CN114854992B - Method for separating arsenic and antimony from arsenic caustic sludge leaching solution by deep oxidation - Google Patents
Method for separating arsenic and antimony from arsenic caustic sludge leaching solution by deep oxidation Download PDFInfo
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- CN114854992B CN114854992B CN202210568948.1A CN202210568948A CN114854992B CN 114854992 B CN114854992 B CN 114854992B CN 202210568948 A CN202210568948 A CN 202210568948A CN 114854992 B CN114854992 B CN 114854992B
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- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 60
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 55
- 238000002386 leaching Methods 0.000 title claims abstract description 49
- 230000003647 oxidation Effects 0.000 title claims abstract description 48
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 35
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000003518 caustics Substances 0.000 title claims abstract description 23
- 239000010802 sludge Substances 0.000 title claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000011572 manganese Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 9
- 150000002696 manganese Chemical class 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000002893 slag Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 230000005587 bubbling Effects 0.000 claims abstract description 3
- CIWAOCMKRKRDME-UHFFFAOYSA-N tetrasodium dioxido-oxo-stibonatooxy-lambda5-stibane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Sb]([O-])(=O)O[Sb]([O-])([O-])=O CIWAOCMKRKRDME-UHFFFAOYSA-N 0.000 claims abstract description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 64
- 238000003723 Smelting Methods 0.000 description 8
- 238000007664 blowing Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003673 groundwater Substances 0.000 description 3
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 229910003174 MnOOH Inorganic materials 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019446 NaSb Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- DLISVFCFLGSHAB-UHFFFAOYSA-N antimony arsenic Chemical compound [As].[Sb] DLISVFCFLGSHAB-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for separating arsenic and antimony from arsenic caustic sludge leaching liquid by deep oxidation, which comprises the steps of placing the arsenic caustic sludge leaching liquid in a reaction vessel; adding soluble manganese salt into the leaching solution according to a certain As (III)/Mn molar ratio, bubbling oxygen-containing gas into the leaching solution, stirring, and filtering after the oxidation reaction is completed to obtain oxidizing slag and oxidized solution; standing the oxidized solution, and separating to obtain antimony-precipitating solution and sodium pyroantimonate. The invention has the advantages of simple operation flow, high oxidation efficiency, low cost, recyclable catalyst and the like, and solves the problems of high oxidation cost, low efficiency, difficult separation of arsenic and antimony in the current arsenic-alkali residue leaching solution.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a method for separating arsenic and antimony from arsenic caustic sludge leaching liquid by deep oxidation.
Background
Arsenic alkali slag is a typical byproduct produced in an antimony refining process and mainly contains 15-20% of arsenic, 18-22% of antimony and a certain amount of caustic alkali, wherein the arsenic mainly exists in the form of sodium arsenite and sodium arsenite, and the antimony exists in the form of sodium antimonite and sodium antimonate and also contains a small amount of metallic antimony. Arsenic caustic sludge has relatively simple components and is rich in valuable metal antimony, but because of the similar properties of arsenic and antimony, the separation of the arsenic and the antimony is difficult, so that the disposal of the arsenic caustic sludge is always a serious problem in the antimony smelting industry. The current mainstream technology for arsenic caustic sludge treatment is a water leaching-oxidation process.
In addition to the completion of arsenic and antimony separation, reduction of arsenic toxicity and convenient arsenic solidification are another purpose of carrying out oxidation treatment of arsenic alkali residue leaching solution, so that oxidation treatment is one of the essential steps of treatment of As (III) -containing solution. The oxidizing agents reported so far for As (III) -containing solutions are mainly hydrogen peroxide, chlorine, ozone, potassium permanganate, etc. Among them, hydrogen peroxide is most commonly used. The excess hydrogen peroxide can act As an effective arsenic oxidizing agent over a wide pH range, especially in alkaline solutions, reducing the As (III) concentration in the solution by a factor of 10-15 in a short period of time. It is needless to say that the strong oxidizing agent has high oxidation efficiency on As (III), the oxidation effect of As (III) is very ideal, but the consumption is high, the price is high, and meanwhile, most oxidizing agents have the problem of introducing impurities, so that the development of a low-cost As (III) oxidation method is one of the hot spot directions of the current arsenic-containing material treatment research.
