CN106987721B - A kind of nothing of sludge containing heavy metal is useless to utilize method - Google Patents
A kind of nothing of sludge containing heavy metal is useless to utilize method Download PDFInfo
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- CN106987721B CN106987721B CN201710150084.0A CN201710150084A CN106987721B CN 106987721 B CN106987721 B CN 106987721B CN 201710150084 A CN201710150084 A CN 201710150084A CN 106987721 B CN106987721 B CN 106987721B
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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
- C22B7/007—Wet processes by acid leaching
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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
- 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
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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
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
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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
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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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
- C22B3/18—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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The nothing that the present invention provides a kind of sludge containing heavy metal, which is given up, utilizes method, it include copper, chromium, ferro element in sludge containing heavy metal, without it is useless using method the following steps are included: step S1, in acidophilic microbes' addition sludge containing heavy metal carrying out Bioleaching processing, it is separated by solid-liquid separation, leached mud and leachate is prepared；Step S2, the leachate prepared in step S1 is extracted using to copper selective hydroximic species of extractants solution, the cupric extract liquor and raffinate A that can individually recycle copper is prepared；Step S3, it is added in raffinate A with sulphite, adjusts solution ph≤2.0, heat and be added phosphate, the chromium phosphate precipitating that can individually recycle chromium is made；Step S4, with the surplus solution B after chromium heavy in oxidizing agent treatment steps S3, solution ph is adjusted to 1.0~1.5, sodium sulphate is added under the conditions of 80~95 DEG C, the sodium jarosite that can individually recycle iron is made.Without giving up, using method, it has the advantages that sludge utilizes comprehensively, utilization rate is high, free of contamination.
Description
Technical field
The invention belongs to a kind of useless utilization sides of the nothing of disposition of solid waste technical field more particularly to sludge containing heavy metal
Method.
Background technique
Accelerate in face of China's industry rapid development and urbanization process, a large amount of poisonous and harmful solid waste generated therewith
Quantity rapidly rises, thus in bring field of industrial production " large solid waste " safe disposal form very severe, in addition to pass
It further include that industrial source contains outside harmful heavy metal CHARACTERISTICS OF TAILINGS SAND, gangue, metallurgical slag, ardealite, red mud and carbide slag in industry of uniting
Heavy metal sewage sludge, every annual emissions have been up to 23,060,000 tons, and contained all kinds of heavy metals are more than 1000 tons.
Currently, sludge containing heavy metal processing method is more, such as resource utilization, solidification landfill, incineration disposal and cement kiln
Cooperative disposal etc..Wherein resource utilization has pyrogenic process disposition and wet process to dispose two major classes: energy consumption is high for pyrogenic process disposal process, and pollution is tight
Weight, resource utilization is not high, and iron, chromium can not be utilized, and is only applicable to the higher material of copper, nickel, belongs to the skill being phased out
Art；And wet-treating disposal technology has the following deficiencies: that (1) disposition scale is limited, and technique is imperfect, it makes a low multiple use,
If the waste water, exhaust gas and improper conduct oneself well of waste residue in production process are set, secondary pollution is easily caused；(2) treatment process is simple, to original
The bad adaptability of material can only carry out processing recycling to the higher sludge of nickeliferous and cupric；(3) majority can only produce crude product, warp
Help inefficiencies.
Patent CN101643243 discloses a kind of method that copper, nickel, chromium, zinc, iron are recycled from electroplating sludge, main to produce
Product include the fine chemical products such as copper sulphate, basic nickel carbonate, chromic salts, zinc sulfate, iron chloride, have metal resource utilization rate
It is high, process waste residue amount is few, the removing toxic substances remarkable advantages such as thoroughly, but to leach acid consumption higher for two steps in the method, furthermore heavy using sulfide
Shallow lake zinc-nickel is separated with ferrochrome, and sulfide precipitation object hot pressing conversion carries out next step extracting copper, carbonic acid at the solution of cupric, zinc, nickel again
Heavy nickel, tail washings condensing crystallizing prepare zinc sulfate, and ferrochrome solution using hot-pressure oxidation at Cr VI, and iron pressure oxidation Cheng Tie
Red slag is dissolved with iron chloride acid solution, and condensing crystallizing requires height to appointed condition at iron chloride, the method, and leach repeatedly-heavy
Shallow lake-hot-pressure leaching causes certain process procedures tediously long, and trivalent chromium is oxidized to Cr VI, and not only chromium salt solution needs further deep
Degree removes iron, and iron oxide red slag entrainment Cr VI easily pollutes downstream product, although leached mud meets toxicity and leaches standard, and often
Still some heavy metals are remained in classical acid, when the environment changes, still there is the risk being dissolved.
Usual industrial source sludge containing heavy metal is using the comprehensive utilization of copper, nickel, zinc, iron as main target, but obtained regeneration
Product quality is difficult to control, and usually generates new waste residue, waste water, exhaust gas etc. during the treatment, although part metals obtain
To comprehensive utilization, but pollution problem still has, or even causes bigger environmental pollution.Currently, there is no a kind of technology that can incite somebody to action
Sludge reduction and it is innoxious while, the metals such as copper, chromium, iron, zinc, nickel in sludge are separately separated and obtain corresponding metal
Or metal salt product.
