CN115369266A - Method for removing and recycling arsenic in chloride acid leaching solution - Google Patents
Method for removing and recycling arsenic in chloride acid leaching solution Download PDFInfo
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- CN115369266A CN115369266A CN202210999305.2A CN202210999305A CN115369266A CN 115369266 A CN115369266 A CN 115369266A CN 202210999305 A CN202210999305 A CN 202210999305A CN 115369266 A CN115369266 A CN 115369266A
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 120
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 71
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 32
- 239000002253 acid Substances 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title claims abstract description 13
- 238000002386 leaching Methods 0.000 title abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 51
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052802 copper Inorganic materials 0.000 claims abstract description 44
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000002893 slag Substances 0.000 claims abstract description 31
- 230000009467 reduction Effects 0.000 claims abstract description 25
- 230000002378 acidificating effect Effects 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 21
- 238000001556 precipitation Methods 0.000 claims abstract description 17
- 150000001804 chlorine Chemical class 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000006722 reduction reaction Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 12
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims description 6
- 229940000489 arsenate Drugs 0.000 claims description 6
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 6
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- CNALVHVMBXLLIY-IUCAKERBSA-N tert-butyl n-[(3s,5s)-5-methylpiperidin-3-yl]carbamate Chemical compound C[C@@H]1CNC[C@@H](NC(=O)OC(C)(C)C)C1 CNALVHVMBXLLIY-IUCAKERBSA-N 0.000 claims description 6
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 5
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 abstract description 8
- 238000003723 Smelting Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012141 concentrate Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000011133 lead Substances 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000010842 industrial wastewater Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229940000488 arsenic acid Drugs 0.000 description 2
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 description 2
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- GSYZQGSEKUWOHL-UHFFFAOYSA-N arsenic calcium Chemical compound [Ca].[As] GSYZQGSEKUWOHL-UHFFFAOYSA-N 0.000 description 1
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229940103357 calcium arsenate Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- BPQWCZKMOKHAJF-UHFFFAOYSA-N scheele's green Chemical compound [Cu+2].O[As]([O-])[O-] BPQWCZKMOKHAJF-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- -1 sulfur ion Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
-
- 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
The invention discloses a method for removing and recovering arsenic in chloride acid leachate, which specifically comprises the following steps: first-stage reduction for removing copper and arsenic: adding a certain amount of reducing agent into a chlorine salt acidic leaching solution, controlling the temperature, and separating reducing slag from a reduced solution to obtain reducing slag containing copper and arsenic and a first-stage reduced solution; and (3) two-stage reduction arsenic precipitation: and adding a certain amount of reducing agent into the first-stage reduced liquid, controlling the temperature, and separating the reducing slag from the reduced liquid to obtain reducing slag only containing the arsenic simple substance and a second-stage reduced liquid. The method for reducing and removing arsenic in the chloride acidic leaching solution and recycling the arsenic has the advantages of simple operation, high arsenic removal rate, short flow, good selective reduction effect and the like. Under a proper proportion, the total removal rate of arsenic can reach more than 99 percent; the first-stage reducing slag can be used as high-quality copper concentrate to return to the copper smelting process, and the second-stage reducing slag can be used as a high-quality raw material to carry out elemental arsenic refining, so that the removal and resource recovery of arsenic in the chloride acid leaching solution are realized.
Description
Technical Field
The invention relates to a method for removing and recycling arsenic in chloride acid leachate, which is suitable for the fields of hydrometallurgy and industrial wastewater pollution treatment.
