CN106244816B - The method that in water logging and heavy tin extracts valuable metal tin component is used from antimony regulus, tin metallurgy alkaline residue - Google Patents
The method that in water logging and heavy tin extracts valuable metal tin component is used from antimony regulus, tin metallurgy alkaline residue Download PDFInfo
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- CN106244816B CN106244816B CN201610747774.XA CN201610747774A CN106244816B CN 106244816 B CN106244816 B CN 106244816B CN 201610747774 A CN201610747774 A CN 201610747774A CN 106244816 B CN106244816 B CN 106244816B
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- ball milling
- alkaline
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910001868 water Inorganic materials 0.000 title claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 18
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 241000722270 Regulus Species 0.000 title claims abstract description 16
- 238000005272 metallurgy Methods 0.000 title claims abstract description 13
- 239000002184 metal Substances 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 11
- 239000000284 extract Substances 0.000 title description 5
- 238000002386 leaching Methods 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 238000000498 ball milling Methods 0.000 claims abstract description 28
- 239000003513 alkali Substances 0.000 claims abstract description 25
- 238000007654 immersion Methods 0.000 claims abstract description 15
- 235000021110 pickles Nutrition 0.000 claims abstract description 11
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims description 82
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 238000004458 analytical method Methods 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000004062 sedimentation Methods 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 230000001351 cycling effect Effects 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 238000010828 elution Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 6
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000003701 mechanical milling Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 3
- 239000011707 mineral Substances 0.000 abstract description 3
- 239000002893 slag Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- 238000003828 vacuum filtration Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000003518 caustics Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000011020 pilot scale process Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910020212 Na2SnO3 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910001134 stannide Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910009112 xH2O Inorganic materials 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
- C22B7/04—Working-up slag
-
- 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
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- 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
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- 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
Abstract
It is a kind of to be realized from antimony regulus, tin metallurgy alkaline residue using in water logging with the method for heavy tin extraction valuable metal tin component, this method including following (1) or any one of (2) or (3)：(1) tin component is individually extracted in alkali immersion liquid；(2) tin component is individually extracted in pickle liquor；(3) it is that alkali immersion liquid is mixed to neutralization to adjust the heavy tin component in PH=6~7 with pickle liquor；With technological process is short, equipment is simple, at low cost, ball milling water logging, safe operation, environmentally safe, tin leaching rate ﹥ 99.7% are carried out at normal temperatures and pressures, and national mineral resources have been obtained with the advantages of effective recycling is ensured with utilizing.
Description
Technical field
It is more particularly to a kind of from antimony regulus, tin metallurgy the invention belongs to recycle the technical field of tin from the alkaline residue of antimony regulus, tin metallurgy
Using the method with heavy tin extraction valuable metal tin component in water logging in alkaline residue.
Background technology
At present, antimony regulus, tin metallurgy alkaline residue in also containing a certain amount of valuable tin element, general processing method is directly to make
It is abandoned for lean ore discarded object, so causes substantial amounts of tin resource waste, while contamination hazard will also result in environment.
But antimony pyrometallurgical smelting, tin, lead obtain alkaline residue technique, the tin in alkaline residue is lean tin, and material is difficult to recycle, and to pass through
The treatment process such as batch mixing, pelletizing, roasting, flue dust, gas consumption processing cost is high.
The content of the invention
The invention reside in the shortcomings of the prior art is overcome, propose that a kind of technological process is short, equipment is simple, at low cost,
Ball milling water logging, safe operation, environmentally safe, tin leaching rate ﹥ 99.7%, to national mineral resources are carried out at normal temperatures and pressures
It has obtained using in water logging in effective recycling guarantee and the slave antimony regulus utilized, tin metallurgy alkaline residue and heavy tin extracts valuable metal tin group
The method of part.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：One kind is used from antimony regulus, tin metallurgy alkaline residue
In water logging and the method for heavy tin extraction valuable metal tin component, this method include following (1) or any one of (2) or (3) side
Formula is realized：
(1) alkaline leaching recycling tin component step：
(1.1) tin raw material alkaline residue will be contained and carry out ball milling, cycling elution alkaline residue when mechanical milling process is continuously added water as ball milling
Use water；The water of addition is with raw material alkaline residue according to liquid:Gu=7~8：1 mass ratio addition, is milled to slurry fineness more than 120 mesh
；
(1.2) by the alkaline residue slurry obtained after step (1) ball milling through 3~5 standing when small；It can be naturally completely into alkalescence
Leach (reach containing after tin concentration can press filtration its slag rate for 32-36% be that alkaline leaching is complete, and calculated through chemical analysis
Reach stanniferous index concentration for foundation)；
(1.3) material after step (2) is stood carries out press filtration, obtains alkali immersion liquid (filtrate) and alkaline ball milling phase analysis (filter
Slag), the pH controls of alkali immersion liquid are>11~12；
(1.4) and then in reactive tank stir alkali immersion liquid and add in dilute sulfuric acid and adjust pH=6.5~7, neutralize heavy tin；It stirs
Stop stirring after mixing 35~40min, when making its natural sedimentation 1-2 small；
(1.5) using after natural sedimentation supernatant liquor press filtration, obtain filtrate as ball milling workshop cycling elution alkaline residue use
Water (neutralization mother liquid coming)；Lower sediment layer separately carries out press filtration, obtains water content:The tin end product of 35-40%.
