CN115369266B - Method for removing and recycling arsenic in chlorohydrochloric acid leaching solution - Google Patents
Method for removing and recycling arsenic in chlorohydrochloric acid leaching solution Download PDFInfo
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- CN115369266B CN115369266B CN202210999305.2A CN202210999305A CN115369266B CN 115369266 B CN115369266 B CN 115369266B CN 202210999305 A CN202210999305 A CN 202210999305A CN 115369266 B CN115369266 B CN 115369266B
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 123
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 238000000034 method Methods 0.000 title claims abstract description 63
- 239000002253 acid Substances 0.000 title claims abstract description 48
- 238000002386 leaching Methods 0.000 title claims abstract description 42
- 238000004064 recycling Methods 0.000 title abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 49
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 39
- 239000002893 slag Substances 0.000 claims abstract description 31
- 230000009467 reduction Effects 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 23
- 238000001556 precipitation Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 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 11
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 8
- 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 7
- 229910001382 calcium hypophosphite Inorganic materials 0.000 claims description 7
- 229940064002 calcium hypophosphite Drugs 0.000 claims description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 7
- 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 7
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 6
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 6
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims description 5
- 229940000489 arsenate Drugs 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 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
- 239000000460 chlorine Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000011133 lead Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 239000011575 calcium Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000047 product 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 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
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-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
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229940000488 arsenic acid Drugs 0.000 description 1
- GSYZQGSEKUWOHL-UHFFFAOYSA-N arsenic calcium Chemical compound [Ca].[As] GSYZQGSEKUWOHL-UHFFFAOYSA-N 0.000 description 1
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-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
- 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
- 150000001804 chlorine Chemical class 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
- 238000007599 discharging 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
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012528 membrane Substances 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
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 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
- -1 sulphur ions Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 230000001457 vasomotor Effects 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
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
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)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for removing and recycling arsenic in chlorohydrochloric acid leaching solution, which specifically comprises the following steps: copper and arsenic are removed by one-stage reduction: adding a certain amount of reducing agent into a chlorohydrochloric acid leaching solution, controlling the temperature, and separating reducing slag from reduced liquid to obtain reducing slag containing copper and arsenic and a first-stage reduced liquid; and (3) carrying out two-stage reduction and arsenic precipitation: 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 containing only arsenic simple substances and a second-stage reduced liquid. The reduction removal and recycling recovery method for arsenic in chlorohydrochloric acid leaching solution has the advantages of simplicity in operation, high arsenic removal rate, short process, good selective reduction effect and the like. Under the 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 a copper smelting process, and the second-stage reducing slag can be used as a high-quality raw material to remove simple substance arsenic and refine, so that the removal and recycling recovery of arsenic in the chlorohydrochloric acid leaching solution are realized.
Description
Technical Field
The invention relates to a method for removing and recycling arsenic in chlorohydrochloric acid leaching solution, which is suitable for the fields of hydrometallurgy and industrial wastewater pollution treatment.
