CN117144155A - Method for separating and extracting arsenic-containing phase from copper slag and application thereof - Google Patents
Method for separating and extracting arsenic-containing phase from copper slag and application thereof Download PDFInfo
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- CN117144155A CN117144155A CN202311128692.3A CN202311128692A CN117144155A CN 117144155 A CN117144155 A CN 117144155A CN 202311128692 A CN202311128692 A CN 202311128692A CN 117144155 A CN117144155 A CN 117144155A
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 95
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000002893 slag Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 56
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 44
- 239000010949 copper Substances 0.000 title claims abstract description 44
- 238000000605 extraction Methods 0.000 claims abstract description 48
- 239000000706 filtrate Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 230000001590 oxidative effect Effects 0.000 claims abstract description 31
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 12
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 19
- 238000004090 dissolution Methods 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 5
- -1 hydrogen ions Chemical class 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 21
- 229940000489 arsenate Drugs 0.000 description 20
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 238000000967 suction filtration Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000005368 silicate glass Substances 0.000 description 8
- 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 7
- 238000003723 Smelting Methods 0.000 description 7
- 229910000413 arsenic oxide Inorganic materials 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 6
- 229960002594 arsenic trioxide Drugs 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000001495 arsenic compounds Chemical class 0.000 description 5
- 229940093920 gynecological arsenic compound Drugs 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052729 chemical element Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 230000000750 progressive effect Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- MKOYQDCOZXHZSO-UHFFFAOYSA-N [Cu].[Cu].[Cu].[As] Chemical compound [Cu].[Cu].[Cu].[As] MKOYQDCOZXHZSO-UHFFFAOYSA-N 0.000 description 2
- LAISNASYKAIAIK-UHFFFAOYSA-N [S].[As] Chemical compound [S].[As] LAISNASYKAIAIK-UHFFFAOYSA-N 0.000 description 2
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 description 2
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 description 2
- 229910052964 arsenopyrite Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052957 realgar Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- YBQWEUNEYYXYOI-UHFFFAOYSA-N arsenamide Chemical compound NC(=O)C1=CC=C([As](SCC(O)=O)SCC(O)=O)C=C1 YBQWEUNEYYXYOI-UHFFFAOYSA-N 0.000 description 1
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000012306 spectroscopic technique Methods 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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 belongs to the field of environmental engineering, and particularly relates to a method for separating and extracting an arsenic-containing phase from copper slag. The method comprises the following steps: 1) Adding copper slag into water, heating and dissolving materials, and filtering and separating to obtain filter residue A and filtrate A; 2) Placing the filter residue A in organic acid, dissolving part of materials, and filtering and separating to obtain filter residue B and filtrate B; 3) Adding the filter residue B into non-oxidizing inorganic acid, dissolving part of materials, and filtering and separating to obtain filter residue C and filtrate C; 4) Adding the filter residue C into alkali liquor, heating and dissolving materials, and filtering and separating to obtain filter residue D and filtrate D; 5) Adding the filter residue D into an oxidizing acid solution, performing oxidation extraction, and filtering to obtain filter residue E and filtrate E; 6) And adding the filter residue E into the strong oxidizing solution, and dissolving to obtain an extracting solution F. The invention adopts a selective step-by-step extraction method, and each step of extraction aims at arsenic-containing phases with specific forms, thereby solving the problem of difficult research on detecting trace arsenic form content in slag.
Description
Technical Field
The invention belongs to the field of metallurgy, and particularly relates to a method for separating and extracting an arsenic-containing phase from copper slag.
Background
The flash smelting slag contains copper and arsenic which are mixed, copper-rich slag concentrate is generally selected back by a beneficiation method, and the rest part is used as slag tailings to be opened from a system. When copper in slag is recovered by adopting a beneficiation method, part of arsenic enters selected copper concentrate and part of arsenic enters slag tailings, arsenic is used as heavy metal impurities, the solubility and chemical stability of different forms of arsenic in water are greatly different, for example, arsenic oxide/soluble arsenate and slightly soluble arsenate are all high in leaching toxicity, and if the proportion of arsenic is high, certain risk exists when the slag tailings enter the environment; while arsenic in silicate glass phase is stable and solidified safely, and the entering slag tailings is relatively safe.
