CN107815544A - Noble metal is obtained using synthesized environmental protection method processing industrial solid castoff - Google Patents
Noble metal is obtained using synthesized environmental protection method processing industrial solid castoff Download PDFInfo
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- CN107815544A CN107815544A CN201710947848.9A CN201710947848A CN107815544A CN 107815544 A CN107815544 A CN 107815544A CN 201710947848 A CN201710947848 A CN 201710947848A CN 107815544 A CN107815544 A CN 107815544A
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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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
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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
- C22B11/00—Obtaining noble metals
- C22B11/06—Chloridising
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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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
Abstract
The present invention relates to noble metal is obtained using synthesized environmental protection method processing industrial solid castoff, belong to non-ferrous metal metallurgy technical field, there is provided a kind of method from Copper Anode Slime environmental protection recovery valuable metal, comprise the following steps：（A）Except selenium, earth of positive pole sulfating roasting generation selenium dioxide selenium dioxide, which with water react, generates the selenous acid for being dissolved in water, and input sodium sulfite is reduced, and impure selenium is filtrated to get by carborundum porous ceramics.（B）Sulfur dioxide absorption, placement polypropylene polyhedron hollow ball filler makes waste gas absorption improved efficiency in alkali lye in absorption tower（C）Diluted acid divides copper to obtain copper leached solution,（D）Chlorination parting：Addition industrial table salt and sodium chlorate in copper ashes, gold dissolving, silver generation silver nitride precipitation are stayed in slag, and the zinc powder of 5~6 times of parting liquid addition enters line replacement and obtains thick gold, and (E) bronze refines：Thick bronze, which is dissolved in chloroazotic acid, obtains gold chloride, then reduces to obtain with oxalic acid and refine bronze,（F）Divide silver：Ammonia solvent silver chlorate, add water conjunction hydrazine and reduced to obtain thick silver, (G) silver powder refines：Titanium starting sheet is as negative electrode, and logical direct current is electrolysed in silver nitrate solution, and in electrolytic process, negative electrode output essence is silver-colored.
Description
Technical field
The invention belongs to non-ferrous metal metallurgy technical field, and your gold more particularly to reclaimed from Copper Anode Slime environmental protection
Category.
Background technology
Copper anode mud is the product of electrolytic refining course of copper, containing essential element include gold, silver, selenium, tellurium, arsenic, antimony, bismuth,
Nickel, tin, lead and silica etc..The purpose of the processing earth of positive pole is recovery Au Ag Pt Pd therein and selenium, tellurium, antimony, bismuth, tin
Deng valuable metal.The firing method process length used in the past, labor intensity is big, and cost is high, and pollution is big.Based on this present situation, the present invention
A kind of synthetical recovery effect of plan exploitation is good while reclaims a variety of noble metals, and pollutant is disposable, is easy to the copper sun of commercial application
Pole mud comprehensively recovering valuable metal new technology.
The content of the invention
For overcome the deficiencies in the prior art, the present invention proposes a kind of from the side of Copper Anode Slime recovery valuable metal
Method, this method is in terms of environmental protection by using carborundum porous ceramics, polypropylene polyhedron ball filler so that selenium recovery
Improve, Sour gas disposal rate improves, and the synthesized environmental protection method has short, simple to operate, metal the rate of recovery height of flow, production
The features such as cost is low, environmental pollution is small.
The purpose of the present invention is achieved through the following technical solutions is discarded using synthesized environmental protection method processing industrial solid
Thing obtains noble metal, including following steps：
Noble metal is obtained using synthesized environmental protection method processing industrial solid castoff, including following steps：（A selenium) is removed,（B）
The sour gas containing sulfur dioxide is handled,（C) diluted acid divides copper, (D) chlorination parting, (E) thick aurin system, (F) point silver, (G) silver
It is refined.
Noble metal is obtained using synthesized environmental protection method processing industrial solid castoff, including following steps：
（A selenium) is removed：The earth of positive pole and 98% concentrated sulfuric acid are pressed 1：The ratio of 1.2 mass ratioes is mixed, and is put into pulp kettle and is stirred
Mix, and be heated to 200-300 DEG C, reaction time 2.5-3h removes CuO, FeO, NiO, Cu base metals, the selenium in the earth of positive pole with
Selenides Ag2Se、Cu2The form of Se and selenium simple substance is present, and adds sulfuric acid, controls 220-280 DEG C of temperature, selenides is anti-with sulfuric acid
Selenium dioxide should be generated, the material after pulp is transferred in rotary kiln and is calcined, 600 DEG C~650 DEG C of sintering temperature；During reaction
Between 1.2~1.5h, selenium sublimated into baking flue gas in the form of selenium dioxide, and baking flue gas is passed through into the bubbler equipped with water
In, selenium dioxide and water reaction generation selenous acid, being absorbed by two-stage bubbler, selenium dioxide is completely converted into selenous acid, then
Selenous acid solution in bubble absorption device is discharged, puts into sodium sulfite, the reaction time is 1-2h wherein sodium sulfites and sub- selenium
The mass ratio of acid is 1.2:1, react removing after the selenium solid matter carborundum porous ceramics material enrichment of generation.
