CN116495776B - Method for co-catalytic oxidation of high-concentration trivalent arsenic by using copper and nickel - Google Patents
Method for co-catalytic oxidation of high-concentration trivalent arsenic by using copper and nickel Download PDFInfo
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- CN116495776B CN116495776B CN202310524373.8A CN202310524373A CN116495776B CN 116495776 B CN116495776 B CN 116495776B CN 202310524373 A CN202310524373 A CN 202310524373A CN 116495776 B CN116495776 B CN 116495776B
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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 57
- 238000000034 method Methods 0.000 title claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 21
- 239000010949 copper Substances 0.000 title claims abstract description 21
- 230000003647 oxidation Effects 0.000 title claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 239000002699 waste material Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- YFLLTMUVNFGTIW-UHFFFAOYSA-N nickel;sulfanylidenecopper Chemical compound [Ni].[Cu]=S YFLLTMUVNFGTIW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 230000001105 regulatory effect Effects 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 6
- 239000012065 filter cake Substances 0.000 claims description 18
- 238000003723 Smelting Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003546 flue gas Substances 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 3
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims description 2
- CUGMJFZCCDSABL-UHFFFAOYSA-N arsenic(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[As+3].[As+3] CUGMJFZCCDSABL-UHFFFAOYSA-N 0.000 claims 3
- 238000005486 sulfidation Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000002920 hazardous waste Substances 0.000 abstract description 2
- 238000009867 copper metallurgy Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- XPDICGYEJXYUDW-UHFFFAOYSA-N tetraarsenic tetrasulfide Chemical compound S1[As]2S[As]3[As]1S[As]2S3 XPDICGYEJXYUDW-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000005070 sampling Methods 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
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYZMAFWCKGTUMA-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane;dihydrate Chemical compound O.O.[Fe+3].[O-][As]([O-])([O-])=O UYZMAFWCKGTUMA-UHFFFAOYSA-K 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to the technical field of hazardous waste treatment, in particular to a method for co-catalytic oxidation of high-concentration trivalent arsenic by using copper and nickel. The method specifically comprises the following steps: mixing a material containing trivalent arsenic with copper-nickel sulfide, and adding an acidity regulating solution to regulate the acidity of the mixed material to obtain a mixed solution; and (3) placing the obtained mixed solution in an autoclave, stirring at a certain rotating speed, introducing oxidizing gas, heating and pressurizing, and performing oxidation reaction under a certain pressure to obtain pentavalent arsenic and waste acid. The method has the advantages of simple process, convenient operation and easy realization of the conditions required by the reaction; the reaction does not need special equipment, and the used raw materials of copper sulfate, nickel sulfate and sulfuric acid are common byproducts in the copper metallurgy industry, and are low in price and easy to obtain; in the implementation process, other byproducts are not generated, copper and nickel are free from loss, and the generated waste acid can be recycled without complex subsequent treatment processes.
Description
Technical Field
The invention relates to the technical field of hazardous waste treatment, in particular to a method for co-catalytic oxidation of high-concentration trivalent arsenic by using copper and nickel.
Background
Arsenic is a toxic element, is widely accompanied in nonferrous metal minerals, and has strong toxicity and carcinogenicity as simple substances and compounds. For decades, the nonferrous metal industry of China has been actively developed, and the problem of arsenic pollution is increasingly prominent while nonferrous metal minerals are widely mined.
After arsenic passes through a nonferrous smelting system, most of arsenic enters pyrometallurgical slag, smoke dust, wet smelting wastewater, waste slag and electrolytic anode mud. The existing common wet arsenic fixing methods, such as lime neutralization method, sulfuration precipitation method, iron-arsenic coprecipitation method, scorodite method and the like, mainly aim at high arsenic concentration waste liquid and have wider application in purifying wet smelting waste water. Generally, for part of high-arsenic materials which cannot be stably piled up, arsenic in the high-arsenic materials can enter a liquid phase in an ionic form through a wet leaching process to obtain high-concentration arsenic-containing leaching solution, and then the high-concentration arsenic-containing leaching solution is solidified through the method, or arsenic is prepared into arsenic trioxide products. The methods used for wet-process arsenic fixation or production of arsenic trioxide are developed based on As (V) As a main phase, and these methods fix arsenic in the form of pentavalent compounds or further produce arsenic trioxide by reducing As (V). Because As (V) is less toxic and less mobile than As (III), as (V) arsenic-precipitating minerals are also generally more stable. In general, acid wastewater produced by acid making, smelting and copper electrorefining processes and solutions produced by treating smelting smoke dust all contain a large amount of As (III), so that before arsenic is fixed, the As (III) is oxidized into As (V) in advance.