Therefore, the method has important significance for guiding the safe treatment of slag and tailings, the recovery of copper in smelting slag and the like by knowing the occurrence state of arsenic in the copper slag in detail.
The existing state of arsenic in the arsenic-copper slag is various and complex in form, the arsenic content in the slag is low (< 0.5 wt%) and conventional spectroscopic techniques such as X-ray diffraction (XRD), X-ray fluorescence (XRF), X-ray photoelectron spectroscopy (XPS) and Raman Spectroscopy (RS) can only roughly measure the total arsenic content at low concentration, cannot accurately identify the existing state of arsenic, and cannot analyze the chemical stability of arsenic.
The patent entitled "separation and detection method of complex mixed state arsenic in coal" (CN 103335991A) discloses a method for separating and detecting complex mixed state arsenic in coal, which adopts a selective progressive extraction (SSE) method to separate arsenic phases in coal into eight occurrence states of water-soluble state, ion exchange state, alkali-soluble organic combination state, insoluble organic combination state, hydrochloric acid extraction state, hydrofluoric acid extraction state, nitric acid extraction state and strong combination state, and uses the combination of density classification, progressive extraction and column chromatography to separate and detect mixed inorganic and organic combination state arsenic in different macroscopic coal-rock components in coal. The scheme has reference value only for the research of soil and sediment, and the extracted target products comprise adsorption state As-Fe codeposit, organic arsenic and the like. The arsenic in the copper smelting slag is various arsenic-containing phases generated by high-temperature slag-forming reaction, and phases such as adsorption state, organic arsenic and the like are basically not contained, so that the traditional progressive extraction method is not suitable for progressive extraction and identification of the arsenic-containing phases in the slag generated by high-temperature smelting.
Therefore, it is imperative to find a method suitable for separating and extracting arsenic phases in copper slag.
Disclosure of Invention
The invention provides a method for separating and extracting an arsenic-containing phase from copper slag, which aims to solve the problems that the separation and extraction of the arsenic-containing phase in slag cannot be realized and the occurrence form of arsenic is difficult to carry out in-depth research and determination and the like in the prior art.
The invention aims at: 1. realizing the selective extraction of arsenic-containing phases in slag;
2. realizing the selective separation and determination of arsenic-containing phases in slag;
3. improves the purity of the extracted arsenic-containing phase and reduces impurities.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
A method for separating, extracting and determining an arsenic-containing phase from copper slag, characterized by: extracting copper slag with water, organic acid, non-oxidizing inorganic acid, alkali liquor, oxidizing acid liquor and strong oxidizing solution in sequence to obtain six extracting solutions, and measuring arsenic content in the six extracting solutions respectively.
The method comprises the following steps:
1) Adding copper slag into water, heating and dissolving materials, and filtering and separating to obtain filter residue A and filtrate A;
2) Placing the filter residue A in organic acid, dissolving part of materials, and filtering and separating to obtain filter residue B and filtrate B;
3) Adding the filter residue B into non-oxidizing inorganic acid, dissolving part of materials, and filtering and separating to obtain filter residue C and filtrate C;
4) Adding the filter residue C into alkali liquor, heating and dissolving materials, and filtering and separating to obtain filter residue D and filtrate D;
5) Adding the filter residue D into an oxidizing acid solution, performing oxidation extraction, and filtering to obtain filter residue E and filtrate E;
6) And adding the filter residue E into the strong oxidizing solution, and dissolving to obtain an extracting solution F.
In the above technical scheme, the main extraction steps of the arsenic-containing phase in the copper slag are classified into the following categories. 1. Water-soluble arsenic compounds including arsenic oxides and sodium and potassium arsenates; 2. slightly soluble arsenate and amorphous iron arsenate, wherein the slightly soluble arsenate mainly comprises arsenate such as aluminum, magnesium, calcium and the like; 3. insoluble arsenates such as crystalline ferric arsenate and the like; 4. arsenic sulfide, including estramur, realgar, and amorphous arsenic sulfide; 5. arsenic compounds and insoluble arsenic minerals, including arsenopyrite, copper arsenide, and arsenic-containing substances such as elemental arsenic in a metallic bond or atomic state; 6. arsenic in silicate glass phase.