Therefore, it is necessary to which the method for innocent treatment of existing industrial source sludge containing heavy metal is further improved, mention
Method is utilized without useless for a kind of high, the free of contamination industrial source sludge containing heavy metal of utilization rate.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, one kind is provided
The nothing of sludge containing heavy metal is useless to utilize method, has the advantages that sludge utilizes comprehensively, utilization rate is high, free of contamination.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows: a kind of innoxious place of sludge containing heavy metal
Reason method includes copper, chromium, ferro element, the presence of heavy metal element in the sludge containing heavy metal in the sludge containing heavy metal
Form in addition to exchangeable species, carbonate combine state etc. be easy to leach form other than, further include Fe-Mn oxide, organically combine state,
Sulfide reference state, residual form.
The nothing it is useless using method the following steps are included:
Step S1, it Bioleaching: is added in sludge containing heavy metal with acidophilic microbes and carries out Bioleaching processing, solid-liquid
Separation, is prepared leached mud and leachate.Bioleaching has the leaching that reaction condition is mild, low energy consumption, water consume is few, obtains
The low advantage of slag tenor.
Step S2, the extraction of copper: using to the selective hydroximic species of extractants solution of copper to being prepared in the step S1
Leachate extracted, the cupric extract liquor and raffinate A that can individually recycle copper is prepared.
Step S3, the extraction of chromium: being added in the raffinate A with sulphite, adjusts solution ph≤2.0, heating is simultaneously
Phosphate is added, the chromium phosphate precipitating that can individually recycle chromium is made.
Step S4, the extraction of iron: the surplus solution B in the step S3 described in oxidizer treatment after heavy chromium adjusts pH value of solution
Value is added sodium sulphate under the conditions of 80~95 DEG C, the sodium jarosite that can individually recycle iron is made to 1.0~1.5.Pass through step S3
Sulphite is added by the Fe in raffinate A3+It is reduced to Fe2+, reduce entrainment of the iron ion in the precipitation process of downstream, again
Oxidant is slowly added to by Fe by step S42+It is oxidized to Fe3+, it is conducive to generate sodium jarosite, effectively avoids a large amount of iron hydroxides
The generation of colloid, metal clip band are few.
The nothing of above-mentioned sludge containing heavy metal is useless to utilize method, it is preferred that in the step S2, the hydroximic species of extractants
Solution is mainly made of hydroximic species of extractants and diluent, and the diluent is to extract one of industrial diluent or a variety of,
Extraction phase ratio O/A when extraction is 1/1~5/1.The hydroximic species of extractants is preferred984N、973N, N902 and
One of M5640 or a variety of.The diluent is 260# kerosene, EscaidTMThe one kind such as hydrocarbon solvent, Mextral DT100
Or it is a variety of, wherein 260# kerosene is sulfonated kerosene.
The nothing of above-mentioned sludge containing heavy metal is useless to utilize method, it is preferred that in the step S1, by the leaching wash heat
Land plaster is made after washing, dry, roasting；In the step S2, the cupric is extracted using the sulfuric acid solution of 150~250g/L
It takes liquid to be stripped, copper-bath is made, tough cathode is made in electrodeposition copper-bath, and the extraction phase ratio O/A of back extraction is
1/1~5/1,10~60min of settling time.Land plaster can be made after leached mud roasting in step S1, be stripped in step S2
After organic solvent afterwards is washed and the electric effusion of electrodeposition copper-bath generation is re-used in the step S2.Entire step
S1 and step S2 treatment process realize harmless treatment and without useless utilizations.
The nothing of above-mentioned sludge containing heavy metal is useless to utilize method, it is preferred that in the step S3, the sulphite is Asia
At least one of sodium bisulfate, sodium sulfite and sodium pyrosulfite, the additional amount of sulphite are by Fe in raffinate A3+Entirely
Portion is reduced to Fe2+1.5~2.0 times of theoretical amount, reaction time are 30~90min.
The nothing of above-mentioned sludge containing heavy metal is useless to utilize method, it is preferred that in the step S3, phosphate be sodium phosphate,
One of disodium hydrogen phosphate, sodium dihydrogen phosphate are a variety of, are heated to 85~95 DEG C；The step 3 further includes by resulting phosphorus
Sour chromium precipitating is added in the sodium hydroxide solution that concentration is 4~8mol/L, and liquid-solid ratio control is 4:1~10:1, reaction temperature control
System obtains chromium hydroxide at 85~95 DEG C after reaction.Sodium radio-phosphate,P-32 solution is reusable in the step S3, realizes without useless benefit
With.
The nothing of above-mentioned sludge containing heavy metal is useless to utilize method, it is preferred that in the step S4, the oxidant is oxygen
At least one of gas, hydrogen peroxide, ozone；Obtained sodium jarosite is added to the sodium hydroxide solution desulfurization of 2~6mol/L, is taken off
30~60min of reaction of Salmon-Saxl, reaction temperature are 85~95 DEG C, and liquid-solid ratio control is 4:1~10:1；Desulfurization product is through drying, roasting
Di-iron trioxide is made, the temperature of roasting is 400~600 DEG C, 30~90min of calcining time；Doctor solution condensing crystallizing is made
Sodium sulphate.The sodium sulphate wherein prepared can be repeated for the step S4, realizes and utilizes without useless.