In order to increase the oxidation rate of As (III), the oxidation of arsenic in the treatment of high-arsenic materials generally depends on a plurality of high-cost and active strong oxidants, such As hydrogen peroxide, permanganate and the like. Oxygen can also be used as an oxidizing agent for arsenic and is inexpensive and easy to prepare, but the reaction is very slow when no catalyst is present. Common catalysts include manganese dioxide, potassium permanganate, ultraviolet light, and the like. The common concentration of the arsenic-containing waste liquid in the metallurgical industry is several grams liter or even tens of grams liter, and the production process of oxidation is adopted at present without adopting air as an oxidant, so that the air is low in price, convenient to prepare and low in danger.
Disclosure of Invention
The invention discloses a method for co-catalytic oxidation of high-concentration trivalent arsenic by using copper and nickel, which aims to solve any one of the above and other potential problems in the prior art.
In order to solve the problems, the technical scheme of the invention is as follows: a method for the synergistic catalytic oxidation of high-concentration trivalent arsenic by using copper and nickel, which specifically comprises the following steps:
S1) mixing a material containing trivalent arsenic with copper-nickel sulfide, and then adding an acidity regulating solution to regulate the acidity of the mixed material to obtain a mixed solution;
S2) placing the mixed solution obtained in the step S1) into an autoclave, stirring at a certain rotating speed, introducing oxidizing gas, heating and pressurizing, and performing oxidation reaction under a certain pressure to obtain pentavalent arsenic and waste acid.
Further, the concentration of trivalent arsenic in the mixed solution in the step S1) is 5-30 g/l;
further, the concentration of copper ions in the mixed solution is 30-50 g/l;
Further, the concentration of nickel ions in the mixed solution is 3-20 g/l;
further, the acidity is 50 to 250g/l.
Further, the material containing trivalent arsenic in S1) is arsenic sulfide filter cake or arsenite.
Further, the arsenic sulfide filter cake is the arsenic filter cake after the non-ferrous smelting purification waste acid is vulcanized.
Further, the copper-nickel sulfide is copper-nickel sulfide or a mixture of copper sulfate and nickel sulfate in an arsenic sulfide filter cake after copper smelting flue gas purification treatment.
Further, the acidity regulating liquid in S1) is sulfuric acid.
Further, the stirring speed in the step S2) is 100-1000rpm; the heating temperature is 80-150 ℃; the amount of the oxidizing gas is 100-1000 Nm 3/h, and the pressure is 0.8-1.5Mpa; the duration is 1-6h.
Further, the oxidizing gas is air.
Further, the oxidation rate of trivalent arsenic is not lower than 40%.
Further, the spent acid is used as the acidity regulating liquid in S1).
According to the invention, copper nickel sulfide in the arsenic sulfide filter cake after copper sulfate, nickel sulfate or copper smelting flue gas purification treatment is added into a high-concentration trivalent arsenic solution or arsenic sulfide filter cake slurry, and air is introduced into an autoclave to enable a reaction system to have a high-pressure environment, and meanwhile, the oxidation of trivalent arsenic can be promoted by heating in the autoclave. Compared with the prior art, the invention has the following beneficial effects:
(1) The process is simple, the operation is convenient, and the equipment required by the reaction is widely applied in industry.
(2) The used reagents copper sulfate and nickel sulfate are selected from nonferrous smelting byproducts or copper nickel sulfide in arsenic sulfide filter cakes after copper smelting flue gas purification treatment, are easy to obtain in copper smelting enterprises, and have low price even if purchased.
(3) In the implementation process, other byproducts are not generated, copper and nickel are free from loss, the generated waste acid can be reused, and particularly, the waste acid can be matched with a wet method arsenic trioxide process to be added with copper and nickel and sulfuric acid once, and can be recycled in the follow-up process without repeated supplement.
(4) The method is suitable for treating high-concentration trivalent arsenic and is suitable for strong-acid trivalent arsenic solution, thus providing great convenience for metallurgical industry, having great significance and great economic value compared with other methods.
