CN106367596A - Method for separating copper, bismuth, lead, silver and indium from iron powder replacement slag - Google Patents
Method for separating copper, bismuth, lead, silver and indium from iron powder replacement slag Download PDFInfo
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- CN106367596A CN106367596A CN201610750328.4A CN201610750328A CN106367596A CN 106367596 A CN106367596 A CN 106367596A CN 201610750328 A CN201610750328 A CN 201610750328A CN 106367596 A CN106367596 A CN 106367596A
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- bismuth
- copper
- indium
- leaching
- lead
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 100
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 100
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 86
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 78
- 239000010949 copper Substances 0.000 title claims abstract description 78
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 68
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002893 slag Substances 0.000 title claims abstract description 28
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 21
- 239000004332 silver Substances 0.000 title claims abstract description 21
- 238000002386 leaching Methods 0.000 claims abstract description 52
- 230000007062 hydrolysis Effects 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 34
- 238000004458 analytical method Methods 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 230000004044 response Effects 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000011550 stock solution Substances 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006396 nitration reaction Methods 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000005189 flocculation Methods 0.000 claims description 4
- 230000016615 flocculation Effects 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000006713 insertion reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000004965 peroxy acids Chemical class 0.000 abstract description 10
- 238000000605 extraction Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 9
- 238000003825 pressing Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 208000035126 Facies Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- -1 Shao Liangqian Chemical compound 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/044—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
-
- 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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/06—Obtaining bismuth
-
- 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
- C22B58/00—Obtaining gallium or indium
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for separating copper, bismuth, lead, silver and indium from iron powder replacement slag. The method comprises the preparing steps that firstly, second-section dilute acid is selected for leaching the copper component at the normal temperature; secondly, a three-leaching procedure is conducted for leaching the bismuth, the lead and the indium; thirdly, peracid hydrolysis is conducted for bismuth settlement; fourthly, iron powder replacement and neutralization are conducted for copper settlement; and fifthly, the indium extraction separation procedure is conducted. The method has the beneficial effects that the copper, the bismuth, the lead, the silver and the indium can be extracted and recycled from waste in a centralized manner, the added value and the utilization efficiency of products are improved, and the environment pollution can be reduced.
Description
Technical field
The invention belongs to reclaiming high-copper, high bismuth, Shao Liangqian, silver, the technical field of indium from iron replacement slag, particularly to
Copper, bismuth, lead, silver, the method for indium is separated a kind of slag from iron replacement.
Background technology
At present, (obtained using iron replacement enrichment during smelting indium after extracting indium component from smelt flue dust material
The valuable metals such as copper, bismuth, lead, indium be enriched with composition), also substantial amounts of valuable metal is enriched in side-product, such as copper, bismuth, lead,
The solution such as indium are replaced by divalent fe powder and are enriched with；Due to reclaim from side-product again copper, bismuth, lead, the element such as indium it is necessary to
Through improvement and the innovation of technique, therefore, producer of most enterprise selects not processed to separate with recovery, but directly will
Side-product containing copper, bismuth, lead, silver, indium is sold；Thus cannot efficient profit economy be worth, meanwhile, therein
Copper, bismuth, lead, silver, indium etc. are mixed in together, are also unfavorable for the effectively utilizes in later stage, and this side-product is due to value simultaneously
Not high, will also result in certain discarding, cause the pollution of environment.
Content of the invention
The invention reside in overcoming the shortcomings of that prior art exists, proposing one kind can collect copper, bismuth, lead, silver, indium from waste material
Middle extraction is reclaimed, and improves added value of product and the utilization ratio of product, and can reduce dividing from iron replacement slag of environmental pollution
From copper, bismuth, lead, silver, indium method,
In order to solve above-mentioned technical problem, the technical solution used in the present invention is: a kind of separate from iron replacement slag copper,
Bismuth, lead, silver, the method for indium, preparation process includes:
(1) select two-stage nitration diluted acid leaching copper component under room temperature；(2) three leaching operation leaching bismuths, lead and indium；(3) high acid hydrolysis sink
Bismuth, with heavy copper in (4) iron replacement；(5) extract and separate indium operation.