In considering ferrochrome and other metal separation processes, due to the Fe in leachate3+Ionic radius (0.0645nm) and
Cr3+Ionic radius (0.0615nm) is close, and chemical property is similar, and separating difficulty is very big, affects the quality of chromic salts product.Using
Fe (OH) in neutralizing hydrolysis method3Easily at colloid, filterability is poor, can adsorb other metal ions；In the solution containing chromium, yellow potassium
(sodium) Jarosite process easily forms yellow potassium (sodium) chrome alum in part, causes chromium to lose, and formation condition is similar to goethite, it is easy to because
Control improper generation goethite；The extraction mechanism of organic extraction is very complicated, and technique is cumbersome, and higher cost；Using goethite
Except iron needs to control Fe in solution3+Concentration is less than 1g/L, Fe2+Oxidation process be difficult to control and form colloid, lead to sediment
Adsorb other metal ions.
The present invention is using the heavy chromium of phosphate, reaction equation are as follows:
Cr3++PO4 3-→CrPO4(s) (1)
Since chromium phosphate is the sediment of indissoluble under conditions of pH value is less than 2, and bivalent metal ion then stays in solution
Middle carry out later separation.
Ferrous iron in solution is completely oxidized to ferric iron with oxidant by liquid after heavy chromium, is precipitated using yellow sodium (ammonium) ferrovanadium molten
Iron in liquid, and the metal ions such as zinc, nickel stay and carry out later separation in the solution, obtained siderotil carries out caustic digestion again, reaction
Equation are as follows:
MeFe3(SO4)2(OH)6(s)+3OH-→Me++3Fe(OH)3(s)+2SO4 2- (2)
Me can be Na+、NH4+。
The nothing of above-mentioned sludge containing heavy metal is useless to utilize method, it is preferred that in the butt sludge of the sludge containing heavy metal
Copper, chromium, iron, zinc, nickel content be above 3%；The nothing of the sludge containing heavy metal is useless to utilize method further include:
Step S5, the extraction of zinc: the pH value control that the surplus solution C after sodium jarosite is isolated in the step S4 is existed
2.5~3.5, it is then extracted using acid phosphatase esters extractant solution, obtains the extract liquor containing zinc and extraction that can individually recycle zinc
Extraction raffinate D；
Step S6, the extraction of nickel: being added in the raffinate D with carbonate and/or bicarbonate, sufficiently mistake after reaction
Filter obtains the nickelous carbonate precipitating that can individually recycle nickel.By being flowed so that recycling using the nickel ion in carbonate ions precipitation solution
Journey is short, is conducive to the extraction recycling of downstream nickel, and, precipitating with high purity product nontoxic, good to the sedimentation effect of nickel with raw material itself
The good advantage of matter.
The nothing of above-mentioned sludge containing heavy metal is useless to utilize method, it is preferred that in the step S5, the acid phosphatase esters
Extraction agent solution is mainly made of acid phosphatase esters extractant and diluent, and the diluent extracts one in industrial diluent
Kind or it is a variety of, extraction phase ratio O/A when extraction is 1/1~5/1；Zinc is contained to described using the sulfuric acid solution of 150~250g/L again
Extract liquor is stripped, and the extraction phase ratio O/A of back extraction is 1/1~5/1,10~60min of settling time, and the sulphur containing zinc is made
Acid salt solution and back extraction extraction raffinate, the sulfate liquor condensing crystallizing containing zinc obtain zinc sulfate crystal.The acid phosphatase esters extraction
One of agent P507 and Cyanex272.
The nothing of above-mentioned sludge containing heavy metal is useless to utilize method, it is preferred that in the step S6, takes sodium hydroxide that institute is added
It states in raffinate D, adjusts pH value to 4.5~5.5, add sodium carbonate and adjust pH value to 8.0~9.0, nickelous carbonate is obtained by filtration
Precipitating and filtrate E, nickelous carbonate precipitating, which is added in the concentrated sulfuric acid solution of 150~250g/L, redissolves, and cathode nickel is obtained after electrodeposition；Filtrate
E is concentrated by evaporation, sodium sulphate is made after aging crystallization.Wherein electric effusion is reusable in the step S6；Pass through concentration simultaneously
Crystallization, is processed as sodium sulphate for the sodium ion added in metallic element extraction process；The distilled water of generation can re-use described
The culture of acidophilic microbes in step S1 is realized and is utilized without useless, and the reuse of distilled water ensure that a variety of acidophilus in technique
Property microorganism high efficiently multiplying in mill solution system.
The nothing of above-mentioned sludge containing heavy metal is useless to utilize method, it is preferred that in the step S1, when in sludge containing heavy metal
Sulfide reference state heavy metal is less than the 1% of total metals, uses acidophilic microbes for thiobacillus ferrooxidans' category
(Acidithiobacillus spp.), hook end screw rod Pseudomonas (Leptospirillum spp.), iron Ureaplasma
There are the one or more of the microorganism of iron oxidability, when sulfide reference state weight in sludge in (Ferroplasma spp.)
Metal is more than the 1% of total metals, is at least also belonged to comprising thiobacillus ferrooxidans using acidophilic microbes
There is iron sulphur oxygen simultaneously in (Acidithiobacillus spp.) and vulcanization bacillus (Sulfobacillus spp.)
The microorganism of change ability it is one or more.
Thinking of the present invention is aiming at the problem that residual form and sulfide reference state heavy metal are difficult to leach, using acidophilia iron
There is oxidizing bacteria the activities such as absorption mineral, formation high-speed rail, secretion metabolin can promote the dissolution of residual form heavy metal, and adopt
It is conducive to the preparation of high-quality product with Bioleaching；Have the acidophilic microbes of sulphur oxidation characteristic to sulphur using further addition
Compound is more thoroughly leached.Obtained leached mud residual metal level is low, and innoxious degree is high, and leached mud main component is
Dihydrate gypsum can be used as gypsum powder raw material.