（B）Handle the sour gas containing sulfur dioxide：It is 30% that 500kg piece alkali configuration concentration is put into absorption tower
Sodium hydroxide solution, introduce step（A）The sour gas containing sulfur dioxide is produced, it is empty that polypropylene polyhedron is placed in alkali lye
Bulbus cordis filler；Sour gas is passed through by the alkaline reaction in polypropylene polyhedron hollow ball filler and absorption tower after detection is qualified
Smoke stack emission.
（C) diluted acid divides copper：Removing step（A）The copper contained in fired slags, 1.5~2 times of sulfuric acid of addition fill in fired slags
Point reaction, then solid-liquor separation is carried out by being pumped into filter press, with water by copper ion rinsed clean in slag, copper leached solution is obtained, it is right
Contained valuable metal is reclaimed in liquid, divides copper ashes to enter chlorination parting process.
(D) chlorination parting：In rapid 3 copper ashes will be divided to add in reactor, then add 5 times of mass equivalent industrial table salts and chloric acid
Sodium is stirred, and gold fully dissolving, the slightly solubility precipitation form that argent is converted into silver chlorate are stayed in slag, by being pumped into pressure
Filter carries out solid-liquor separation, by the remaining parting liquid rinsed clean in slag, obtains parting liquid, parting liquid adds 5~6 times of quality
The zinc powder of equivalent enters line replacement, and after displacement completely, filter residue carries out pickling with 30% dilute sulfuric acid, removes whole zinc remaining in filter residue,
Obtained filter residue after pickling is thick bronze.
(E) thick aurin system：Step D is obtained into thick bronze feeding aqua regia dissolution reactor to be reacted, under conditions of 90 DEG C
4-6h is dissolved, gold therein is leached, the gold in raw material is dissolved into gold chloride HAuCl4, reaction solution is through cooling down, filtering and wash
Filter residue, gold chloride is reduced from oxalic acid, chlorauric acid solution is heated to 70 DEG C~90 DEG C, adjusted with 20% sodium hydroxide solution
PH value is to 1.5, under stirring state, once adds the solid oxalic acid of 1.5~3 times of mass equivalents, reaction start it is fierce carry out, when anti-
When should produce gas flow and gradually decreasing, a small amount of sodium hydroxide solution is added again, and reaction is accelerated again, until adding sodium hydroxide
When bubble-free produces during solution, then 0.5 times of oxalic acid is added, make the gold reduction in solution complete, filtering gained bronze is washed through pure water
After washing, you can ingot casting.
(F) silver is divided：According to step（D）Middle silver is to exist in the form of silver chlorate in filter residue, and complexing point silver is carried out with ammoniacal liquor.
One of washings is pumped into, by the parting slag silver-colored kettle of input point and is stirred, is slowly passed through ammonia, ammonia intake is carried out through weighing
Control, intake is 0.5~0.6 times of mass equivalent, is stirred continuously in a kettle, reacts 2h, and filtering gained filter residue is entered with water
Row rinsing, washings storage are used as to divide next time silver-colored, and filter residue returns to oxygen-enriched air smelting stove, and filtrate addition hydrazine hydrate is reduced, added
It is 0.3~0.5 times of mass equivalent to enter amount, reacts 1.5~2h, filtering, you can obtain thick silver.
(G) silver is refined：Step（F）The thick silver of gained is placed on anode, and nitric acid silver electrolyte is configured with outsourcing silver powder and nitric acid,
It is silver-colored in obtained silver nitrate solution：Nitric acid：The mass ratio of water is 1：1~1.1：0.6~0.7, appropriate water is incorporated, with titanium kind
As negative electrode, logical direct current is electrolysed plate in silver nitrate solution, and in electrolytic process, fine silver is separated out on negative electrode, is electrolysed 20h
Afterwards, groove cleaning is gone out, ingot casting is sent in drying.
Noble metal is obtained wherein using synthesized environmental protection method processing trade waste：Handle the sour gas containing sulfur dioxide
In body step, the polypropylene polyhedron hollow ball filling-material structure being related to is as follows：The annulus of polyhedron hollow ball second（4）It is interior concentric
It is placed with the first annulus（3）, described the first annulus（3）Upside be placed with first small circle ring（1）；The first described circle
Ring（3）Downside be placed with second small circle ring（11）；The second described annulus（4）Upper surface, the first annulus（3）It is upper
End face, the first small circle ring（1）End face outside pass through the circular arc ball clack of annular spread（2）It is fixedly linked；The second described circle
Ring（4）Lower surface, the first annulus（3）Lower surface, the second small circle ring（11）End face outside also pass through annular spread
Circular arc ball clack（2）It is fixedly linked；Described support bar（6）Upper end pass through equally distributed support bar（6）With the first small circle ring
（1）Inwall be fixedly linked；Described support bar（6）Lower end pass through equally distributed support bar（6）With the second small circle ring
（11）Inwall be fixedly linked；Each piece of described circular arc ball clack（2）On be provided with equally distributed rectangular through-hole.
