CN109097579B - Supercritical water treatment method for arsenic sulfide slag - Google Patents
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/005—Oxides; Hydroxides; Oxyacids
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- 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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- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to a supercritical water treatment method of arsenic sulfide slag, belonging to the technical field of waste slag treatment. Adding water, excessive oxidant, arsenic sulfide slag and sulfur-containing additive into a high-temperature high-pressure reaction kettle, sealing the high-temperature high-pressure reaction kettle, heating and pressurizing until a reaction system in the high-temperature high-pressure reaction kettle reaches a supercritical state, reacting for 15-105 min, rapidly relieving pressure of the high-temperature high-pressure reaction kettle when the temperature of the supercritical state is 460-680 ℃, carrying out gas-solid separation on a reaction product system, wherein a solid product is heavy metal oxide, the gas of the reaction product system is cooled, arsenic trioxide gas is converted into solid arsenic trioxide, and the solid arsenic trioxide is settled and further cooled, and a liquid product is a sulfuric acid solution; when the temperature of the supercritical state is 378-460 ℃ (460 ℃ is not contained), the temperature of a reaction product system in the high-temperature high-pressure reaction kettle is reduced to be below 100 ℃, solid-liquid separation is carried out to obtain a solid product arsenic trioxide, and the liquid product is sulfuric acid solution containing metal ions.
Description
Technical Field
The invention relates to a supercritical water treatment method of arsenic sulfide slag, belonging to the technical field of waste slag treatment.
Background
As arsenic-containing waste residues are used as persistent pollutants, most of the arsenic-containing waste residues are treated by a stockpiling and storing method for a long time, and along with the accumulation of more and more high-concentration arsenic-containing waste residues, the accumulated arsenic-containing solid waste residues cause serious sudden hidden dangers to local soil and water environment, cause serious pollution and cause more and more serious phenomena of harming the life health of people. In order to prevent secondary pollution, the treatment of arsenic-containing waste residues is a problem to be solved urgently at present. At present, the methods for harmless and resource treatment of arsenic-containing waste residues mainly comprise: solidifying and burying, converting into arsenic trioxide, converting into simple substance arsenic, directly recovering and the like.
Meanwhile, as an important resource, arsenic is used as a compound, and a plurality of compounds of arsenic are often used for manufacturing pesticides, preservatives, dyes, medicines and the like. It is also often used in the manufacture of paints, wallpaper and crockery. As an alloy additive, it can be used for producing lead shot, printing alloy, brass (for condenser), accumulator grid plate, antiwear alloy, high-strength structural steel and corrosion-resistant steel, etc. Expensive cupronickel alloys are also made by alloying copper with arsenic. The arsenic in the waste residue is recovered, which is not only beneficial to environmental protection, but also is an important way for obtaining arsenic resources. The arsenic sulfide slag has high arsenic content relative to other arsenic-containing waste slag, and has the value of arsenic recovery.
Chinese patent CN102115166B discloses a method for preparing arsenic trioxide from arsenic sulfide slag, which comprises adding three times of filtration (sequentially adding sodium hydroxide, concentrated sulfuric acid and sodium sulfide) to obtain purified arsenic sulfide, and adding arsenic acid, oxygen and sulfur dioxide in the subsequent reaction process, which is complicated. Chinese patent CN102151690B discloses a method for treating arsenic sulfide slag, wherein the arsenic sulfide slag is added with an inorganic flocculant, and then a solid powder adsorbent and asbestos wool are sequentially added to complete the solidification of the arsenic sulfide slag, and the recovery of arsenic resources is not realized. Chinese patent CN103388076B discloses a method for recovering simple substance arsenic from arsenic sulfide slag, which comprises the steps of adding water, sodium hydroxide and hydrogen peroxide in sequence, reacting for 6 hours, heating and concentrating, adjusting pH with concentrated hydrochloric acid, adding stannous chloride, reacting for 8 hours, and finally obtaining the simple substance arsenic by solid-liquid separation and drying, wherein the reagent has multiple types and the reaction time is long. Chinese patent CN105963902A discloses a harmless treatment method for arsenic sulfide slag, which comprises the steps of sequentially adding water, sodium sulfide, an oxidant, an iron salt (aluminum salt) and cement, curing for 3-15 days after the completion of the above process, finally realizing curing harmless treatment, wherein the curing process is long, and the recycling of arsenic resources cannot be realized.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the supercritical water treatment method of the arsenic sulfide slag, which has the advantages of simple process, less operation steps, reagent consumption reduction, secondary pollution avoidance and process flow simplification.
