CN113617801A - Method for microwave industrial treatment of sulfur-containing and arsenic-containing material - Google Patents

Method for microwave industrial treatment of sulfur-containing and arsenic-containing material Download PDF

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Publication number
CN113617801A
CN113617801A CN202110919854.XA CN202110919854A CN113617801A CN 113617801 A CN113617801 A CN 113617801A CN 202110919854 A CN202110919854 A CN 202110919854A CN 113617801 A CN113617801 A CN 113617801A
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microwave
arsenic
materials
sulfur
treatment
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欧阳晓平
毛评生
毛亮程
陈静
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Hainan Walker New Material Technology Co ltd
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Hunan Trailblazer Environmental Protection Technology Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00Destroying solid waste or transforming solid waste into something useful or harmless
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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Abstract

The invention relates to a method for microwave industrial treatment of sulfur-containing and arsenic-containing materials, which belongs to the technical field of hazardous waste treatment and comprises the steps of waste pretreatment, material mixing, material paving, microwave oxidation, microwave detoxification and cooling, wherein oxygen is added in a potassium ferrate and aeration mode to oxidize arsenic into pentavalent arsenic oxide, reduce the toxicity of arsenic and widen the pH value of subsequent treatment, sulfur is oxidized into trivalent sulfur oxide and is dissolved in water and then is removed by reaction with alkaline treatment liquid, the pentavalent arsenic oxide and the trivalent sulfur oxide are removed along with evaporated steam at high temperature to realize effective separation of sulfur and arsenic from the materials, and the characteristics of microwave heating effect and traditional industrial treatment are fully combined to provide simple microwave equipment which is suitable for the microwave equipment disclosed by the invention, is simple to operate and is suitable for industrial treatment of sulfur-containing and arsenic-containing materials.