(2) acid (can extract the tin component that content is 51% or so in acid condition) leaches recycling tin component step：
(2.1) step (1.3) press filtration is obtained alkaline ball milling phase analysis to mix with neutralizing mother liquid coming, be made into liquid-solid ratio be 2~
3：1 (i.e. 2-3g solids correspond to the batch mixing of 1ml liquid)；Mixed process first adds in water and then adds in alkaline ball milling leaching while stirring
Slag is stirred into slurry；
(2.2) dilute sulfuric acid of 0.7moL/L is added in into the slurry of step (2.1), it is small for 1-2 that reaction is stirred at room temperature
When, speed of agitator is 50-600 revolutions per minute, leaches 4 valency tin and obtains acid stanniferous leachate；
(2.3) filter, obtaining pickle liquor (filtrate) and filter residue, (an acidity filtering blob of slag is the 10~11% of alkaline residue raw material total amount
Between, reach rate of recovery purpose, it is stanniferous through chemical analysis results in tailings between product tin grade 25~39%<0.3~
Between 0.6%)；
(2.4) filtrate, that is, pickle liquor is added in into dilute sulfuric acid and adjusts pH=6.5~7, neutralize heavy tin；After stirring 35~40min
Stop stirring, when making its natural sedimentation 1-2 small；
(2.5) using after natural sedimentation supernatant liquor press filtration, obtain filtrate as ball milling workshop cycling elution alkaline residue use
Water (neutralization mother liquid coming)；Lower sediment layer separately carries out press filtration, obtains water content:The tin end product of 35-40%；
(3) alkali immersion liquid mixes neutralization adjusting PH=6~7 with pickle liquor and recycles tin component：
By the alkali immersion liquid of step (1.1)-(1.3) acquisition and by step (2.1)-(2.3) or pickle liquor mixing is obtained,
Then PH=6~7 are adjusted, neutralize heavy tin；Stop stirring after stirring 35~40min, when making its natural sedimentation 1-2 small；By nature
Supernatant liquor press filtration after precipitation, the filtrate obtained are as ball milling workshop cycling elution alkaline residue with water (neutralization mother liquid coming)；Lower floor
The beds of precipitation separately carry out press filtration, obtain water content:The tin end product of 35-40%.
The metal component of present invention alkaline residue containing tin raw material is：Sn:2~7%, Sb：1~2.3%, Fe：3%, Na：32%,
Other elements that the alkaline residue that surplus is antimony regulus, tin, lead obtain contains.
The mass concentration of dilute sulfuric acid is 25~75% in above-mentioned steps (1.4) of the present invention；Use dilute H2SO4Purpose be in order to
Safety.
The step (2.2) that acidic leaching of the present invention recycling is carried in tin component add in 0.7moL/L dilute sulfuric acid it
Afterwards, the operation of addition sodium chlorate or hydrogen peroxide is further included, the additive amount of the sodium chlorate is the stanniferous of step (1.1) addition
The 2% of raw material alkaline residue weight, the additive amount of hydrogen peroxide is the 8~10% of the weight of alkaline residue containing tin raw material of step (1.1) addition；This
Two kinds of reagents are all technical grade industrial chemicals, apply and are used in acidleach process, and one of which medicament is used alone；
, can be according to mineral resources property in oxidizer using upper, dosage can flexibly plus alkali changes and uses.
Neutralization mother liquid coming in above-mentioned steps (2.1) of the present invention is above-mentioned steps after neutralizing the heavy tin in adjusting PH=6~7
(1.5) the press filtration aqueous solution of solid-liquor separation is also referred to as " tail water " " waste water ", and " tail water " or " waste water " is used to cycle in production
Operation, the water idiom for producing reuse claim " neutralization mother liquid coming ".