Drawings
FIG. 1 is a schematic flow chart of the disclosed method for co-catalytic oxidation of high concentration trivalent arsenic using copper nickel.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As shown in fig. 1, the method for co-catalytic oxidation of high-concentration trivalent arsenic by copper and nickel according to the invention specifically comprises the following steps:
S1) mixing a material containing trivalent arsenic with copper-nickel sulfide, and then adding an acidity regulating solution to regulate the acidity of the mixed material to obtain a mixed solution;
S2) placing the mixed solution obtained in the step S1) into an autoclave, stirring at a certain rotating speed, introducing oxidizing gas, heating and pressurizing, and performing oxidation reaction under a certain pressure to obtain pentavalent arsenic and waste acid.
The concentration of trivalent arsenic in the mixed solution in the step S1) is 5-30 g/l;
the concentration of copper ions in the mixed solution is 30-50 g/l;
the concentration of nickel ions in the mixed solution is 3-20 g/l;
The acidity is 50-250 g/l.
The material containing trivalent arsenic in the S1) is arsenic sulfide filter cake or arsenite.
The arsenic sulfide filter cake is the arsenic filter cake after the non-ferrous smelting purification waste acid is vulcanized.
The copper-nickel sulfide is copper-nickel sulfide or a mixture of copper sulfate and nickel sulfate in an arsenic sulfide filter cake after copper smelting flue gas purification treatment.
The acidity regulating liquid in the step S1) is sulfuric acid.
The stirring speed in the step S2) is 100-1000rpm; the heating temperature is 80-150 ℃; the amount of the oxidizing gas is 100-1000 Nm 3/h, and the pressure is 0.8-1.5Mpa; the duration is 1-6h.
The oxidizing gas is air.
The oxidation rate of the trivalent arsenic is not lower than 40%.
The spent acid is used as the acidity regulating liquid in S1).
Example 1
Preparing copper-containing 35.8g/l, nickel-containing 5.9g/l and acidity (calculated by sulfuric acid) 179.8g/l of waste acid, mixing with arsenic sulfide filter cake (dry base arsenic-containing 40%), wherein the liquid-solid ratio is 8:1, transferring into an autoclave, introducing air, raising the pressure and the temperature while raising the temperature in the autoclave to 115 ℃, raising the pressure to 1.0MPa, and maintaining the stirring speed of 900rpm to fully stir the solution at a constant speed. After the temperature and pressure rise are finished, the reaction is maintained for 180min, sampling is carried out every 30min, and detection analysis is carried out on samples obtained in 30min, 60min, 90min, 120min, 150min and 180 min. The oxidation rates of the obtained trivalent arsenic were 16.7%, 42.8%, 52.9%, 67.8%, 83.3% and 91.7%, respectively.
Example 2
The liquid-solid ratio was adjusted to 12:1 according to the conditions of example 1. After the temperature and pressure rise are finished, the reaction is maintained for 180min, sampling is carried out every 30min, and detection analysis is carried out on samples obtained in 30min, 60min, 90min, 120min, 150min and 180 min. The oxidation rates of the obtained trivalent arsenic were 34.2%, 57.6%, 82.7%, 90.8%, 91.6% and 92.3%, respectively.
Example 3
The reaction temperature was controlled at 135℃under the conditions of example 1. After the temperature and pressure rise are finished, the reaction is maintained for 180min, sampling is carried out every 30min, and detection analysis is carried out on samples obtained in 30min, 60min, 90min, 120min, 150min and 180 min. The oxidation rates of the obtained trivalent arsenic were 20.1%, 53.9%, 68.3%, 85.6%, 89.3% and 92.1%, respectively.
Example 4
Preparing copper 43.9g/l, nickel 10.8g/l and acidity (calculated by sulfuric acid) 200.7g/l of waste acid, mixing with arsenic sulfide filter cake (dry basis arsenic 40%), wherein the liquid-solid ratio is 8:1, transferring into an autoclave, introducing air, raising the pressure and the temperature while raising the temperature in the autoclave to 115 ℃, raising the pressure to 1.0MPa, and maintaining the stirring speed at 900rpm to fully stir the solution at a constant speed. After the temperature and pressure rise are finished, the reaction is maintained for 180min, sampling is carried out every 30min, and detection analysis is carried out on samples obtained in 30min, 60min, 90min, 120min, 150min and 180 min. The oxidation rates of the obtained trivalent arsenic were 18.9%, 50.1%, 68.7%, 79.6%, 86.8% and 93.7%, respectively.