Air/pure oxygen is clearly the most ideal oxidant, is inexpensive and readily available, and does not introduce impurities. Oxidation of As (III) with air/pure oxygen is thermodynamically viable, but for kinetic reasons its oxidation efficiency is low, the oxidation rate of As (III) by oxygen is very slow, with half-lives of up to about 1 year. Therefore, the introduction of a catalyst into an air/pure oxygen oxidation As (III) reaction system to solve the problem of improving the reaction efficiency has become common knowledge of a large number of researchers. As patent CN113754040a discloses a method for oxidizing trivalent arsenic in water by using micro/nano activated carbon powder, the method is to add micro/nano activated carbon powder into solution containing trivalent arsenic, adjust the pH of the solution to slightly alkaline (pH is about 7-9.5) with alkali liquor, and introduce air/oxygen to stir and react for 1-3 days, so As to oxidize As (III) in the polluted water into As (V). As patent CN110204030a discloses a method for oxidizing trivalent arsenic in groundwater by using biochar, the method is to add the biochar into the groundwater containing As (III), and simultaneously introduce oxygen-containing gas, and stir and react for 1-3 days, so As to oxidize As (III) in the groundwater into As (V). However, the time required for completely oxidizing As (III) into As (V) is still long, and the problems that the catalyst cannot be reused are faced, and how to further increase the catalytic oxidation rate of As (III) and reuse the catalyst is a major concern in the industry.
Disclosure of Invention
The invention relates to a method for separating arsenic and antimony from arsenic caustic sludge leaching liquid by deep oxidation, which realizes the purposes of separating arsenic and antimony from the arsenic caustic sludge leaching liquid by deep efficient oxidation and recycling a catalyst.
In order to achieve the above purpose, the invention provides a method for separating arsenic and antimony from arsenic caustic sludge leaching solution by deep oxidation, which comprises the following steps:
placing arsenic caustic sludge leaching liquid into a reaction container;
adding soluble manganese salt into the leaching solution according to a certain As (III)/Mn molar ratio, bubbling oxygen-containing gas into the leaching solution, stirring, and filtering after the oxidation reaction is completed to obtain oxidizing slag and oxidized solution;
standing the oxidized solution, and separating to obtain antimony-precipitating solution and sodium pyroantimonate.
Preferably, the soluble manganese salt is added in solution.
Preferably, the As (III)/Mn molar ratio is 1.27 to 50.96:1.
Preferably, the oxygen-containing gas is selected from one of air and industrial pure oxygen, and the flow rate of the oxygen-containing gas is 0-1.2L/min.
Preferably, the temperature in the reaction vessel is from 30 to 90 ℃.
Preferably, the stirring speed is controlled to be 200-500 r/min during stirring.
Preferably, aeration strips are added in the reaction vessel.
Preferably, the oxidation reaction time is controlled to be 1 to 5 hours.
Preferably, the oxidation slag is recycled for oxidation of fresh arsenic caustic sludge leachate.
Preferably, the standing time of the oxidized liquid is controlled to be 6-12 hours.