Secondly it is directed in leachate and contains a large amount of bivalent cupric ion, ferrous ion, ferric ion, trivalent chromium simultaneously
Ion, divalent zinc ion, bivalent nickel ion, separating technology is complicated, and halfway problem.Copper extraction strong using selectivity first
Agent is taken, under conditions of pH value is less than 2.0, copper ion can enter organic phase, and other metals are hardly extracted, using anti-
Extraction electrodeposition can prepare tough cathode；Secondly under conditions of pH value is less than 2.0, phosphate radical can preferentially make the trivalent in solution heavy
It forms sediment, reducing agent is first added by the ferric ion in solution and is converted into ferrous ion, trivalent chromic ion is heavy after phosphate radical is added
It forms sediment, other metals hardly precipitate；Ferrous ion is gradually aoxidized by oxidant again, not only excessive phosphate radical meeting and trivalent
Iron ion combines and forms precipitating, and under conditions of pH value is less than 3.0, adds sodium sulphate further in the form of ferrovanadium by trivalent
Precipitation of iron ions, other metals do not precipitate, and iron precipitate can neither prepare di-iron trioxide；Then, energy is separated using zinc-nickel
The strong acidic extractant of power, the efficient extraction of zinc can be achieved in extractant in 3.0~3.5 range of pH value, and nickel is hardly extracted
It takes, zinc sulfate can be further prepared after extraction；Then, pH value is adjusted by addition sodium carbonate salt and precipitates nickel, it can be into one
Step prepares high-purity cathode nickel；Finally, for liquid through cleaning, distillation and concentration can prepare sodium sulfate crystal after heavy nickel, removal of impurities slag returns to leaching
The distilled water of system out, collection returns to microculture or Leaching Systems.It is utilized it is thus achieved that the nothing of sludge containing heavy metal is useless.
Compared with the prior art, the advantages of the present invention are as follows:
1, the waste water generated during present invention processing sludge containing heavy metal is recycled, and is generated waste residue and is able to rationally
Resource conversion, without waste water and waste residue is increased newly, the exhaust gas of generation is mainly that nickelous carbonate redissolves the carbon dioxide generated, copper/nickel electrodeposition
Acid mist that process generates, the sulfur dioxide generated in roasting, vapor in heating process etc., these exhaust gas discharge capacities are few, and
It can be controlled by corresponding simple process equipment；
2, the present invention successively separates copper, chromium, iron, zinc, the nickel in leachate respectively in a mild condition, every onestep extraction
Metal ion residual quantity is corresponded to afterwards in 50mg/L hereinafter, separating while in compared to the prior art, the present invention obtains cathode
Copper, cathode nickel, chromium hydroxide product impurity content are low, and large-scale production easy to accomplish；
3, the nothing of sludge containing heavy metal provided by the invention is useless will be contained by Combination Design with minimum cost using method
Metal sludge is innoxious, and the nothing of high added value is given up recycling, copper, chromium, iron, zinc, nickel direct recovery rate 90% or more,
Metal resource utilization rate is high；
4, the nothing of sludge containing heavy metal provided by the invention is useless utilizes method under experimental conditions and under preparation of industrialization,
Use can be stablized.
Detailed description of the invention
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 technical 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 useless flow diagram using one preferred embodiment of method of nothing of sludge containing heavy metal provided by the invention.
Specific embodiment
To facilitate the understanding of the present invention, invention herein 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 embodiments.
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, and it is of the invention to be not intended to limitation
Protection scope.
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.
Unless otherwise specified, in the present invention P507 that uses be 2- ethylhexyl phosphoric acid -2- ethylhexyl,
Cyanex272 is two (2,4,4- tri-methyl-amyl) hypophosphorous acid, and existing method can be commercially available or can passed through by market
It is prepared；984N and973N business extractant is purchased from German BASF joint-stock company (BASF Chemistry),
N902 business extractant is purchased from Zhengzhou Qin Shi Science and Technology Ltd., and Acorga M5640 business extractant is purchased from Qing Te company of the U.S.
(Cytec Solvay Group), EscaidTMIt is serially diluted agent to purchase in Exxon Mobil Corporation, Mextral is serially diluted agent
It purchases in Chongqing Kang Pu chemical industry limited liability company.
Embodiment 1
Referring to Fig. 1, being the useless preferred embodiment using method of nothing of sludge containing heavy metal provided by the invention
Flow diagram.Sludge containing heavy metal is done from the waste water treatment plant of Guangdong surface treatment garden, moisture content about 65%
Contain chromium 5.74% in base sludge, iron 7.7%, copper 0.54%, nickel 0.54%, zinc 3.87%, oxide morphology heavy metal accounts for accordingly
The 0.8% of total metals, the nothing of sludge containing heavy metal it is useless using method the following steps are included:
Step S1, Bioleaching: 1kg sludge containing heavy metal is weighed as in 5L polypropylene stirred reactor, acidophilus is added
Property microorganism, control liquid-solid ratio 5:1, sulphur acid for adjusting pH value to 1.8, with 500rpm revolving speed stirring, stir completions in 4 hours biology soak
It handles out, is separated by solid-liquid separation, leached mud and leachate is prepared.Leached mud and leachate are detected, sludge containing heavy metal
Middle zinc, nickel, copper, chromium leaching rate be up to 98% or more, iron leaching rate about 70%, leachate contains Cr3+35.18g/L、
TFe14.21g/L、Cu2+6.17g/L、Ni2+8.91g/L、Zn2+6.34g/L、Cr6+0g/L.It is obtained after leached mud washing innoxious
Leached mud, moisture content about 60%, main component is land plaster, iron content 1.62%, other copper, zinc, chromium, nickel total metal content after drying
Less than 1%；
Specifically, acidophilic microbes are containing the Acidithiobacillus ferrooxidans ATCC after domestication
23270 (culture presevation number: ATCC 23270, purchased from American Type Culture Collection, U.S. typical case culture
Object collection) solution sizes mixing.