A supercritical water treatment method of arsenic sulfide slag comprises the following specific steps:
adding water, excessive oxidant, arsenic sulfide slag and sulfur-containing additive into a high-temperature high-pressure reaction kettle, sealing the high-temperature high-pressure reaction kettle, heating and pressurizing until a reaction system in the high-temperature high-pressure reaction kettle reaches a supercritical state, and reacting for 15-105 min, wherein the temperature of the supercritical state is 378-680 ℃, and the pressure is 22.5-52 Mpa;
when the temperature of the supercritical state is 460-680 ℃, quickly decompressing the high-temperature high-pressure reaction kettle, carrying out gas-solid-liquid separation on a reaction product system, wherein a solid product at the bottom of the high-temperature high-pressure reaction kettle is heavy metal oxide, cooling the gas of the reaction product system, converting the arsenic trioxide gas into solid arsenic trioxide, settling the solid arsenic trioxide, and further cooling to obtain a liquid product which is a sulfuric acid solution;
when the temperature of the supercritical state is 378-460 ℃ (460 ℃ is not contained), cooling a reaction product system in the high-temperature high-pressure reaction kettle to the temperature below 100 ℃, and carrying out solid-liquid separation to obtain a solid product arsenic trioxide, wherein the liquid product is a sulfuric acid solution containing metal ions;
the oxidant is hydrogen peroxide, oxygen or ozone;
the sulfur-containing additive is one or more of ammonium sulfate, sulfuric acid, sulfurous acid, sulfur dioxide, elemental sulfur, carbonyl sulfur and carbon disulfide, and the molar ratio of sulfur atoms in the sulfur-containing additive to arsenic atoms in the arsenic sulfide slag is (3-13): 2;
the mass ratio of the water to the arsenic sulfide slag is (1-8) to 1;
the high-temperature high-pressure reaction kettle is an intermittent reaction kettle or a continuous reaction kettle.
The invention has the beneficial effects that:
(1) according to the invention, water and oxidizing gas are mutually soluble in a supercritical state, and the mass transfer resistance between phases is eliminated, so that arsenic sulfide slag can be quickly oxidized, the conveying speed is increased, and the utilization rate is improved; in supercritical water, reacting sulfur in the arsenic sulfide slag with an oxidant to produce sulfuric acid; under the condition of low-temperature supercritical water, metal of the arsenic sulfide slag reacts with sulfuric acid and an oxidant to generate metal ions, the metal ions are dissolved in the sulfuric acid, and under the condition of high-temperature supercritical water, the oxidant reacts with the metal to generate metal oxide; at high temperature (460-600 ℃), the arsenic trioxide is volatile and separated from the metal oxide (the metal oxide obtained by decomposing sulfate and oxidizing an oxidant);
(2 in the supercritical state, the sulfur-containing additive is oxidized to produce sulfuric acid, which can dissolve and leach arsenic, so that the arsenic exists in the form of arsenous acid;
(3) in the oxidation action of supercritical water, when sulfuric acid exists, other metals in the arsenic sulfide slag can be separated by adopting a high-temperature pressure relief mode at the high-temperature volatilization stage (the temperature is 460-600 ℃) of the supercritical water, and the other metals exist in a reaction kettle in the form of oxides (decomposition of sulfate and oxidation of an oxidant); in the supercritical water low-temperature cooling stage, other metals in the solution exist in sulfuric acid in the form of ions;