Background
Currently, many industries, particularly in non-ferrous metal mining, smelting and sulfuric acid production processes, produce acidic wastewater (contaminated acid, acidic mine wastewater, etc.) containing arsenic at high concentrations. According to incomplete statistics, only the smelting industry of nonferrous metals copper, lead and zinc discharges 400 million tons of acidic wastewater every year. Such waste water is highly acidic (>10 -3 M), high arsenic content, large production amount and the like. In such wastewater, arsenic exists mainly in two forms of arsenous acid (As (III)) and arsenic acid (As (V)). In the acidic stateBefore the wastewater reaches the standard to be discharged or recycled, arsenic in the wastewater must be removed. At present, the most widely applied method in removing arsenic from acidic wastewater is a neutralization precipitation method and a vulcanization precipitation method. The principle of removing arsenic by a neutralization precipitation method is to utilize CaO to neutralize the acidity of wastewater and form arsenic-calcium coprecipitation (calcium arsenate (Ca) 3 (AsO 3 ) 2 ) And calcium arsenite (Ca) 3 (AsO 4 ) 2 ) So as to achieve the purpose of removing arsenic. However, this process produces large amounts of low-grade arsenic-containing mixed hazardous waste residues (CaSO) 4 -Ca 3 (AsO 3 ) 2 -Ca 3 (AsO 4 ) 2 ) The treatment is extremely difficult, and the risk of secondary pollution exists. The sulfidation precipitation method is carried out by arsenic and sulfur ion (S) 2- ) The reaction produces arsenic sulfide precipitate (As) with very low solubility 2 S 3 ) The arsenic is removed, the arsenic precipitate obtained by the method has high grade, and the precipitation yield is greatly reduced compared with a neutralization precipitation method. However, the obtained As 2 S 3 The sediment value is low, the resource recovery is difficult to realize, and the sediment is extremely unstable and is easy to be partially converted into As under the action of illumination or oxygen 2 O 3 Thereby producing As 2 S 3 -As 2 O 3 Mixing hazardous wastes. In a word, the existing arsenic removal method for the acid wastewater generates a large amount of arsenic-containing hazardous waste which is extremely difficult to treat and dispose, greatly increases the cost of factory operation and treatment and disposal, and poses potential environmental threats.
Arsenic can bind with sulfhydryl-containing enzyme in cell, inhibit cell oxidation process, and paralyze blood vessel motor center, so as to paralyze blood capillary, dilate and increase permeability. Therefore, arsenic removal and recovery is essential.
In the prior art, the method particularly relates to a method for efficiently removing arsenic in contaminated acid under a strong acid system, and belongs to the fields of hydrometallurgy and industrial wastewater treatment. Filtering contaminated acid to remove insoluble impurities, adding iodide according to the arsenic content, slowly adding finely ground and sieved copper powder, controlling the reaction temperature and continuously stirring for a certain time, performing solid-liquid separation after the reaction is finished, recovering sulfuric acid from filtrate by adopting ICP (inductively coupled plasma) through a membrane treatment process, washing filter residues with water, and then gradually treating to realize iodide regeneration and prepare arsenic-copper alloy or elemental arsenic.
And the arsenic trioxide is prepared by neutralization impurity removal, arsenic precipitation, washing, leaching, evaporative crystallization and dissolution, so that the arsenic-containing waste acid is recycled. According to the method, arsenic in arsenic-containing waste acid is prepared into arsenic trioxide through precipitation and conversion, the defect that sulfur dioxide reduces copper arsenite to prepare arsenic trioxide is overcome, high-standard arsenic trioxide is obtained, and waste acid treatment and recycling of copper arsenic resources are achieved.
The processes aim at removing and recovering arsenic from different industrial wastewater, but the arsenic removal and recovery of the industrial wastewater in a chloride system are not reported. Therefore, the research on a new method for removing and recovering arsenic in the chloride acid leaching solution has important practical significance.
Disclosure of Invention
The invention aims to solve the problem that no chloride system is available for removing and recycling arsenic at present, and provides a novel method for removing and recycling arsenic in chloride acid leachate. The method adopts first-stage reduction to remove copper and arsenic and second-stage reduction to precipitate arsenic. The method is simple in operation method, easy to industrialize, capable of realizing efficient arsenic removal and resource recovery, and has important economic, environmental and social benefits.