Based on the above classification, the hierarchical extraction as shown in fig. 1 is performed. In step 1), arsenic oxide is dissolved in hot water to form arsenite, depending on the water-solubility of the alkali arsenate and the nature of arsenic oxide. The reaction equation for the dissolution of arsenic oxide in hot water is as follows: as As 2 O 3 +3H 2 O→2H 3 AsO 3 . In step 1), arsenic oxide is removed by dissolution in hot water, so that the subsequent reaction of arsenic oxide with acid, alkali or an oxidizing compound to produce impurities can be avoided, and the judgment of each occurrence form in slag can be prevented from being affected. In step 2), the sparingly soluble arsenate may be extracted with an organic acid, the complexation of which facilitates the dissolution of the sparingly soluble arsenate. Taking magnesium arsenate as an example, the reaction equation is as follows: 4n H + +C 6 H 6 O 7 2－ +n Mg 3 (AsO 4 ) 2 →[Mg 3n (C 6 H 6 O 7 )] 6n-2 +2n H 2 AsO 4 － . In step 3), the insoluble arsenate is represented by ferric arsenate, which has extremely low solubility in water and citric acid, but can be dissolved with hydrochloric acid to produce arsenate. The reaction equation is as follows: feAsO 4 +3H + →Fe 3+ +H 3 AsO 4 The method comprises the steps of carrying out a first treatment on the surface of the The extraction of arsenic sulphide with a strong base solution in step 4) is performed because arsenic sulphide is insoluble in water and acid, but forms thioarsenate or thioarsenite in alkaline conditions, with sodium hydroxide solution and As 2 S 3 The reaction is exemplified by the following reaction equation: as As 2 S 3 +6NaOH→Na 3 AsO 3 +Na 3 AsS 3 +3H 2 O; and 5) combining organic acid and inorganic acid, and adding hydrogen peroxide as an oxidant to extract metal arsenides and sulfur-arsenic minerals. Because of such intermetallic compounds or arsenic-containing minerals, arsenic tends to exist in the form of a metal bond or a covalent bond of a metal bond coexisting, insoluble in non-oxidizing acids and alkaline solutions. The arsenic-containing phase in the slag can be effectively extracted by taking hydrogen peroxide as an oxidant and adopting a mode of promoting dissolution by inorganic and organic acids. Taking arsenopyrite and copper arsenide as examples, the reaction equation is as follows: feAsS+7H 2 O 2 +H + →Fe 3+ +H 3 AsO 4 +SO 4 2－ +6H 2 O、2Cu 3 As+11H 2 O 2 +12H + →6Cu 2+ +2H 3 AsO 4 +14H 2 O; in the step 6), nitric acid, hydrofluoric acid and hydrogen peroxide are used for thoroughly digesting the slag, so that As in the residual slag is thoroughly released, the arsenic is mainly in an amorphous silicate glass phase in the slag, the existence form is stable, the hydrofluoric acid can break a silica bond, the arsenic in the glass phase is released, and the reaction equation of the hydrofluoric acid and silicon dioxide is As follows: siO (SiO) 2 +4HF＝SiF 4 ↑+2H 2 O。
As a preferred alternative to this,
in the heating and dissolving process of the step 1): the heating temperature is 80-100 ℃ and the duration time is 2-4 h.
The above parameters can accelerate the dissolution process, improve the dissolution efficiency, and more effectively improve the separation efficiency of alkali arsenate.
As a preferred alternative to this,
the organic acid in the step 2) is citric acid, and the concentration of the citric acid solution is 0.5-0.8 wt%;
the dissolution process is carried out at 25-35 ℃ for 1-3 hours.