(4) according to the method, a high-temperature supercritical water state is utilized, arsenic trioxide volatilizes, and other metals are deposited in the form of oxides, so that the collection and purification of arsenic trioxide are facilitated; in the process of low-temperature cooling, the main component (arsenic trioxide) of arsenous acid can be directly separated out, and other metals are dissolved in the solution in an ionic form under the action of sulfuric acid;
(5) the method has the advantages of simple process, few operation steps, reagent consumption reduction, effective arsenic recovery, secondary pollution avoidance and process simplification.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: in the embodiment, the mass percent of arsenic in the arsenic sulfide slag is 45%, and the arsenic sulfide slag also contains a small amount of heavy metals such as copper, iron, lead, chromium, cadmium and the like;
a supercritical water treatment method of arsenic sulfide slag comprises the following specific steps:
adding water, excessive oxidant (oxygen), arsenic sulfide slag and sulfur-containing additive (sulfur dioxide) into a high-temperature high-pressure reaction kettle to obtain a reaction system, heating and pressurizing the reaction system in the high-temperature high-pressure reaction kettle under a closed condition until the reaction system reaches a supercritical state, and reacting for 105min to obtain a reaction product system, wherein the temperature of the supercritical state is 378 ℃, and the pressure is 27.5 Mpa; cooling a reaction product system in the high-temperature high-pressure reaction kettle to the temperature of 95 ℃, and carrying out solid-liquid separation to obtain solid arsenic trioxide and a liquid product, wherein the liquid product is a sulfuric acid solution containing heavy metal ions such as copper, iron, lead, chromium, cadmium and the like; the mass ratio of the water to the arsenic sulfide slag is 1:1, and the molar ratio of sulfur atoms in sulfur dioxide of the sulfur-containing additive to arsenic atoms in the arsenic sulfide is 3: 2;
in the embodiment, the high-temperature high-pressure reaction kettle is an intermittent reaction kettle;
in this example, the purity of arsenic trioxide was 99.3% and the recovery of arsenic was 97.7%.
Example 2: in the embodiment, the mass percent of arsenic in the arsenic sulfide slag is 55%, and the arsenic sulfide slag also contains a small amount of heavy metals such as copper, iron, lead, chromium, cadmium and the like;
adding water, excessive oxidant (hydrogen peroxide), arsenic sulfide slag and sulfur-containing additive (sulfurous acid) into a high-temperature high-pressure reaction kettle to obtain a reaction system, heating and pressurizing the reaction system in the high-temperature high-pressure reaction kettle under a closed condition until the reaction system reaches a supercritical state, and reacting for 35min to obtain a reaction product system, wherein the temperature of the supercritical state is 420 ℃, and the pressure is 45 Mpa; cooling a reaction product system in the high-temperature high-pressure reaction kettle to the temperature of 90 ℃, and carrying out solid-liquid separation to obtain solid arsenic trioxide and a liquid product, wherein the liquid product is a sulfuric acid solution containing heavy metal ions such as copper, iron, lead, chromium, cadmium and the like; the mass ratio of the water to the arsenic sulfide slag is 5:1, and the molar ratio of sulfur atoms in the sulfurous additive sulfurous acid to arsenic atoms in the arsenic sulfide is 13: 2;
in the embodiment, the high-temperature high-pressure reaction kettle is a continuous reaction kettle;
in this example, the purity of arsenic trioxide was 99.3% and the recovery of arsenic was 97.8%.