The technical scheme adopted by the invention is as follows: a method for removing and recycling arsenic in chloride acid leachate comprises the following steps:
s1) first-stage reduction for removing copper and arsenic: adding a reducing agent into the chloride acid leachate according to a certain proportion, carrying out reduction reaction, filtering and washing to obtain a first-stage reduced solution containing a small part of copper and arsenic and a reducing slag containing a large part of copper and arsenic, and removing the reducing slag containing the large part of copper and arsenic;
s2) two-stage reduction and arsenic precipitation: and (2) adding a reducing agent into the first-stage reduced liquid containing a small part of copper and arsenic obtained in the step (1), and filtering and washing to obtain a second-stage reduced liquid and recovered reducing slag only containing arsenic simple substances.
Further, the specific process of the reduction reaction in S1) is as follows: the reaction temperature is 50-100 ℃, the reaction time is 0.5-5h, the stirring speed is 100-600r/min, the removal rate of arsenic in the chlorine salt acidic leaching solution treated by S1) is more than 90%, and the precipitation rate of copper is more than 45%.
Further, the specific process of the reduction reaction in S2) is as follows: the reaction temperature is 40-80 ℃, the reaction time is 0.5-3h, and the stirring speed is 100-600r/min.
Further, the molar ratio of the reducing agent in the S1) to the arsenic content in the chloride acid leaching solution is 1-10:1.
further, the addition amount of the reducing agent in the S2) is that the molar ratio of the raw agent to the arsenic content in the chlorine salt acidic leaching solution is 1-5:1.
further, the arsenic is in the form of arsenate, arsenite or a mixture of arsenate and arsenite.
Further, the reducing agent is a solid or liquid containing hypophosphite.
Further, the hypophosphite-containing salts include potassium hypophosphite, sodium hypophosphite, and calcium hypophosphite.
Further, the chlorine salt acidic leaching solution in the S1) is a copper anode mud pretreatment solution.
Further, the total removal rate of arsenic in the chloride acid leachate treated by the method can reach more than 99%.
The invention has the advantages that:
1. the novel method for removing and recycling arsenic in the chloride acid leaching solution can remove more than 99% of arsenic in the chloride acid leaching solution, provides qualified raw materials for a simple substance arsenic purification system, and realizes efficient removal and resource recycling of arsenic;
2. the novel method for removing and recovering arsenic in the chlorine salt acidic leaching solution can reduce arsenic acid and arsenous acid into simple substance arsenic precipitate, and is beneficial to recycling of the chlorine salt acidic waste liquid;
3. the novel method for removing and recycling arsenic in the chloride acid leaching solution does not generate new waste water, reduces the environmental pollution, and is safe and environment-friendly;
4. the method has the advantages of cheap reagent, simple operation method, easy industrialization and important economic and social benefits.
Drawings
FIG. 1 is a process flow diagram of the method for removing and recovering arsenic from the chloride acid leachate according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
As shown in fig. 1, the method for removing and recovering arsenic from a chloride acid leachate according to the present invention comprises the following steps:
s1) first-stage reduction for removing copper and arsenic: adding a reducing agent into the chloride acid leaching solution according to a certain proportion, carrying out reduction reaction, and filtering and washing to obtain reducing slag containing copper and arsenic and a first-stage reduced solution; the copper-containing and arsenic-containing reducing slag can be used as a high-quality copper-containing material to enter a smelting production system, and the liquid after the first-stage reduction enters the next working procedure;
s2) two-stage reduction arsenic precipitation: and (2) adding a reducing agent into the first-stage reduced liquid containing copper and arsenic obtained in the step (1), and filtering and washing to obtain reducing slag only containing arsenic simple substances and second-stage reduced liquid. The reducing slag is mainly arsenic simple substance, enters the arsenic refining and purifying process, and the liquid after the second-stage reduction enters the process flow for extracting other valuable metals.
The specific process of the reduction reaction in the S1) comprises the following steps: the reaction temperature is 50-100 ℃, the reaction time is 0.5-5h, the stirring speed is 100-600r/min, the removal rate of arsenic in the treated chlorine salt acidic leaching solution is more than 90%, and the precipitation rate of copper is more than 45%.
The specific process of the reduction reaction in the S2) comprises the following steps: the reaction temperature is 40-80 ℃, the reaction time is 0.5-3h, the stirring speed is 100-600r/min, and the removal rate of arsenic in the treated first-stage reduced solution is more than 90%.
