CN107012340A - The technique that a kind of Whote-wet method extracts arsenic from arsenones waste residue - Google Patents
The technique that a kind of Whote-wet method extracts arsenic from arsenones waste residue Download PDFInfo
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- CN107012340A CN107012340A CN201710203220.8A CN201710203220A CN107012340A CN 107012340 A CN107012340 A CN 107012340A CN 201710203220 A CN201710203220 A CN 201710203220A CN 107012340 A CN107012340 A CN 107012340A
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- Prior art keywords
- arsenic
- waste residue
- technique
- arsenones
- whote
- Prior art date
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 93
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 239000000284 extract Substances 0.000 title claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 33
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002386 leaching Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000001603 reducing Effects 0.000 claims abstract description 20
- 239000002893 slag Substances 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 18
- GCPXMJHSNVMWNM-UHFFFAOYSA-N Trihydroxyarsenite(Iii) Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229960002594 arsenic trioxide Drugs 0.000 claims abstract description 17
- 239000005864 Sulphur Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000003638 reducing agent Substances 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N oxygen atom Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 4
- 239000010413 mother solution Substances 0.000 claims description 3
- 238000010307 liquid-reduction process Methods 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims 1
- 238000004781 supercooling Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 7
- 238000001816 cooling Methods 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000005712 crystallization Effects 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000012065 filter cake Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000007654 immersion Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000010269 sulphur dioxide Nutrition 0.000 description 3
- 229910017251 AsO4 Inorganic materials 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000003009 desulfurizing Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001590 oxidative Effects 0.000 description 2
- 230000001698 pyrogenic Effects 0.000 description 2
- UKUVVAMSXXBMRX-UHFFFAOYSA-N 2,4,5-trithia-1,3-diarsabicyclo[1.1.1]pentane Chemical compound S1[As]2S[As]1S2 UKUVVAMSXXBMRX-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L Copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 sulphur arsenic Chemical compound 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 239000002351 wastewater 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
- 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
- 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
Abstract
A kind of technique for extracting arsenic from arsenones waste residue the invention discloses Whote-wet method, the technique is that, by oxygen leaching, separation of solid and liquid obtains sulphur slag and containing pentavalent arsenic and H by arsenones waste residue2SO4Oxygen leaching liquid；Pentavalent arsenic is reduced using arsenones waste residue as reducing agent, separation of solid and liquid obtains solution and slag phase containing trivalent arsenic；Solution containing trivalent arsenic passes through crystallisation by cooling, dries, obtains the white product of arsenic, slag phase then returns to oxygen leaching.The technique has the advantages that short, economical and practical flow, good operational environment, solution closed circulation, and arsenic and sulphur content can be made not with arsenic trioxide product and sulphur recovery, solves traditional SO2The problem of reduction causes acid plumping, is conducive to industrial popularization and application.
Description
Technical field
The present invention relates to a kind of processing method of arsenones waste residue, it is more particularly to a kind of by Whote-wet method from arsenones waste residue
The middle cleaning disposing technique for extracting separation arsenic element, belongs to non-ferrous metal extractive technique and environment protection treating field.
Background technology
In the smelting process such as copper and gold, the arsenic filter produced when gas cleaning is washed in ore oxidation desulfurization acid manufacturing processes
Cake is mainly arsenones (As2S3) based on slag, because the slag is higher containing pozzuolite, intractability is big, and many smelteries all stack.