The citric acid with the concentration can remove the slightly soluble arsenate in the copper slag more effectively, and promote the dissolution and separation of the slightly soluble arsenate through complexation effect. And citric acid has no strong acidity and oxidizing property, and can realize high-purity and targeted extraction and separation.
As a preferred alternative to this,
step 3), the concentration of hydrogen ions in the non-oxidative inorganic acid is 1-3 mol/L;
the dissolution process is carried out at 25-80 ℃ for 1-3 hours.
The inorganic acid is optimally selected to be hydrochloric acid, the hydrochloric acid is laboratory hydrochloric acid, and the concentration is 36-38 wt%.
Under the above conditions, the insoluble arsenate such as ferric arsenate can be effectively dissolved and separated by hydrochloric acid.
As a preferred alternative to this,
step 4) the alkali liquor is alkali metal hydroxide solution;
the concentration of the alkali liquor is 1-3 mol/L, and the dissolution process is carried out at 70-90 ℃ for 1-3 h.
Sodium hydroxide and potassium hydroxide are readily available alkali metal compounds, having strong basicity. The sulfide of arsenic can be effectively extracted through the strong alkali, so that the sulfide can form thioarsenate or hexaarsenite, and the sulfide can be effectively separated.
As a preferred alternative to this,
step 5), glacial acetic acid and hydrogen peroxide are contained in the oxidizing acid solution, and the pH value is adjusted to be acidic by non-oxidizing acid;
the dissolution process is carried out at 60-70 ℃ for 2-4 hours.
Wherein the inorganic acid and the non-oxidizing acid are used to promote the oxidation of hydrogen peroxide. Under the conditions, the method has relatively better extraction and separation efficiency and extraction and separation effect.
As a preferred alternative to this,
the content of glacial acetic acid in the oxidizing acid solution in the step 5) is 35-45 wt%, the content of hydrogen peroxide is 4-6 wt% and the content of non-oxidizing inorganic acid is 1.6-2.5 wt%.
The oxidizing acid is a strong acid, which can effectively separate and extract metal arsenides and sulfur-arsenic minerals.
As a preferred alternative to this,
step 6), the strong oxidizing solution contains nitric acid, hydrogen fluoride and hydrogen peroxide;
the dissolution process lasts for 0.5-2 hours.
Under the conditions, the separation of residual As in the amorphous silicate glass phase in the copper slag can be effectively realized, wherein hydrogen fluoride plays a key role in destroying silicon-oxygen bonds, so that the key for realizing effective extraction is realized.
As a preferred alternative to this,
the concentration of the nitric acid is 20-25 wt%;
the concentration of the hydrogen fluoride is 8-10wt%;
the concentration of the hydrogen peroxide is 10-15 wt%.
Under the concentration ratio, the extraction and separation effects on As in the amorphous silicate glass phase are optimal.
An application of a method for separating and extracting arsenic-containing phase from copper slag,
the method can also be used for the purification treatment of copper slag and/or arsenic extraction.
According to the scheme, the copper slag can be effectively subjected to arsenic removal and purification treatment, various phases of arsenic can be separated at the same time, and the separated arsenic can be used for refining or reprocessing and utilization.
The beneficial effects of the invention are as follows:
1) The arsenic-containing phases existing in the slag are finely divided by adopting a selective step-by-step extraction method, and each step of extraction aims at the arsenic-containing phases with specific forms, so that the problem of difficulty in researching the trace arsenic occurrence forms and the contents of all forms in the slag is solved;
2) The specific occurrence form of arsenic in slag is identified, which has important significance for deep understanding of arsenic behavior in the copper smelting process and practical applicability;
3) Through fine measurement of arsenic-containing species, important references are provided for evaluating arsenic stability and leaching toxicity of slag;
4) The required extracting solutions are all common reagents, so that the cost is low, and the operation is convenient.
Drawings
FIG. 1 is a process flow diagram of the selective extraction of example 1 of the present invention;
FIG. 2 is an XRD pattern of slag used in example 1 of the present invention;
FIG. 3 is a graph showing the mass distribution of arsenic phase extracted in each of the steps of examples 1 to 3 of the present invention.