Two-stage nitration diluted acid leaching copper component is selected, specific step includes under the above-mentioned room temperature of the present invention:
(1.1) (for during smelting indium, copper, bismuth, lead, indium etc. are obtained using iron replacement enrichment to iron replacement slag first
Valuable metal is enriched with composition) the middle dilute h adding 50～80g/l2so4It is uniformly mixed and is reacted, and control compound
Liquid: Gu weight is than=3～8:1, react 6～10 hours, 40～60 revs/min of speed of agitator；
(1.2) compound completing step (1) reaction is filtered, and realizes solid-liquor separation；Filtering residue is used for for phase analysis
The raw material of two leachings, filtrate is a leaching cupric liquid；
(1.3) with phase analysis as raw material, two leachings are carried out using step (1.1) identical reaction condition, then filters, filtrate
For two leaching cupric liquid, this step is completed the leaching of copper and completes copper simultaneously and separated with pb, bi, in；Filtering residue treats lower step leaching
Bismuth, lead and indium use.
The above-mentioned three leaching operation leaching bismuths of the present invention, lead and indium, specific step includes:
(2.1) using the h of the mixed liquor containing following components and concentration: 100～180g/l2so4, the chlorine of 40～150g/l
Compound, 8～20g/l sodium chlorate is made leaching bismuth solvent and is added in the filtering residue that step (1.3) obtains, mixed liquor (liquid): filtering residue (Gu)
Weight than=1～6:1；
(2.2) it is 85～95 DEG C in reaction temperature, response time 3～6h, it is stirred reacting；Filter after the completion of reaction,
Filtrate is bismuth-containing leachate, bismuth-containing leachate suction special liquid storage tank groove；This operation lead, silver are enriched with into slag, and bismuth, indium enter liquid.
After the completion of the above-mentioned reaction of the present invention, before filtration, also include adding flocculation agent (as polyacrylamide) to stir
Step, addition is 102～20g/m3, (i.e. 1 cubic metre of reaction mass adds the flocculation agent of 10～20g) stirring 25-
35min；This process can be with accelerated filtration.
The above-mentioned high acid hydrolysis of the present invention sink bismuth, and specific operating procedure includes:
(3.1) the heavy bismuth of peracid neutralizing hydrolysis, the total acidity (h in sample analysis bismuth-containing leachate+), it is how many g/l；
(3.2) determine that peracid sinks bismuth test data constant, with the h of 25～35g/l2so4Medium is the constant of the heavy bismuth of hydrolysis；
The hydrolysis formula of bismuth: bicl3+h2O=biocl+2hcl；
(3.3) high acid hydrolysis heavy bismuth dilute conversion, total acidity (referring to step 3.1) ÷ constant (step 3.2)=add
Water multiplying power；Example: the volume of total acidity 80g/l ÷<25～35>constant=2.3～2.9 adds water multiplying power；
(3.4) bismuth-containing leachate is added in reaction agitator tank, by the calculated multiplying power dilute that adds water, while adding water
Side stirring promotes hydrolysis to be uniformly dispersed, and adds to capacity volume required；
(3.5), after adding water dilution, then high acid hydrolysis heavy bismuth reaction starts, and (reaction is heavy for response time 45～120min
Whether bismuth completes, and must make qualitative detection, and method is: takes upper strata reaction solution, filters in beaker with quantitative filter paper, toward filtering excessively
Deca saturation thiourea 3～5 in liquid, displaing yellow is not that the heavy bismuth of high acid hydrolysis reacts complete operation)；
(3.6) filter after the completion of heavy bismuth, filtering residue is bismuth-containing product；Filtrate mix with cupric leachate carry out reclaim copper,
Indium is processed (has a small amount of copper and indium not to be leached after there is heavy bismuth and have cupric and indium component, copper is not produced with indium component in said process
Unboiled water solution, next step operation to be made is reclaimed, and pressing filtering liquid after heavy bismuth is mixed with cupric leachate and carries out recovery copper, at indium
Reason).
The above-mentioned high acid hydrolysis of the present invention sink bismuth, and peracid sinks the end product of bismuth and is: biocl x h2O, through production application
Experience, the content analysis grade of bismuth reaches bi 30～75%, reaches enterprise's sale and requires commodity.