For slags containing pozzuolite such as arsenic filter cakes, existing handling process mainly has pyrogenic process oxidizing roasting, produce sulfur dioxide and
Arsenic trioxide, the sulfur dioxide flue gas that this method is produced is high-leveled and difficult to handle containing arsenic, and operating environment is poor, three obtained oxidations of gathering dust
Two arsenic purity are not high, do not reach Product-level.The problem of existing for pyrogenic process oxidizing roasting technique, wet processing can be solved well
Certainly, general wet processing process is replaced using copper sulphate, output arsenic trioxide, but the technique copper consumption is excessive,
Serious waste of resources.Another wet processing process is oxygen leaching, and output pentavalent arsenic solution, using sulphur dioxide reduction, is obtained
To product-level arsenic trioxide, one ton of arsenic is reduced in theory and produces 1.31t sulfuric acid, actual production is more taller than this, causes
System acid plumping, a series of environmental protection and Cost Problems can be produced by causing the high acid solution of high arsenic to dispose.Obtain a kind of good work
Skill, can not only obtain product arsenic but also solve acid plumping, realize that sealing and circulating technique disposal arsenic filter cake is one and gets a good eye value
Thing.
The content of the invention
For the technological deficiency that the technique for overcoming existing processing pozzuolite waste residue is present, the purpose of the present invention is to be to provide
A kind of technological process is short, economical and practical, good operational environment, solution closed circulation, the technique of cleaning disposal arsenones waste residue, the work
Skill can not only make arsenic with arsenic trioxide Product recycling, and the problem of solve acid plumping, be conducive to industrial popularization and application.
In order to realize above-mentioned technical purpose, the work of arsenic is extracted from arsenones waste residue the invention provides a kind of Whote-wet method
Skill, the technique is that, by oxygen leaching, separation of solid and liquid obtains sulphur slag and containing pentavalent arsenic and H by arsenones waste residue2SO4Oxygen pressure leaching
Go out liquid；Arsenones waste residue is reduced to the pentavalent arsenic in oxygen leaching liquid as reducing agent, separation of solid and liquid is obtained containing the molten of trivalent arsenic
Liquid and slag phase；The solution containing trivalent arsenic passes through crystallisation by cooling, and the white product of arsenic is obtained after drying；The slag phase returns to oxygen pressure leaching
Go out.
It is preferred that scheme, arsenic content is 20~50g/L, H in the oxygen leaching liquid2SO4Concentration is 60~200g/L.
More preferably scheme, the condition of the oxygen leaching liquid reduction process is：Liquid-solid ratio is 5~10:1L/kg, temperature
For 80~100 DEG C, under agitation, react 0.5~2 hour.
Arsenic content is 40~60g/L in more preferably scheme, the solution containing trivalent arsenic.
Further preferred scheme, the solution containing trivalent arsenic is cooled to 0~30 DEG C, separates out arsenic trioxide crystal,
The crystalline mother solution that arsenic content is 15~25g/L is obtained, crystalline mother solution returns to oxygen leaching.
It is preferred that scheme, arsenic content is less than 1wt% in the sulphur slag, and sulfur content is more than 60wt%.
The arsenones raw slag material of the present invention is mainly the higher waste residue of pozzuolite content of by-product in metallurgical technology, such as copper and
In the smelting processes such as gold, the arsenic filter cake that produces when gas cleaning is washed in ore oxidation desulfurization acid manufacturing processes, arsenic in raw material
Content is 15~35wt%, and the content of sulphur is 20~40wt%.
The sulphur slag sulfur-bearing rate of the present invention is high, is used as the sulphur source of simple substance sulfur recovery.
The present invention oxygen leaching condition be：Solid-to-liquid ratio is 5~10:1L/kg, H2SO460~200g/L, 105~115
DEG C, oxygen pressure 0.5~1MPa, 60~100min of extraction time obtain oxygen leaching liquid 20~50g/L containing pentavalent arsenic, H2SO460~
200g/L。
The present invention utilizes HAsO2The characteristics of difference in solubility is larger at different temperatures, the solution containing trivalent arsenic is passed through
Crystallisation by cooling, separates out arsenic trioxide, and arsenic trioxide crystal is scrubbed, it is white to obtain product arsenic after drying.
The process that arsenic is extracted from arsenones waste residue of the present invention mainly includes oxygen leaching and arsenic reduction and three oxidations two
Arsenic precipitation process.