Detailed Description
The invention is described in further detail below with reference to specific examples and figures of the specification. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
The raw materials used in the examples of the present invention are all commercially available or available to those skilled in the art unless specifically stated otherwise; the methods used in the examples of the present invention are those known to those skilled in the art unless specifically stated otherwise.
Example 1
A method for separating and extracting arsenic-containing phase from copper slag,
the method comprises the following steps:
1) Extracting water-soluble arsenic in copper slag: adding a proper amount of deionized water into a conical flask, heating to 80 ℃, grinding a slag sample to pass through a 30-mesh screen, adding 10g/L of slag and deionized water into the conical flask, oscillating for 4 hours in a constant-temperature water bath in a horizontal oscillator, carrying out suction filtration, separating to obtain filtrate and residue A, and detecting the As concentration in the filtrate by using ICP-MS;
2) Extracting slightly soluble arsenate and amorphous iron arsenate: an appropriate amount of 0.5wt% citric acid solution was added to the flask and incubated at 25 ℃. Adding the residue A into the conical flask, controlling the solid-liquid ratio to be 10g/L, oscillating for 3 hours in a constant-temperature water bath in a horizontal oscillator, carrying out suction filtration, separating to obtain filtrate and residue B, and detecting the As concentration in the filtrate by using ICP-MS;
3) Extracting insoluble arsenate: an appropriate amount of 1mol/L hydrochloric acid solution was added to a conical flask, and the flask was incubated at 25 ℃. Adding the residue B into the conical flask, controlling the solid-liquid ratio to be 10g/L, oscillating for 3 hours in a constant-temperature water bath in a horizontal oscillator, carrying out suction filtration, separating to obtain filtrate and residue C, and detecting the As concentration in the filtrate by using ICP-MS;
4) Extraction of arsenic sulfide: an appropriate amount of 1mol/L NaOH solution is added into a conical flask, and the flask is incubated at 70 ℃. Adding the residue C into the conical flask, controlling the solid-liquid ratio to be 10g/L, oscillating for 3 hours in a constant-temperature water bath in a horizontal oscillator, carrying out suction filtration, separating to obtain filtrate and residue D, and detecting the As concentration in the filtrate by using ICP-MS;
5) Extracting arsenic compounds and insoluble arsenic minerals: mixing deionized water, glacial acetic acid, 30wt% hydrogen peroxide and 36wt% concentrated hydrochloric acid according to a volume ratio of 8:8:3:1, adding into a conical flask, heating to 60 ℃, adding residues D into the conical flask, controlling the solid-liquid ratio to be 10g/L, oscillating in a constant-temperature water bath in a horizontal oscillator, dropwise adding 2ml of hydrogen peroxide every 10min, filtering after 4h, separating to obtain filtrate and residues E, and detecting the As concentration in the filtrate by using ICP-MS;
6) Extraction of arsenic in silicate glass phase: 68wt% of concentrated nitric acid, 48wt% of hydrofluoric acid and 30wt% of hydrogen peroxide are mixed according to a volume ratio of 3:2:5 and added into a conical flask, residue E is added into the conical flask, the solid-liquid ratio is controlled to be 10g/L, and after the residue E is completely dissolved, the concentration of As in the filtrate is detected by ICP-MS.
The chemical element composition of the copper slag used in this example was examined as shown in the following table.
| Element(s) | Fe | Si | As | Cu | S | Al | Ca | Mg | Na | Zn | Pb |
| Content (wt%) | 42.40 | 13.82 | 0.30 | 2.18 | 0.17 | 2.28 | 1.77 | 0.6 | 5.36 | 0.41 | 0.10 |
The arsenic phase distribution extracted at each step of this example was statistically calculated and the purity was characterized, and the results are shown in the following table.