Noble metal is obtained using synthesized environmental protection method processing trade waste, wherein：Except the carborundum that selenium step is related to is more
The preparation method of hole ceramic material is as follows：Using carborundum, kaolin, aluminum oxide and talcum powder as raw material, carborundum in dispensing：It is high
Ridge soil：Aluminum oxide：The quality parts ratio of talcum powder is 50-70：10-20:5-15:10-20, preparation process heating are as follows：Using
3-4 DEG C/min speed is warming up to first 800 DEG C of temperature stage, then accelerates heating rate, then the speed with 5-7 DEG C/min
1350 DEG C i.e. sintering temperature is warming up to from 800 DEG C, is then incubated 3h, by 1350 DEG C to 1280 DEG C cooling 0.5h, then 1280 DEG C of guarantors
Warm 3h, after naturally cool to room temperature, you can carborundum porous ceramics materials is made.
Beneficial effect：What the present invention used uses polypropylene porous hollow sphere packing material absorbing dusty gas, and the feature of environmental protection is preferable,
Absorbing SO2Sulfuric acid mist, Pb, flue dust etc. all have a distinct increment, smaller to ambient contamination, are filtered with carborundum porous ceramics
Impure selenium effect is good, and yield is higher, chlorination parting, and the purity of oxalic acid reduction gold, the rate of recovery is high, silver-colored electrorefining purity, recovery
Rate is high, and technical indicator is stable, and labor intensity is small, can separate a variety of noble metals simultaneously, and synthesized environmental protection meets sustainable development
Policy.
Brief description of the drawings
Fig. 1 is the structural representation of polyhedron hollow ball of the present invention.
Fig. 2 is the first annulus positional structure schematic diagram of polyhedron hollow ball of the present invention.
Fig. 3 is the positional structure schematic diagram of the support bar of polyhedron hollow ball of the present invention.
Fig. 4 is present invention process flow chart.
Embodiment
Embodiment 1
1.（A earth of positive pole 50t) is contained into Cu10%~20%, containing Au0.008%~0.01%, containing Ag3%~6%, Ni1%~2%, Se 1%
~2%, and sulfuric acid 45.025t（93%）It is stirred in input pulp kettle, is heated to 250 degrees Celsius, conduct is heated using motor
Thermal source.Base metal and metallic compound carry out reaction generation sulfate, rotary kiln baking temperature 625 with sulfuric acid in the earth of positive pole
DEG C, baking flue gas is through two-stage bubble absorption, and selenium dioxide, which with water react, generates the selenous acid for being dissolved in water, by bubble absorption kettle
In selenous acid solution discharge, input 1.6t sodium sulfites reduced.
（B the sour gas containing sulfur dioxide) is handled：It is 30% that 500kg piece alkali configuration concentration is put into absorption tower
Sodium hydroxide solution, introduce step（A）The sour gas containing sulfur dioxide is produced, it is empty that polypropylene polyhedron is placed in alkali lye
Bulbus cordis filler；Sour gas passes through the alkaline reaction in polypropylene polyhedron hollow ball filler and absorption tower.Smoke absorption effect
It see the table below.
Table 1
Torrefaction waste gas pollutant produces and discharge capacity
By placing 200 every cubic metre of polypropylene polyhedron ball fillers in absorption tower, dusty gas concentration of emission is 60
mg/m3Meet discharge standard, treatment effeciency is up to 80%, and content of sulfur dioxide is less, sulfuric acid mist, and the discharge of Pb flue dust is also less.
（C) diluted acid divides copper：Be pumped into washings with it is upper together with diluted acid, fired slags are added in reactor and stirred by machinery
Mix, copper fully dissolves in sulfuric acid medium and generates copper sulphate, by be pumped into filter press carry out solid-liquor separation, by copper in slag from
Sub- rinsed clean, output divide copper ashes to enter chlorination parting process.
（D) chlorination parting：Be pumped into washings with it is upper together with diluted acid, add industrial table salt 9t and sodium chlorate 1.2t, will point
Copper ashes is added in reactor and reacted by mechanical agitation, noble metal in acid medium and nascent state chlorine atom, fully dissolving,
Argent is fully reacted conversion and stayed in the form of silver chlorate in slag.Solid-liquor separation is carried out by being pumped into filter press, by slag
Remaining parting liquid rinsed clean.Parting liquid is obtained, the zinc powder that parting liquid adds 5 times of equivalent 1.04t enters line replacement, replaced
Quan Hou, filter residue carry out pickling with 30% dilute sulfuric acid, remove zinc remaining in filter residue, the filter residue after pickling is thick bronze.