Example 3: in the embodiment, the arsenic sulfide slag contains 53% of arsenic by mass and also contains a small amount of heavy metals such as copper, iron, lead, chromium, cadmium and the like;
adding water, excessive oxidant (oxygen), arsenic sulfide slag and sulfur-containing additive (sulfuric acid) into a high-temperature high-pressure reaction kettle to obtain a reaction system, heating and pressurizing the reaction system in the high-temperature high-pressure reaction kettle under a closed condition until the reaction system reaches a supercritical state, and reacting for 75min to obtain a reaction product system, wherein the temperature of the supercritical state is 455 ℃, and the pressure is 22.5 Mpa; cooling a reaction product system in the high-temperature high-pressure reaction kettle to 85 ℃, and carrying out solid-liquid separation to obtain solid arsenic trioxide and a liquid product, wherein the liquid product is a sulfuric acid solution containing heavy metal ions such as copper, iron, lead, chromium, cadmium and the like; the mass ratio of the water to the arsenic sulfide slag is 8:1, and the molar ratio of sulfur atoms in the sulfur-containing additive sulfuric acid to arsenic atoms in the arsenic sulfide is 7: 2;
in the embodiment, the high-temperature high-pressure reaction kettle is a continuous reaction kettle;
in this example, the purity of arsenic trioxide was 99.1%, and the recovery of arsenic was 98.3%.
Example 4: in the embodiment, the mass percent of arsenic in the arsenic sulfide slag is 49%, and the arsenic sulfide slag also contains a small amount of heavy metals such as copper, iron, lead, chromium, cadmium and the like;
a supercritical water treatment method of arsenic sulfide slag comprises the following specific steps:
adding water, excessive oxidant (oxygen), arsenic sulfide slag and sulfur-containing additive (sulfur dioxide) into a high-temperature high-pressure reaction kettle to obtain a reaction system, heating and pressurizing the reaction system in the high-temperature high-pressure reaction kettle under a closed condition until the reaction system reaches a supercritical state, and reacting for 90min to obtain a reaction product system, wherein the temperature of the supercritical state is 400 ℃, and the pressure is 52 Mpa; cooling a reaction product system in the high-temperature high-pressure reaction kettle to the temperature of 90 ℃, and carrying out solid-liquid separation to obtain solid arsenic trioxide and a liquid product, wherein the liquid product is a sulfuric acid solution containing heavy metal ions such as copper, iron, lead, chromium, cadmium and the like; the mass ratio of the water to the arsenic sulfide slag is 3:1, and the molar ratio of sulfur atoms in sulfur dioxide of the sulfur-containing additive to arsenic atoms in the arsenic sulfide is 9: 2;
in the embodiment, the high-temperature high-pressure reaction kettle is a continuous reaction kettle;
in this example, the purity of arsenic trioxide was 99.2% and the recovery of arsenic was 97.4%.
Example 5: in the embodiment, the arsenic sulfide slag contains 53% of arsenic by mass and also contains a small amount of heavy metals such as copper, iron, lead, chromium, cadmium and the like;
a supercritical water treatment method of arsenic sulfide slag comprises the following specific steps:
adding water, excessive oxidant (ozone), arsenic sulfide slag and sulfur-containing additive (elemental sulfur) into a high-temperature high-pressure reaction kettle to obtain a reaction system, heating and pressurizing the reaction system in the high-temperature high-pressure reaction kettle under a closed condition until the reaction system reaches a supercritical state, and reacting for 60min to obtain a reaction product system, wherein the temperature of the supercritical state is 460 ℃, and the pressure is 46 Mpa; rapidly relieving the pressure of the high-temperature high-pressure reaction kettle, carrying out gas-solid separation on a reaction product system, wherein solid products at the bottom of the high-temperature high-pressure reaction kettle body are oxides of heavy metals such as copper, iron, lead, chromium, cadmium and the like, cooling the gas of the reaction product system, converting the arsenic trioxide gas into solid arsenic trioxide, settling the solid arsenic trioxide, further cooling, and obtaining a liquid product which is a sulfuric acid solution; the mass ratio of the water to the arsenic sulfide slag is 7:1, and the molar ratio of sulfur atoms in elemental sulfur of the sulfur-containing additive to arsenic atoms in the arsenic sulfide is 5: 2;
in the embodiment, the high-temperature high-pressure reaction kettle is a continuous reaction kettle;
in this example, the purity of arsenic trioxide was 99.7%, and the recovery rate of arsenic was 97.4%.