Background
At present, various industrial industries produce acidic wastewater (waste acid, acidic mine wastewater and the like) containing high-concentration arsenic particularly in nonferrous metal exploitation, smelting and sulfuric acid production processes. According to incomplete statistics, only nonferrous metal copper, lead and zinc smelting industries discharge 400 ten thousand tons of acid wastewater in year. The waste water has strong acidity>10 -3 M), high arsenic content, large production amount and the like. In this type of wastewater, arsenic exists mainly in two forms, arsenite (As (III)) and arsenite (As (V)). Before the acid wastewater reaches the standard for emission or recycling, arsenic in the wastewater must be removed. Currently, the most widely used methods in the removal of arsenic from acidic wastewater are neutralization precipitation and sulfidation precipitation. The principle of arsenic removal by the neutralization precipitation method is to neutralize the acidity of wastewater by CaO and form calcium arsenic coprecipitate (calcium arsenate (Ca) 3 (AsO 3 ) 2 ) And calcium arsenite (Ca) 3 (AsO 4 ) 2 ) So as to achieve the aim of removing arsenic. However, this method produces a large amount of low-grade arsenic-containing mixed hazardous waste (CaSO) 4 -Ca 3 (AsO 3 ) 2 -Ca 3 (AsO 4 ) 2 ) Is very difficult to treat and dispose, and has secondary pollution risk. By sulphide precipitation with arsenic and sulphur ions (S 2- ) The reaction produces arsenic sulfide precipitate (As) 2 S 3 ) Realizes the removal of arsenic, and the arsenic sediment obtained by the method has high grade and greatly reduces the sediment production compared with the neutralization sediment method. However, the As obtained 2 S 3 PrecipitationThe value is low, the recycling recovery is difficult to realize, the recycling recovery is extremely unstable, and the recycling recovery is easy to partially convert into As under the action of illumination or oxygen 2 O 3 Thereby producing As 2 S 3 -As 2 O 3 Mixing and dangerously discharging. In summary, the current method for removing arsenic from acidic wastewater generates a large amount of hazardous arsenic-containing waste which is extremely difficult to treat and dispose, greatly increases the running and treatment and disposal costs of manufacturers, and causes potential environmental threats.
Arsenic can combine with sulfhydryl-containing enzyme in cells, inhibit cell oxidation process, and paralyze vasomotor center to paralyze capillary vessel, dilate and increase permeability. Therefore, the removal and recovery of arsenic is necessary.
In the prior art, particularly relates to a method for efficiently removing arsenic in polluted acid under a strong acid system, and belongs to the fields of hydrometallurgy and industrial wastewater treatment. Filtering the contaminated acid to remove insoluble impurities, adding iodide according to arsenic content, slowly adding finely ground and sieved copper powder, controlling the reaction temperature, 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 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 recycling of arsenic-containing contaminated acid is realized. The method prepares arsenic trioxide from arsenic in arsenic-containing contaminated acid through precipitation and conversion, overcomes the defect that arsenic trioxide is prepared by reducing copper arsenite by sulfur dioxide, obtains high-standard arsenic trioxide, and realizes the treatment of the contaminated acid and the recycling of copper and arsenic resources.
The processes aim at removing and recycling arsenic from different industrial wastewater, but the arsenic removal and recycling of the industrial wastewater under a chloride system are not reported. Therefore, the research on a new method for removing and recycling arsenic in chlorohydrochloric acid leaching solution has important practical significance.
Disclosure of Invention
The invention aims to solve the problem that no method for removing and recycling arsenic in a chloride system exists at present, and provides a novel method for removing and recycling arsenic in chlorohydrochloric acid leaching solution. The method adopts a first stage reduction to remove copper and arsenic and a second stage reduction to precipitate arsenic. The method has the advantages of simple operation method, easy industrialization, realization of high-efficiency removal and recycling of arsenic, and important economic, environmental and social benefits.
The invention adopts the technical scheme that: the method for removing and recovering arsenic in chlorohydrochloric acid leaching solution comprises the following steps:
s1) one-stage reduction copper and arsenic removal: adding a reducing agent into the chlorohydrochloric acid leaching solution 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 reducing slag containing a large part of copper and arsenic, and removing the reducing slag containing a large part of copper and arsenic;
s2) two-stage reduction arsenic precipitation: and (2) adding a reducing agent into the primary reduced liquid containing a small part of copper and arsenic obtained in the step (S1), and filtering and washing to obtain secondary reduced liquid and recovered reducing slag containing only arsenic simple substance.
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 chlorohydrochloric acid leaching solution after S1) treatment 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 chlorohydrochloric 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 chlorohydrochloric acid 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 chlorohydrochloric acid leaching solution in the step S1) is copper anode slime pretreatment solution.
