entrainment of obtained two level leached mud Metal ion；
It is described mainly including acidophilia iron sulfur oxidizing bacterium, acidophilia heterotroph and nutrient solution in the complex microorganism culture solution Acidophilia iron sulfur oxidizing bacterium includes Thiobacillus (Acidithiobacillus spp.), hook end screw rod Pseudomonas (Leptospirillum spp.), iron Ureaplasma (Ferroplasma spp.), vulcanization bacillus One or more of (Sulfobacillus spp.), the acidophilia heterotroph include acidophilus Pseudomonas (Acidiphilium Spp.) and/or one or more of acidophilus candida albicans (Candida spp.), the acidophilia iron sulfur oxidizing bacterium and acidophilia The inoculum concentration ratio of heterotroph is (5~30):1；In the complex microorganism culture solution, microculture mode is to be extracted using copper Extraction raffinate is continuously cultivated；
Step B：Extractant is added in the level-one leachate obtained after to step A and diluent carries out copper extraction, obtains copper raffinate Additive is added in the copper rich solution in liquid and copper rich solution, handles to obtain tough cathode through electrodeposition, then obtain copper after washing and drying Product.
2. according to the method described in claim 1, it is characterized in that, the step A level-ones leach in, pretreated concrete operations Include the following steps：
To moisture content less than 40% copper-contained sludge removal bulky grain foreign matter after, be ground to -200 mesh through dry ball hereinafter, The dilution heat of sulfuric acid that the pH value of 1~2 times of copper-contained sludge quality is 2.0~3.0 is added, carries out homogenized；
To moisture content after 55%~75% copper-contained sludge removes bulky grain foreign matter, copper-contained sludge quality 15%~25% is added The dilution heat of sulfuric acid that pH value is 2.0~3.0 carries out homogenized；
Copper-contained sludge to moisture content more than 75% directly carries out homogenized.
3. according to the method described in claim 1, it is characterized in that, the step A level-ones leach in, level-one leach temperature control 60~90 DEG C are made as, stirs the impeller linear velocity used as 1~5m/s, mixing time is 2~4h.
4. according to the method described in claim 1, it is characterized in that, the step A two levels leach in, two level leach temperature control 30~45 DEG C are made as, stirs the impeller linear velocity used as 1~5m/s, mixing time is 4~6h.
5. method according to any one of claims 1 to 4, which is characterized in that in the step B, extractant is hydroxyl oxime Kind of extractants, the hydroximic species of extractants include LIX973N, LIX984N, Acorga M5640, N902 and Mextral 5640H In it is one or more, the volumetric concentration of the extractant is 10%~20%；The diluent is sulfonated kerosene.
6. method according to any one of claims 1 to 4, which is characterized in that in the step B, additive includes sulphur Sour 250~300mg/L of cobalt, 0.5~5mg/L of 0.1~2mg/L of guar gum and thiocarbamide.
7. method according to any one of claims 1 to 4, which is characterized in that in the step B, electrodeposition processing includes The current density of tablet electrodeposition, eddy flow electrodeposition, parallel jet electrodeposition or diaphragm electrodeposition, electrodeposition is 180~300A/m2。
8. method according to any one of claims 1 to 4, which is characterized in that micro- in the complex microorganism culture solution Biological concentration is (0.5~10) × 108A/mL, Fe2+Yangization Su Shuai≤0.6g/ (Lh).
9. according to the method described in claim 8, it is characterized in that, the specific preparation method of the nutrient solution includes following step Suddenly：
0.5~3.5g/L of ammonium sulfate, 0.3~0.6g/ of bitter salt are added in the dilution heat of sulfuric acid of pH value 1.0~2.0 L, 0.3~0.6g/L of dipotassium hydrogen phosphate, 0.05~0.15g/L of potassium chloride, 0.01~0.02g/L of calcium nitrate, seven hydrated sulfuric acids are sub- 40~50g/L of iron is to get the culture solution；Or the copper raffinate is adsorbed with activated carbon Filter column and carries out oil removal treatment, make COD is reduced to 100mg/L hereinafter, 0.5~5g of ammonium sulfate and dipotassium hydrogen phosphate is added in every liter of copper raffinate in the copper raffinate The nutrient solution is obtained after 0.15~1g.
CN201710045860.0A 2017-01-20 2017-01-20 A kind of method of copper-contained sludge harmless treatment and higher value application Active CN106834699B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710045860.0A CN106834699B (en) 2017-01-20 2017-01-20 A kind of method of copper-contained sludge harmless treatment and higher value application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710045860.0A CN106834699B (en) 2017-01-20 2017-01-20 A kind of method of copper-contained sludge harmless treatment and higher value application

Publications (2)

Publication Number Publication Date
CN106834699A CN106834699A (en) 2017-06-13
CN106834699B true CN106834699B (en) 2018-09-18

Family

ID=59119426

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710045860.0A Active CN106834699B (en) 2017-01-20 2017-01-20 A kind of method of copper-contained sludge harmless treatment and higher value application

Country Status (1)