Example 2
A method for separating and extracting arsenic-containing phase from copper slag,
the method comprises the following steps:
1) Extracting water-soluble arsenic in slag samples: adding a proper amount of deionized water into a conical flask, heating to 90 ℃, grinding a slag sample to pass through a 60-mesh screen, adding 10g/L of slag and deionized water into the conical flask, oscillating for 3 hours in a constant-temperature water bath in a horizontal oscillator, carrying out suction filtration, separating to obtain filtrate and residue A, and detecting the As concentration in the filtrate by using ICP-MS;
2) Extracting slightly soluble arsenate and amorphous iron arsenate: an appropriate amount of 0.5wt% citric acid solution was added to the flask and incubated at 35 ℃. Adding the residue A into the conical flask, controlling the solid-liquid ratio to be 10g/L, oscillating for 1h in a constant-temperature water bath in a horizontal oscillator, carrying out suction filtration, separating to obtain filtrate and residue B, and detecting the As concentration in the filtrate by using ICP-MS;
3) Extracting insoluble arsenate: an appropriate amount of 1mol/L hydrochloric acid solution is added into a conical flask, and the flask is incubated at 80 ℃. Adding the residue B into the conical flask, controlling the solid-liquid ratio to be 10g/L, oscillating for 2 hours in a constant-temperature water bath in a horizontal oscillator, carrying out suction filtration, separating to obtain filtrate and residue C, and detecting the As concentration in the filtrate by using ICP-MS;
4) Extraction of arsenic sulfide: an appropriate amount of 1mol/L NaOH solution is added into a conical flask, and the flask is incubated at 90 ℃. Adding the residue C into the conical flask, controlling the solid-liquid ratio to be 10g/L, oscillating for 1h in a constant-temperature water bath in a horizontal oscillator, carrying out suction filtration, separating to obtain filtrate and residue D, and detecting the As concentration in the filtrate by using ICP-MS;
5) Extracting arsenic compounds and insoluble arsenic minerals: mixing deionized water, glacial acetic acid, 30% hydrogen peroxide and 36wt% concentrated hydrochloric acid according to a volume ratio of 8:8:3:1, adding the mixture into a conical flask, heating to 70 ℃, adding residue D into the conical flask, controlling the solid-liquid ratio to be 10g/L, oscillating in a constant-temperature water bath in a horizontal oscillator, dropwise adding 2ml hydrogen peroxide every 10min, filtering after 2h, separating to obtain filtrate and residue E, and detecting the As concentration in the filtrate by using ICP-MS;
6) Extraction of arsenic in silicate glass phase: 68wt% of concentrated nitric acid, 48wt% of hydrofluoric acid and 30wt% of hydrogen peroxide are mixed according to a volume ratio of 3:2:5 and added into a conical flask, residue E is added into the conical flask, the solid-liquid ratio is controlled to be 10g/L, and after the residue E is completely dissolved, the concentration of As in the filtrate is detected by ICP-MS.
The chemical element composition of the copper slag used in this example was examined as shown in the following table.
| Element(s) | Fe | Si | As | Cu | S | Al | Ca | Mg | Na | Zn | Pb |
| Content (wt%) | 42.40 | 13.82 | 0.30 | 2.18 | 0.17 | 2.28 | 1.77 | 0.6 | 5.36 | 0.41 | 0.10 |
Statistical calculations were performed on the arsenic phase assignments extracted at each step of this example, with the results shown in the following table.