The molar ratio of the reducing agent in the S1) to the arsenic content in the chloride acid leaching solution is (1-10): 1.
the addition amount of the reducing agent in the S2) is that the molar ratio of the raw agent to the arsenic content in the chloride acid leaching solution is 1-5:1.
the form of the arsenic is arsenate, arsenite or the mixture of arsenate and arsenite.
The reducing agent is solid or liquid containing hypophosphite.
The hypophosphite containing salts include potassium hypophosphite, sodium hypophosphite and calcium hypophosphite.
The chlorine salt acidic leaching solution in the S1) is a copper anode mud pretreatment solution.
The total removal rate of arsenic in the chloride acid leachate treated by the method can reach more than 99 percent.
Example 1
The composition of the chlorine salt acidic leaching solution of the copper anode slime is shown in table 1. Adding a reducing agent into the chlorine salt acidic leaching solution according to a certain proportion, wherein the molar ratio of the reducing agent to arsenic is 3:1, the reaction temperature is 70 ℃, the reaction time is 4h, and the stirring speed is 300r/min. The reducing agent is potassium hypophosphite, and copper and arsenic-containing reducing slag and a first-stage reduced liquid are obtained after filtration and washing, and the components of the first-stage reduced liquid are shown in Table 2.
TABLE 1 copper anode slime chloride leachate composition (g/l)
| Kind of element | Cu | As | Sb | Bi | Pb | Cl |
| Content (wt.) | 36.37 | 21.22 | 18.87 | 8.19 | 0.66 | 158.78 |
TABLE 2 composition of the first-stage reduced solution (g/l)
As is clear from tables 1 and 2, the first-stage reduction arsenic removal rate was 91.69%, which was more than 90%, and the copper precipitation rate was 50.78%. The first stage reducing slag can be used as a high-quality copper-containing material to enter a smelting production system, and the first stage reduced liquid enters the next working procedure.
(2) Adding a reducing agent into the first-stage reduced solution according to a certain proportion, wherein the molar ratio of the reducing agent to arsenic is 2:1, the reaction temperature is 70 ℃, the reaction time is 4h, and the stirring speed is 300r/min. The reducing agent is potassium hypophosphite, and two-stage reducing slag and two-stage reduced liquid are obtained after filtration and washing, and the component results of the two-stage reduced liquid are shown in a table 3.
TABLE 3 composition of the two-stage reduced liquid (g/l)
| Kind of element | Cu | As | Sb | Bi | Pb | Cl |
| Content (wt.) | 16.76 | 0.14 | 17.93 | 7.94 | 0.69 | 152.78 |
As can be seen from Table 3, the two-stage reduction arsenic removal rate was 92.22%, which was greater than 90%. The obtained reducing slag is mainly arsenic simple substance, and enters an arsenic refining and purifying procedure, and the liquid after the second-stage reduction enters a process flow for extracting other valuable metals.
The arsenic removal rate of the whole process is more than 99 percent, the first-stage reduction copper removal rate is 50.78 percent, other metals are not reduced and removed by hypophosphorous acid basically, and the selectivity of the reducing agent is good; the second-stage arsenic-containing reducing slag has low impurity content, is beneficial to the next refining and purification, and improves the added value of products.
Example 2
The composition of the chlorine salt acidic leaching solution of the copper anode slime is shown in table 4. Adding a reducing agent into the chlorine salt acidic leaching solution according to a certain proportion, wherein the molar ratio of the reducing agent to arsenic is 4:1, the reaction temperature is 80 ℃, the reaction time is 4h, and the stirring speed is 300r/min. The reducing agent is sodium hypophosphite, and copper and arsenic-containing reducing slag and a first-stage reduced liquid are obtained after filtration and washing, and the components of the first-stage reduced liquid are shown in Table 5.
TABLE 4 copper anode slime chloride leachate composition (g/l)
TABLE 5 composition of the reduced solution (g/l)
| Kind of element | Cu | As | Sb | Bi | Pb | Cl |
| Content (wt.) | 19.68 | 1.83 | 16.89 | 7.83 | 0.72 | 166.92 |
As is clear from tables 4 and 5, the first-stage reduction arsenic removal rate was 92.31%, which was more than 90%, and the copper precipitation rate was 49.87%. The first stage reducing slag can be used as a high-quality copper-containing material to enter a smelting production system, and the first stage reduced liquid enters the next working procedure.