Country Link
CN (1) CN106834699B (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107385219B (en) * 2017-08-04 2019-03-19 俞振元 Utilize the method for cyclone electrolytic cell processing nickel plated copper sludge recycling copper and mickel
CN107385220A (en) * 2017-08-04 2017-11-24 俞振元 A kind of method of the reclaiming high purity nickel from waste nickel catalyst
CN107746161A (en) * 2017-09-12 2018-03-02 大唐环境产业集团股份有限公司 A kind of chemical extraction method and system of desulfurization wastewater sludge heavy-metal
CN108546820A (en) * 2018-05-11 2018-09-18 云南驰宏锌锗股份有限公司 A kind of refractory copper oxide ore sulfuric acid curing preprocess method
CN108505065A (en) * 2018-05-11 2018-09-07 云南驰宏锌锗股份有限公司 A kind of method that difficulty selects glutenite copper mine production tough cathode
CN111041191A (en) * 2019-12-12 2020-04-21 云南大学 Roasting leaching process for lead-zinc ore tailings
CN110923456A (en) * 2019-12-13 2020-03-27 陕西易莱德新材料科技有限公司 Method for preparing high-purity copper and copper sulfate by adsorption from copper-plating sludge
CN111197171A (en) * 2020-02-18 2020-05-26 华建彬 Wet copper extraction process
CN112522514B (en) * 2020-11-17 2022-05-03 陕西三秦环保科技股份有限公司 Recycling treatment method for copper-containing etching solution
CN112941562B (en) * 2021-01-13 2024-07-16 湖南埃格环保科技有限公司 Combined treatment method for copper-containing sludge and copper-containing etching waste liquid

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101497942A (en) * 2009-03-11 2009-08-05 南京农业大学 Biological leaching-solvent extraction-electrodeposition recovering method for heavy metal copper in sludge
JP2012197492A (en) * 2011-03-22 2012-10-18 Jx Nippon Mining & Metals Corp RECOVERING METHOD OF Cu, Co, AND Ni FROM LEACHATE OF In CONTAINING DRAINAGE SLUDGE
CN103451437B (en) * 2013-09-06 2015-07-08 聂源 Recovery and utilization method of valuable metal sludge containing copper, nickel and cobalt
CN104593598A (en) * 2014-12-18 2015-05-06 北京矿冶研究总院 Method for resource utilization of multiple metals in electroplating sludge

Also Published As

Publication number Publication date
CN106834699A (en) 2017-06-13

Similar Documents

Publication Publication Date Title
CN106834699B (en) A kind of method of copper-contained sludge harmless treatment and higher value application
CN101195859B (en) Technique for processing low concentration heavy metal sulfate liquor with microorganism method
CN101497942A (en) Biological leaching-solvent extraction-electrodeposition recovering method for heavy metal copper in sludge
CN101956071B (en) Biological metallurgy mineral leaching microorganism combined bacterium fluid for copper ore and method for recycling metallic copper
CN108570557B (en) Method for separating iron, chromium, nickel, copper and zinc from high-iron high-chromium electroplating sludge leachate
CN102719657B (en) Method for recycling heavy metal in electroplating sludge
CN104862250B (en) Acidophilic iron-oxidizing composite microbial agent and preparation method thereof
CN104877933B (en) Can be used for preparation and have a liking for bacterial strain and the application thereof of sour iron oxidizing microorganisms composite bacteria agent capable
CN101898861B (en) Microorganism detoxification, and solidification and hazard-free treatment method for metal substrate sludge
CN103451437B (en) Recovery and utilization method of valuable metal sludge containing copper, nickel and cobalt
Zhao et al. Bioleaching of spent Ni–Cd batteries by continuous flow system: Effect of hydraulic retention time and process load
GB2606659A (en) Method and system for biologically treating acidic mine wastewater while recovering iron ion
CN104862474A (en) Method for biologically leaching heavy metal from heavy metal-contained waste based on pH and potential co-regulation
CN107267755A (en) A kind of method of secondary copper sulfide mineral biological dump leaching
CN1260376C (en) Combined heap leaching process for copper ore
CN1904091A (en) Method of extractin zinc from low grade zinc ore
CN109957649B (en) Method for preparing high-quality iron ore concentrate and cooperatively recovering copper and zinc from complex sulfur ore concentrate
Dan et al. Reductive leaching of manganese from manganese dioxide ores by bacterial-catalyzed two-ores method
CN100404705C (en) Method for extracting metal copper using microbe and its use
CN105132319B (en) A kind of acidophilic microorganism composite bacteria agent and preparation method thereof and the application in copper-clad plate flotation residue is given up in processing
CN107352767A (en) A kind of bioleaching hardening agent and the method for removing sludge heavy-metal
CN111321294A (en) Method for improving leaching efficiency of chalcopyrite by directionally regulating and controlling indigenous microbial community
CN102162033A (en) Method for leaching copper and rhenium from high-sulfur high-arsenic rhenium-containing waste material by thermophilic bacteria
CN1204691A (en) Microbe and its application
CN1230565C (en) Method for recovering economic metal bacteria from slag

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant