CN109355508A - A kind of comprehensive recovering process of the more metal materials containing indium of high arsenic - Google Patents
A kind of comprehensive recovering process of the more metal materials containing indium of high arsenic Download PDFInfo
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- CN109355508A CN109355508A CN201811390213.4A CN201811390213A CN109355508A CN 109355508 A CN109355508 A CN 109355508A CN 201811390213 A CN201811390213 A CN 201811390213A CN 109355508 A CN109355508 A CN 109355508A
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- arsenic
- containing indium
- metal materials
- dust
- materials containing
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 155
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 79
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 70
- 230000008569 process Effects 0.000 title claims abstract description 44
- 239000007769 metal material Substances 0.000 title claims abstract description 42
- 239000003546 flue gas Substances 0.000 claims abstract description 68
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000428 dust Substances 0.000 claims abstract description 63
- 239000003500 flue dust Substances 0.000 claims abstract description 47
- 239000007787 solid Substances 0.000 claims abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- 238000002844 melting Methods 0.000 claims abstract description 34
- 230000008018 melting Effects 0.000 claims abstract description 34
- 230000009467 reduction Effects 0.000 claims abstract description 28
- 238000011084 recovery Methods 0.000 claims abstract description 27
- 230000005611 electricity Effects 0.000 claims abstract description 22
- 239000003517 fume Substances 0.000 claims abstract description 22
- 238000000605 extraction Methods 0.000 claims abstract description 20
- 239000012528 membrane Substances 0.000 claims abstract description 15
- 238000002386 leaching Methods 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 13
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 11
- 238000007664 blowing Methods 0.000 claims abstract description 8
- 239000004615 ingredient Substances 0.000 claims abstract description 8
- 230000004907 flux Effects 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910001152 Bi alloy Inorganic materials 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 239000002893 slag Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 229910052958 orpiment Inorganic materials 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000002918 waste heat Substances 0.000 claims description 12
- 239000003245 coal Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 235000019738 Limestone Nutrition 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- 239000006028 limestone Substances 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 4
- 238000007499 fusion processing Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 abstract description 51
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 18
- 239000000779 smoke Substances 0.000 description 15
- 238000003723 Smelting Methods 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- BLBNEWYCYZMDEK-UHFFFAOYSA-N $l^{1}-indiganyloxyindium Chemical compound [In]O[In] BLBNEWYCYZMDEK-UHFFFAOYSA-N 0.000 description 8
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 5
- 229910052924 anglesite Inorganic materials 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 235000019504 cigarettes Nutrition 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UXNBTDLSBQFMEH-UHFFFAOYSA-N [Cu].[Zn].[Pb] Chemical compound [Cu].[Zn].[Pb] UXNBTDLSBQFMEH-UHFFFAOYSA-N 0.000 description 2
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BMSYAGRCQOYYMZ-UHFFFAOYSA-N [As].[As] Chemical compound [As].[As] BMSYAGRCQOYYMZ-UHFFFAOYSA-N 0.000 description 1
- BFVBQNYINQMZDO-UHFFFAOYSA-N [O].[As] Chemical compound [O].[As] BFVBQNYINQMZDO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C22B7/02—Working-up flue dust
-
- 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
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—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
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/0052—Reduction smelting or converting
-
- 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
- C22B30/04—Obtaining arsenic
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- 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
-
- 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
- C22B7/001—Dry processes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- 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 kind of comprehensive recovering process of high more metal materials containing indium of arsenic, the following steps are included: (1) the more metal materials containing indium of high arsenic, reducing agent and flux ingredient, which are added in oxygen-enriched side-blowing furnace, carries out reduction melting, matte, lead bismuth alloy, melting flue gas and reducing slag are obtained；(2) electricity is carried out after being aoxidized, being cooled down after mixing with air melting flue gas again to gather dust, obtains a solid flue dust and an arsenical fume；(3) one times arsenical fume is filtered by intermetallic compound flexible membrane, obtains secondary solid flue dust and secondary arsenical fume；(4) secondary arsenical fume is quenched and receives arsenic, obtain As2O3And tail gas；Solid flue dust and secondary solid flue dust are mixed and carry out oxygen leaching, gained leachate passes through extraction and recovery indium.(5) raffinate for obtaining extraction process returns to extraction process and is recycled.The rate of recovery of arsenic and indium of the present invention is high, and has many advantages, such as efficient, environmentally friendly, safe.
Description
Technical field
The invention belongs to the comprehensive of non-ferrous metal Comprehensive Recovery Technology field more particularly to a kind of more metal materials containing indium of high arsenic
Close recovery method.
Background technique
In the mineral deposit of the non-ferrous metals such as copper-lead zinc, arsenic is main accompanying element, and in smelting process, arsenic can be with smelting
Refining metal enrichment, (the arsenic amount that copper smelting plant generates is 32500t/a, and lead smeltery is 16100t/a, zinc smelting factory 22400t/
A), form the more metalliferous materials of high arsenic (when the mass percent of arsenic in material >=2%, material is referred to as high-arsenic material).Copper essence
Arsenic in mine is finally mainly enriched in smelting ash by complicated smelting process, forms high arsenic smoke dust, these high arsenic smoke dusts
Middle valuable metal rich content has very high recovery value, and still, the presence of arsenic will lead to more metalliferous materials and integrate back
Receive during there are metal dispersion, direct yield is low the problems such as.In recent years, with the scarcity of resource, the high more metalliferous material resources of arsenic
Synthetical recovery, have become a kind of trend.Wherein, indium is exactly a kind of rare precious metal common in high arsenic smoke dust.Arsenic is in indium
Extraction process will disperse in each process procedure and various intermediate materials, and influence product quality big on environmental hazard solves indium
Removal process in arsenic pollution and with rational method progress safe disposal be finally problem in indium removal process by arsenic.
Currently, the difficult point of synthetical recovery of more metals containing high arsenic material containing indium is with deficiency:
(1) arsenic-containing smoke dust is difficult to trap completely, is also easy to produce secondary pollution.There is no corresponding installations and facilities to catch arsenic
Collection, is directly volatized into flue gas for the compound of arsenic, pollutes to air.Have by the arsenic-containing smoke dust that reduction melting obtains
The features such as exhaust gas volumn is big, temperature is high, dust-laden is high, smoke granularity is thin, routinely the mode of gathering dust is using sack cleaner, bag collection
Used filter bag is common material, is easy bonding filter bag, causes dust-collecting efficiency not high, it is not high to receive arsenic purity.
(2) obtained arsenic product purity is not high.Now in the art most of processing to arsenic primarily directed to cigarette containing arsenic
The processing of dirt, and often think that the arsenic in flue dust is existed in the form of arsenic trioxide during handling this kind of flue dust,
Other phases of object containing arsenic are had ignored, therefore cause finally obtained arsenic product purity not high.
(3) noble metals such as indium are difficult to realize recycle.The presence of arsenic will lead to more metalliferous materials and deposit during synthetical recovery
Dispersing.Therefore, arsenic is efficiently trapped, is by the premise of wherein noble metal synthetical recovery.
(4) extraction raffinate is extracted in indium removal process to be difficult to recycle.The reason is that the presence of arsenic, will affect indium hydrometallurgic recovery mistake
The recycling of liquid after in journey.
10628282584 A of Publication No. CN discloses a kind of side of complicated high-arsenic-containing copper smelting flue dust valuable metal recovery
Method, this method first by the reduction melting at high temperature of high-arsenic-containing copper smelting flue dust, enter the reduction of lead bismuth tin in metallic lead, arsenic indium enters
In flue dust, copper enters in slag；Obtained flue dust is handled with rotary kiln dearsenification, and obtained calcining uses reverberatory furnace further to take off again
Arsenic obtains arsenic trioxide product；Metal lead smelting obtains qualified metallic lead product, and bismuth tin, which enters in slag, smelts original with tin
The recycling of material form；Copper is entered in slag in the form of matte as Copper making raw materials recovery.But blast furnace pair is used in the technique
The more metal materials containing indium of high arsenic carry out reduction melting, and the recovery time is lower compared with long, efficiency and obtained flue gas content is big, flue gas
Dust-laden is high, and smoke granularity is thin.The treating capacity for increasing subsequent technique, is unfavorable for the enrichment of wherein noble metal (In), influences noble metal
(In) the rate of recovery.In addition, not referring to the recovery processing technique of liquid after processing during using wet processing recovery indium.
Application No. is CN 201410650579.6, " processing method of arsenic in high-arsenic material melting flue gas ", which passes through
+ two sections of dedustings of two sections of coolings, the theoretically higher arsenic of available purity, but in actual operation, aerial cooler is cold
But more difficult during that temperature is controlled, it is thus possible to incomplete to the recycling of arsenic.And bagroom is in negative pressure exhausting
When may be mixed into arsenic flue dust separated solid flue dust was smoked again with arsenic originally.And biggish flue gas content can increase
Electricity in this big technique pressure of gathering dust so that the pressure for increasing bag collection in subsequent technique is larger leads to subsequent receipts arsenic efficiency
It is not high.And in the technique subsequent two sections gather dust and all arsenic-containing smoke dust be filtered using bag collection, and obtained by reduction melting
Arsenic-containing smoke dust granularity is relatively thin, viscosity is higher, bag collection be easy to cause during gathering dust bonding and can not grade of filtration compared with
Thin solid flue dust, causes the purity of arsenic not high.
It would therefore be highly desirable to develop it is a kind of efficiently, environmental protection, safety dearsenic technique, can by the more metalliferous materials of high arsenic arsenic with
More metalliferous materials efficiently separate, and realize the safe disposal of the synthetical recovery and arsenic of valuable metal in the more metalliferous materials of high arsenic.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, the rate of recovery for providing a kind of arsenic and indium is high,
Efficiently, the comprehensive recovering process of environmentally friendly, safety the more metal materials containing indium of high arsenic.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of comprehensive recovering process of the more metal materials containing indium of high arsenic, comprising the following steps:
(1) the more metal materials containing indium of high arsenic, reducing agent and flux ingredient are added in oxygen-enriched side-blowing furnace and carry out reduction melting,
Obtain matte, lead bismuth alloy, melting flue gas and reducing slag；
(2) it is aoxidized after mixing with air the resulting melting flue gas of step (1), obtains mixed flue gas, the mixing
Electricity is carried out again after flue gas is cooling to gather dust, and obtains a solid flue dust and an arsenical fume；
(3) the resulting arsenical fume of step (2) is filtered by intermetallic compound flexible membrane, is obtained secondary
Solid flue dust and secondary arsenical fume；
(4) arsenic is received into the resulting secondary arsenical fume quenching of step (3), obtains As2O3And tail gas；Step (2) is resulting
Solid flue dust and the resulting secondary solid flue dust mixing of step (3) carry out oxygen leaching, and gained leachate is by extracting back
Receive indium；
(5) raffinate for obtaining extraction process returns to extraction process and is recycled.
Key of the invention is: using the method for reduction melting, the metals such as Cu, Bi, Pb disposably separated with arsenic, and
Indium (In2O、In2O3), arsenic (As2O3、As2S3) be volatized into gaseous form flue gas (the step for mainly utilize Cu, Bi, Pb
Equal metals and As2O3、As2S3、In2O、In2O3The difference of boiling point realizes separation), arsenic-containing smoke dust come out after by add air into
Row secondary oxidation is on the one hand to the content (explosion-proof) that strict control enters the electric middle CO that gathers dust, and being on the other hand can be by flue gas
In As2S3It is converted into As2O3, improve the quality of subsequent arsenic product.Since flue dust is other than As, In content are high, also there is temperature
The features such as degree is high, dust-laden is high, smoke granularity is thin, therefore the reduction melting flue gas after aoxidizing is cooling through waste heat boiler, on the one hand reduces
On the other hand flue dust temperature carries out deashing using the high-efficient elastic rapping machine cooperation explosion deashing device of preboiler.After cooling
Reduction melting flue gas due to still dustiness it is big, therefore through electric dust-collecting and dust-removing, practice have shown that, electricity gathers dust can be by above-mentioned reduction melting
90% of solid flue dust in flue gas removes, and remaining 10% solid flue dust is since granularity is relatively thin and solid flue dust contains in flue gas
Amount is lower, admittedly passing through metal film precision filtering, solid smoke content is lower to ensure that As during metal film precision is gathered dust
Efficiently separate, it is intended to improve the purity for the arsenic trioxide that metal film is collected into.Again by the arsenical fume after high-effective dust-removing
Quenching, is converted to solid-state by gaseous state for arsenic, realizes effective removing of arsenic；By technique of gathering dust twice, the solid cigarette that will be collected into
Arsenic content in dirt is effectively controlled 10% hereinafter, therefore can be incited somebody to action by the way of adding iron to consolidate arsenic the arsenic in solid flue dust
In is enriched in leachate, then using extraction by the way of realize In recycling and by raffinate return extraction process recycle
(by that could recycle raffinate after adding iron to consolidate arsenic technique arsenic removal), realizes entire process flow wastewater zero discharge, entirely
Process carries out in closed system.
Main chemical equation is as follows in the oxygen enriched molten bath reduction melting stage:
C+O2(g)=CO2(g) (1)
2C+O2(g)=2CO (g) (2)
C+CO2(g)=2CO (g) (3)
PbSO4+ C=PbO+SO2(g)+CO(g) (4)
PbO+CO=Pb+CO2(g) (5)
PbSO4+ C=PbS+O2(g)+CO2(g) (6)
PbSO4+ 4C=PbS+4CO (g) (7)
PbSO4+ PbS=2Pb+2SO2(g) (8)
2PbS+3O2=2PbO+2SO2(g) (9)
2PbO+PbS=3Pb+SO2(g) (10)
PbSO4+ 2C=Pb+SO2+2CO(g) (11)
Bi2O3+ 3C=2Bi+3CO (g) (12)
Bi2O3+ 3Fe=FeO+2Bi (13)
As2O3+ 3C=2As ↑+3CO ↑ (14)
As2S3+O2=As2O3+SO2 (15)
The comprehensive recovering process of the more metal materials containing indium of above-mentioned high arsenic, it is preferred that the high more metal materials containing indium of arsenic
In, contain: As 5wt%~30wt%, Pb 20wt%~40wt%, Cu 0.5wt%~10wt%, Bi 0.5wt%~
5wt%, S 0.5wt%~5wt%, In 0.05wt%~0.5wt%.
The comprehensive recovering process of the more metal materials containing indium of above-mentioned high arsenic, it is preferred that the high more metal materials containing indium of arsenic
Water content is 5wt%~8wt%, and the partial size of the high more metal materials containing indium of arsenic is less than 20mm.
The comprehensive recovering process of the more metal materials containing indium of above-mentioned high arsenic, it is preferred that in the step (1), the reduction
Agent is coal, and the additional amount of the reducing agent is 8%~the 13% of the more metal quality of material containing indium of high arsenic；It is logical during reduction melting
Enter oxygen, the ratio of the oxygen and coal is 600~800Nm3:t；The temperature of the reduction melting is 1200 DEG C~1300 DEG C,
The reduction melting time is 90~120min.It is carbon monoxide etc. that the purpose for being passed through oxygen, which is by coal combustion heat release, and by oxidation of coal,
Reducing atmosphere is provided.
The comprehensive recovering process of the more metal materials containing indium of above-mentioned high arsenic, it is preferred that in the step (1), the flux
For one of lime stone, quartz, iron filings or a variety of, the flux dosage be the more metal quality of material containing indium of high arsenic 6~
15%.
Via above-mentioned reducing condition, Cu, Bi, Pb, As, In in the high more metal materials containing indium of arsenic are latter by reduction melting
Secondary property separation, arsenic is mainly with As2O3、As2S3(As2O3457.2 DEG C of boiling point, As2S3707 DEG C of boiling point), indium is with In2O、In2O3(In2O
800 DEG C of boiling point or so, In2O3850 DEG C of boiling point) gas form is volatized into flue dust；The essential element content of matte:
Cu15~50%, Pb1~10%, Fe1~10%, S5~30%；Essential element content Pb80~95% of lead bismuth alloy,
Bi0.5~10%, Sn0.5~6%, Ag0.05~0.2%, Sb0.5~2%.
The comprehensive recovering process of the more metal materials containing indium of above-mentioned high arsenic, it is preferred that the CO concentration in the mixed flue gas
Lower than 8% and the mixed flue gas is free of As2S3。
Through detecting, the main component containing arsenic, indium flue gas is As2O3, As2S3, CO, CO2, SO2, In2O、In2O3, temperature is
1100~1150 DEG C, As2O3、As2S3、In2O、In2O3All in gaseous state, detection is obtained, which is that high arsenic is more
20~the 25% of metal quality of material containing indium, therefore the higher dust collection device of dust-collecting efficiency should be selected.It is special in control flue gas
Removal of impurities while different content of material guarantee gathers dust safe, improves the subsequent purity for receiving arsenic, and flue gas should be mended before gathering dust into electricity
Add air secondary to aoxidize, the CO in flue gas is oxidized to CO2, As2S3Be converted to As2O3。
One side strict control flue gas enters the concentration (explosion-proof) of CO when electricity gathers dust, on the other hand makes the As in flue gas2S3Turn
It is changed to As2O3, make subsequent receipts arsenic operation that can obtain the higher arsenic of purity.Preferably, the flue dust after the oxidation is entering electricity receipts
CO concentration detector and As should be first passed through before dirt2S3Concentration detector.Guarantee that flue gas CO concentration when gathering dust into electricity is lower than
8% and be free of As2S3。
The comprehensive recovering process of the more metal materials containing indium of above-mentioned high arsenic, it is preferred that in the step (2), the step
(2) in, the mixed flue gas is cooled down by waste heat boiler, the waste heat boiler quantity of steam 13~17t/h is after cooling
The temperature of mixed flue gas is 400~450 DEG C.Waste heat boiler cools down to flue gas while playing recovery waste heat.
Purpose by the temperature control of reduction melting flue gas at 400~450 DEG C are as follows: by controlling reduction melting flue gas temperature
Degree, the i.e. temperature of the reduction melting flue gas of guarantee heat boiler outlet are higher than 40~50 DEG C of acid dew-point temperature (if flue-gas temperature
Lower than dew-point temperature, on the one hand can cause so that acid equipment is caused to corrode, on the other hand can cause to bond in electricity gathers dust, shadow
Ring dust-collecting efficiency), the calculation formula t of the acid dew-point temperaturedew=186+20logVH2O+26logVso2(tdewThe acid dew of-flue gas
Point temperature, VH20The percentage (%) of-flue gas water vapor gas, Vso2- flue gas SO2The percentage (%) of gas).Protect equipment
Acid corrosion does not improve electric dust-collecting efficiency simultaneously, alleviates the pressure of gathering dust of metal film, guarantees the secondary filter of metal film, to protect
Demonstrate,prove the purity of arsenic trioxide.
Mixed flue gas gathers dust after coming out from waste heat boiler into electricity, and electricity gathers dust the arsenic and solid dust point in mixed flue gas
From, it is greater than 90% by carrying out the dust-collecting efficiency that strict control makes electricity gather dust to the mixed flue gas temperature in gathering dust into electricity,
The pressure of gathering dust of metal film is alleviated significantly.
The comprehensive recovering process of the more metal materials containing indium of above-mentioned high arsenic, it is preferred that in the step (3), the metal
Between compound flexible membrane be Al series intermetallic compound anisotropic membrane, by intermetallic compound flexible membrane filter once containing arsenic
The temperature of flue gas is 350~400 DEG C, and the intermetallic compound flexible membrane rate of filtration is 1.0~1.3m/min, the metal
Between compound flexibility membrane area be 1000~1300m2。
The metal film is selected between the metal of Novel corrosion, high temperature resistant, resistance to thermal shock, high intensity and is changed according to system condition
It closes object flexible membrane filter bag and carrys out filtering high temperature flue gas；Solid can be effectively set to be trapped in filter filter under high temperature strong corrosion environment
Bag surface.After solid filter cake is formed, and through reversed high temperature pulse, being formed in a predetermined pressure drop or in the time
Filter cake dispose.Filter filter cake recycles after being fallen down due to gravity into the lower cone part of filter.By anti-
Multiple circulation blowback and the substantially constant for keeping pressure drop, flue gas is complete continuous flow forward in maintenance system in whole process
's.Dustiness≤5mg/m after filtering3, 0.1 μm of dust catching minimum grain size.
Dust-laden, arsenic trioxide gas in 350 DEG C or more progress high temperature secondary filters, solid dust is blocked logical
Ash flue bucket discharge, arsenic pass through the special filtering material of metal film (see the oxidation of attached drawing 1: three two in the form of arsenic trioxide gas
Arsenic saturated vapor pressure figure), to realize that secondary filter efficiently separates arsenic and dust, obtains higher by lesser pressure of gathering dust
The arsenic product of purity, efficiency of dust collection >=99.99%.
The comprehensive recovering process of the more metal materials containing indium of above-mentioned high arsenic, it is preferred that in the step (4), the cooling
Rate be 60~80 DEG C/s, the secondary arsenical fume is cooled to 180 DEG C hereinafter, so as to by the As in flue gas2O3Sublimate for
Solid powder, As2O3The rate of recovery be greater than 90%.
The comprehensive recovering process of the more metal materials containing indium of above-mentioned high arsenic, it is preferred that the leachate of the oxygen leaching is
Sulfuric acid solution, the sulfuric acid concentration are 90~120g/L, contain ferric sulfate in the sulfuric acid solution；Oxygen leaching condition: Fe/As
=0.6~1.2, liquid-solid ratio=5:1~12:1,0.5~1.0MPa of oxygen pressure, 60~120min of reaction time, temperature 80~
140 DEG C, acid is in 15~20g/L eventually.
It is gathered dust after gathering dust twice with metal film by electricity, the arsenic content in flue gas is controlled 10% hereinafter, ensure that
Arsenic can leach completely under the conditions of peracid in oxygen leaching technique.The realization that recycles for the raffinate of subsequent indium may.
The comprehensive recovering process of the more metal materials containing indium of above-mentioned high arsenic, it is preferred that the extraction for obtaining the extraction process
Extraction raffinate returns to extraction process and is recycled, and realizes the wastewater zero discharge of hydrometallurgic recovery indium process.
Compared with the prior art, the advantages of the present invention are as follows:
1, the present invention realizes the disposable separation of the materials such as Cu, Bi, Pb, As, and is gathered dust by two sections and combine realization
Solid flue dust and As's efficiently separates, and the rate of recovery of arsenic and indium is high, and can with obtain the higher arsenic product of purity and indium
Product.
2, present invention process realizes the zero-emission of indium spent process water in the more metal materials containing indium of the high arsenic of hydrometallurgic recovery.
Detailed description of the invention
Fig. 1 is arsenic trioxide saturated vapor pressure figure.
Fig. 2 is the process flow chart of the embodiment of the present invention.
Specific embodiment
Below in conjunction with specific preferred embodiment, the invention will be further described, but not thereby limiting the invention
Protection scope.
The more metal materials containing indium of high arsenic in Examples 1 to 2 and comparative example 1 refine lead institute from Hunan copper-lead-zinc smelting factory
The high concn. arsenic and lead flue dust obtained, specific ingredient are as shown in table 1.
Specific ingredient/wt% of the more metal materials containing indium of the high arsenic of table 1
| Element | As | Pb | Cu | Bi | S | In |
| Content/% | 25.3 | 34.2 | 5.8 | 2.3 | 4.6 | 0.3 |
Flue gas condition:
Tolerance (operating condition): 20000m3/ h, (mark condition) :~10000Nm3/h；
SO2Content :~4.2%；
CO content: 5~10%
Flue-gas temperature: 1100 DEG C；
Dust contained flue gas :~100g/m3。
Arsenic content: 26.60g/m3。
Waste heat boiler basic fundamental parameter:
Saturation vapour pressure: 3.9Mpa (gauge pressure)
Vapor (steam) temperature: 251.8 DEG C
Nominal steam amount: 15t/h
Feed temperature: 104 DEG C
Boiler export flue gas negative pressure :~600Pa
Boiler export flue-gas temperature: 380 DEG C.
Electricity gathers dust:
Model: HXDC45/3/1
Number of units: 1.
Metal film basic fundamental parameter: the YT- filter of Chengdu YiTai Science Co., Ltd's production is changed between Al system metal
Close object anisotropic membrane
The rate of filtration: 1.1m/min
Area: 1024m2。
Embodiment 1:
By coal, iron filings, quartz, lime stone press respectively more metal material containing indium (25t) quality of high arsenic 10.34%,
6.91%, 4.11% and 1.66% ingredient is added in oxygen-enriched side-blowing furnace, oxygen-enriched air (purity is blasted in oxygen-enriched side-blown reducing furnace
50%, oxygen coal ratio is 650Nm3/ t), reduction melting 90min, in fusion process, lead are carried out under conditions of temperature is 1200 DEG C
Than great, sink to side-blown converter, melt upper layer is clinker, metal (matte Cu35.26%, Pb5.27%, Fe2.45%,
S5.78%；Lead bismuth alloy Pb92.21%, Bi1.34%, Sn0.56%, Ag0.05%, Sb0.57%) by side-blown converter lead outlet
It releases.Flue dust temperature is 1150 DEG C of (main components are as follows: As2O3, As2S3, CO, CO2, SO2, In2O、In2O3), it is blasted into flue dust
Air (956Nm3) oxidation, it is detected that flue dust is placed in after waste heat boiler is cooled to 400 DEG C up to after requiring and is gathered dust by electricity, gained
Arsenical fume enters metallic high temperature filter with 360 DEG C of temperature, and metallic high temperature deduster is by the powder in an arsenical fume
Dirt intercepts, and arsenic trioxide is in gaseous state across metal film filter (see Fig. 1: arsenic trioxide saturated vapor
Pressure figure), realize the separation of arsenic trioxide and solid flue dust.Resulting secondary arsenical fume is using rapid cooling 70 after filter
DEG C/s, control temperature is reduced to 180 DEG C hereinafter, arsenic trioxide in gas forms solid-state because of the decline of temperature, recycles
The method that natural subsidence and bag-type dust combine collects high-grade arsenic trioxide.The solid that finally two sections are gathered dust
Flue dust presses Ore Leaching, sulfuric acid concentration 100g/L by adding ferric sulfate to consolidate arsenic oxygen, and oxygen presses Ore Leaching technique are as follows: Fe/As=1.2, l/s
=12: 1, oxygen pressure 0.8MPa, reaction time 90min, 120 DEG C of temperature, it is solid that ferric sulfate is added in 15~20g/l in acid eventually
Arsenic leaches, and the arsenic of oxygen leaching liquid is less than 0.5g/l, Gu arsenic rate is 98.8%, so that indium is enriched in leachate, then passes through
The mode of extraction recycles, and raffinate is finally recycled to extraction process, realizes entire process flow zero-emission.By entire technique
Process, after testing, the different obtained flue dust parameters of workshop section are as shown in table 2.The rate of recovery of As is up to 99.95%, solid powder
Middle As2O3Content be 98.23%, In direct yield be 81.45%.
Table 2
| Flue gas | Dustiness g/m3 | Dust-collecting efficiency/% |
| Heat boiler outlet | 83.33 | — |
| Electricity gathers dust outlet | 7.31 | 91.23 |
| Metal film gathers dust outlet | <1 | 99.82 |
Embodiment 2:
By coal, iron filings, quartz, lime stone press respectively more metal material containing indium (25t) quality of high arsenic 13.12%,
7.41%, 4.65% and 2.01% ingredient is added in oxygen-enriched side-blowing furnace, oxygen-enriched air (purity is blasted in oxygen-enriched side-blown reducing furnace
50%, oxygen coal ratio is 650Nm3/ t), reduction melting 120min, in fusion process, lead are carried out under conditions of temperature is 1250 DEG C
Than great, sink to side-blown converter, melt upper layer is clinker, metal (matte Cu37.23%, Pb7.83%, Fe3.45%,
S2.45%；Lead bismuth alloy Pb89.45%, Bi2.34%, Sn0.63%, Ag0.04%, Sb0.65%) by side-blown converter lead outlet
It releases.Flue dust temperature is 1150 DEG C of (main components are as follows: As2O3, As2S3, CO, CO2, SO2, In2O、In2O3), it is blasted into flue gas
Air (956Nm3) oxidation, it is detected that flue dust is placed in after waste heat boiler is cooled to 400 DEG C up to after requiring and is gathered dust by electricity；Gained
Arsenical fume enters metallic high temperature filter with 360 DEG C of temperature, and metallic high temperature deduster is by the powder in an arsenical fume
Dirt intercepts, and arsenic trioxide is in gaseous state and passes through filter (see Fig. 1: arsenic trioxide saturated vapor pressure figure),
Realize the separation of arsenic trioxide and solid.Resulting secondary arsenical fume is using 70 DEG C/s of rapid cooling, control temperature after filter
Degree is reduced to 180 DEG C hereinafter, arsenic trioxide in gas forms solid-state because of the decline of temperature, recycles natural subsidence and cloth
The method that bag dedusting combines collects high-grade arsenic trioxide.The solid flue dust that finally two sections are gathered dust is by adding iron
Gu arsenic leaches, oxygen presses Ore Leaching technique are as follows: sulfuric acid concentration 120g/L, Fe/As=1.2, l/s=12: 1, oxygen pressure 0.8MPa,
Reaction time 120min, 120 DEG C of temperature, acid is added ferric sulfate and consolidates arsenic leaching, the arsenic of oxygen leaching liquid in 15~20g/l eventually
So that indium is enriched in leachate, then recycled by way of extraction less than 0.5g/l Gu arsenic rate is 98.6%, finally will
Raffinate is recycled to extraction process, realizes entire process flow zero-emission.By entire process flow, after testing, different works
The obtained flue dust parameter of section is as shown in table 3.The rate of recovery of As is up to 99.24%, As in solid powder2O3Content be
The direct yield of 99.12%, In are 82.63%.
Table 3
| Flue gas | Dustiness g/m3 | Dust-collecting efficiency/% |
| Heat boiler outlet | 89.45 | — |
| Electricity gathers dust outlet | 8.38 | 90.63 |
| Metal film gathers dust outlet | <1 | 99.94 |
Comparative example 1:
By coke, iron filings, quartz, lime stone by the more metal quality of material containing indium of high arsenic 30.34%, 3.34%,
3.51%, 3.41% ingredient is passed through oxygen (purity 25.6%, 2712Nm3/ h) oxidation, reduction melting in blast furnace is added, also
Former smelting temperature is 1250 DEG C, and the reduction melting time is 8h, and generation exhaust gas volumn is 3892m3The flue gas of/h.High-arsenic material melting cigarette
Gas gathers dust after waste heat boiler is cooled to 360~380 DEG C into electric precipitator, then using cooling equipment by flue gas be quenched to
125~145 DEG C obtain low-grade arsenic-containing smoke dust, and flue gas dust collection after cooling is obtained low-grade arsenic dirt with sack cleaner, low-grade
Arsenic-containing smoke dust and low-grade arsenic dirt mix to obtain crude arsenic dirt.Crude arsenic dirt is heated up to 600~700 DEG C with electric heating rotary kiln again, is made
Arsenic in crude arsenic dirt, at gaseous state, generates high-grade arsenic flue gas by solid state transformed.High-grade arsenic flue gas is used into aerial cooler
It is cooled to 120 DEG C or less and obtains solid-state arsenic dirt, flue gas dust collection after cooling is obtained into high-grade arsenic dirt (arsenic flue dust) with sack cleaner.
The solid-state arsenic dirt that this step obtains can return to electric heating rotary kiln and heat again.By entire process flow, the rate of recovery of As is
85.45%, As in solid powder2O3Content less than 90%.
There are difference on effect comparisons with comparative example for embodiment:
1. stove is different, efficiency is different.It is stock column form in blast furnace in production process, furnace bottom is that intensity is big, ventilative
Property good coke, be harsh control silicon, iron, ca proportion into the material in furnace, the agglomerate of good permeability, lower part coke, on
Portion's agglomerate is gradually accumulated, and stock column is formed.It without stock column in oxygen-enriched side-blowing furnace, melts, is formed molten quickly into the material in furnace
Body, without obvious solid layer, so oxygen-enriched side-blowing furnace is typical bath smelting furnace.This characteristic of oxygen-enriched side-blowing furnace determines reaction
Rate is fast, and low energy consumption, and specific capacity is high.
2. technique of gathering dust is different, receives arsenic efficiency and purity is different.Embodiment is special for the flue gas of oxygen-enriched side-blown reducing melting
Point: 1. arsenic mutually enters flue dust with not jljl；2. dust contained flue gas is high；3. smoke granularity is thin etc..Be respectively adopted plus Secondary Air oxidation,
The techniques such as the higher electricity of dust-collecting efficiency gathers dust, the metal film of secondary filter gathers dust combine.Comparative example then use electricity gather dust+cloth bag receive
The technique of gathering dust of dirt.The arsenic being simply considered that in flue dust is all mutually to exist with the object of arsenic trioxide, and have ignored solid in flue dust
This smaller feature of body granularity of dust is difficult the lesser solid dust filtering of granularity using bag collection, therefore will affect arsenic
Efficiency and purity.Therefore the effect and efficiency presence of two kinds of receipts arsenic technique.
3. pair solid flue dust processing difference being collected into.Embodiment is to the noble metal in solid flue dust using the work leached
Skill realizes recycling for the wherein recycling of valuable metal indium and raffinate, realizes the zero-emission of wet process.Comparison
Example is not handled then accordingly.
The above is only the preferred embodiment of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of comprehensive recovering process of the more metal materials containing indium of high arsenic, comprising the following steps:
(1) the more metal materials containing indium of high arsenic, reducing agent and flux ingredient are added in oxygen-enriched side-blowing furnace and carry out reduction melting, obtained
Matte, lead bismuth alloy, melting flue gas and reducing slag；
(2) it is aoxidized after mixing with air the resulting melting flue gas of step (1), obtains mixed flue gas, the mixed flue gas
Electricity is carried out after cooling again to gather dust, obtains a solid flue dust and an arsenical fume；
(3) the resulting arsenical fume of step (2) is filtered by intermetallic compound flexible membrane, obtains secondary solid
Flue dust and secondary arsenical fume；
(4) by the cooling receipts arsenic of the resulting secondary arsenical fume of step (3), As is obtained2O3And tail gas；Step (2) is resulting primary
Solid flue dust and the resulting secondary solid flue dust mixing of step (3) carry out oxygen leaching, and gained leachate passes through extraction and recovery indium；
(5) raffinate for obtaining extraction process returns to extraction process and is recycled.
2. the comprehensive recovering process of the more metal materials containing indium of high arsenic according to claim 1, which is characterized in that the high arsenic
In more metal materials containing indium, contain: As 5wt%~30wt%, Pb 20wt%~40wt %, Cu 0.5wt%~10wt %, Bi
0.5wt%~5wt%, S 0.5wt%~5wt %, In 0.05wt%~0.5wt%.
3. the comprehensive recovering process of the more metal materials containing indium of high arsenic according to claim 1, which is characterized in that the high arsenic
More metal material moistures containing indium are the wt of 5wt%~8 %, and the partial size of the high more metal materials containing indium of arsenic is less than 20mm.
4. the comprehensive recovering process of the more metal materials containing indium of high arsenic according to claim 1, which is characterized in that the step
(1) in, the reducing agent is coal, and the additional amount of the reducing agent is 8%~the 13% of the more metal quality of material containing indium of high arsenic；Reduction
It is passed through oxygen in fusion process, the ratio of the oxygen and coal is 600~800 Nm3:t；The temperature of the reduction melting is
1200 DEG C~1300 DEG C, the reduction melting time is 90~120min.
5. the comprehensive recovering process of the more metal materials containing indium of high arsenic according to claim 1, which is characterized in that the step
(1) in, the flux is one of lime stone, quartz, iron filings or a variety of, and the flux dosage is that the more metals of high arsenic contain indium
The 6~15% of quality of material.
6. the comprehensive recovering process of the more metal materials containing indium of high arsenic according to claim 1, which is characterized in that the mixing
CO concentration in flue gas is lower than 8% and the mixed flue gas is free of As2S3。
7. the comprehensive recovering process of the more metal materials containing indium of high arsenic according to claim 1, which is characterized in that the step
(2) in, the mixed flue gas is cooled down by waste heat boiler, the waste heat boiler quantity of steam 13~17t/h is after cooling
The temperature of mixed flue gas is 400~450 DEG C.
8. the comprehensive recovering process of the more metal materials containing indium of high arsenic according to claim 1, which is characterized in that the step
(3) in, the intermetallic compound flexible membrane is Al series intermetallic compound anisotropic membrane, passes through intermetallic compound flexible membrane
The temperature of arsenical fume of filtering is 350~400 DEG C, and the intermetallic compound flexible membrane rate of filtration is 1.0~1.3
M/min, the intermetallic compound flexibility membrane area are 1000~1300m2。
9. the comprehensive recovering process of the more metal materials containing indium of high arsenic according to claim 1, which is characterized in that the step
(4) in, the rate of the cooling is 60 ~ 80 DEG C/s, and the secondary arsenical fume is cooled to 180 DEG C or less.
10. the comprehensive recovering process of the more metal materials containing indium of described in any item high arsenic, feature exist according to claim 1~9
In the leachate of the oxygen leaching is sulfuric acid solution, and the sulfuric acid concentration is 90~120g/L, is contained in the sulfuric acid solution
Ferric sulfate；Oxygen leaching condition: Fe/As=0.6~1.2, liquid-solid ratio=5:1~12:1,0.5~1.0MPa of oxygen pressure, reaction
60~120min of time, 80~140 DEG C of temperature, acid is in 15~20 g/L eventually.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110438346A (en) * | 2019-07-30 | 2019-11-12 | 山东恒邦冶炼股份有限公司 | A kind of method of side-blown converter processing high arsenic content ore |
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| CN115505762A (en) * | 2022-09-22 | 2022-12-23 | 湖南锐异资环科技有限公司 | Indium extraction method of indium-containing multi-metal smelting slag |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760654A (en) * | 2008-12-24 | 2010-06-30 | 深圳市东江环保股份有限公司 | Method for recovering indium from indium-containing waste |
| CN102534227A (en) * | 2012-03-01 | 2012-07-04 | 郴州市金贵银业股份有限公司 | Method for extracting indium from indium-rich smoke dust by using oxygen pressure technology |
| JP5119524B2 (en) * | 2006-03-16 | 2013-01-16 | Ｄｏｗａメタルマイン株式会社 | Indium recovery method |
| JP2015196848A (en) * | 2014-03-31 | 2015-11-09 | Jx日鉱日石金属株式会社 | Arsenic treatment method |
| CN205495238U (en) * | 2016-01-16 | 2016-08-24 | 成都易态科技有限公司 | A clean system that is used for non -ferrous metal metallurgy to produce and contains arsenic smoke and dust |
| CN205500810U (en) * | 2016-01-16 | 2016-08-24 | 成都易态科技有限公司 | System for utilize and contain pozzuolite ore preparation arsenic trioxide |
| CN106282584A (en) * | 2015-06-02 | 2017-01-04 | 云南锡业集团有限责任公司研究设计院 | A kind of method of complicated high-arsenic-containing copper smelting flue dust valuable metal recovery |
| CN106834707A (en) * | 2016-12-21 | 2017-06-13 | 中南大学 | A kind of method of arsenic-containing material synthetical recovery and arsenic recycling |
-
2018
- 2018-11-21 CN CN201811390213.4A patent/CN109355508B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5119524B2 (en) * | 2006-03-16 | 2013-01-16 | Ｄｏｗａメタルマイン株式会社 | Indium recovery method |
| CN101760654A (en) * | 2008-12-24 | 2010-06-30 | 深圳市东江环保股份有限公司 | Method for recovering indium from indium-containing waste |
| CN102534227A (en) * | 2012-03-01 | 2012-07-04 | 郴州市金贵银业股份有限公司 | Method for extracting indium from indium-rich smoke dust by using oxygen pressure technology |
| JP2015196848A (en) * | 2014-03-31 | 2015-11-09 | Jx日鉱日石金属株式会社 | Arsenic treatment method |
| CN106282584A (en) * | 2015-06-02 | 2017-01-04 | 云南锡业集团有限责任公司研究设计院 | A kind of method of complicated high-arsenic-containing copper smelting flue dust valuable metal recovery |
| CN205495238U (en) * | 2016-01-16 | 2016-08-24 | 成都易态科技有限公司 | A clean system that is used for non -ferrous metal metallurgy to produce and contains arsenic smoke and dust |
| CN205500810U (en) * | 2016-01-16 | 2016-08-24 | 成都易态科技有限公司 | System for utilize and contain pozzuolite ore preparation arsenic trioxide |
| CN106834707A (en) * | 2016-12-21 | 2017-06-13 | 中南大学 | A kind of method of arsenic-containing material synthetical recovery and arsenic recycling |
Non-Patent Citations (1)
| Title |
|---|
| 《冶炼烟气制酸》编写组: "《冶炼烟气制酸》", 30 September 1977, 冶金工业出版社 * |
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| CN111363928A (en) * | 2020-04-07 | 2020-07-03 | 云南驰宏资源综合利用有限公司 | Method for inhibiting arsine gas during sulfuric acid leaching of high-arsenic lead-zinc smoke dust |
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