Example 6: in the embodiment, the arsenic sulfide slag contains 58% of arsenic by mass and also contains a small amount of heavy metals such as copper, iron, lead, chromium, cadmium and the like;
a supercritical water treatment method of arsenic sulfide slag comprises the following specific steps:
adding water, excessive oxidant (oxygen), arsenic sulfide slag and sulfur-containing additive (carbonyl sulfide) into a high-temperature high-pressure reaction kettle to obtain a reaction system, heating and pressurizing the reaction system in the high-temperature high-pressure reaction kettle under a closed condition until the reaction system reaches a supercritical state, and reacting for 25min to obtain a reaction product system, wherein the temperature of the supercritical state is 680 ℃, and the pressure is 30 Mpa; rapidly relieving the pressure of the high-temperature high-pressure reaction kettle, carrying out gas-solid separation on a reaction product system, wherein solid products at the bottom of the high-temperature high-pressure reaction kettle body are oxides of heavy metals such as copper, iron, lead, chromium, cadmium and the like, cooling the gas of the reaction product system, converting the arsenic trioxide gas into solid arsenic trioxide, settling the solid arsenic trioxide, further cooling, and obtaining a liquid product which is a sulfuric acid solution; the mass ratio of the water to the arsenic sulfide slag is 6:1, and the molar ratio of sulfur atoms in carbonyl sulfide and arsenic atoms in arsenic sulfide as a sulfur-containing additive is 11: 2;
in the embodiment, the high-temperature high-pressure reaction kettle is a continuous reaction kettle;
in this example, the purity of arsenic trioxide was 99.4%, and the recovery rate of arsenic was 97.7%.
Example 7: in the embodiment, the mass percent of arsenic in the arsenic sulfide slag is 51%, and the arsenic sulfide slag also contains a small amount of heavy metals such as copper, iron, lead, chromium, cadmium and the like;
a supercritical water treatment method of arsenic sulfide slag comprises the following specific steps:
adding water, excessive oxidant (oxygen), arsenic sulfide slag and sulfur-containing additive (carbon disulfide) into a high-temperature high-pressure reaction kettle to obtain a reaction system, heating and pressurizing the reaction system in the high-temperature high-pressure reaction kettle under a closed condition until the reaction system reaches a supercritical state, and reacting for 70min to obtain a reaction product system, wherein the temperature of the supercritical state is 625 ℃, and the pressure is 40 Mpa; rapidly relieving the pressure of the high-temperature high-pressure reaction kettle, carrying out gas-solid separation on a reaction product system, wherein solid products at the bottom of the high-temperature high-pressure reaction kettle body are oxides of heavy metals such as copper, iron, lead, chromium, cadmium and the like, cooling the gas of the reaction product system, converting the arsenic trioxide gas into solid arsenic trioxide, settling the solid arsenic trioxide, further cooling, and obtaining a liquid product which is a sulfuric acid solution; the mass ratio of the water to the arsenic sulfide slag is 1:1, and the molar ratio of sulfur atoms in the sulfur-containing additive carbon disulfide to arsenic atoms in the arsenic sulfide is 8: 2;
in the embodiment, the high-temperature high-pressure reaction kettle is a continuous reaction kettle;
in this example, the purity of arsenic trioxide was 99.4%, and the recovery rate of arsenic was 98.3%.