Step S2, the extraction of copper: taking the leachate prepared in 400mL step S1 to be placed in 1L beaker, and 400mL is added and contains
20%984N extracts organic phase, diluent EscaidTM110, mixing time 15min are clarified in separatory funnel
30min has arrived extraction organic phase through three-level extracting copper ion-transfer, cupric extract liquor and raffinate A is prepared.Clear water is used again
Washing obtains cupric extract liquor, and O/A=2/1 is compared in washing, and the cupric extract liquor washed through level-one uses the sulfuric acid of 180g/L molten again
Liquid carries out two-stage and is stripped obtained copper-bath, compares O/A=2/1, settling time 10min.Copper-bath is taken to repeat to join
With it is aforementioned extraction, washing, be stripped until in copper-bath copper content be more than 45g/L, be more than 45g/L copper sulphate by copper content
Solution is transferred to eddy flow electrowinning plant, electrodeposition area 0.04m2, appropriate smooth agent electrodeposition is added, tough cathode is prepared.
Through containing Cr in detection raffinate A3+35.00g/L、TFe 13.91g/L、Cu2+0.07g/L、Ni2+8.51g/L、Zn2+
6.04g/L, cupric is up to 99.98% in tough cathode, is No. 1 tough cathode.
Step S3, the extraction of chromium: taking the raffinate A prepared in 400mL step S2 to be placed in 1L beaker, and sulfurous acid 5g is added
10min is stirred, solution ph≤2.0 are adjusted, by the Fe in solution3+Thoroughly it is reduced to Fe2+, 85 DEG C are heated to, sulfurous is added
Sour sodium 2g and ten phosphate dihydrate sodium 123g controls pH value to 1.8 with sulfuric acid in adding procedure, and stirring 60min is complete by trivalent chromium
Precipitating, separation of solid and liquid obtain surplus solution B and chromium phosphate precipitating；Chromium phosphate precipitating converts at 85 DEG C of NaOH solution through 4mol/L
60min, conversion liquid-solid ratio are 4:1, and reaction temperature is controlled at 90 DEG C, and chromium hydroxide precipitation is made for separation of solid and liquid and sodium phosphate is molten
Liquid, sodium radio-phosphate,P-32 solution are cooled into phosphoric acid sodium crystal, re-use after collection and use in step S3；
Chromium hydroxide precipitation appearance is black, is detected phosphorous 0.3% after washed, contains chromium 32.5%；It is remaining through detection
Contain Cr in solution B3+0.60g/L、Fe2+12.31g/L、Ni2+8.51g/L、Zn2+6.04g/L。
Step S4, the extraction of iron: taking the surplus solution B prepared in 400mL step S3, adds 10mL hydrogen peroxide for Fe2+It is complete
Total oxygen turns to Fe3+, pH value is adjusted to 1.5, is heated to 85 DEG C, 4g sodium sulfate crystal is added into solution and reacts 60min, solid-liquid point
From sodium jarosite and surplus solution C must be made；90 DEG C of conversion desulfurization of NaOH solution of Huang sodium ferrovanadium 2mol/L obtained
30min converts liquid-solid ratio 4:1, and the sodium jarosite after desulfurization roasts 1 hour under the conditions of 500 DEG C, obtains iron oxide red slag and desulfurization
Liquid, doctor solution are repeated several times for converting desulfurization, and when the sulfate radical in doctor solution is enriched with to a certain extent, condensing crystallizing is made
Sodium sulphate, sodium sulphate can be re-used to be used in step S4；
Through specifically containing Fe in detection iron oxide red slag2O397.35%, Al2O30.17%, SiO20.54%, Na2O 0.71%.
Step S5, the extraction of zinc: take the surplus solution C after isolating sodium jarosite in 400mL step S4 as 1L beaker
It is interior, pH value is adjusted to 3.0, and 400mL is added containing 15%P507 and extracts organic phase, diluent is 260# kerosene, 15min is stirred,
30min is clarified in separatory funnel, has been transferred to organic phase through the zinc ion in three-level extraction surplus solution C and has been made containing the organic of zinc
Solution and raffinate D, extraction phase ratio O/A when extraction are 2/1.The organic solution containing zinc is washed with clear water, O/A=is compared in washing
2:1, the organic solution containing zinc through level-one washing carry out two-stage with the sulfuric acid solution of 180g/L and are stripped obtained solution of zinc sulfate,
Compared to O/A=2:1, settling time 10min, multiple batches of extraction, is stripped until solution of zinc sulfate zinc content is more than washing
100g/L, the crystallization of concentrated vitriol zinc solution are zinc sulfate crystal；
Contain Cr through detection raffinate D3+0.20g/L、TFe 0.91g/L、Cu2+0.07g/L、Ni2+8.51g/L、Zn2+
0.24g/L。
Step S6, the extraction of nickel: the raffinate D for taking 400mL step S5 to prepare takes sodium hydroxide to be added as in 1L beaker
In raffinate D, adjust pH value to 4.5, sodium carbonate be slowly added in whipping process, adjust pH value to 8.6, by the nickel in solution from
The nickelous carbonate precipitating and filtrate E that can individually recycle nickel is made in sub precipitating completely.The nickelous carbonate being prepared precipitating is used again
The sulfuric acid solution of 200g/L dissolves, and after adding appropriate guar gum, electrodeposition obtains nickeliferous 99.91% cathode nickel；
20mg/L is below through copper, chromium, iron, zinc, the nickel plasma concentration in detection filtrate E.Filtrate E is concentrated by evaporation knot
Crystalline substance, obtains purer sodium sulphate, and distilled water adds certain nutriment after collecting and is re-used in incubation step S1
Acidophilic microbes.