Example 3
A method for separating and extracting arsenic-containing phase from copper slag,
the method comprises the following steps:
1) Extracting water-soluble arsenic in slag samples: adding a proper amount of deionized water into a conical flask, heating to 100 ℃, grinding a slag sample to pass through a 100-mesh screen, adding 10g/L of slag and deionized water into the conical flask, oscillating for 2 hours in a constant-temperature water bath in a horizontal oscillator, carrying out suction filtration, separating to obtain filtrate and residue A, and detecting the As concentration in the filtrate by using ICP-MS;
2) Extracting slightly soluble arsenate and amorphous iron arsenate: an appropriate amount of 0.8wt% citric acid solution was added to the flask and incubated at 25 ℃. Adding the residue A into the conical flask, controlling the solid-liquid ratio to be 10g/L, oscillating for 2 hours in a constant-temperature water bath in a horizontal oscillator, carrying out suction filtration, separating to obtain filtrate and residue B, and detecting the As concentration in the filtrate by using ICP-MS;
3) Extracting insoluble arsenate: an appropriate amount of 3mol/L hydrochloric acid solution is added into a conical flask, and the flask is incubated at 80 ℃. Adding the residue B into the conical flask, controlling the solid-liquid ratio to be 10g/L, oscillating for 2 hours in a constant-temperature water bath in a horizontal oscillator, carrying out suction filtration, separating to obtain filtrate and residue C, and detecting the As concentration in the filtrate by using ICP-MS;
4) Extraction of arsenic sulfide: an appropriate amount of 2mol/L NaOH solution is added into a conical flask, and the flask is incubated at 80 ℃. Adding the residue C into the conical flask, controlling the solid-liquid ratio to be 10g/L, oscillating for 2 hours in a constant-temperature water bath in a horizontal oscillator, carrying out suction filtration, separating to obtain filtrate and residue D, and detecting the As concentration in the filtrate by using ICP-MS;
5) Extracting arsenic compounds and insoluble arsenic minerals: mixing deionized water, glacial acetic acid, 30wt% hydrogen peroxide and 36wt% concentrated hydrochloric acid according to a volume ratio of 8:8:3:1, adding into a conical flask, heating to 70 ℃, adding residues D into the conical flask, controlling the solid-liquid ratio to be 10g/L, oscillating in a constant-temperature water bath in a horizontal oscillator, dropwise adding 2ml of hydrogen peroxide every 10min, filtering after 4h, separating to obtain filtrate and residues E, and detecting the As concentration in the filtrate by using ICP-MS;
6) Extraction of arsenic in silicate glass phase: 68wt% of concentrated nitric acid, 48wt% of hydrofluoric acid and 30wt% of hydrogen peroxide are mixed according to a volume ratio of 3:2:5 and added into a conical flask, residue E is added into the conical flask, the solid-liquid ratio is controlled to be 10g/L, and after the residue E is completely dissolved, the concentration of As in the filtrate is detected by ICP-MS.
The chemical element composition of the copper slag used in this example was examined as shown in the following table.
| Element(s) | Fe | Si | As | Cu | S | Al | Ca | Mg | Na | Zn | Pb |
| Content (wt%) | 42.40 | 13.82 | 0.30 | 2.18 | 0.17 | 2.28 | 1.77 | 0.6 | 5.36 | 0.41 | 0.10 |
Statistical calculations were performed on the arsenic phase assignments extracted at each step of this example, with the results shown in the following table.
| Step (a) | S1 | S2 | S3 | S4 | S5 | S6 |
| Arsenic partition ratio% | 0.55 | 4.09 | 9.14 | 17.87 | 11.87 | 56.48 |
| Arsenic phase purity (%) | 99.8 | 99.6 | 99.5 | 99.9 | 99.5 | 99.5 |
As is apparent from the above examples 1 to 3, the method of the present invention can effectively achieve the effect of separating and extracting arsenic phases stepwise. Meanwhile, the distribution ratios of the arsenic phase extraction results of examples 1 to 3 were integrated to obtain a distribution chart shown in fig. 3. As can be seen from the figure, the concentration, the amount of the reagent, the treatment parameters (temperature, time) and the like in each step have a significant influence on the extraction and separation effects in a single step.
Compared with the smelting extraction mode for ores in the prior art, the method can be more effectively used for smelting the generated slag, can effectively separate and remove the arsenic phase in the slag, and has great significance for recycling valuable metals and researching the form and content of the arsenic phase in the slag.
Comparative example
Based on the specific implementation mode of each step in the example 1, only under the condition of changing the sequence of the steps, separating and extracting the arsenic phase in the copper slag, and characterizing the distribution ratio of the arsenic product and the purity of the arsenic phase in each stage.
The chemical element composition of the copper slag used in this example was examined as shown in the following table.
| Element(s) | Fe | Si | As | Cu | S | Al | Ca | Mg | Na | Zn | Pb |
| Content (wt%) | 42.40 | 13.82 | 0.30 | 2.18 | 0.17 | 2.28 | 1.77 | 0.6 | 5.36 | 0.41 | 0.10 |
The specific results are shown in the following table.