Example 8: in the embodiment, the arsenic sulfide slag contains 48% of arsenic by mass and also contains a small amount of heavy metals such as copper, iron, lead, chromium, cadmium and the like;
a supercritical water treatment method of arsenic sulfide slag comprises the following specific steps:
adding water, excessive oxidant (ozone), arsenic sulfide slag and sulfur-containing additive (ammonium sulfate) into a high-temperature high-pressure reaction kettle to obtain a reaction system, heating and pressurizing the reaction system in the high-temperature high-pressure reaction kettle under a closed condition until the reaction system reaches a supercritical state, and reacting for 40min to obtain a reaction product system, wherein the temperature of the supercritical state is 540 ℃, and the pressure is 35 Mpa; rapidly relieving the pressure of the high-temperature high-pressure reaction kettle, carrying out gas-solid separation on a reaction product system, wherein solid products at the bottom of the high-temperature high-pressure reaction kettle body are oxides of heavy metals such as copper, iron, lead, chromium, cadmium and the like, cooling the gas of the reaction product system, converting the arsenic trioxide gas into solid arsenic trioxide, settling the solid arsenic trioxide, and further cooling the solid arsenic trioxide, wherein liquid products are sulfuric acid and nitric acid solution; the mass ratio of the water to the arsenic sulfide slag is 3:1, and the molar ratio of sulfur atoms in the ammonium sulfate as the additive to arsenic atoms in the arsenic sulfide is 10: 2;
in the embodiment, the high-temperature high-pressure reaction kettle is a continuous reaction kettle;
in this example, the purity of arsenic trioxide was 99.6%, and the recovery rate of arsenic was 97.5%.
Example 9: in the embodiment, the arsenic sulfide slag contains 58% of arsenic by mass and also contains a small amount of heavy metals such as copper, iron, lead, chromium, cadmium and the like;
a supercritical water treatment method of arsenic sulfide slag comprises the following specific steps:
adding water, excessive oxidant (hydrogen peroxide), arsenic sulfide slag and additive (elemental sulfur) into a high-temperature high-pressure reaction kettle to obtain a reaction system, heating and pressurizing the reaction system in the high-temperature high-pressure reaction kettle under a closed condition until the reaction system reaches a supercritical state, and reacting for 40min to obtain a reaction product system, wherein the temperature of the supercritical state is 500 ℃, and the pressure is 28 Mpa; rapidly relieving the pressure of the high-temperature high-pressure reaction kettle, carrying out gas-solid separation on a reaction product system, wherein solid products at the bottom of the high-temperature high-pressure reaction kettle body are oxides of heavy metals such as copper, iron, lead, chromium, cadmium and the like, cooling the gas of the reaction product system, converting the arsenic trioxide gas into solid arsenic trioxide, settling the solid arsenic trioxide, further cooling, and obtaining a liquid product which is a sulfuric acid solution; the mass ratio of the water to the arsenic sulfide slag to be treated is 6:1, and the molar ratio of sulfur atoms in elemental sulfur of the sulfur-containing additive to arsenic atoms in the arsenic sulfide is 7: 2;
in the embodiment, the high-temperature high-pressure reaction kettle is a continuous reaction kettle;
in this example, the purity of arsenic trioxide was 99.3%, and the recovery rate of arsenic was 98.5%.
