CN107012340B - A kind of technique that Whote-wet method extracts arsenic from arsenones waste residue - Google Patents
A kind of technique that Whote-wet method extracts arsenic from arsenones waste residue Download PDFInfo
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- CN107012340B CN107012340B CN201710203220.8A CN201710203220A CN107012340B CN 107012340 B CN107012340 B CN 107012340B CN 201710203220 A CN201710203220 A CN 201710203220A CN 107012340 B CN107012340 B CN 107012340B
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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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a kind of Whote-wet methods to extract the technique of arsenic from arsenones waste residue, which is to be separated by solid-liquid separation arsenones waste residue by oxygen leaching, obtains sulphur slag and contains pentavalent arsenic and H2SO4Oxygen leaching liquid；Pentavalent arsenic is restored using arsenones waste residue as reducing agent, is separated by solid-liquid separation, obtains the solution containing trivalent arsenic and slag phase；Solution containing trivalent arsenic passes through crystallisation by cooling, dry, obtains the white product of arsenic, slag phase then returns to oxygen leaching.The technique has many advantages, such as short flow, economical and practical, good operational environment, solution closed circulation, and arsenic and sulphur content can be made with arsenic trioxide product and sulphur recovery, not to solve traditional SO2The problem of reduction causes acid plumping, is conducive to industrially promote and apply.
Description
Technical field
The present invention relates to a kind of processing method of arsenones waste residue, more particularly to it is a kind of by Whote-wet method from arsenones waste residue
The cleaning disposing technique of middle extraction separation arsenic element, belongs to non-ferrous metal extractive technique and environment protection treating field.
Background technology
In the smelting processes such as copper and gold, the arsenic generated when gas cleaning is washed in ore oxidation desulfurization acid manufacturing processes is filtered
Cake is mainly arsenones (As2S3) based on slag, due to the slag containing pozzuolite it is higher, intractability is big, and many smelteries are all stacked.
For slags containing pozzuolite such as arsenic filter cakes, existing treatment process mainly has pyrogenic process oxidizing roasting, generate sulfur dioxide and
Arsenic trioxide, the sulfur dioxide flue gas that this method generates is high-leveled and difficult with processing containing arsenic, and operating environment is poor, three oxidations gathered dust
Two arsenic purity are not high, and Product-level is not achieved.For pyrogenic process oxidizing roasting technique there are the problem of, wet processing can solve 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 is obtained using sulphur dioxide reduction
To product-level arsenic trioxide, theoretically restores one ton of arsenic and generate 1.31t sulfuric acid, actual production is more taller than this, causes
System acid plumping causes the high acid solution of high arsenic that need to dispose and will produce a series of environmental protection and cost problem.Obtain a kind of good work
Skill can not only obtain product arsenic but also solve acid plumping, realize that sealing and circulating technique disposition arsenic filter cake is one and gets a good eye value
Thing.
Invention content
In order to overcome technological deficiency existing for the technique of existing processing pozzuolite waste residue, the purpose of the invention is to provide
A kind of technological process is short, economical and practical, good operational environment, solution closed circulation, the technique of cleaning disposition arsenones waste residue, the work
Skill not only can make arsenic with arsenic trioxide Product recycling, and solve the problems, such as acid plumping, be conducive to industrially promote and apply.
In order to achieve the above technical purposes, the present invention provides a kind of Whote-wet methods extracts the work of arsenic from arsenones waste residue
Skill, the technique are to be separated by solid-liquid separation arsenones waste residue by oxygen leaching, obtain sulphur slag and contain pentavalent arsenic and H2SO4Oxygen pressure leaching
Go out liquid；The pentavalent arsenic in oxygen leaching liquid is restored using arsenones waste residue as reducing agent, is separated by solid-liquid separation, obtains 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 dry；The slag phase returns to oxygen pressure leaching
Go out.
Preferred scheme, arsenic content is 20~50g/L, H in the oxygen leaching liquid2SO4A concentration of 60~200g/L.
The condition of more preferably scheme, the oxygen leaching liquid reduction process is：Liquid-solid ratio is 5~10:1L/kg, temperature
It is 80~100 DEG C, under agitation, reacts 0.5~2 hour.
More preferably scheme, arsenic content is 40~60g/L in the solution containing trivalent arsenic.