The above-mentioned high acid hydrolysis of the present invention sink bismuth, after step (3.4) dilute, according to 0.5～5kg/m3Add
Hydrogen peroxide, 0.5～5kg/m3Add naoh (uniform dilute of addition of above-mentioned hydrogen peroxide and naoh to reaction solution
Reactant liquor volume afterwards is carried out for standard)；Carry out the heavy bismuth reaction of high acid hydrolysis；Add the purpose of above-mentioned hydrogen peroxide and naoh
It is to make the composition of part bismuth be transformed into bi (oh)3Xh2O, realizing saves time is rapidly completed the heavy bismuth operation of peracid, improves original technique
Deficiency, be also technological process difference rare both at home and abroad.
With heavy copper in iron replacement of the present invention, concrete steps include:
(4.1) take step (1.2) and a leaching cupric liquid that (1.3) obtain and two leaching cupric liquid to sink copper as iron replacement former
Liquid；
(4.2) the heavy copper stock solution of sampling 10～50ml send laboratory analysis acidity is h+Content is it is desirable to one soaks cupric liquid and two
Leaching cupric liquid (heavy copper stock solution) dilute reaches h2so4Concentration carries out next step reaction for 35～70g/l；
(4.3) using cupric leachate as iron replacement cupric stock solution, dilute h with the method adding water+Reach required h+Will
Ask；After reactive tank fixing fabric structure completes, iron powder is added in reactive tank according to the consumption of 1.3 mol times for copper and carries out
Displacement copper process；Reaction mixing time 30～120min, is carried out at normal temperatures；
(4.5) with making qualitative detection in iron wire insertion reaction liquid, the no attached collection rufous thing in iron wire surface, remain iron wire former
Sample, displacement heavy copper reaction is just calculated completely；Filter after the completion of heavy copper reaction, filtering residue is cupric target product.
With heavy copper in the above-mentioned iron replacement of the present invention, the heavy copper rate of displacement answers more than 99.5% to be defined, and sampling analyzes to obtain it
As a result, after below 0.010g/l containing cu, can shut down and carry out filter pressing.
Solid-liquor separation of the present invention must carry copper sponge, between chemical analyses cu grade 65～95%, reach enterprise and sell sponge
Copper standard, after its heavy copper, pressing filtering liquid enters and carries indium extraction process and < also directly can add na under the good situation of exhaust equipment2S is molten
Liquid carries out being enriched with heavy indium >.Take 20ml solution to add water after filtering and adjust ph=4, it is terminal that qualitative survey indium does not produce white precipitate.
The present invention above-mentioned extract and separate indium operation is industry Conventional process steps, and substantially technique is as follows:
Note: the p of organic phase composition 30%204Extraction organic faciess made by the kerosene plus 70%.
Advantages of the present invention and beneficial effect:
1. the present invention will be effectively treated containing copper, indium, lead, the side-product such as bismuth sb, ag first, obtain high the containing of grade
There is the product of copper, indium and bismuth, improve adnexa value and the utilization ratio of product, and environmental pollution can be reduced.
2. the raw material iron replacement slag of the present invention, its material approximate composition content is: containing cu 2～12.85%, indium 0.04
～0.06%, bismuth 3～18%, lead 2～5%, sb, ag etc. do not elaborate.Being specific to property reclaims to separate has main valency
The valuable metal of value, after separating, pb is enriched in slag<including sb, ag etc.>, and the response rate 97～99.6% of lead, in bi tailings
Containing 0.3～0.64%, micro in indium tailings, contain 0.15～0.36% in copper tailings, realize leaching the response rate be all higher than 96～
More than 99% effect.
Brief description
The process chart of accompanying drawing 1 present invention.
Specific embodiment
Below by embodiment, the present invention is described in further detail, but the present invention is not limited solely to following examples.
Embodiment
Step one, at normal temperatures selection two-stage nitration diluted acid leaching copper component, dilute h of one section of use 50～80g/l2so4Leach,
Reaction equation: cuo+h2so4=cuso4+h2O, liquid: Gu=3～8:1, react in anti-corrosion agitator tank < has for 6～10 hours possessing
Under the situation of 90～95 DEG C of conditions that heat up, the response time halves, 3～5 hours.40～60 revs/min of rotating speed.
Step 2, complete one section of leaching process after, take liquid sample 10～20ml to send into chemical analyses room, analysis result leaches
Rate judges, leaching rate should be greater than 60～72%, then carries out solid-liquor separation.Filter-press residues are that phase analysis are used for two leachings, a leaching cupric
Liquid suction storage pool is stand-by.