（E) silver is present in the form of silver chlorate in parting slag, is pumped into one of washings, by the silver-colored kettle of parting slag input point
And be stirred, ammonia is slowly passed through, ammonia intake is controlled through weighing, intake 1.15t.It is continuous in a kettle
Stirring, 2h is reacted, filtering gained filter residue is rinsed with water, and washings divide silver to add 0.97t hydrazine hydrates with filtrate next time
Reduced, you can obtain thick silver, refining crude bronze：The refined input of thick bronze 98% nitric acid 0.018t, 36% hydrochloric acid 0.147t match somebody with somebody
Put chloroazotic acid（Matching while using）Thick bronze obtained by parting is sent into aqua regia dissolution reactor and carries out next step reaction.In 90 DEG C of condition
Lower dissolving 5h, leaches gold therein, and the gold in raw material is dissolved into gold chloride HAuCl4.Reaction solution is through cooling down, filtering and wash
Filter residue.
（F chlorauric acid solution) is heated to 70 DEG C, adjusted with 20% sodium hydroxide solution under pH value to 1.5 stirring states,
The solid oxalic acid of 1.5 times of mass equivalents is once added, reacts and starts fierceness progress, when reacting balance, is added again on a small quantity
Sodium hydroxide solution, reaction is accelerated again, when when adding sodium hydroxide solution without significant reaction, then adds appropriate oxalic acid,
Make the gold reduction in solution complete.Consume sodium hydroxide 5.04t, oxalic acid 0.048t.
Filtering gained bronze is after pure water, you can ingot casting obtains ingot 0.045t（99.99%）The rate of recovery 95.0%.
（G) silver is refined
Outsourcing silver powder configures with nitric acid, silver in obtained silver nitrate solution：Nitric acid：The mass ratio of water is 1：1.05：0.65.Supplying
Appropriate water, make the electrolyte met needed for electrolysis.By the use of titanium starting sheet as negative electrode, direct current is led in silver nitrate solution
It is electrolysed.In electrolytic process, the reaction on negative electrode is that the precipitation process of silver obtains silver ingot 2.715t,（99.95%）The rate of recovery
97.6%。
Acid waste gas processing method, sour gas is passed through in alkali lye in step B, there is substantial amounts of polypropylene multiaspect in alkali lye
Body hollow ball filler, sour gas increase contact area wherein, and absorption rate improves, and polyhedron hollow ball uses polypropylene plastics
Material is made spherical, and its structure is as shown in Figure of description：The annulus of polyhedron hollow ball second（4）It is interior concentric to be placed with the first circle
Ring（3）, described the first annulus（3）Upside be placed with first small circle ring（1）；The first described annulus（3）Downside
It is placed with second small circle ring（11）；The second described annulus（4）Upper surface, the first annulus（3）Upper surface, first small
Annulus（1）End face outside pass through the circular arc ball clack of annular spread（2）It is fixedly linked；The second described annulus（4）Lower end
Face, the first annulus（3）Lower surface, the second small circle ring（11）End face outside also pass through the circular arc ball clack of annular spread（2）
It is fixedly linked；Described support bar（6）Upper end pass through equally distributed support bar（6）With the first small circle ring（1）Inwall consolidate
It is fixed to be connected；Described support bar（6）Lower end pass through equally distributed support bar（6）With the second small circle ring（11）Inwall fix
It is connected；Each piece of described circular arc ball clack（2）On be provided with equally distributed rectangular through-hole.
Carborundum porous ceramics material preparation method is：Using carborundum, kaolin, aluminum oxide and talcum powder as raw material, its
Carborundum in middle dispensing：Kaolin：Aluminum oxide：The quality parts ratio of talcum powder is 60：15:10:15, preparation process heats up such as
Under：First 800 DEG C of temperature stage is warming up to using 3 DEG C/min speed, then accelerates heating rate, then with 6 DEG C/min's
Speed is warming up to 1350 DEG C i.e. sintering temperature from 800 DEG C, is then incubated 3h, by 1350 DEG C to 1280 DEG C cooling half an hour, then
1280 DEG C of insulation 3h, after naturally cool to room temperature, you can carborundum porous ceramics materials is made.
Selenium is obtained with carborundum porous ceramics filter plate, and output selenium 1.45t, the rate of recovery of selenium is up to 92.3%, 15min
Absorb complete.
Embodiment 2：
Earth of positive pole 50t and 1 same batch of sample size of embodiment are similarly earth of positive pole 50t is contained into Cu10%~20%, contained
Au0.008%~0.01%, containing Ag3%~6%, Ni1%~2%, Se 1%~2%, and sulfuric acid 45.025t（93%）Put into pulp kettle
It is stirred, remaining step is the same as embodiment 1.
Table 2
By placing 150 every cubic metre of polypropylene polyhedron ball fillers in absorption tower, dusty gas concentration of emission is 63
mg/m3Meet discharge standard treatment effeciency up to 75%.