Embodiment 2
Waste water treatment plant of the sludge containing heavy metal from Tianjin surface treatment garden, moisture content about 68%, butt
Contain chromium 7.11% in sludge, iron 3.28%, copper 7.56%, nickel 7.9%, zinc 5.72%, wherein sulfide reference state heavy metal divides
Do not account for the 4% of corresponding total metals, the nothing of sludge containing heavy metal it is useless using method the following steps are included:
Step S1,50kg wet mud is weighed as in 300L polypropylene stirred reactor, and acidophilic microbes, acidophilus is added
Property microorganism be containing the 23270 (culture presevation number: ATCC of Acidithiobacillus ferrooxidans ATCC after domestication
23270, it is purchased from American Type Culture Collection, American type culture collection),
Ferroplasma acidiphilum CS1 (culture presevation number: CCTCC M 2015017, in China typical culture collection
The heart) and Sulfobacillus acidophilus CS5 (culture presevation number: CCTCC M 2015006, Chinese Typical Representative culture
Collection) mixed microorganism solution sizes mixing, and controls liquid-solid ratio 6:1, sulphur acid for adjusting pH value to 1.9, and speed of agitator 300rpm is stirred
4 hours completion Bioleachings are mixed, sludge zinc, nickel, copper, chromium substantially completely leach, iron leaching rate about 64%, and leachate contains Cr3+
11.73g/L、TFe 9.50g/L、Cu2+12.35g/L、Ni2+13.04g/L、Zn2+9.44g/L、Cr6+0g/L, after leached mud washing
Innoxious leached mud is obtained, dry slag rate 63%, main component is gypsum after drying, and iron content 1.87%, other copper, zinc, chromium, nickel close
Mass fraction is measured less than 0.8%.
Step S2, the extraction of copper: leachate refined filtration removes particulate matter, extracts organic phase with containing 15%M5640, diluent is
Mextral DT100.In small-sized extraction tank, (single-stage mixing chamber 300mL, single-stage clarifying chamber 900mL, three-level extract level-one to the process
Wash second level back extraction) in carry out, extract and cupric extract liquor and raffinate A be made, cupric extract liquor is stripped, copper sulphate is made
Solution and back extraction extraction raffinate.Specifically, flow velocity 100mL/min is leached in setting, to wash as distilled water, O/A=2:1 is compared in washing,
Stripping workshop is the sulfuric acid solution of 200g/L, compares O/A=2/1, settling time 20min, when copper ion concentration in back extraction extraction raffinate
Fresh stripping workshop is replaced when higher than 45g/L, raffinate contains Cr3+11.73g/L、TFe 9.45g/L、Cu2+0.20g/L、Ni2+
12.98g/L、Zn2+9.34g/L.Copper-bath is transferred to small-sized eddy flow electrowinning plant, electrodeposition area 0.04m2, it is added suitable
Amount smooth agent electrodeposition prepares cathode copper pipe, and copper pipe cupric is up to 99.98%, is No. 1 tough cathode.
Step S3, the extraction of chromium: the raffinate A prepared in the step S2 of 4L the stirred autoclave with temperature control that is placed in 10L is taken
It is interior, sodium sulfite 36g, Fe is added3+All it is reduced to Fe2+1.5 times of theoretical amount stir 10min, by the Fe in solution3+It is thorough
Bottom is reduced to Fe2+, 85 DEG C are heated to, sodium sulfite 10g is added, avoids Fe during reaction2+Oxidation by air and 12 water phosphorus
Sour sodium 411g is stirred 60min and is precipitated trivalent chromium completely with sulphur acid for adjusting pH value to 1.8, be separated by solid-liquid separation surplus solution B and
Chromium phosphate.Through containing Cr in detection surplus solution B3+0.75g/L、Fe2+9.11g/L、Ni2+12.53g/L、Zn2+9.21g/L；
Chromium phosphate converts liquid-solid ratio 4:1 with 60min is converted at 85 DEG C of NaOH solution of 4mol/L, and separation of solid and liquid is made
Chromium hydroxide precipitation and sodium radio-phosphate,P-32 solution phosphorous 0.27% after chromium hydroxide precipitation is washed, contain chromium 31.8%, and appearance is black
Color.Sodium radio-phosphate,P-32 solution is cooled into phosphoric acid sodium crystal, re-uses after collection and uses in step S3.