Further preferred scheme, the solution containing trivalent arsenic are cooled to 0~30 DEG C, and arsenic trioxide crystal is precipitated,
The crystalline mother solution that arsenic content is 15~25g/L is obtained, crystalline mother solution returns to oxygen leaching.
Preferred 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 generates 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 presses 0.5~1MPa, 60~100min of extraction time, obtains oxygen leaching liquid 20~50g/L containing pentavalent arsenic, H2SO460~
200g/L。
The present invention utilizes HAsO2The larger feature of difference in solubility at different temperatures passes through the solution containing trivalent arsenic
Arsenic trioxide is precipitated in crystallisation by cooling, and arsenic trioxide crystal is washed, it is white to obtain product arsenic after drying.
The process of extraction arsenic includes mainly oxygen leaching and arsenic reduction and three oxidations two in the slave arsenones waste residue of the present invention
Arsenic precipitation process.
1) during oxygen leaching, mainly under high temperature and pressure, acid condition, using air or oxygen as oxidation
Sulphur in arsenones is oxidized to elemental sulfur by agent, and arsenic is oxidized to pentavalent arsenic, and key reaction formula is as follows：
As2S3+4O2+6H+=2H3AsO4+3S；
2) in arsenic reduction process, by arsenones waste residue (the mainly presence in the form of arsenones) for reducing agent, by oxygen pressure
Pentavalent arsenic is reduced to trivalent arsenic in leachate, while the sulphur in arsenones is oxidized to elemental sulfur, and the arsenic in arsenones is converted into
HAsO2And it leaches.
Key reaction formula in arsenic reduction process is as follows：
As2S3+3H3AsO4=5HAsO2+3S+2H2O；
3) according to HAsO2Prodigious difference is presented in solubility at different temperatures in the solution, and directly cooling is i.e. crystallizable
Arsenic trioxide is precipitated；
The key reaction during arsenic trioxide is precipitated：
HAsO2=As2O3(s)+H2O；
Compared with the prior art, the advantageous effect that technical scheme of the present invention is brought：
1) technical scheme of the present invention can make arsenic in arsenones waste residue and sulphur all efficiently be leached and be recycled, and can obtain
Obtain the arsenic trioxide and sulphur product of high-purity.
2) technical scheme of the present invention, the main component arsenones taken full advantage of in arsenones waste residue have reproducibility
Feature can not only make in leachate pentavalent arsenic Restore All at trivalent arsenic, while the arsenic in arsenones is also with HAsO2Form
Dissolution is improved the recovering effect of arsenic, is enriched in the form of elemental sulfur after sulphion oxidation, and it is swollen to solve acid for the not generation of sulfuric acid
Swollen problem, while reducing the use cost of additional reducing agent.
3) technical scheme of the present invention realizes the closed cycle processing of sulphur arsenic waste residue, and the generation of no acid-bearing wastewater is intermediate
Waste liquid is all recycled well, not only reduces production cost, while being also beneficial to environmental protection, is a kind of high-efficiency cleaning
The method for disposing arsenones waste residue.
4) technical scheme of the present invention is easy to operate, and process conditions are mild, is conducive to industrial applications.
Description of the drawings
【Fig. 1】For the process flow diagram of the present invention.
Specific implementation mode
Present invention will be further explained below with reference to the attached drawings and examples, and the claims in the present invention protection domain not by with
Lower embodiment limitation.
The concrete technology of following example 1~5 is referring to Fig. 1, a kind of cleaning place of the extraction separation arsenic element from arsenic sulfide slag
Technique is set, raw material utilizes the arsenic filter cake of copper smelting plant, and the major metal and its content in raw material are 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 presses 0.5~1MPa, 60~100min of extraction time, obtains oxygen leaching liquid and (contains 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 is soaked
Go out the pentavalent arsenic 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 stirs
It is restored under conditions of mixing 0.5~2 hour, after reaction heat filtering, solution after being restored (40~60g/L containing trivalent arsenic,
H2SO480~200g/L) and slag phase (contain 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, and 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 reduction rate 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, and heat filtering, leachate is cooled to 25
DEG C, it can get and contain As2O3Up to 99.2% arsenic trioxide solid, reduction process pentavalent arsenic reduction rate 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, liquid-solid ratio 25L: 4kg, reaction temperature are 100 DEG C, and mechanical agitation is reacted 0.5 hour, and heat filtering is cooled to 25
DEG C, it can get and contain As2O3Up to 99.1% arsenic trioxide solid, reduction process pentavalent arsenic reduction rate 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, and heat filtering is cooled to 30 DEG C, can get
Containing As2O3Up to 99.4% arsenic trioxide solid, reduction process pentavalent arsenic reduction rate 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, and heat filtering is cooled to 15 DEG C, can get
Containing As2O3Up to 99.3% arsenic trioxide solid, reduction process pentavalent arsenic reduction rate 93.9%.