Carborundum porous ceramics material preparation method：The carborundum porous ceramics material is with carborundum, kaolin, oxygen
Change aluminium and talcum powder, by reacting the carborundum porous ceramics material prepared, the principal phase of the carborundum porous ceramics material is
Carborundum, with reference to being mutually cordierite, carborundum porous ceramics material has interconnected open-celled structure, is wherein carbonized in dispensing
Silicon：Kaolin：Aluminum oxide：The quality parts ratio of talcum powder is 50：10:5:10, preparation process heating is as follows：Using 4 DEG C/min
Speed is warming up to first 800 DEG C of temperature stage, then accelerates heating rate, then heated up from 800 DEG C with 5 DEG C/min speed
To 1350 DEG C i.e. sintering temperature, 3h is then incubated, is cooled half an hour by 1350 DEG C to 1280 DEG C, then 1280 DEG C of insulation 3h, afterwards certainly
So it is cooled to room temperature, you can carborundum porous ceramics material is made.
Obtain selenium with carborundum porous ceramics filter plate, output selenium 1.35t, rate of recovery selenium for 85.4%, 17min
Absorb completely, obtain silver ingot 2.705t,（99.95%）The rate of recovery 97.3%, ingot 0.044t（99.99%）The rate of recovery 94.7%.
Embodiment 3
1. earth of positive pole 50t and 1 same batch of sample size of embodiment being similarly earth of positive pole 50t being contained into Cu10%~20%, contain
Au0.008%~0.01%, containing Ag3%~6%, Ni1%~2%, Se 1%~2%, and sulfuric acid 45.025t（93%）Put into pulp kettle
It is stirred, remaining step is the same as embodiment 1.
By placing 100 every cubic metre of polypropylene polyhedron ball fillers in absorption tower, dusty gas concentration of emission is
90 mg/m3Meet discharge standard treatment effeciency up to 68.5%.
2. carborundum porous ceramics material preparation method：The carborundum porous ceramics material be with carborundum, kaolin,
Aluminum oxide and talcum powder, by reacting the carborundum porous ceramics material prepared, the principal phase of the carborundum porous ceramics material
It is carborundum, with reference to being mutually cordierite, carborundum porous ceramics material is with interconnected open-celled structure, wherein carbon in dispensing
SiClx：Kaolin：Aluminum oxide：The quality parts ratio of talcum powder is 70：20:15:20, preparation process heating is as follows：Using 4 DEG C/
Min speed is warming up to first 800 DEG C of temperature stage, then accelerates heating rate, then risen from 800 DEG C with 7 DEG C/min speed
Temperature is sintering temperature to 1350 DEG C, is then incubated 3h, is cooled half an hour by 1350 DEG C to 1280 DEG C, then 1280 DEG C of insulation 3h, after
Naturally cool to room temperature, you can carborundum porous ceramics material is made.
3. obtaining selenium with carborundum porous ceramics filter plate, output selenium 1.32t, the rate of recovery of selenium is 83.5%,
19min absorbs completely, obtains silver ingot 2.70t,（99.95%）The rate of recovery 97.3%, ingot 0.044t（99.99%）The rate of recovery
94.6%。
Comparative example 1:
1. earth of positive pole 50t and 1 same batch of sample size of embodiment being similarly earth of positive pole 50t being contained into Cu10%~20%, contain
Au0.008%~0.01%, containing Ag3%~6%, Ni1%~2%, Se 1%~2%, and sulfuric acid 45.025t（93%）Put into pulp kettle
It is stirred, remaining step is the same as embodiment 1.
The processing method of torrefaction waste gas is：Handling the method for generation sulfur dioxide is：Acidity is introduced directly into absorption tower
Flue gas polypropylene porous hollow sphere filler.
Absorption efficiency reduces, and sulfur dioxide treatment rate only has 60%, and absorption efficiency is relatively low, and its discharge capacity reaches 120 mg/m3 Sulphur
The treatment effeciency of acid mist, Pb, flue dust etc. reduces.Environmental pollution is more serious.Selenium is obtained with conventional ceramic filter plate, is produced
Go out selenium 1.25t.The rate of recovery 80% of selenium.Its concentration effect is not so good as carborundum porous ceramics, and 100min absorbs completely, obtains silver ingot
2.6t（99.95%）The rate of recovery 96.3%, ingot 0.044t（99.99%）The rate of recovery 93.6%.
Above example illustrates the use polypropylene porous hollow sphere packing material absorbing dusty gas that the present invention uses, the feature of environmental protection
Preferably, SO is being absorbed2, sulfuric acid mist, Pb, flue dust etc. all have a distinct increment, it is smaller to ambient contamination, made pottery with silicon carbide porous
Porcelain filtering impure selenium effect is good, and yield is higher, chlorination parting, and the purity of oxalic acid reduction gold, the rate of recovery is high, and silver-colored electrorefining is pure
Degree, the rate of recovery is high, and technical indicator is stable, and labor intensity is small, can separate a variety of noble metals simultaneously, synthesized environmental protection meets sustainable
The policy of development.
Claims (5)
1. noble metal is obtained using synthesized environmental protection method processing industrial solid castoff, it is characterised in that comprise the following steps：（A)
Except selenium,（B）The sour gas containing sulfur dioxide is handled,（C) diluted acid divides copper, (D) chlorination parting, (E) thick aurin system, (F) point
Silver, (G) silver are refined.