Step 3, two-stage nitration leach copper, are raw material with phase analysis: according to step one condition, same procedure carries out two leachings, sampling
Analysis tailings result, cu 0.23～0.6%, after leaching rate 95～98%, can filter pressing, complete the leaching of copper and pb, bi, in
Separation process.Cross filtering residue and treat lower step leaching bismuth, lead and indium.
Note: 1. because bismuth just can be dissolved under the peracid condition of high temperature, so lead, bismuth ag enter slag, but indium is leached no by a small amount of
Harm, takes recycling in technical process.2. for example: about dilute h of 50～80g/l2so4Outfit method: can be converted into dilute
h2so4Equivalent concentration: between 50 ÷ 49=1～1.6n, also suitably can be changed according to mineral aggregate property and use sulfuric acid concentration, according to
Use acid normality formula, use h2so4Consumption is w, and equivalent concentration is n, and v is to use volume, then formula: w=n × v ÷ 36
× 1.84, < 36n is technical grade h2so4, equivalent concentration constant >, 1.84 is h2so4Proportion.
Step 4, patent of the present invention three leaching operation leaching bismuth, lead and indium, step 3 filter-press residues are carried out soaking bismuth operation:
1. use 100～180g/l h2so4+ chloride<naci>40～150g/l+ sodium chlorate 8～20g/l is (for industrialization
Work raw material), make leaching bismuth and leach formula, liquid: Gu=1～6:1.
2. reaction temperature: require to be more than 85～95 DEG C, < I am using compression liquid: Gu proportional manner to complete temperature-rise period,
Save heating device and the energy >
3. stirring reaction time: 3～6h
4. add water and rush dilute aqueous liquid: Gu=3～6:1, the appropriate flocculation agent of stirring washery slag 30min < addition < polyacrylamide,
15g/m3> can be with accelerated filtration >.
5. take slag sample analysis to filter bismuth in tailings, analysis result leaching rate should reach 95～98% just to be calculated and complete estimated leaching
Go out effect.
6. slag-liquid separation, is press-filtered out bismuth-containing leachate.
7., special for bismuth-containing leachate suction liquid storage tank groove, this leaching bismuth operation finishes.
Note: this operation lead, silver are enriched with into slag, and bismuth, indium enter liquid, this operation is pressed step 3<note 2>and is used w=n × v
÷ 36 × 1.84, calculates complex acid with sour formula.
The high acid hydrolysis of step 5, invention sink bismuth:
1. the heavy bismuth of peracid neutralizing hydrolysis, sample analysis bismuth-containing leachate send assay room to calculate total h+, be how many grams/
Rise.
2. obtain the heavy bismuth test data constant of peracid, the composition property of different leachates is different, then calculate the normal of heavy bismuth
Number is also different, and I has made adaptive constant myself is 25～35g/l h2so4Medium is the heavy bismuth constant of hydrolysis.
3. the hydrolysis formula of bismuth: bici3+h2O=bioci+2hci
4. high acid hydrolysis heavy bismuth dilute conversion, total acidity ÷ constant=add water multiplying power
Example: the volume of total acidity 80g/l ÷ (25～35g/l) constant=2.3～2.9 adds water multiplying power
5. bismuth-containing leachate is added in reaction agitator tank, by volume capacity multiplying power dilute, stir rush when adding water
So that hydrolysis is uniformly dispersed, add to capacity volume required.
6., in order to promote acceleration to complete to react hydrolytic process, add 0.5 by every cube of liquor capacity～5 kilograms of hydrogen peroxide
(technical grade industrial chemicals), and naoh<technical grade industrial chemicals>add it is therefore an objective to make part bismuth by 0.5～5 kilogram every cube
Composition transition bi<oh>3xh2O, saves time and is rapidly completed the heavy bismuth operation of peracid, improve the deficiency of original technique, be also domestic and international
Rare technological process difference.
7. the heavy bismuth response time 45～120min of high acid hydrolysis.
8. complete at normal temperatures to react heavy bismuth operation.
9. react whether heavy bismuth completes, qualitative detection must be made, method is: take upper strata reaction solution, filtered with quantitative filter paper
In beaker, toward crossing Deca saturation thiourea 3～5 in cleaner liquid, displaing yellow is not that the heavy bismuth of high acid hydrolysis reacts complete operation.