The advantages of the present invention：
1. the present invention inexpensively extracts valuable gold for lean tin resource material situation, exploitation one kind from antimony regulus tin lead alkaline residues
Belong to the component of tin；It is proved after multiple lab scale, pilot scale, using production, the leaching rate and direct yield of tin>95~98% phases
It closes；Economic benefit can be created for manufacturing enterprise, the foundation of recycling tin component is according to the stanniferous material of alkaline residue and soluble easily in water
Characteristic, key are the stanniferous material lump of alkaline residue liquid at room temperature:Gu=7~8:/ 1, by ball milling into slurry, when 3~5 is small
Leaching dissolving is naturally done afterwards and decomposes this process, reduces alkaline leaching operation process and the big deficiency for the treatment of capacity,
It has saved the time, required component Na has been directly obtained after filtering2SnO3.xH2O solution, then dilute sulfuric acid leachate is added to adjust PH=
6.5~7, you can be settled out tin compound component Sn<OH>4×H2O. it is end product to cross filter residue；Stanniferous Sn grades>30~
39%. return to production operation ball milling recycle-water up to enterprise's its filtering tail water of vending articles requirement.
2. a process control parameter is that alkaline ball milling leaches and acidic leaching, purpose be all face upward tin processed be hydrolyzed to mesh
, finally just the comprehensive hydrolytic precipitation for completing tin is precipitated stannide and obtains end product；In antimony regulus, tin metallurgy alkaline residue known to this patent
Extracted component is mainly：Sn2SnO3, wherein divalent tin accounts for 48.7%, and 4 valency Sn account for 51.3%；The present invention utilizes the both sexes of tin
Matter recycles divalent tin, recycles 4 valency tin in acid condition in alkaline conditions；The two leachate tune PH=6.0~7.1 integrate back
Tin component is received, reaches entire production technology industrial water for neutrality, for cycling industrial water operation.
3. the present invention is using antimony regulus, tin metallurgy alkaline residue by adding water for ball milling, Na+The property of water is dissolved in, Na2SnO3Conversion
Into aqueous alkali, operation is neutralized beneficial to hydrolysis, basic slag is soluble to be more than 65.7%~70%, water-soluble Na+Slag rate ﹤ afterwards
34%, this process is not chemical reaction process, but dissolves decomposable process, and reaction is more gentle.
4. the present invention utilizes the amphotericity of tin, Sn is recycled from alkali immersion liquid2+Component leaches 4 valency tin from one slag of acidleach
Component makees leaching agent, sodium chlorate or hydrogen peroxide with sulfuric acid and makees cosolvent, leaching rate ﹥ 99.7%, leached mud ﹤ 12%, technique stream
Journey is shown in attached drawing,.
5. the related Na of the present invention+Ion moves towards to make production sodium salt byproduct, reach the disadvantage of replenishment of process because；Work of the present invention
Skill flow is short, equipment is simple, production cost is low, is polluted using water logging without fuel gas and dust, non-hazardous to ecological environment, produces tail water
Without outer row, for making production cycle water, so as to reach entire project construction operation, environment friendly and pollution-free requirement.
Description of the drawings
Attached drawing 1 is present invention process flow chart.
Specific embodiment
The present invention is described in further detail below by attached drawing, but the present invention is not limited solely to following embodiment.
Not less than 20 times or more, case alkaline residue raw material is stanniferous for lab scale and pilot scale in example：4.5%, Fe:5.1%, Pb:
0.12%, other elements are micro.
Example 1
(1) alkaline residue lean ore raw material Sn：4.5%, Fe:5.1%, Pb:0.12%, containing H20:29.13%, weigh alkaline residue drying
To constant weight material：100 grams, more than 120 mesh, more than 70% is accounted for, liquid：Gu=7:1.It is stirred to react at ambient temperature：45min,
Speed of agitator：200 revs/min.After reaction time reaches, vacuum filtration：Easily.Cross 105 DEG C of filter residue drying 10 it is small when, until constant weight is not
Become, its slag rate of weighing is：34.21%, Sn is analyzed in alkaline residue：6.13%, leaching rate is Sn in alkalies：53.3%.
(2) one caustic dip slag of acidic leaching is raw material, is used：The dilute H of 0.7moL/L2S04Make leaching agent, 15% hydrogen peroxide is added to make
Oxidant, liquid：Gu=2~3：1, temperature：Reaction heat reach 50 DEG C of ﹤, 200 revs/min of speed of agitator, 1.5 it is small when, vacuum filtration,
Drying slag weight is：11.16%, tailings Sn chemical analyses Sn：0.36%, leaching rate 99.1%, rate of recovery Sn ﹥ 97.3%, production
Product Sn:38.5%.