2. obtaining noble metal using synthesized environmental protection method processing industrial solid castoff according to claim 1, its feature exists
In comprising the following steps：
（A selenium) is removed：The earth of positive pole and 98% concentrated sulfuric acid will be obtained by 1：The ratio of 1.2 mass ratioes is mixed, and puts into pulp kettle
Row stirs, and is heated to 200-300 DEG C, reaction time 2.5-3h, removing CuO, FeO, NiO, Cu base metals, in the earth of positive pole
Selenium is with selenides Ag2Se、Cu2The form of Se and selenium simple substance is present, and adds sulfuric acid, controls 220-280 DEG C of temperature, selenides and sulphur
Acid reaction generates selenium dioxide, and the material after pulp is transferred in rotary kiln and is calcined, 600 DEG C~650 DEG C of sintering temperature；Instead
1.2~1.5h between seasonable, selenium are sublimated into baking flue gas in the form of selenium dioxide, and baking flue gas is passed through into the drum equipped with water
In bubbler, selenium dioxide and water reaction generation selenous acid, absorbed by two-stage bubbler, selenium dioxide is completely converted into selenous acid
, then by bubble absorption device selenous acid solution discharge, put into sodium sulfite, reaction time 1-2h, the sodium sulfite with
The mass ratio of selenous acid is 1.2:1, react removing after the selenium solid matter carborundum porous ceramics material enrichment of generation；
（B）Handle the sour gas containing sulfur dioxide：The hydrogen-oxygen that 500kg piece alkali configuration concentration is 30% is put into absorption tower
Change sodium solution, introduce step（1）The sour gas containing sulfur dioxide is produced, polypropylene polyhedron hollow ball is placed in alkali lye
Filler；Sour gas is by the alkaline reaction in polypropylene polyhedron hollow ball filler and absorption tower, through chimney after detection is qualified
Discharge；
（C) diluted acid divides copper：Removing step（1）The copper contained in fired slags, it is fully anti-that 1.5~2 times of sulfuric acid are added in fired slags
Should, then solid-liquor separation is carried out by being pumped into filter press, with water by copper ion rinsed clean in slag, copper leached solution is obtained, to liquid
In contained valuable metal reclaimed, divide copper ashes to enter chlorination parting process；
(D) chlorination parting：In rapid 3 copper ashes will be divided to add in reactor, then add 5 times of mass equivalent industrial table salts and sodium chlorate to enter
Row stirring, gold fully dissolving, the slightly solubility precipitation form that argent is converted into silver chlorate is stayed in slag, by being pumped into filter press
Solid-liquor separation is carried out, by the remaining parting liquid rinsed clean in slag, obtains parting liquid, parting liquid adds 5~6 times of mass equivalents
Zinc powder enter line replacement, after displacement completely, filter residue carries out pickling with 30% dilute sulfuric acid, remaining whole zinc, pickling in removal filter residue
Obtained filter residue afterwards is thick bronze；
(E) thick aurin system：Step 4 is obtained into thick bronze feeding aqua regia dissolution reactor to be reacted, dissolved under conditions of 90 DEG C
4-6h, gold therein is leached, the gold in raw material is dissolved into gold chloride HAuCl4, reaction solution through cooling down, filtering and wash filter residue,
From oxalic acid reduce gold chloride, chlorauric acid solution is heated to 70 DEG C~90 DEG C, with 20% sodium hydroxide solution adjust pH value to
1.5, under stirring state, once add the solid oxalic acid of 1.5~3 times of mass equivalents, reaction start it is fierce carry out, when reaction produces
When gas flow gradually decreases, a small amount of sodium hydroxide solution is added again, reaction is accelerated again, when adding sodium hydroxide solution
When bubble-free produces, then 0.5 times of oxalic acid is added, make the gold reduction in solution complete, filtering gained bronze is after pure water, i.e.,
Can ingot casting；
(F) silver is divided：According to step（4）Middle silver is to exist in the form of silver chlorate in filter residue, carries out complexing point silver with ammoniacal liquor, is pumped into
One of washings, by the parting slag silver-colored kettle of input point and it is stirred, is slowly passed through ammonia, ammonia intake is controlled through weighing
System, intake is 0.5~0.6 times of mass equivalent, is stirred continuously in a kettle, reacts 2h, and filtering gained filter residue is carried out with water
Rinsing, washings storage are used as to divide next time silver-colored, and filter residue returns to oxygen-enriched air smelting stove, and filtrate adds hydrazine hydrate and reduced, addition
Measure as 0.3~0.5 times of mass equivalent, 1.5~2h of reaction, filtering, you can obtain thick silver；
(G) silver is refined：Step（6）The thick silver of gained is placed on anode, is configured nitric acid silver electrolyte with outsourcing silver powder and nitric acid, is made
Silver nitrate solution in silver：Nitric acid：The mass ratio of water is 1：1~1.1：0.6~0.7, appropriate water is incorporated, is made with titanium starting sheet
For negative electrode, logical direct current is electrolysed in silver nitrate solution, and in electrolytic process, fine silver is separated out on negative electrode, after being electrolysed 20h,
Go out groove cleaning, ingot casting is sent in drying.