10. because having a small amount of copper and indium not to be leached the heavy bismuth of presence and have cupric and indium component, copper and indium in step 3 phase analysis
Component does not produce hydrolysis, and next step operation to be made is reclaimed, and pressing filtering liquid after heavy stannum is mixed with cupric leachate and is reclaimed
Copper, indium are processed.
The end product of the heavy bismuth of 11. peracid is: bioci, x h2O, through more than 3 years experiences of production application, the content of bismuth is divided
Analysis of products position reaches bi 30～75%, reaches enterprise's sale and requires commodity.
Step 6: as follows with heavy copper operation sequence in invention iron replacement:
1. take copper-containing solution in step one leachate storage pool groove to be the heavy copper stock solution of iron replacement, reaction equation is cuso4+fe
=feso4+cu
2. sampling 10～50ml copper-containing solution send laboratory analysis acidity < h+>, analysis result h+Control, 35～70g/l < h+=
0.6～1.6n > h2so4Medium h+Between<note: as to the purer copper sponge of output, must process through solution purification remove impurity operation>.
3., cupric leachate as iron replacement cupric stock solution, dilute h with the method adding water+Reach required h+Require.
After reactive tank fixing fabric structure completes, add in reactive tank by 1.3 times of iron powder consumptions and enter line replacement copper process.
4. react mixing time 30～120min, carry out at normal temperatures.
5. operational control, with making qualitative detection in iron wire insertion reaction liquid, the no attached collection rufous thing in iron wire surface, remain
Iron wire former state, displacement heavy copper reaction is just calculated completely.
6. replacing heavy copper rate answers more than 99.5% to be defined, and sampling is analyzed as a result, after below 0.010g/l containing cu,
Can shut down and carry out filter pressing.
7. solid-liquor separation must carry copper sponge, between chemical analyses cu grade 65～95%, reach enterprise and sell copper sponge mark
Standard, after its heavy copper, pressing filtering liquid enters and carries indium extraction process and < also directly can add na under the good situation of exhaust equipment2S solution enters
The heavy indium of row enrichment >.Take 20ml solution to add water after filtering and adjust ph=4, it is terminal that qualitative survey indium does not produce white precipitate.
Step 7, invention extract and separate indium operation are all more maturation process because of national smelting indium industry, do not remake
Concrete detailed description, substantially technique is as follows:
Note: extraction organic faciess made by the kerosene that the p204 of organic phase composition 30% adds 70%.
Production instance 2. raw material iron replacement slag charge property substantially situation component content: containing cu2～12.85%, indium
In0.04～0.06%, lead 2～5%, bismuth 3～18%, sb, ag etc. do not elaborate.Being specific to property reclaims and separates mainly
It is worth valuable metal, after separating, pb is enriched in slag<including sb, ag etc.>, and the response rate 97～99.6% of lead, in bi tailings
Containing 0.3～0.64%, in indium tailings: micro-, contain 0.15～0.36% in copper tailings, realize leaching the response rate and be all higher than 96～99%
More than.
Raw material iron replacement slag charge property substantially situation component content: containing cu2～12.85%, indium in0.04～0.06%,
Lead 2～5%, bismuth 3～18%, sb, ag etc. do not elaborate.Being specific to property reclaims and separates chief value valuable metal, point
From rear, pb is enriched in slag<including sb, ag etc.>, the response rate 97～99.6% of lead, contains 0.3～0.64%, indium in bi tailings
In tailings: micro-, contain 0.15～0.36% in copper tailings, realize the leaching response rate and be all higher than more than 96～99%.
Claims (7)
1. a kind of slag from iron replacement separate copper, bismuth, lead, silver, indium method it is characterised in that: preparation process includes:
(1) select two-stage nitration diluted acid leaching copper component under room temperature；(2) three leaching operation leaching bismuths, lead and indium；(3) the heavy bismuth of high acid hydrolysis,
(4) in iron replacement and heavy copper；(5) extract and separate indium operation.