The technical principle and conception of the invention are as follows:
as (III) in alkaline solution is mainly AsO in open system 2 - Exists in a form; mn (II) in solid form in alkaline solutionOf the formula, e.g. Mn (OH) 2 ，MnO 2 ·nH 2 O，Mn 3 O 4 ，MnOOH，MnO 2 And the like, introducing oxygen-containing gas and manganese salt into the arsenic alkali residue leaching solution, and MnSO 4 Mn (II) ions are provided, when free Mn (II) ions exist in the solution, the dissolved oxygen in the solution reacts with the Mn (II) ions to oxidize the Mn (II) ions into MnOOH, mnO 2 As (III) is then oxidized to As (V) by direct oxidation with As (III) in solution or catalytic air/pure oxygen oxidation. MnO (MnO) 2 The direct oxidation process of As (III) is divided into two steps: first oxidation of As (III) to As (V) is usually accompanied by reduction of Mn (IV) to Mn (III), which is then further reduced by an electron transfer mechanism to dissolved Mn (II) ions. Thus, the reactions that may occur inside the system are represented by the following formulas (1) to (6):
2Μn(II)+Ο 2 +4OH - →2Μn IV Ο 2 +2H 2 O (1)
4Mn(II)+Ο 2 +8OH-→4Μn III ΟOH+2H 2 O(2)4Μn III ΟOH+Ο 2 →4Μn IV Ο 2 +2H 2 O
(3)
2Μn IV Ο 2 +AsO 2 - +2OH - →2Μn III ΟOH+AsO 4 3- (4)
2Μn III ΟOH+AsO 2 - +2H + →2Mn(II)+AsO 4 3- +2H 2 O (5)
in the oxidation of As (III), there is also an accompanying oxidation of Sb (III). After Sb (III) is oxidized into Sb (V), the mixture is mixed with Na in the solution + And OH (OH) - Bonding to form NaSb (OH) 6 And (5) precipitation. The chemical reactions involved in this process are shown in the following formulas (7) - (8):
MnO 2 +Sb(OH) 3 +4H 2 O+OH - →Sb(OH) 6 - +Mn(OH) 2 (7)
catalytic oxidation of As (III) and MnO 2 The cyclic regeneration process consumes dissolved oxygen, and along with the continuous blowing of air, the dissolved oxygen in the solution is continuously supplemented, so that the MnO in the solution is theoretically recovered 2 Through cyclic regeneration, mnO in the solution 2 The content will remain unchanged, and better direct oxidation and catalytic oxidation performances are achieved. MnO obtained by filtration after completion of the oxidation reaction 2 The method can continue to return to the oxidation process for recycling.
Compared with the prior art, the invention has the following advantages:
(1) The invention has the advantages of cleanness, high efficiency, low cost, simple operation, low energy consumption, no special equipment requirement, convenience for the subsequent treatment process and easy realization of industrialization.
(2) According to the technical scheme, the manganese-based catalyst is synthesized in one step in a solution system, the input amount of catalyst raw materials is small, the oxidant is low-cost and easily-obtained oxygen-containing gas, as (III) in the leaching solution can be efficiently and thoroughly oxidized, the deep separation of As and Sb is realized, the concentration of Sb in the solution after antimony precipitation is reduced to below 37mg/L, and the recycling of Sb is ensured.
(3) The filter residue after the oxidation leaching solution is completed is MnO 2 The method has strong recycling performance, can return to the oxidation process to continuously oxidize a new part of leaching solution, realizes recycling, and is environment-friendly and free from waste gas and waste residue.
Drawings
FIG. 1 is a schematic flow chart of a method for separating arsenic and antimony from arsenic caustic sludge leachate by deep oxidation.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, wherein the following examples are provided on the premise of the present technical solution, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the examples.
Example 1:
the sample is taken from an antimony smelting plant in China, the main components of the leaching solution obtained by leaching different arsenic alkaline residues are greatly changed, the initial pH value of the solution is 13.4, and the main components are as follows:
taking 1.2L of leaching solution, controlling the molar ratio of As (III)/Mn to be 1.27:1, 4.25:1, 6.37:1, 12.74:1, 25.48:1 and 50.96:1 respectively, adding manganese sulfate monohydrate in the form of solution, keeping the temperature of the solution to be 90 ℃, then blowing air, wherein the air flow rate is 1L/min, the stirring speed is 300r/min, stirring and oxidizing for 2 hours under normal pressure, respectively taking the liquid sample to test the content of As (III) to be 0mg/L, 181.4mg/L and 393.1mg/L, and the oxidation rate of As (III) to be 100%, 72.09% and 39.53% of As (V).