3. use synthesized environmental protection method processing trade waste according to claim 1 obtains noble metal and is characterized in that：
The polypropylene polyhedron hollow ball filling-material structure that processing is related in the sour gas step containing sulfur dioxide is as follows：Polyhedron is empty
The annulus of bulbus cordis second（4）It is interior concentric to be placed with the first annulus（3）, described the first annulus（3）Upside be placed with one
One small circle ring（1）；The first described annulus（3）Downside be placed with second small circle ring（11）；The second described annulus（4）
Upper surface, the first annulus（3）Upper surface, the first small circle ring（1）End face outside pass through the circular arc ball clack of annular spread
（2）It is fixedly linked；The second described annulus（4）Lower surface, the first annulus（3）Lower surface, the second small circle ring（11）It is outer
Side end face also passes through the circular arc ball clack of annular spread（2）It is fixedly linked；Described support bar（6）Upper end by being uniformly distributed
Support bar（6）With the first small circle ring（1）Inwall be fixedly linked；Described support bar（6）Lower end pass through it is equally distributed
Support bar（6）With the second small circle ring（11）Inwall be fixedly linked；Each piece of described circular arc ball clack（2）On be provided with uniformly point
The rectangular through-hole of cloth.
4. obtaining noble metal using synthesized environmental protection method processing trade waste according to claim 1 or 3, its feature exists
In：The preparation method for the carborundum porous ceramics material being related to except selenium step is as follows：With carborundum, kaolin, aluminum oxide and cunning
Stone flour is raw material, carborundum in dispensing：Kaolin：Aluminum oxide：The quality parts ratio of talcum powder is 50-70：10-20:5-15:
10-20, preparation process heating are as follows：First 800 DEG C of temperature stage is warming up to using 3-4 DEG C/min speed, then accelerates to rise
Warm speed, then 1350 DEG C i.e. sintering temperature is warming up to from 800 DEG C with 5-7 DEG C/min speed, 3h is then incubated, by 1350 DEG C
To 1280 DEG C of cooling half an hour, then 1280 DEG C of insulation 3h, after naturally cool to room temperature, you can carborundum porous ceramics materials is made.
5. the use synthesized environmental protection method processing trade waste as described in claim 1-4 obtains noble metal and is characterized in that：
Concretely comprise the following steps：
（A earth of positive pole 50t) is contained into Cu10%~20%, containing Au0.008%~0.01%, containing Ag3%~6%, Ni1%~2%, Se 1%~
It is stirred in 2%, and sulfuric acid 45.025t input pulp kettles, is heated to 250 DEG C, thermal source is used as using motor heating,
Base metal and metallic compound and sulfuric acid carry out reaction generation sulfate in the earth of positive pole, 625 DEG C of rotary kiln baking temperature,
Baking flue gas is through two-stage bubble absorption, and selenium dioxide, which with water react, generates the selenous acid for being dissolved in water, by bubble absorption kettle
Selenous acid solution discharge, input 1.6t sodium sulfites reduced；
（B the sour gas containing sulfur dioxide) is handled：The hydrogen-oxygen that 500kg piece alkali configuration concentration is 30% is put into absorption tower
Change sodium solution, introduce step（A）The sour gas containing sulfur dioxide is produced, polypropylene polyhedron hollow ball is placed in alkali lye
Filler；Sour gas passes through the alkaline reaction in polypropylene polyhedron hollow ball filler and absorption tower；
（C) diluted acid divides copper：Be pumped into washings with it is upper together with diluted acid, will fired slags add reactor in pass through mechanical agitation, copper
Fully dissolved in sulfuric acid medium and generate copper sulphate, carried out solid-liquor separation by being pumped into filter press, copper ion in slag is floated
Wash clean, output divide copper ashes to enter chlorination parting process；
（D) chlorination parting：Be pumped into washings with it is upper together with diluted acid, add industrial table salt 9t and sodium chlorate 1.2t, copper ashes will be divided
Add in reactor and reacted by mechanical agitation, noble metal in acid medium and nascent state chlorine atom, fully dissolving, metal
Silver-colored fully reaction conversion is stayed in slag in the form of silver chlorate, and solid-liquor separation is carried out by being pumped into filter press, will be residual in slag
The parting liquid rinsed clean deposited, parting liquid is obtained, the zinc powder that parting liquid adds 5 times of equivalent 1.04t enters line replacement, and displacement is complete
Afterwards, filter residue carries out pickling with 30% dilute sulfuric acid, removes zinc remaining in filter residue, the filter residue after pickling is thick bronze；