Example 2
(1) alkaline residue lean ore raw material Sn：4.5%, other indexs weigh 100 grams of alkaline residue raw material, 120 mesh granularity ﹥ with example 1
70%, liquid：Gu=8:1, be stirred at room temperature leaching, 200 revs/min of rotating speed, 1 it is small when after, shut down vacuum filtration, cross filter residue
It is constant that drying to constant weight at 105 DEG C, slag rate is referred to as 33.96%, tin is in chemical analysis alkaline residue：Sn：6.08%, alkali leaching rate is
54.1%.
(2) acidleach raw material uses a caustic dip slag, uses 0.7moL/L, H2S04Add in H2O2Dosage is 10%, liquid：Gu=8:
1, be stirred to react 1.5 it is small when after, survey reaction heat is 45 DEG C of ﹤, vacuum filtration, acid leaching residue drying to constant weight constant, slag rate 11.6%,
Tailings chemical analysis results Sn：0.35%, comprehensive leaching rate 99.28%, the rate of recovery 97.5%, product Sn：39.1%.
Example 3
(1) alkaline residue raw material Sn：2.7%, other elements ingredient does not refer in advance.Weigh that drying to constant weight substance 500g, mesh degree ﹥
120 mesh account for more than 75% (weigh ratio), liquid：Gu=4:1,300 revs/min at room temperature, stirring 1.5 it is small when after shut down vacuum
It filters, drying to constant weight does not become 182.77 grams for filter residue, and alkali phase analysis rate is 37.55%, and tailings analysis is 3.97%, and leaching rate is
46.3%, consider that alkali phase analysis up to requirement, does not repeat alkali leaching, liquid：Gu=6:1, at room temperature after leaching 40min, vacuum filtration,
Drying to constant weight at 105 DEG C of tailings is weighed as 175.61 grams, and alkaline residue rate is 35.1%.
(2) acidleach is that a caustic dip slag is raw material, uses dilute H of 0.8moL/L2S04Make leaching agent, when stirring 1 is small, rotating speed 250
Rev/min, vacuum filtration, drying to constant weight for tailings for 56.9%, and acid leaching residue chemical analysis is 0.91%, leaching rate synthesis ﹥
96.2%, product Sn：31.2%.
Note：The Pilot-scale of tin component is extracted according to above example lab scale and my the alkaline residue raw material more than 10kg, completely
Meet the application feasibility of production, operation control parameter must possess the following conditions step：
One step, it is necessary to water for ball milling be added to be not less than 70% up to 120 mesh alkaline residue lump material.
Two steps, ball milling water, liquid：Admittedly it is maintained at 7~8:1 is suitable, and it is synchronous to complete ball milling leaching process.
Three steps, the alkali phase analysis rate of ball milling are maintained at premised on 34% ± 2, tin component process are taken to complete alkali extraction, to change
Credit analysis completes the mechanical milling process leaching rate of leaching by alkali immersion liquid total volume × need the concentration of index containing Sn to calculate.
Four steps, H of the selection more than 0.7moL/L under the conditions of acidleach2S04Make leaching agent, add by the 8~10% of alkali leaching property slag
Enter H202A caustic dip slag is leached as oxidant.
Five steps, in comprehensive alkali immersion liquid and pickle liquor and adjusting PH=6.5~7 hydrolyze the tin compound that settles out, obtain terminal enterprise
Industry index S n<OH>4×H20 product saves special row adjusting sulphate reagent cost (H2S04)。
Six steps, end product must be dehydrated drying, and moisture is controlled between 40% ± 2, and grade containing Sn is between 25~39%.