Example 2:
the sample is taken from an antimony smelting plant in China, the main components of the leaching solution obtained by leaching different arsenic alkaline residues are greatly changed, the initial pH value of the solution is 13.4, and the main components are as follows:
taking 1.2L of leaching solution, adding anhydrous manganese chloride in the form of solution according to the molar ratio of As (III)/Mn of 25.48:1, keeping the temperature of the solution at 90 ℃, then blowing air at the air flow rate of 1L/min and the stirring speed of 300r/min, and respectively stirring and oxidizing for 0.5 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours and 3 hours under normal pressure. The As (III) content of the liquid sample assay was 476.16mg/L, 370.35mg/L, 249.42mg/L, 181.40mg/L and 0mg/L, respectively, and the oxidation rates of As (III) to As (V) were 26.74%, 43.02%, 61.63%, 72.09%, 88.37% and 100.00%, respectively.
Example 3:
the sample is taken from an antimony smelting plant in China, the main components of the leaching solution obtained by leaching different arsenic alkaline residues are greatly changed, the initial pH value of the solution is 13.4, and the main components are as follows:
taking 1.2L of leaching solution, adding manganese nitrate in the form of solution according to the molar ratio of As (III)/Mn of 12.74:1, then blowing air, wherein the air flow rate is 1L/min, the stirring speed is 300r/min, stirring and oxidizing for 2 hours under normal pressure, and controlling the reaction temperature to be 30 ℃, 45 ℃, 60 ℃, 75 ℃ and 90 ℃ respectively. The As (III) contents of the liquid sample assays were 211.63mg/L, 181.40mg/L, 136.05mg/L, 60.47mg/L and 0mg/L, respectively, and the oxidation rates of As (III) to As (V) were 67.44%, 72.09%, 79.07%, 90.70% and 100.00%, respectively.
Example 4:
the sample is taken from an antimony smelting plant in China, the main components of the leaching solution obtained by leaching different arsenic alkaline residues are greatly changed, the initial pH value of the solution is 13.4, and the main components are as follows:
taking 1.2L of leaching solution, adding manganese sulfate in the form of solution according to the molar ratio of As (III)/Mn of 12.74:1, keeping the temperature of the solution at 90 ℃, then blowing air, stirring at 300r/min, stirring and oxidizing for 2 hours under normal pressure, and controlling the flow rate of reverse air to be 0L/min, 0.6L/min, 1L/min and 1.2L/min respectively. The contents of As (III) in the liquid sample test were 453.49mg/L, 90.70mg/L, 0mg/L and 0mg/L, respectively, and the oxidation rates of As (III) to As (V) were 30.23%, 86.05%, 100% and 100.00%, respectively.
Example 5:
the sample is taken from an antimony smelting plant in China, the main components of the leaching solution obtained by leaching different arsenic alkaline residues are greatly changed, the initial pH value of the solution is 13.4, and the main components are as follows:
adding manganese sulfate in the form of solution into 1.2L of leaching solution at the molar ratio of As (III)/Mn of 12.74:1, keeping the temperature of the solution at 90 ℃, then blowing air at the air flow rate of 1L/min, stirring and oxidizing for 2 hours under normal pressure, controlling the stirring speed to be 200r/min, 300r/min, 400r/min and 500r/min respectively, taking the content of As (III) in liquid sample tests to be 45.35mg/L, 0mg/L, 15.12mg/L and 30.23mg/L respectively, and the oxidation rate of As (III) to be As (V) to be 93.02%, 100%, 97.67% and 95.35% respectively.
Example 6:
the sample is taken from an antimony smelting plant in China, the main components of the leaching solution obtained by leaching different arsenic alkaline residues are greatly changed, the initial pH value of the solution is 13.4, and the main components are as follows:
taking 1.2L of leaching solution, adding manganese chloride tetrahydrate in the form of solution according to the molar ratio of As (III)/Mn of 12.74:1, keeping the temperature of the solution at 90 ℃, then blowing air, stirring at the air flow rate of 1L/min and the stirring speed of 300r/min, stirring and oxidizing for 2 hours under normal pressure, collecting oxidized filter residues, oxidizing a new part of leaching solution, and circulating for 5 times. As (III) content of liquid sample taking test is respectively 0mg/L, 7.63mg/L and 20.05mg/L, and oxidation rates of As (III) oxidized into As (V) are respectively 100%, 98.83% and 96.92%, which indicate that the catalyst has strong recycling performance.