As is evident from the above comparative examples of the respective groups, strict requirements are imposed on the control of the step sequence in the technical solution of the present invention. A change in the order of the steps will have a significant effect, especially a back shift of the S1 step will result in a significant decrease in the purity of the arsenic phase obtained from the preceding step. The extraction sequence of the original effective process of the invention focuses on reducing the interference of byproducts to the subsequent extraction process, and also does not simply extract time sequence from easy to difficult, but is carried out according to the extraction range corresponding to the method and in a mode of front-to-front after, so that the front-step does not influence the rear-step and the rear-step basically covers the extraction range of the front-step to a certain extent, and the selection and sequencing of the extraction method are the core for realizing the scheme of the invention.
Claims (10)
1. A method for separating and extracting arsenic-containing phase from copper slag is characterized in that,
the method comprises the following steps:
1) Adding copper slag into water, heating and dissolving materials, and filtering and separating to obtain filter residue A and filtrate A;
2) Placing the filter residue A in organic acid, dissolving part of materials, and filtering and separating to obtain filter residue B and filtrate B;
3) Adding the filter residue B into non-oxidizing inorganic acid, dissolving part of materials, and filtering and separating to obtain filter residue C and filtrate C;
4) Adding the filter residue C into alkali liquor, heating and dissolving materials, and filtering and separating to obtain filter residue D and filtrate D;
5) Adding the filter residue D into an oxidizing acid solution, performing oxidation extraction, and filtering to obtain filter residue E and filtrate E;
6) And adding the filter residue E into the strong oxidizing solution, and dissolving to obtain an extracting solution F.
2. A process for the separation and extraction of an arsenic-containing phase from copper slag according to claim 1,
in the heating and dissolving process of the step 1): the heating temperature is 80-100 ℃ and the duration time is 2-4 h.
3. A process for the separation and extraction of an arsenic-containing phase from copper slag according to claim 1,
the organic acid in the step 2) is citric acid, and the concentration of the citric acid solution is 0.5-0.8 wt%;
the dissolution process is carried out at 25-35 ℃ for 1-3 hours.
4. A process for the separation and extraction of an arsenic-containing phase from copper slag according to claim 1,
step 3), the concentration of hydrogen ions in the non-oxidative inorganic acid is 1-3 mol/L;
the dissolution process is carried out at 25-80 ℃ for 1-3 hours.
5. A process for the separation and extraction of an arsenic-containing phase from copper slag according to claim 1,
step 4) the alkali liquor is alkali metal hydroxide solution;
the concentration of the alkali liquor is 1-3 mol/L, and the dissolution process is carried out at 70-90 ℃ for 1-3 h.
6. A process for the separation and extraction of an arsenic-containing phase from copper slag according to claim 1,
step 5), glacial acetic acid and hydrogen peroxide are contained in the oxidizing acid solution, and the pH value is adjusted to be acidic by non-oxidizing acid;
the dissolution process is carried out at 60-70 ℃ for 2-4 hours.
7. A process for the separation and extraction of an arsenic-containing phase from copper slag according to claim 6,
the content of glacial acetic acid in the oxidizing acid solution in the step 5) is 35-45 wt%, the content of hydrogen peroxide is 4-6 wt% and the content of non-oxidizing inorganic acid is 1.6-2.5 wt%.
8. A process for the separation and extraction of an arsenic-containing phase from copper slag according to claim 1,
step 6), the strong oxidizing solution contains nitric acid, hydrogen fluoride and hydrogen peroxide;
the dissolution process lasts for 0.5-2 hours.
9. A process for the separation and extraction of an arsenic-containing phase from copper slag according to claim 8,
the concentration of the nitric acid is 20-25 wt%;
the concentration of the hydrogen fluoride is 8-10wt%;
the concentration of the hydrogen peroxide is 10-15 wt%.
10. The use of a method according to any one of claims 1 to 9,
the method is used for purifying copper slag and/or refining arsenic.
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