Example 10: in the embodiment, the arsenic sulfide slag contains 58% of arsenic by mass and also contains a small amount of heavy metals such as copper, iron, lead, chromium, cadmium and the like;
a supercritical water treatment method of arsenic sulfide slag comprises the following specific steps:
adding water, excessive oxidant (ozone), arsenic sulfide slag and sulfur-containing additive (carbon disulfide) into a high-temperature high-pressure reaction kettle to obtain a reaction system, heating and pressurizing the reaction system in the high-temperature high-pressure reaction kettle under a closed condition until the reaction system reaches a supercritical state, and reacting for 20min to obtain a reaction product system, wherein the temperature of the supercritical state is 600 ℃, and the pressure is 52 Mpa; rapidly relieving the pressure of the high-temperature high-pressure reaction kettle, carrying out gas-solid separation on a reaction product system, wherein solid products at the bottom of the high-temperature high-pressure reaction kettle body are oxides of heavy metals such as copper, iron, lead, chromium, cadmium and the like, cooling the gas of the reaction product system, converting the arsenic trioxide gas into solid arsenic trioxide, settling the solid arsenic trioxide, further cooling, and obtaining a liquid product which is a sulfuric acid solution; the mass ratio of the water to the arsenic sulfide slag is 5:1, and the molar ratio of sulfur atoms in the sulfur-containing additive carbon disulfide to arsenic atoms in the arsenic sulfide is 5: 2;
in the embodiment, the high-temperature high-pressure reaction kettle is a continuous reaction kettle;
in this example, the purity of arsenic trioxide was 99.1%, and the recovery rate of arsenic was 98.2%.
Claims (3)
1. A supercritical water treatment method for arsenic sulfide slag is characterized by comprising the following specific steps:
adding water, excessive oxidant, arsenic sulfide slag and sulfur-containing additive into a high-temperature high-pressure reaction kettle, sealing the high-temperature high-pressure reaction kettle, heating and pressurizing until a reaction system in the high-temperature high-pressure reaction kettle reaches a supercritical state, and reacting for 15-105 min, wherein the temperature of the supercritical state is 400-680 ℃, and the pressure is 22.5-52 Mpa;
when the temperature of the supercritical state is 460-680 ℃, quickly decompressing the high-temperature high-pressure reaction kettle, carrying out gas-solid-liquid separation on a reaction product system, wherein a solid product at the bottom of the high-temperature high-pressure reaction kettle is heavy metal oxide, cooling the gas of the reaction product system, converting the arsenic trioxide gas into solid arsenic trioxide, settling the solid arsenic trioxide, and further cooling to obtain a liquid product which is a sulfuric acid solution;
when the temperature of the supercritical state is 400-460 ℃ (460 ℃ is not contained), cooling a reaction product system in the high-temperature high-pressure reaction kettle to the temperature of below 100 ℃, and carrying out solid-liquid separation to obtain a solid product arsenic trioxide, wherein the liquid product is a sulfuric acid solution containing metal ions;
the sulfur-containing additive is one or more of ammonium sulfate, sulfuric acid, sulfurous acid, sulfur dioxide, elemental sulfur, carbonyl sulfur and carbon disulfide, and the molar ratio of sulfur atoms in the sulfur-containing additive to arsenic atoms in the arsenic sulfide slag is (3-13): 2; the mass ratio of the water to the arsenic sulfide slag is (1-8): 1.
2. The supercritical water treatment method of arsenic sulfide slag according to claim 1, characterized in that: the oxidant is hydrogen peroxide, oxygen or ozone.
3. The supercritical water treatment method of arsenic sulfide slag according to claim 1, characterized in that: the high-temperature high-pressure reaction kettle is an intermittent reaction kettle or a continuous reaction kettle.
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| CN101418376A (en) * | 2008-11-27 | 2009-04-29 | 东华大学 | A kind of method and apparatus of beneficiation and metallurgy of refractory gold ore by supercritical water oxidation |
| CN106823238B (en) * | 2017-02-24 | 2020-02-14 | 中南大学 | Hydrothermal stable curing treatment method for arsenic sulfide slag |
| CN107385209A (en) * | 2017-07-19 | 2017-11-24 | 中南大学 | A kind of method of white metal synthetical recovery |
| CN108315571A (en) * | 2018-01-17 | 2018-07-24 | 中国瑞林工程技术有限公司 | A kind for the treatment of process of Containing Sulfur arsenic material |
| CN108220618A (en) * | 2018-01-19 | 2018-06-29 | 中国地质科学院矿产综合利用研究所 | Arsenic-fixing and copper-extracting method for high-arsenic copper sulfide ore |
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