Claims (3)
1. a kind of exist from antimony regulus, tin metallurgy alkaline residue using in water logging with the method for heavy tin extraction valuable metal tin component, feature
In：This method includes following（1）Or（2）Or（3）Any one of mode realize：
（1）Alkaline leaching recycles tin component step：
（1.1）Tin raw material alkaline residue will be contained and carry out ball milling, cycling elution alkaline residue water when mechanical milling process is continuously added water as ball milling；
The water of addition is with raw material alkaline residue according to liquid:Gu=7 ~ 8：1 mass ratio addition, is milled to slurry fineness more than 120 mesh；
（1.2）By step（1.1）The alkaline residue slurry obtained after ball milling is through 3 ~ 5 standing when small；
（1.3）By step（1.2）Material after standing carries out press filtration, obtains alkali immersion liquid and alkaline ball milling phase analysis, the pH of alkali immersion liquid
It controls and is>12；
（1.4）Then alkali immersion liquid is stirred in reactive tank and adds in dilute sulfuric acid and adjusts pH=6.5 ~ 7, neutralizes heavy tin；Stirring 35 ~
Stop stirring after 40min, when making its natural sedimentation 1-2 small；
（1.5）Using after natural sedimentation supernatant liquor press filtration, obtain filtrate as ball milling workshop cycling elution alkaline residue water；Under
The layer beds of precipitation separately carry out press filtration, obtain water content:The tin end product of 35-40%；
（2）Acidic leaching recycles tin component step：
（2.1）By step（1.3）Press filtration obtains alkaline ball milling phase analysis and is mixed with neutralizing mother liquid coming, is made into liquid-solid ratio as 2 ~ 3：1；It is mixed
Conjunction process first adds in water and then adds in alkaline ball milling phase analysis while stirring, is stirred into slurry；
（2.2）To step（2.1）Slurry in add in 0.7moL/L dilute sulfuric acid, be stirred at room temperature reaction for 1-2 it is small when, stir
Mix rotating speed is 50-600 revolutions per minute, acid stanniferous leachate；
（2.3）Filtering, obtains pickle liquor and filter residue；
（2.4）Filtrate, that is, pickle liquor is added in into dilute sulfuric acid and adjusts pH=6.5 ~ 7, neutralizes heavy tin；Stop stirring after 35 ~ 40min of stirring
It mixes, when making its natural sedimentation 1-2 small；
（2.5）Using after natural sedimentation supernatant liquor press filtration, obtain filtrate as ball milling workshop cycling elution alkaline residue water；Under
The layer beds of precipitation separately carry out press filtration, obtain water content:The tin end product of 35-40%；
（3）Alkali immersion liquid mixes neutralization adjusting PH=6~7 with pickle liquor and recycles tin component：
Pass through step（1.1）-（1.3）The alkali immersion liquid of acquisition and pass through step（2.1）-（2.3）Pickle liquor mixing is obtained, is then adjusted
PH=6~7 are saved, neutralize heavy tin；Stop stirring after stirring 35 ~ 40min, when making its natural sedimentation 1-2 small；After natural sedimentation
Supernatant liquor press filtration, the filtrate obtained are as ball milling workshop cycling elution alkaline residue water；Lower sediment layer separately carries out press filtration, obtains
Water content is:The tin end product of 35-40%；
The metal component of the alkaline residue containing tin raw material is：Sn:2~7%, Sb：1~2.3%, Fe：3%,Na：32%, surplus is antimony regulus, tin obtains
Other elements that the alkaline residue obtained contains.
2. it is according to claim 1 from antimony regulus, tin metallurgy alkaline residue using in water logging and heavy tin extraction valuable metal tin component
Method, it is characterised in that：Step（1.4）The mass concentration of middle dilute sulfuric acid is 25~75%.
3. it is according to claim 1 from antimony regulus, tin metallurgy alkaline residue using in water logging and heavy tin extraction valuable metal tin component
Method, it is characterised in that：The acidic leaching recycling puies forward the step in tin component（2.2）Add in the dilute sulfuric acid of 0.7moL/L
Afterwards, the operation of addition sodium chlorate or hydrogen peroxide is further included, the additive amount of the sodium chlorate is step（1.1）Addition contains
The 2% of tin raw material alkaline residue weight, the additive amount of hydrogen peroxide is step（1.1）The 8~10% of the weight of alkaline residue containing tin raw material of addition.
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| CN101768668A (en) * | 2010-01-07 | 2010-07-07 | 株洲冶炼集团股份有限公司 | Method for comprehensive recovery of lead and tin from alkaline refining slag of lead |
| CN104032131A (en) * | 2013-06-27 | 2014-09-10 | 中石化上海工程有限公司 | Method for processing high-tin anode slurry |
| CN104152701A (en) * | 2014-08-18 | 2014-11-19 | 汨罗市绿岩金属有限公司 | Method for recycling tin from coarse tin refining slag |
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| CN101768668A (en) * | 2010-01-07 | 2010-07-07 | 株洲冶炼集团股份有限公司 | Method for comprehensive recovery of lead and tin from alkaline refining slag of lead |
| CN104032131A (en) * | 2013-06-27 | 2014-09-10 | 中石化上海工程有限公司 | Method for processing high-tin anode slurry |
| CN104152701A (en) * | 2014-08-18 | 2014-11-19 | 汨罗市绿岩金属有限公司 | Method for recycling tin from coarse tin refining slag |
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