(2) Adding a reducing agent into the first-stage reduced solution according to a certain proportion, wherein the molar ratio of the reducing agent to arsenic is 3:1, the reaction temperature is 80 ℃, the reaction time is 4h, and the stirring speed is 300r/min. The reducing agent is sodium hypophosphite, and after filtration and washing, a second-stage reducing slag and a second-stage reduced liquid are obtained, and the composition results of the second-stage reduced liquid are shown in Table 6.
TABLE 6 composition of the two-stage reduced liquid (g/l)
| Kind of element | Cu | As | Sb | Bi | Pb | Cl |
| Content (wt.) | 19.52 | 0.13 | 16.49 | 7.64 | 0.70 | 163.38 |
As can be seen from Table 6, the secondary reduction arsenic removal rate was 92.94%, which was more than 90%. The obtained reducing slag is mainly arsenic simple substance, enters an arsenic refining and purifying process, and the liquid after the second-stage reduction enters a process flow for extracting other valuable metals.
The arsenic removal rate of the whole process is more than 99 percent, the first-stage reduction copper removal rate is 49.87 percent, other metals are basically not reduced and removed by sodium hypophosphite, and the selectivity of a reducing agent is good; the second-stage arsenic-containing reducing slag has low impurity content, is beneficial to the next refining and purification, and improves the added value of products.
Example 3
The composition of the chlorine salt acidic leaching solution of the copper anode slime is shown in Table 7. Adding a reducing agent into the chlorine salt acidic leaching solution according to a certain proportion, wherein the molar ratio of the reducing agent to arsenic is 5:1, the reaction temperature is 90 ℃, the reaction time is 4h, and the stirring speed is 300r/min. The reducing agent is calcium hypophosphite, and copper and arsenic-containing reducing slag and a first-stage reduced liquid are obtained by filtering and washing, wherein the components of the first-stage reduced liquid are shown in a table 8.
TABLE 7 copper anode slime chloride leachate composition (g/l)
| Kind of element | Cu | As | Sb | Bi | Pb | Cl |
| Content (wt.) | 37.71 | 25.46 | 17.12 | 8.32 | 0.77 | 172.19 |
TABLE 8 composition of the first-stage reduced solution (g/l)
| Kind of element | Cu | As | Sb | Bi | Pb | Cl |
| Content (wt.) | 18.95 | 1.98 | 16.81 | 8.14 | 0.75 | 168.79 |
As is clear from tables 7 and 8, the first-stage reduction arsenic removal rate was 92.34%, which was more than 90%, and the copper precipitation rate was 50.50%. The first stage reducing slag can be used as a high-quality copper-containing material to enter a smelting production system, and the first stage reduced liquid enters the next working procedure.
(2) Adding a reducing agent into the first-stage reduced solution according to a certain proportion, wherein the molar ratio of the reducing agent to arsenic is 4:1, the reaction temperature is 90 ℃, the reaction time is 4h, and the stirring speed is 300r/min. The reducing agent is calcium hypophosphite, secondary reducing slag and secondary reduced liquid are obtained after filtration and washing, and the component results of the secondary reduced liquid are shown in table 9.
TABLE 9 composition of the two stages of the reduced solution (g/l)
| Kind of element | Cu | As | Sb | Bi | Pb | Cl |
| Content (wt.) | 18.99 | 0.14 | 16.52 | 7.95 | 0.75 | 166.39 |
As can be seen from Table 9, the secondary reduction arsenic removal rate was 92.97%, which was more than 90%. The obtained reducing slag is mainly arsenic simple substance, and enters an arsenic refining and purifying procedure, and the liquid after the second-stage reduction enters a process flow for extracting other valuable metals.