Step S4,80mL hydrogen peroxide the extraction of iron: is added in the surplus solution B prepared in step s3 by Fe2+Complete oxygen
Turn to Fe3+, pH value is adjusted to 1.5, is heated to 85 DEG C, 32g sodium sulfate crystal is added into solution, stir 60min, be separated by solid-liquid separation
Yellow sodium ferrovanadium and surplus solution C must be made；
90 DEG C of conversion desulfurization 30min of NaOH solution of sodium jarosite 5mol/L convert liquid-solid ratio 4:1, after desulfurization
Sodium jarosite roasts 1 hour under the conditions of 500 DEG C, obtains iron oxide red slag and desulfuration solution.Through specifically containing in detection iron oxide red slag
Fe2O396.76%, Al2O30.58%, SiO20.36%, Na2O 0.78%.Desulfuration solution is repeated as many times and is used to convert desulfurization,
When sulfate radical in desulfuration solution is enriched with to a certain extent, sodium sulphate is made in condensing crystallizing, and sodium sulphate is re-used in step S4
Middle use.
Step S5, the extraction of zinc: the pH value of the surplus solution C of regulating step S4 preparation to 3.0, with containing 15%
Cyanex272 extracts organic extractant phase zinc, diluent EscaidTM110.The process is in small-sized extraction tank (single-stage mixing chamber
300mL, single-stage clarifying chamber 900mL, three-level extract the back extraction of level-one washing second level) in carry out, extract and extract liquor containing zinc and extraction be made
Sulfate liquor and back extraction extraction raffinate containing zinc is made in the back extraction of extract liquor containing zinc by extraction raffinate D.Specifically, flow velocity is leached in setting
100mL/min washs as distilled water, and O/A=2/1 is compared in washing, and stripping workshop is the sulfuric acid solution of 200g/L, compares O/A=
2/1, settling time 10min.Fresh strip liquor is replaced when being stripped when zinc ion concentration is higher than 80g/L in zinc-rich liquid, is stripped extraction raffinate
Containing Cr3+0.32g/L、TFe 0.65g/L、Cu2+0.08g/L、Ni2+12.48g/L、Zn2+0.57g/L。
Step S6, the extraction of nickel: the raffinate D of whipping step S5 preparation, and sodium carbonate is slowly added in whipping process,
PH value is adjusted to 8.6, the nickel ion in solution is precipitated completely, be made nickelous carbonate precipitating and copper in filtrate E, filtrate E, chromium,
Iron, zinc, nickel plasma concentration are below 20mg/L；
Nickelous carbonate precipitating is dissolved with the sulfuric acid solution of 200g/L again, and after adding appropriate guar gum, electrodeposition obtains cathode nickel, cathode
Nickeliferous up to 99.91% in nickel；
Filtrate E evaporating, concentrating and crystallizing, obtains sulfuric acid sodium powder, is detected the sulfuric acid sodium powder containing Na2SO495.6%, Mg
0.3%, Ni 0.01%, Fe 0.01%, Zn 0.005%, Cr0.003%, distilled water add certain nutriment after collecting
For the acidophilic microbes in incubation step S1.
Comparative example:
It using the sludge containing heavy metal in embodiment 2 as subjects, is handled using the prior art, specific steps
Are as follows:
(1) electroplating sludge roasts under the conditions of being blended in 1300 DEG C with coke first, obtains bottom ash；
(2) nickel, zinc, chromium leaching rate be respectively 95.69%, 58.17%, 61.30%, 1%；
(3) to contain 30%973 sulfonated kerosenes are extraction organic phase, extraction time 2min, O/A=1/1, two-stage countercurrent
Extraction, the extraction yield of copper reach 99.38%, and nickel, zinc loss are stripped condition O/A=3/1, sulfuric acid concentration 2.5mol/L close to zero,
Stripping times 2min, back extraction ratio is up to 99.18%, obtained high copper solution；
(4) condensing crystallizing prepares technical grade sulfuric acid copper to high copper solution again.
Experiment obtains every correlation data and please refers to table 1, and table 1 is embodiment 2 and the comparative example difference table of comparisons.
1 embodiment 2 of table and the comparative example difference table of comparisons
Claims (9)
- It include copper, chromium, iron, zinc, nickel member in the sludge containing heavy metal 1. a kind of nothing of sludge containing heavy metal is useless to utilize method Element, which is characterized in that the nothing it is useless using method the following steps are included:Step S1, Bioleaching: being added in sludge containing heavy metal with acidophilic microbes and carry out Bioleaching processing, solid-liquid point From leached mud and leachate is prepared；Step S2, the extraction of copper: using the leaching to the selective hydroximic species of extractants solution of copper to being prepared in the step S1 Liquid is extracted out, and the cupric extract liquor and raffinate A that can individually recycle copper is prepared；Step S3, the extraction of chromium: being added in the raffinate A with sulphite, is adjusted solution ph≤2.0, is heated and be added The chromium phosphate precipitating that can individually recycle chromium is made in phosphate；Step S4, the extraction of iron: in the step S3 described in oxidizer treatment sink chromium after surplus solution B, adjust solution ph to 1.0~1.5, sodium sulphate is added under the conditions of 80~95 DEG C, the sodium jarosite that can individually recycle iron is made；Step S5, the extraction of zinc: the pH value that the surplus solution C after sodium jarosite is isolated in the step S4 is controlled 2.5 ~3.5, it is then extracted using P507 or Cyanex272 solution, obtains the extract liquor containing zinc and raffinate D that can individually recycle zinc；Step S6, the extraction of nickel: being added in the raffinate D with carbonate and/or bicarbonate, is sufficiently filtered, is obtained after reaction It is precipitated to the nickelous carbonate that can individually recycle nickel；In the step S1, when sulfide reference state heavy metal is less than the 1% of total metals in sludge containing heavy metal, use is thermophilic Acid microorganism is that thiobacillus ferrooxidans belong to (Acidithiobacillus spp.), hook end screw rod Pseudomonas One of microorganism in (Leptospirillum spp.), iron Ureaplasma (Ferroplasma spp.) with iron oxidability Kind is a variety of, when 1% of sulfide reference state heavy metal more than total metals in sludge, at least also using acidophilic microbes Belong to (Acidithiobacillus spp.) and vulcanization bacillus (Sulfobacillus spp.) comprising thiobacillus ferrooxidans In simultaneously have iron sulphur oxidability microorganism it is one or more.