1) during oxygen leaching, mainly under HTHP, acid condition, oxidation is used as by the use of air or oxygen
Agent, elemental sulfur is oxidized to by the sulphur in arsenones, and arsenic is oxidized to pentavalent arsenic, and key reaction formula is as follows：
As2S3+4O2+6H+=2H3AsO4+3S；
2) in arsenic reduction process, with arsenones waste residue (mainly with the form presence of arsenones) for reducing agent, by oxygen pressure
Pentavalent arsenic is reduced to trivalent arsenic in leachate, while the arsenic that the sulphur in arsenones is oxidized in elemental sulfur, arsenones is converted into
HAsO2And leach.
Key reaction formula in arsenic reduction process is as follows：
As2S3+3H3AsO4=5HAsO2+3S+2H2O；
3) according to HAsO2Very big difference is presented in solubility at different temperatures in the solution, and directly cooling is crystallizable
Separate out arsenic trioxide；
Separate out the key reaction during arsenic trioxide：
HAsO2=As2O3(s)+H2O；
Compared with the prior art, the beneficial effect that technical scheme is brought：
1) technical scheme can make arsenic and sulphur in arsenones waste residue all efficiently be leached and reclaimed, and can obtain
Obtain the arsenic trioxide and sulphur product of high-purity.
2) technical scheme, the main component arsenones taken full advantage of in arsenones waste residue possess reproducibility
Feature, can not only make in leachate that pentavalent arsenic Restore All is into trivalent arsenic, while the arsenic in arsenones is also with HAsO2Form
Dissolution, improves the recovering effect of arsenic, is enriched with after sulphion oxidation in elemental sulfur form, the generation without sulfuric acid solves acid swollen
Swollen problem, while reducing the use cost of additional reducing agent.
3) technical scheme realizes the closed cycle processing of sulphur arsenic waste residue, and the generation of no acid-bearing wastewater is middle
Waste liquid is all recycled well, not only reduces production cost, is a kind of high-efficiency cleaning while being also beneficial to environmental protection
The method for disposing arsenones waste residue.
4) technical scheme is simple to operate, and process conditions are gentle, are conducive to industrial applications.
Brief description of the drawings
【Fig. 1】For the process flow diagram of the present invention.
Embodiment
The present invention is further described with reference to the accompanying drawings and examples, and the claims in the present invention protection domain not by with
Lower embodiment limitation.
The concrete technology of example 1 below~5 is referring to Fig. 1, at a kind of cleaning that separation arsenic element is extracted from arsenic sulfide slag
Put technique, raw material utilizes the major metal and its content in the arsenic filter cake of copper smelting plant, raw material to be respectively：As15~35%, S20
~40%.Arsenones waste residue first carries out oxygen leaching, and oxygen leaching condition is：Solid-to-liquid ratio 5~10:1L/kg, H2SO460~
200g/L, 105~115 DEG C, oxygen pressure 0.5~1MPa, 60~100min of extraction time obtain oxygen leaching liquid and (contain pentavalent arsenic 20
~50g/L, H2SO480~200g/L) and sulphur slag (containing As≤1%, S >=60%).Arsenic filter cake is pressed as reducing agent oxygen reduction and soaked
The pentavalent arsenic gone out in liquid, the addition of arsenic filter cake is 1~2 times of pentavalent arsenic theory of reduction amount, and in 80~100 DEG C of temperature, machinery is stirred
Reduced under conditions of mixing 0.5~2 hour, reaction terminates rear heat filtering, solution after being reduced (40~60g/L containing trivalent arsenic,
H2SO480~200g/L) and slag phase (containing As3~15%, S30~50%), the solution containing trivalent arsenic be cooled to 0~30 DEG C of crystallization,
As is obtained after drying2O3>=99% product arsenic is white, and reduction slag phase then returns to oxygen leaching.