Further, the total arsenic removal rate of the chlorohydrochloric acid leaching solution treated by the method can reach more than 99 percent.
The invention has the advantages that:
1. according to the novel method for removing and recycling arsenic in the chlorohydrochloric acid leaching solution, more than 99% of arsenic in the chlorohydrochloric acid leaching solution can be removed, and qualified raw materials are provided for a simple substance arsenic purification system, so that efficient removal and recycling of arsenic are realized;
2. the novel method for removing and recycling arsenic in the chlorohydrochloric acid leaching solution can reduce arsenic acid and arsenite into simple substance arsenic precipitation, and is beneficial to recycling chlorohydrochloric acid waste liquid;
3. the novel method for removing and recycling arsenic in the chlorohydrochloric acid leaching solution does not generate new wastewater, reduces environmental pollution, and is safe and environment-friendly;
4. the method has the advantages of low price of the used reagent, simple operation method, easy industrialization and important economic and social benefits.
Drawings
FIG. 1 is a process flow diagram of a method for removing and recovering arsenic from chlorohydrochloric acid leachate according to the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
As shown in figure 1, the method for removing and recovering arsenic in chlorohydrochloric acid leaching solution comprises the following steps:
s1) one-stage reduction copper and arsenic removal: adding a reducing agent into the chlorohydrochloric acid leaching solution according to a certain proportion, carrying out a reduction reaction, filtering and washing to obtain reducing slag containing copper and arsenic and a first-stage reduced solution; the reduction slag containing copper and arsenic can be used as a high-quality copper-containing material to enter a smelting production system, and the liquid after one-stage reduction enters the next working procedure;
s2) two-stage reduction arsenic precipitation: and (2) adding a reducing agent into the first-stage reduction solution containing copper and arsenic obtained in the step (S1), and filtering and washing to obtain reduction slag containing only arsenic simple substances and a second-stage reduction solution. The reducing slag is mainly arsenic simple substance, and 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 specific process of the reduction reaction in the 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 arsenic removal rate in the treated chlorohydrochloric acid leaching solution is more than 90%, and the copper precipitation rate is more than 45%.
The specific process of the reduction reaction in the S2) is as follows: 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 liquid is more than 90%.
The molar ratio of the reducing agent in the S1) to the arsenic content in the chlorohydrochloric 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 chlorohydrochloric acid leaching solution is 1-5:1.
the arsenic is in the form of arsenate, arsenite or a 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 chlorohydrochloric acid leaching liquid in the step S1) is copper anode slime pretreatment liquid.
The total removal rate of arsenic in the chlorohydrochloric acid leaching solution treated by the method can reach more than 99 percent.
Example 1
The components of the chlorine-containing leaching solution of the copper anode slime are shown in table 1. Adding a reducing agent and arsenic into the chlorohydrochloric acid leaching solution according to a certain proportion, wherein the molar ratio of the reducing agent to the arsenic is 3:1, the reaction temperature is 70 ℃, the reaction time is 4 hours, and the stirring rotating speed is 300r/min. The reducing agent is potassium hypophosphite, and the reducing slag containing copper and arsenic and the first-stage reduced liquid are obtained through filtering and washing, wherein the composition of the first-stage reduced liquid is shown in table 2.
TABLE 1 copper anode slime chloride leaching solution composition (g/l)
| Species of element | Cu | As | Sb | Bi | Pb | Cl |
| Content of | 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 removal rate of reduced arsenic in one stage was 91.69%, more than 90%, and the precipitation rate of copper 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 liquid 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 4 hours, and the stirring rotating speed is 300r/min. The reducing agent is potassium hypophosphite, and the two-stage reducing slag and the two-stage reduced liquid are obtained through filtering and washing, wherein the composition results of the two-stage reduced liquid are shown in Table 3.