2. the slag from iron replacement according to claim 1 separate copper, bismuth, lead, silver, indium method it is characterised in that: system
Standby step includes: selects two-stage nitration diluted acid leaching copper component under room temperature, specific step includes:
(1.1) add dilute h of 50～80g/l first in iron replacement slag2so4It is uniformly mixed and is reacted, and control mixed
Close the liquid of material: Gu weight is than=3～8:1, react 6～10 hours, 40～60 revs/min of speed of agitator；
(1.2) compound completing step (1) reaction is filtered, and realizes solid-liquor separation；Filtering residue is that phase analysis are used for two leachings
Raw material, filtrate be one leaching cupric liquid；
(1.3) with phase analysis as raw material, two leachings are carried out using step (1.1) identical reaction condition, then filters, filtrate is two
Leaching cupric liquid, this step is completed the leaching of copper and completes copper simultaneously and separated with pb, bi, in；Filtering residue treats lower step leaching bismuth, lead
Use with indium.
3. the slag from iron replacement according to claim 1 separate copper, bismuth, lead, silver, indium method it is characterised in that: institute
Three leaching operation leaching bismuths, lead and the indium stated, specific step includes:
(2.1) using the h of the mixed liquor containing following components and concentration: 100～180g/l2so4, the chloride of 40～150g/l,
8～20g/l sodium chlorate is made leaching bismuth solvent and is added in the filtering residue that step (1.3) obtains, mixed liquor: the weight of filtering residue than=1～
6:1；
(2.2) it is 85～95 DEG C in reaction temperature, response time 3～6h, it is stirred reacting；Filter after the completion of reaction, filtrate
For bismuth-containing leachate, bismuth-containing leachate suction special liquid storage tank groove；This operation lead, silver are enriched with into slag, and bismuth, indium enter liquid.
4. separate the slag from iron replacement according to claim 3 copper, bismuth, lead, silver, indium method it is characterised in that: anti-
After the completion of answering, also include adding flocculation agent step, addition is 10～20g/m3, stir 25-35min.
5. the slag from iron replacement according to claim 1 separate copper, bismuth, lead, silver, indium method it is characterised in that: institute
The heavy bismuth of high acid hydrolysis stated, specific operating procedure includes:
(3.1) total acidity in sample analysis bismuth-containing leachate is how many g/l；
(3.2) with the h of 25～35g/l2so4Medium is the heavy bismuth constant of hydrolysis；
(3.3) total acidity ÷ constant=add water multiplying power；
(3.4) bismuth-containing leachate is added in reaction agitator tank, by the calculated multiplying power dilute that adds water of step (3.3),
Stir when adding water and promote hydrolysis to be uniformly dispersed, add to volume required；
(3.5), after adding water dilution, then high acid hydrolysis heavy bismuth reaction starts, response time 45～120min；
(3.6) filter after the completion of heavy bismuth, filtering residue is bismuth-containing product；Filtrate is mixed with cupric leachate and carries out reclaiming copper, at indium
Reason.
6. the slag from iron replacement according to claim 5 separate copper, bismuth, lead, silver, indium method it is characterised in that:
After step (3.4) dilute, according to 0.5～5kg/m3Add hydrogen peroxide, 0.5～5kg/m3Add naoh to reaction solution
In then carry out high acid hydrolysis sink bismuth reaction.
7. the slag from iron replacement according to claim 1 separate copper, bismuth, lead, silver, indium method it is characterised in that: institute
With heavy copper in the iron replacement stated, concrete steps include:
(4.1) take step (1.2) and a leaching cupric liquid that (1.3) obtain and two leaching cupric liquid sink copper stock solution as iron replacement；
(4.2) the heavy copper stock solution of sampling 10～50ml send laboratory analysis acidity is h+Content is it is desirable to h in heavy copper stock solution+It is converted into
h2so4Concentration carries out next step reaction again for 35～70g/l；
(4.3) using cupric leachate as iron replacement cupric stock solution, dilute h with the method adding water+Reach institute's step (4.2)
Required h+Concentration；After reactive tank fixing fabric structure completes, iron powder is added to according to the consumption of 1.3 mol times for copper
Line replacement copper process is entered in reactive tank；Reaction mixing time 30～120min, is carried out at normal temperatures；
(4.5) with making qualitative detection in iron wire insertion reaction liquid, the no attached collection rufous thing in iron wire surface, remain iron wire former state,
Displacement heavy copper reaction is just calculated completely；Filter after the completion of heavy copper reaction, filtering residue is cupric target product.
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