Embodiment 1
By Fig. 1 processing steps, arsenic filter cake 100g is taken, oxygen immersion liquid is added and (contains H2SO480g/L, pentavalent arsenic 20g/L) 500mL,
Its liquid-solid ratio is 5L: 1kg, and reaction temperature is 85 DEG C, and mechanical agitation is reacted 1 hour, heat filtering, solution is cooled to 10 DEG C, can obtain
As must be contained2O3Up to 99.3% arsenic trioxide solid, reduction process pentavalent arsenic percent reduction 92.6%.
Embodiment 2
By Fig. 1 processing steps, arsenic filter cake 50g is taken, oxygen immersion liquid is added and (contains H2SO4100g/L, pentavalent arsenic 30g/L) 500mL,
Its liquid-solid ratio is 10L: 1kg, and reaction temperature is 90 DEG C, and mechanical agitation is reacted 0.5 hour, heat filtering, leachate is cooled to 25
DEG C, it can obtain containing As2O3Up to 99.2% arsenic trioxide solid, reduction process pentavalent arsenic percent reduction 96.3%.
Embodiment 3
By Fig. 1 processing steps, arsenic filter cake 160g is taken, oxygen immersion liquid is added and (contains H2SO4160g/L, pentavalent arsenic 20g/L)
1000mL, its liquid-solid ratio is 25L: 4kg, and reaction temperature is 100 DEG C, and mechanical agitation is reacted 0.5 hour, heat filtering, is cooled to 25
DEG C, it can obtain containing As2O3Up to 99.1% arsenic trioxide solid, reduction process pentavalent arsenic percent reduction 97.4%.
Embodiment 4
By Fig. 1 processing steps, arsenic filter cake 100g is taken, oxygen immersion liquid is added and (contains H2SO4180g/L, pentavalent arsenic 35g/L) 500mL,
Its liquid-solid ratio is 5L: 1kg, and reaction temperature is 95 DEG C, and mechanical agitation is reacted 0.5 hour, heat filtering, is cooled to 30 DEG C, can obtain
Containing As2O3Up to 99.4% arsenic trioxide solid, reduction process pentavalent arsenic percent reduction 95.7%.
Embodiment 5
By Fig. 1 processing steps, arsenic filter cake 100g is taken, oxygen immersion liquid is added and (contains H2SO4120g/L, As5+30g/L) 1000mL,
Its liquid-solid ratio is 10L: 1kg, and reaction temperature is 95 DEG C, and mechanical agitation is reacted 2 hours, heat filtering, is cooled to 15 DEG C, can obtain
Containing As2O3Up to 99.3% arsenic trioxide solid, reduction process pentavalent arsenic percent reduction 93.9%.
Claims (6)
1. the technique that a kind of Whote-wet method extracts arsenic from arsenones waste residue, it is characterised in that：Arsenones waste residue is pressed by oxygen and soaked
Go out, separation of solid and liquid, obtain sulphur slag and containing pentavalent arsenic and H2SO4Oxygen leaching liquid；It regard arsenones waste residue as reducing agent oxygen reduction
The pentavalent arsenic in leachate is pressed, separation of solid and liquid obtains solution and slag phase containing trivalent arsenic；The solution containing trivalent arsenic is through supercooling
But crystallize, dry, obtain the white product of arsenic；The slag phase returns to oxygen leaching.
2. the technique that Whote-wet method according to claim 1 extracts arsenic from arsenones waste residue, it is characterised in that：The oxygen pressure
Pentavalent arsenic content is 20~50g/L, H in leachate2SO4Concentration is 60~200g/L.
3. the technique that Whote-wet method according to claim 1 or 2 extracts arsenic from arsenones waste residue, it is characterised in that：It is described
The condition of oxygen leaching liquid reduction process is：Liquid-solid ratio is 5~10:1L/kg, temperature is 80~100 DEG C, under agitation,
Reaction 0.5~2 hour.