TABLE 3 composition of the two-stage reduced solution (g/l)
| Species of element | Cu | As | Sb | Bi | Pb | Cl |
| Content of | 16.76 | 0.14 | 17.93 | 7.94 | 0.69 | 152.78 |
As is clear from Table 3, the removal rate of the two-stage reduced arsenic was 92.22% and more than 90%. The obtained reducing slag is mainly arsenic simple substance, and 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%, the first-stage reduction decoppering rate is 50.78%, other metals are not basically reduced and removed by hypophosphorous acid, 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 purifying step and improves the added value of the product.
Example 2
The components of the chlorine-containing leaching solution of the copper anode slime are shown in table 4. Adding a reducing agent and arsenic into the chlorohydrochloric acid leaching solution according to a certain proportion, wherein the molar ratio of the reducing agent to the arsenic is 4:1, the reaction temperature is 80 ℃, the reaction time is 4 hours, and the stirring rotating speed is 300r/min. The reducing agent is sodium hypophosphite, and the reducing slag containing copper and arsenic and the first-stage reduced liquid are obtained through filtering and washing, wherein the composition of the first-stage reduced liquid is shown in table 5.
TABLE 4 copper anode slime chlorine salt leaching solution composition (g/l)
TABLE 5 composition of the first-stage reduced solution (g/l)
| Species of element | Cu | As | Sb | Bi | Pb | Cl |
| Content of | 19.68 | 1.83 | 16.89 | 7.83 | 0.72 | 166.92 |
As is clear from tables 4 and 5, the removal rate of reduced arsenic in one stage was 92.31%, 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 liquid 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 4 hours, and the stirring rotating speed is 300r/min. The reducing agent is sodium hypophosphite, and the two-stage reducing slag and the two-stage reduced liquid are obtained through filtering and washing, and the composition results of the two-stage reduced liquid are shown in Table 6.
TABLE 6 composition of the two-stage reduced solution (g/l)
| Species of element | Cu | As | Sb | Bi | Pb | Cl |
| Content of | 19.52 | 0.13 | 16.49 | 7.64 | 0.70 | 163.38 |
As can be seen from Table 6, the removal rate of the two-stage reduced arsenic was 92.94% and more than 90%. The obtained reducing slag is mainly arsenic simple substance, and 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%, the first-stage reduction decoppering rate is 49.87%, other metals are not basically reduced and removed by sodium hypophosphite, 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 purifying step and improves the added value of the product.
Example 3
The chlorine-containing leaching solution of the copper anode slime has the components shown in table 7. Adding a reducing agent and arsenic into the chlorohydrochloric acid leaching solution according to a certain proportion, wherein the molar ratio of the reducing agent to the arsenic is 5:1, the reaction temperature is 90 ℃, the reaction time is 4 hours, and the stirring rotating speed is 300r/min. The reducing agent is calcium hypophosphite, and the reducing slag containing copper and arsenic and the first-stage reduced liquid are obtained through filtering and washing, wherein the composition of the first-stage reduced liquid is shown in table 8.
TABLE 7 copper anode slime chloride leaching solution composition (g/l)
| Species of element | Cu | As | Sb | Bi | Pb | Cl |
| Content of | 37.71 | 25.46 | 17.12 | 8.32 | 0.77 | 172.19 |
TABLE 8 composition of the first-stage reduced solution (g/l)
| Species of element | Cu | As | Sb | Bi | Pb | Cl |
| Content of | 18.95 | 1.98 | 16.81 | 8.14 | 0.75 | 168.79 |
As is clear from tables 7 and 8, the removal rate of reduced arsenic in one stage was 92.34%, 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 liquid 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 4 hours, and the stirring rotating speed is 300r/min. The reducing agent is calcium hypophosphite, and the two-stage reducing slag and the two-stage reduced liquid are obtained through filtering and washing, wherein the composition results of the two-stage reduced liquid are shown in Table 9.