Example 7:
the sample is taken from an antimony smelting plant in China, the main components of the leaching solution obtained by leaching different arsenic alkaline residues are greatly changed, the initial pH value of the solution is 13.4, and the main components are as follows:
adding anhydrous manganese chloride in the form of a solution into 1.2L of leaching solution according to the molar ratio of As (III)/Mn of 12.74:1, keeping the temperature of the solution at 90 ℃, then blowing air, wherein the air flow rate is 1L/min, the stirring speed is 300r/min, stirring and oxidizing for 2 hours under normal pressure, standing the oxidized solution for 0 hour, 6 hours and 12 hours, respectively, and respectively taking the antimony content of 173.55mg/L, 117.82mg/L and 36.69mg/L in the liquid sample test, wherein the precipitation rate of antimony is 8.66%, 37.99% and 80.69% respectively, which indicates that the arsenic-antimony can be effectively separated by prolonging the standing time.
Various modifications and variations of the present invention will be apparent to those skilled in the art in light of the foregoing teachings and are intended to be included within the scope of the following claims.
Claims (6)
1. The method for separating arsenic and antimony from the arsenic caustic sludge leaching solution by deep oxidation is characterized by comprising the following steps:
placing arsenic caustic sludge leaching liquid into a reaction container;
adding soluble manganese salt into the leaching solution according to a certain As (III)/Mn molar ratio, bubbling oxygen-containing gas into the leaching solution, stirring, and filtering after the oxidation reaction is completed to obtain oxidizing slag and oxidized solution;
standing the oxidized solution, and separating to obtain an antimony-precipitated solution and sodium pyroantimonate;
wherein the soluble manganese salt is added in the form of a solution; the molar ratio of As (III)/Mn is 1.27-50.96:1; the oxygen-containing gas is selected from one of air and industrial pure oxygen, and the flow rate is 0-1.2L/min; the temperature in the reaction vessel is 30-90 ℃.
2. The method for separating arsenic and antimony by deep oxidation from arsenic caustic sludge leaching liquid according to claim 1, wherein the stirring speed is controlled to be 200-500 r/min during stirring.
3. The method for separating arsenic and antimony by deep oxidation from arsenic caustic sludge leaching solution according to claim 1, wherein aeration strips are added in the reaction vessel.
4. The method for deep oxidation separation of arsenic and antimony from arsenic caustic sludge leaching solution according to claim 1, wherein the oxidation reaction time is controlled to be 1-5 h.
5. The method for the deep oxidation separation of arsenic and antimony from arsenic caustic sludge leachate according to claim 1, wherein the oxidation sludge cycle is used for oxidation of new arsenic caustic sludge leachate.
6. The method for separating arsenic and antimony by deep oxidation from arsenic caustic sludge leaching liquid according to claim 1, wherein the standing time of the oxidized liquid is controlled to be 6-12 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CA651934A (en) * | 1962-11-06 | B. Ryland Lloyd | Dehydrogenation process | |
| CN103951026A (en) * | 2014-05-13 | 2014-07-30 | 中南大学 | Method of catalyzing trivalent arsenic in air oxidation liquor by taking manganese dioxide as catalyst |
| CN108486379A (en) * | 2018-03-15 | 2018-09-04 | 中南大学 | The efficient separation method of arsenic and alkali in a kind of arsenic alkaline slag |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA651934A (en) * | 1962-11-06 | B. Ryland Lloyd | Dehydrogenation process | |
| CN103951026A (en) * | 2014-05-13 | 2014-07-30 | 中南大学 | Method of catalyzing trivalent arsenic in air oxidation liquor by taking manganese dioxide as catalyst |
| CN108486379A (en) * | 2018-03-15 | 2018-09-04 | 中南大学 | The efficient separation method of arsenic and alkali in a kind of arsenic alkaline slag |
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