Example 5
Preparing copper-containing 46.8g/l, nickel-containing 3.2g/l and acidity (calculated by sulfuric acid) 110.9g/l of waste acid, mixing with arsenic sulfide filter cake (dry base arsenic-containing 40%) with a liquid-solid ratio of 8:1, transferring into an autoclave, introducing air, raising pressure and temperature while raising the temperature in the autoclave to 125 ℃, raising the pressure to 1.2MPa, and maintaining the stirring rate at 900rpm to fully stir the solution at a constant speed. After the temperature and pressure rise are finished, the reaction is maintained for 180min, sampling is carried out every 30min, and detection analysis is carried out on samples obtained in 30min, 60min, 90min, 120min, 150min and 180 min. The oxidation rates of the obtained trivalent arsenic were 19.8%, 56.9%, 83.6%, 89.3%, 91.8% and 92.9%, respectively.
The above description of embodiments is only for aiding in the understanding of the method of the present application and its core ideas; meanwhile, as those skilled in the art will have variations 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 preset error range, substantially achieving the technical effect. The description hereinafter sets forth a preferred embodiment for practicing the application, but is not intended to limit the scope of the application, as the description is given for the purpose of illustrating the general principles of the application. The scope of the 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 the application is not limited to the forms disclosed herein, but is not to be construed as limited to other embodiments, and is capable of numerous other combinations, modifications and environments and is capable of changes or modifications within the scope of the inventive concept as expressed herein, either as a result of the foregoing teachings or as a result of the knowledge or technology of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the application are intended to be within the scope of the appended claims.
Claims (6)
1. A method for the synergistic catalytic oxidation of high-concentration trivalent arsenic by using copper and nickel, which is characterized by comprising the following steps:
S1) mixing a material containing trivalent arsenic with copper-nickel sulfide, and then adding an acidity regulating solution to regulate the acidity of the mixed material to obtain a mixed solution;
the concentration of trivalent arsenic in the mixed solution in the step S1) is 5-30 g/l;
The concentration of copper ions in the mixed solution is 30-50 g/l; the concentration of nickel ions in the mixed solution is 3-20 g/l; the acidity is 50-250 g/l calculated by sulfuric acid;
the copper-nickel sulfide is copper-nickel sulfide in an arsenic sulfide filter cake after copper smelting flue gas purification treatment or is a mixture of copper sulfate and nickel sulfate;
The acidity regulating liquid is sulfuric acid;
S2) placing the mixed solution obtained in the step S1) into an autoclave, stirring at a certain rotating speed, introducing oxidizing gas, heating and pressurizing, and performing oxidation reaction under a certain pressure to obtain pentavalent arsenic and waste acid;
The stirring speed in the step S2) is 100-1000rpm; the heating temperature is 80-150 ℃; the amount of the oxidizing gas is 100-1000 Nm 3/h, and the pressure is 0.8-1.5Mpa; the duration is 1-6h.
2. The method according to claim 1, wherein the trivalent arsenic-containing material in S1) is arsenic sulfide filter cake or arsenite.
3. The method of claim 1, wherein the arsenic sulfide filter cake is an arsenic filter cake after non-ferrous smelting purification spent acid sulfidation treatment.
4. The method of claim 1, wherein the oxidizing gas is air.
5. The method of claim 1, wherein the oxidation rate of trivalent arsenic is not less than 40%.
6. The method according to claim 1, characterized in that the spent acid is used as acidity regulating liquid in S1).
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105039713A (en) * | 2015-08-25 | 2015-11-11 | 中南大学 | Method for leaching solid arsenic out of arsenic sulfide slag through one step and enriching valuable metal |
| CN109763000A (en) * | 2018-12-10 | 2019-05-17 | 六盘水中联工贸实业有限公司 | A method of from height containing air oxidation removal arsenic in arsenic, zinc acid solution |
| CN112194279A (en) * | 2020-09-08 | 2021-01-08 | 天津大学 | Method for adsorbing arsenic in arsenic-containing wastewater |
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| CN105039713A (en) * | 2015-08-25 | 2015-11-11 | 中南大学 | Method for leaching solid arsenic out of arsenic sulfide slag through one step and enriching valuable metal |
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| CN112194279A (en) * | 2020-09-08 | 2021-01-08 | 天津大学 | Method for adsorbing arsenic in arsenic-containing wastewater |
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