TABLE 9 composition of the two-stage reduced solution (g/l)
| Species of element | Cu | As | Sb | Bi | Pb | Cl |
| Content of | 18.99 | 0.14 | 16.52 | 7.95 | 0.75 | 166.39 |
As is clear from Table 9, the removal rate of the secondary reduced arsenic was 92.97% and more than 90%. The obtained reducing slag is mainly arsenic simple substance, and 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%, the first-stage reduction decoppering rate is 49.98%, other metals are not basically reduced and removed by calcium hypophosphite, 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 purifying step and improves the added value of the product.
The method for removing and recovering arsenic in the chlorohydrochloric acid leaching solution is provided in detail. The above description of embodiments is only for aiding in understanding the method of the present application and its core ideas; meanwhile, as those skilled in the art will have modifications in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
Certain terms are used throughout the description and claims to refer to particular components. Those of skill in the art will appreciate that a hardware manufacturer may refer to the same component by different names. The description and claims do not take the form of an element differentiated by name, but rather by functionality. As referred to throughout the specification and claims, the terms "comprising," including, "and" includes "are intended to be interpreted as" including/comprising, but not limited to. By "substantially" is meant that within an acceptable error range, a person skilled in the art is able to solve the technical problem within a certain error range, substantially achieving the technical effect. The description hereinafter sets forth the preferred embodiment for carrying out the present application, but is not intended to limit the scope of the present application in general, for the purpose of illustrating the general principles of the present application. The scope of the present application is defined by the appended claims.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product 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 product or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or system comprising such elements.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
While the foregoing description illustrates and describes the preferred embodiments of the present application, it is to be understood that this application is not limited to the forms disclosed herein, but is not to be construed as an exclusive use of other embodiments, and is capable of many other combinations, modifications and environments, and adaptations within the scope of the teachings described herein, through the foregoing teachings or through the knowledge or skills of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the present invention are intended to be within the scope of the appended claims.
Claims (4)
1. A method for removing and recovering arsenic from chlorohydrochloric acid leaching solution, which is characterized by comprising the following steps:
s1) one-stage reduction copper and arsenic removal: adding a reducing agent into the chlorohydrochloric acid leaching solution 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 reducing slag containing a large part of copper and arsenic, and removing the reducing slag containing a large part of copper and arsenic;
the specific process of the reduction reaction is as follows: the reaction temperature is 50-100 ℃, the reaction time is 0.5-5h, and the stirring speed is 100-600r/min; the molar ratio of the reducing agent to the arsenic content in the chlorohydrochloric acid leaching solution is 1-10:1, a step of; the reducing agents are all solid or liquid containing hypophosphite; the hypophosphite includes potassium hypophosphite, sodium hypophosphite and calcium hypophosphite;
s2) two-stage reduction arsenic precipitation: adding a reducing agent into the first-stage reduced liquid containing a small part of copper and arsenic obtained in the step S1), filtering and washing to obtain a second-stage reduced liquid and recovered reducing slag containing only arsenic simple substance;
the specific process of the reduction reaction is as follows: the reaction temperature is 40-80 ℃, the reaction time is 0.5-3h, and the stirring speed is 100-600r/min;
the addition amount of the reducing agent is that the molar ratio of the raw agent to the arsenic content in the chlorohydrochloric acid leaching solution is 1-5:1, a step of;
the reducing agents are all solid or liquid containing hypophosphite;
the hypophosphite includes potassium hypophosphite, sodium hypophosphite and calcium hypophosphite.
2. The method of claim 1, wherein the arsenic is in the form of arsenate, arsenite, or a mixture of arsenite and arsenite.
3. The method according to claim 1, wherein the chlorohydrochloric acid leachate in S1) is copper anode slime pretreatment liquid.
4. The method according to claim 1, wherein the total arsenic removal rate of the chlorohydrochloric acid leachate after treatment by the method is more than 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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| 砷锑烟尘综合回收砷锑的试验研究;胡鑫;中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑);摘要 * |
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