Claims (4)
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 is soaked
Go out, be separated by solid-liquid separation, obtain sulphur slag and contains pentavalent arsenic and H2SO4Oxygen leaching liquid；Using arsenones waste residue as reducing agent oxygen reduction
The pentavalent arsenic in leachate is pressed, is separated by solid-liquid separation, obtains the solution containing trivalent arsenic and slag phase；The solution containing trivalent arsenic is through supercooling
But it crystallizes, it is dry, obtain the white product of arsenic；The slag phase returns to oxygen leaching；
Pentavalent arsenic content is 20~50g/L, H in the oxygen leaching liquid2SO4A concentration of 60~200g/L；
The condition of the oxygen leaching liquid reduction process is：Liquid-solid ratio is 5~10:1L/kg, temperature are 80~100 DEG C, are being stirred
Under the conditions of, it reacts 0.5~2 hour.
2. the technique that Whote-wet method according to claim 1 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 valence arsenic.
3. the technique that Whote-wet method according to claim 2 extracts arsenic from arsenones waste residue, it is characterised in that：It is described to contain three
The solution of valence arsenic is cooled to 0~30 DEG C, and arsenic trioxide crystal is precipitated, and obtains the crystalline mother solution that arsenic content is 15~25g/L, knot
Brilliant mother liquor returns to oxygen leaching.
4. the technique that Whote-wet method according to claim 1,2 or 3 extracts arsenic from arsenones waste residue, it is characterised in that：Institute
It states arsenic content in sulphur slag and is less than 1wt%, 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 |
| CN110407250B (en) * | 2019-08-14 | 2021-02-05 | 中国科学院生态环境研究中心 | Method for stabilizing treatment and recycling sulfur by converting arsenic-containing waste residues into arsenite |
| 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 |
| CN113430385B (en) * | 2021-05-13 | 2022-05-20 | 中南大学 | Method for recycling sulfur rhenium from arsenic sulfide slag and harmlessly treating arsenic |
| CN113564372B (en) * | 2021-07-14 | 2023-03-17 | 中南大学 | Comprehensive recovery method of sulfur, copper and rhenium in arsenic sulfide slag |
| CN114934192B (en) * | 2022-06-14 | 2024-01-30 | 长沙有色冶金设计研究院有限公司 | Method for cooperatively leaching zinc concentrate and arsenic sulfide slag |
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| CN1042920C (en) * | 1994-05-07 | 1999-04-14 | 湖南大学 | Method of wet-extraction for white arsenic |
| CN101767822A (en) * | 2008-12-31 | 2010-07-07 | 江西铜业集团公司 | Method for recovering arsenic from scrap material containing arsenic and copper produced in process of copper smelting |
| CN102115162A (en) * | 2010-12-31 | 2011-07-06 | 马艳荣 | Method for preparing arsenic trioxide by using arsenic sulfide waste slags |
| CN102115166B (en) * | 2010-12-31 | 2012-07-25 | 马艳荣 | Method for preparing arsenic trioxide from arsenic sulfide waste |
| CN102602994B (en) * | 2011-12-20 | 2013-08-21 | 湖南展泰有色金属有限公司 | Method for preparing arsenic trioxide by utilizing arsenious waste water |
| CN105154679B (en) * | 2015-09-22 | 2017-09-19 | 中南大学 | A kind of copper arsenic method for separating and processing of arsenic filter cake |
| CN106086426B (en) * | 2016-08-15 | 2018-03-06 | 郴州金山冶金化工有限公司 | A kind of arsenic sulfide slag hyperbaric oxygen continuously leaches resource utilization process |
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