（E) silver is present in the form of silver chlorate in parting slag, is pumped into one of washings, and the silver-colored kettle of parting slag input point is gone forward side by side
Row stirring, is slowly passed through ammonia, ammonia intake is controlled through weighing, and intake 1.15t, is constantly stirred in a kettle
Mix, react 2h, filtering gained filter residue is rinsed with water, and washings divide silver to be entered with filtrate addition 0.97t hydrazine hydrates next time
Row reduction, you can obtain thick silver, refining crude bronze：Thick refined nitric acid 0.018t, 36% hydrochloric acid the 0.147t configuration of input 98% of bronze
Chloroazotic acid（Matching while using）Thick bronze obtained by parting is sent into aqua regia dissolution reactor and carries out next step reaction, under conditions of 90 DEG C
5h is dissolved, gold therein is leached, the gold in raw material is dissolved into gold chloride HAuCl4, reaction solution is through cooling down, filtering and wash filter
Slag；
（F chlorauric acid solution) is heated to 70 DEG C, adjusted with 20% sodium hydroxide solution under pH value to 1.5 stirring states, once
The solid oxalic acid of 1.5 times of mass equivalents is added, reacts and starts fierce progress, when reacting balance, adds a small amount of hydrogen-oxygen again
Change sodium solution, reaction is accelerated again, when when adding sodium hydroxide solution without significant reaction, then adds appropriate oxalic acid, makes molten
Gold reduction in liquid is complete, consumes sodium hydroxide 5.04t, oxalic acid 0.048t；
（G) silver is refined：Outsourcing silver powder configures with nitric acid, silver in obtained silver nitrate solution：Nitric acid：The mass ratio of water is 1：
1.05：0.65, appropriate water is incorporated, the electrolyte met needed for electrolysis is made, by the use of titanium starting sheet as negative electrode, in silver nitrate
Lead to direct current in solution to be electrolysed；
The carborundum porous ceramics material preparation method：Using carborundum, kaolin, aluminum oxide and talcum powder as raw material, wherein
Carborundum in dispensing：Kaolin：Aluminum oxide：The quality parts ratio of talcum powder is 60：15:10:15, preparation process heating is as follows：
First 800 DEG C of temperature stage is warming up to using 3 DEG C/min speed, then accelerates heating rate, then the speed with 6 DEG C/min
1350 DEG C i.e. sintering temperature is warming up to from 800 DEG C, is then incubated 3h, by 1350 DEG C to 1280 DEG C cooling half an hour, then 1280 DEG C
Be incubated 3h, after naturally cool to room temperature, you can carborundum porous ceramics materials is made.
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| CN108828329A (en) * | 2018-04-27 | 2018-11-16 | 中国科学院地质与地球物理研究所 | A kind of ocean electric field measurement sensor and preparation method thereof |
| CN109609754A (en) * | 2019-01-10 | 2019-04-12 | 江西新金叶实业有限公司 | A kind of waste recovery process that noble metal extraction process generates |
| CN109772372A (en) * | 2019-03-16 | 2019-05-21 | 泉州师范学院 | A kind of preparation method and application of the copper selenide nanometer material based on egg shell template |
| CN110172585A (en) * | 2019-04-29 | 2019-08-27 | 北京理工大学 | A method of extracting golden simple substance from gold-containing scrap |
| CN111041212A (en) * | 2019-12-17 | 2020-04-21 | 江西理工大学 | Gold leaching method for copper anode mud |
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| RU2763717C1 (en) * | 2021-09-27 | 2021-12-30 | Открытое акционерное общество "Красноярский завод цветных металлов имени В.Н. Гулидова" | Method for processing concentrate containing selenium and precious metals |
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| CN108828329A (en) * | 2018-04-27 | 2018-11-16 | 中国科学院地质与地球物理研究所 | A kind of ocean electric field measurement sensor and preparation method thereof |
| CN109609754A (en) * | 2019-01-10 | 2019-04-12 | 江西新金叶实业有限公司 | A kind of waste recovery process that noble metal extraction process generates |
| CN109772372A (en) * | 2019-03-16 | 2019-05-21 | 泉州师范学院 | A kind of preparation method and application of the copper selenide nanometer material based on egg shell template |
| CN110172585A (en) * | 2019-04-29 | 2019-08-27 | 北京理工大学 | A method of extracting golden simple substance from gold-containing scrap |
| CN111041212A (en) * | 2019-12-17 | 2020-04-21 | 江西理工大学 | Gold leaching method for copper anode mud |
| CN113151678A (en) * | 2021-04-06 | 2021-07-23 | 贵溪华晋铜业有限公司 | Method for recovering noble metal from raw material containing noble metal |
| RU2775555C1 (en) * | 2021-06-09 | 2022-07-04 | Акционерное общество "Уралэлектромедь" | Method for selective extraction of noble metals from gold-bearing cementate |
| RU2763717C1 (en) * | 2021-09-27 | 2021-12-30 | Открытое акционерное общество "Красноярский завод цветных металлов имени В.Н. Гулидова" | Method for processing concentrate containing selenium and precious metals |
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