- 2. the nothing of sludge containing heavy metal according to claim 1 is useless to utilize method, which is characterized in that in the step S2, The hydroximic species of extractants solution is mainly made of hydroximic species of extractants and diluent, and the diluent is to extract industrial diluent One of or it is a variety of, extraction phase ratio O/A when extraction is 1/1~5/1.
- 3. the nothing of sludge containing heavy metal according to claim 1 is useless to utilize method, which is characterized in that in the step S1 In, land plaster will be made after leached mud washing, drying, roasting；In the step S2, using the sulphur of 150~250g/L Acid solution is stripped the cupric extract liquor, and copper-bath is made, and tough cathode is made in electrodeposition copper-bath, is stripped The extraction phase ratio O/A taken is 1/1~5/1,10~60min of settling time.
- 4. the nothing of sludge containing heavy metal according to claim 1 is useless to utilize method, which is characterized in that in the step S3, The sulphite is at least one of sodium hydrogensulfite, sodium sulfite and sodium pyrosulfite, and the additional amount of sulphite is By Fe in raffinate A3+All it is reduced to Fe2+1.5~2.0 times of theoretical amount, reaction time are 30~90min.
- 5. the nothing of sludge containing heavy metal according to claim 1 is useless to utilize method, which is characterized in that in the step S3, Phosphate is one of sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate or a variety of, is heated to 85~95 DEG C；The step S3 Further include by resulting chromium phosphate precipitate be added concentration be 4~8mol/L sodium hydroxide solution in, liquid-solid ratio control be 4:1~ 10:1mL/g, reaction temperature are controlled at 85~95 DEG C, and chromium hydroxide is obtained after reaction.
- 6. the nothing of sludge containing heavy metal according to claim 1 is useless to utilize method, which is characterized in that in the step S4, The oxidant is at least one of oxygen, hydrogen peroxide, ozone；Obtained sodium jarosite is added to the hydrogen-oxygen of 2~6mol/L Change sodium solution desulfurization, 30~60min of desulphurization reaction, reaction temperature is 85~95 DEG C, and liquid-solid ratio control is 4:1~10:1mL/g； Di-iron trioxide is made through drying, roasting in desulfurization product, and the temperature of roasting is 400~600 DEG C, 30~90min of calcining time；It will Sodium sulphate is made in doctor solution condensing crystallizing.
- 7. the nothing of sludge containing heavy metal according to claim 1 to 6 is useless to utilize method, which is characterized in that described Copper in the butt sludge of sludge containing heavy metal, chromium, iron, zinc, nickel content be above 3%.
- 8. the nothing of sludge containing heavy metal according to claim 1 is useless to utilize method, which is characterized in that in the step S5, P507 the or Cyanex272 solution is mainly made of P507 or Cyanex272 and diluent, and the diluent is extraction industry One of diluent is a variety of, and extraction phase ratio O/A when extraction is 1/1~5/1；It is molten using the sulfuric acid of 150~250g/L again Liquid is stripped the extract liquor containing zinc, and the extraction phase ratio O/A of back extraction is 1/1~5/1,10~60min of settling time, Sulfate liquor and back extraction extraction raffinate, the sulfate liquor condensing crystallizing containing zinc containing zinc is made and obtains zinc sulfate crystal.
- 9. the nothing of sludge containing heavy metal according to claim 1 is useless to utilize method, which is characterized in that in the step S6, Take sodium hydroxide to be added in the raffinate D, adjust pH value to 4.5~5.5, add sodium carbonate adjust pH value to 8.0~ 9.0, nickelous carbonate precipitating and filtrate E is obtained by filtration, nickelous carbonate precipitating, which is added in the concentrated sulfuric acid solution of 150~250g/L, redissolves, electricity Cathode nickel is obtained after product；Filtrate E is concentrated by evaporation, sodium sulphate is made after aging crystallization.
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| CN109004306B (en) * | 2018-08-03 | 2020-10-02 | 浙江长兴中俄新能源材料技术研究院有限公司 | Efficient recovery method of waste terpolymer lithium ion power battery material |
| CN110373544B (en) * | 2019-07-25 | 2020-06-16 | 中国科学院过程工程研究所 | Device and method for deep-sea microbial gradient treatment of metal ions in heavy metal sludge |
| CN111500864A (en) * | 2020-04-27 | 2020-08-07 | 北京首创环境科技有限公司 | Method for recycling electroplating sludge based on chromium recovery |
| CN113073203B (en) * | 2021-03-29 | 2022-01-28 | 中南大学 | A kind of heavy metal sludge biological stirring leaching system and method thereof |
| CN114752766A (en) * | 2021-07-30 | 2022-07-15 | 中南大学 | A kind of method for selective separation of zinc, chromium and iron and recovery of polymetals in electroplating sludge |
| CN114525310B (en) * | 2022-03-07 | 2024-05-03 | 武汉理工大学 | Method for synthesizing basic nickel carbonate based on biomineralization reaction |
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