4. the technique that Whote-wet method according to claim 3 extracts arsenic from arsenones waste residue, it is characterised in that：It is described to contain three
Arsenic content is 40~60g/L in the solution of valency arsenic.
5. the technique that Whote-wet method according to claim 4 extracts arsenic from arsenones waste residue, it is characterised in that：It is described to contain three
The solution of valency arsenic is cooled to 0~30 DEG C, separates out arsenic trioxide crystal, obtains the crystalline mother solution that arsenic content is 15~25g/L, knot
Brilliant mother liquor returns to oxygen leaching.
6. the technique that the Whote-wet method according to claim 1,2,4 or 5 extracts arsenic from arsenones waste residue, it is characterised in that：
Arsenic content is less than 1wt% in the sulphur slag, and sulfur content is more than 60wt%.
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| CN108315571A (en) * | 2018-01-17 | 2018-07-24 | 中国瑞林工程技术有限公司 | A kind for the treatment of process of Containing Sulfur arsenic material |
| CN108570563A (en) * | 2018-06-07 | 2018-09-25 | 广西壮族自治区环境保护科学研究院 | A kind of processing method of phosphoric acid industry arsenic sulfide slag |
| CN109930003A (en) * | 2019-04-01 | 2019-06-25 | 山东恒邦冶炼股份有限公司 | A kind of integrated conduct method of arsenic sulfide slag resource utilization |
| CN110028101A (en) * | 2019-04-30 | 2019-07-19 | 中南大学 | A method of arsenic trioxide is prepared using arsenic sulfide slag |
| CN110407250A (en) * | 2019-08-14 | 2019-11-05 | 中国科学院生态环境研究中心 | A kind of method that arsenic-containing waste residue is converted into mansfieldite stabilization processes and Recovered sulphur |
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| CN113430385A (en) * | 2021-05-13 | 2021-09-24 | 中南大学 | Method for recycling sulfur rhenium from arsenic sulfide slag and harmlessly treating arsenic |
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| CN108315571A (en) * | 2018-01-17 | 2018-07-24 | 中国瑞林工程技术有限公司 | A kind for the treatment of process of Containing Sulfur arsenic material |
| CN108570563A (en) * | 2018-06-07 | 2018-09-25 | 广西壮族自治区环境保护科学研究院 | A kind of processing method of phosphoric acid industry arsenic sulfide slag |
| CN109930003A (en) * | 2019-04-01 | 2019-06-25 | 山东恒邦冶炼股份有限公司 | A kind of integrated conduct method of arsenic sulfide slag resource utilization |
| CN110028101A (en) * | 2019-04-30 | 2019-07-19 | 中南大学 | A method of arsenic trioxide is prepared using arsenic sulfide slag |
| CN110407250A (en) * | 2019-08-14 | 2019-11-05 | 中国科学院生态环境研究中心 | A kind of method that arsenic-containing waste residue is converted into mansfieldite stabilization processes and Recovered sulphur |
| CN110983059A (en) * | 2019-12-09 | 2020-04-10 | 黑龙江紫金铜业有限公司 | Method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake |
| CN110983059B (en) * | 2019-12-09 | 2021-07-06 | 黑龙江紫金铜业有限公司 | Method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake |
| CN112063858A (en) * | 2020-09-08 | 2020-12-11 | 龙岩市宇恒环保科技有限公司 | Process for producing qualified arsenic oxide from arsenic-containing material by full-wet method |
| CN113430385A (en) * | 2021-05-13 | 2021-09-24 | 中南大学 | Method for recycling sulfur rhenium from arsenic sulfide slag and harmlessly treating arsenic |
| WO2022237532A1 (en) * | 2021-05-13 | 2022-11-17 | 中南大学 | Harmless treatment method for recovering sulfur, rhenium, and arsenic from arsenic sulfide slag |
| CN113564372A (en) * | 2021-07-14 | 2021-10-29 | 中南大学 | Comprehensive recovery method of sulfur, copper and rhenium in arsenic sulfide slag |
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