The arsenic removal rate of the whole process is more than 99 percent, the first-stage reduction copper removal rate is 49.98 percent, other metals are basically not reduced and removed by calcium hypophosphite, and the selectivity of a reducing agent is good; the second-stage arsenic-containing reducing slag has low impurity content, is beneficial to the next refining and purification, and improves the added value of products.
The method for removing and recovering arsenic from the chloride acid leaching solution is described in detail above. The above description of the embodiments is only for the purpose of helping to understand the method of the present application and its core ideas; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
As used in the specification and claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. The following description is of the preferred embodiment for carrying out the present application, but is made for the purpose of illustrating the general principles of the application and is not to be taken in a limiting sense. The protection scope of the present application shall be subject to the definitions of the appended claims.
It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a good or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such good or system. Without further limitation, an element defined by the phrases "comprising one of \8230;" does not exclude the presence of additional like elements in an article or system comprising the element.
It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the application as described herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.
Claims (10)
1. The method for removing and recycling arsenic in chloride acid leachate is characterized by comprising the following steps:
s1) first-stage reduction for removing copper and arsenic: adding a reducing agent into the chloride acid leachate according to a certain proportion, carrying out reduction reaction, filtering and washing to obtain a first-stage reduced solution containing a small part of copper and arsenic and a reducing slag containing a large part of copper and arsenic, and removing the reducing slag containing the large part of copper and arsenic;
s2) two-stage reduction and arsenic precipitation: and (2) adding a reducing agent into the first-stage reduced liquid containing a small part of copper and arsenic obtained in the step (1), and filtering and washing to obtain a second-stage reduced liquid and recovered reducing slag only containing arsenic simple substances.
2. The method according to claim 1, wherein the specific process of the reduction reaction in S1) is: the reaction temperature is 50-100 ℃, the reaction time is 0.5-5h, and the stirring speed is 100-600r/min.
3. The method according to claim 1, wherein the specific process of the reduction reaction in S2) is: the reaction temperature is 40-80 ℃, the reaction time is 0.5-3h, and the stirring speed is 100-600r/min.
4. The method according to claim 1, wherein the molar ratio of the reducing agent in S1) to the arsenic content in the chloride acidic leachate is 1-10:1.
5. the method according to claim 1, wherein the reducing agent in S2) is added in an amount that the molar ratio of the raw agent to the arsenic content in the chlorine salt acidic leachate is 1-5:1.
6. the method of claim 4, wherein the arsenic is in the form of arsenate, arsenite, or a mixture of arsenate and arsenite.
7. The method according to claim 1, wherein the reducing agent in S1) and S2) is a solid or a liquid containing hypophosphite.
8. The method of claim 7, wherein the hypophosphite comprises potassium hypophosphite, sodium hypophosphite, and calcium hypophosphite.
9. The method according to claim 1, wherein the chloride acidic leachate in S1) is a copper anode slime pretreatment solution.
10. The method according to claim 1, wherein the total removal of arsenic from the chloride acid leachate after treatment in the method is up to 99%.
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| US5443622A (en) * | 1994-02-28 | 1995-08-22 | Kennecott Corporation | Hydrometallurgical processing of impurity streams generated during the pyrometallurgy of copper |
| JP2010059035A (en) * | 2008-09-08 | 2010-03-18 | Sumitomo Metal Mining Co Ltd | Method for producing aqueous arsenous acid solution of high purity from copper removal slime |
| CN105950874A (en) * | 2016-06-30 | 2016-09-21 | 中南大学 | Combined treatment method for copper smelting soot and polluted acid |
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| US5443622A (en) * | 1994-02-28 | 1995-08-22 | Kennecott Corporation | Hydrometallurgical processing of impurity streams generated during the pyrometallurgy of copper |
| JP2010059035A (en) * | 2008-09-08 | 2010-03-18 | Sumitomo Metal Mining Co Ltd | Method for producing aqueous arsenous acid solution of high purity from copper removal slime |
| CN105950874A (en) * | 2016-06-30 | 2016-09-21 | 中南大学 | Combined treatment method for copper smelting soot and polluted acid |
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| 胡鑫: "砷锑烟尘综合回收砷锑的试验研究", 中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑) * |
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