Description

Method for microwave industrial treatment of sulfur-containing and arsenic-containing material
Technical Field
The invention belongs to the technical field of hazardous waste treatment, and particularly relates to a method for industrially treating a sulfur-containing and arsenic-containing material by microwaves.
Background
As is one of the main associated elements in non-ferrous metal ores, such as high-arsenic copper and gold concentrate, the content of As can even reach 20-30%. Various arsenic-containing solutions, arsenic-containing smoke dust and waste residues are generated in the smelting process of non-ferrous metals, and the arsenic-containing materials are extremely toxic and need to be subjected to harmless treatment.
Microwave heating is a new type of energy conversion method that efficiently converts electromagnetic energy into heat energy, thereby efficiently heating materials in a microwave field. Generally, microwave heating has the characteristics of integral heating, rapid heating and hot spot heating, and has the advantages that conventional heating methods such as promotion of chemical reaction rate, reduction of chemical energy of chemical reaction and the like do not have. Therefore, the application of microwave heating to the smelting of rare mineral metals will undoubtedly shorten the reaction time and improve the reaction conversion rate and production yield.
In the prior art, the microwave heating auxiliary treatment is adopted for arsenic-containing and sulfur-containing waste materials, but in the actual industrial application process, the requirement conditions are harsh, the operation difficulty is high, and the large-scale industrial treatment is not applicable.
Disclosure of Invention
In order to overcome the technical problems mentioned in the background technology, the invention provides a method for industrially treating a sulfur-containing and arsenic-containing material by microwaves.
The purpose of the invention can be realized by the following technical scheme:
a method for industrially treating a sulfur-containing and arsenic-containing material by microwaves specifically comprises the following steps:
step S1: pretreatment of waste materials: detecting the content of sulfur and arsenic in the material, adding the material into a crusher for crushing, and then adding the crushed material into a grinder to prepare a powder material;
step S2: mixing materials: adding the powder material and potassium ferrate into a stirrer, uniformly stirring to prepare mixed powder, then adding a prepared salt solution into the stirrer, and continuously stirring to prepare a mixed wet material;
step S3: spreading materials: adding the mixed wet material into a bin of microwave equipment, spreading the mixed wet material on a material containing plate through a material spreading plate, and conveying the mixed wet material into the microwave equipment by a conveyor;
step S4: microwave oxidation: conveying the material containing plate to an oxidation area, introducing oxygen into the mixed wet material by an aeration rake, and simultaneously carrying out microwave heating;
step S5: microwave detoxification: conveying the material containing plate to a high-heat area, and performing microwave heating again to remove oxides containing sulfur and arsenic;
step S6: and (3) cooling: the material containing plate is conveyed to a cooling area and cooled through a coil heat exchanger, and the material subjected to microwave detoxification is cooled to be lower than 60 ℃.
Furthermore, exhaust fans are arranged at the tops of the oxidation zone, the high heating zone and the cooling zone, and exhaust gas is pumped out to the treatment liquid for sedimentation.
Further, in step S1, the particle size of the powder material is controlled to be 40-300 mesh.
Further, in step S2, the amount of potassium ferrate added is 1.1-1.5 times the total mass of sulfur and arsenic in the powdered material.
Further, in step S2, the salt solution includes one or more of soluble sodium salt, soluble ammonium salt and soluble nitrate, which are mixed in any proportion, and the mass fraction of the salt solution is 1.0% to 10.0%, and the addition amount of the salt solution is 10.0% to 20.0% of the mass of the powder material.
Further, the soluble sodium salt is one or a mixture of more of sodium chloride, sodium carbonate, sodium bicarbonate, sodium bisulfate, sodium sulfate and sodium sulfite.
Further, the soluble ammonium salt is one or a mixture of more of ammonium chloride, ammonium sulfate, ammonium nitrate and the like;
further, the nitrate is one or a mixture of several of sodium nitrate, potassium nitrate, ammonium nitrate and calcium nitrate.
Further, in step S3, the spreading thickness of the mixed wet material in the material containing plate is 1-20 cm.
Further, in step S4, the amount of oxygen and the mixed wet material is 2-5L/100 kg.
Further, in step S4, the microwave heating temperature in the oxidation zone is 80-105 ℃, and the treatment time of the mixed wet material in the oxidation zone is 0.5-3 h.
Further, in step S4, the microwave heating temperature in the high-heat zone is 105-500 ℃, and the processing time of the mixed wet material in the high-heat zone is 0.5-7 h.
Further, in step S4, the processing liquid is a mixture of ferric trichloride, calcium hydroxide and water, and the mass fraction of the ferric trichloride is 10.0-20.0%, and the mass fraction of the calcium hydroxide is 5.5-8%.
Furthermore, microwave equipment is adopted in the treatment process of the mixed wet materials, the microwave equipment comprises a conveyor and a protective cover arranged on the outer side of the conveyor, the protective cover is sequentially divided into an oxidation area, a high-heat area and a cooling area through partition plates, and a plurality of material containing plates are conveyed on the conveyor.
The upper and lower both sides in oxidation zone, high hot district all are provided with the polar plate, and the polar plate distributes in the upper and lower of flourishing flitch, and the protection casing is close to the one side that the high hot district was kept away from in the oxidation zone and is provided with the feed bin, and the top that the protection casing is close to the one end of feed bin is provided with the cylinder, and the output of cylinder runs through the polar plate fixedly connected with aeration harrow above the conveyer, and the inlet end intercommunication oxygen pipeline of aeration harrow through the aeration height of cylinder regulation aeration harrow, adapts to different stone thickness aerations.
The side wall of the protective cover where the cooling area is located is fixed with a coil heat exchanger, so that the treated material is quickly cooled, and sulfur and arsenic oxides are prevented from entering air.
Exhaust fans are arranged at the tops of the protective covers of the oxidation zone, the high heat zone and the cooling zone, and are used for extracting steam containing sulfur and arsenic oxides generated in the process.
The invention has the beneficial effects that:
1. according to the method provided by the invention, potassium ferrate and a salt solution are mixed with a waste material to prepare a mixed wet material, the mixed wet material contains ions with higher concentration, trivalent arsenic is oxidized into pentavalent arsenic by the potassium ferrate, the toxicity of the arsenic is reduced, the divalent sulfur is converted into trivalent sulfur, and oxygen is introduced in an aeration mode, so that on one hand, the oxidation is promoted, on the other hand, pentavalent arsenic oxide and trivalent sulfur oxide are generated, the pentavalent arsenic oxide is easily soluble in water and can be removed along with steam heated by microwave, the trivalent sulfur oxide reacts with water to release heat and promote the oxidation, the trivalent sulfur oxide is easily soluble in water and can be removed along with the steam, thereby realizing desulfurization and dearsenification, and through experimental detection, the waste material with the sulfur content of 5.27 percent and the arsenic content of 18.58 percent has the arsenic removal rate of 96.0 percent and the sulfur removal rate of 96.9 percent, and realizing the effective separation of sulfur, arsenic and the material.
2. In the treatment process, arsenic is converted into pentavalent arsenic which has higher removal rate at the pH value of 5-10, and trivalent arsenic in the material has higher removal rate only at the pH value of 8-10, so that the pH value requirement in the post-treatment process is widened, and the subsequent treatment is facilitated.
3. The invention fully combines the advantages of the microwave heating effect and the traditional industrial treatment, provides simple microwave equipment which is suitable for the invention, has simple operation and is suitable for the industrial treatment of the sulfur-containing arsenic material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of a method for the microwave industrial treatment of sulfur-containing and arsenic-containing materials according to the invention;
fig. 2 is a schematic structural diagram of a microwave apparatus.
In the drawings, the components represented by the respective reference numerals are listed below:
11. a conveyor; 12. a storage bin; 13. a cylinder; 14. an exhaust fan; 15. a polar plate; 16. a material containing plate; 17. a cooling zone; 18. a high heat zone; 19. and an oxidation area.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the embodiment, industrial smoke dust, flue dust, copper arsenic filter cake, acid sludge or a mixed material of raw arsenic-containing ores is selected as a processing object, and the sulfur content and the arsenic content of the processing object are detected to be 5.27% and 18.58%, respectively.
Example 1
The embodiment of the present invention is to process the mixture as shown in fig. 1-2, and the specific process is as follows:
step S1: pretreatment of waste materials: adding 100kg of materials into a crusher for crushing, then adding the materials into a grinder for grinding, sieving the powder materials through a 40-mesh sieve, returning and grinding the materials on the sieve until the granularity of all the powder materials is less than 40 meshes, and preparing the powder materials;
step S2: mixing materials: adding the powder material prepared in the step S1 and 1.65kg of potassium ferrate into a stirrer, controlling the rotating speed to be 180r/min, stirring for 20min to prepare mixed powder, and simultaneously taking sodium chloride, sodium carbonate, ammonium chloride and sodium nitrate according to the mass ratio of 1.5: 1: 0.5:1.3, adding tap water, stirring and completely dissolving to prepare a salt solution, wherein the mass fraction of the salt solution is 1.0%, adding 10kg of the salt solution into the mixed powder under the stirring state, and continuously stirring for 10min to prepare a mixed wet material;
step S3: spreading materials: adding the mixed wet material into a bin 12 of microwave equipment, spreading the mixed wet material on a material containing plate 16 through a material spreading plate, setting the thickness of the spread material to be 1cm, and then conveying the spread material into the microwave equipment by a conveyor 11;
step S4: microwave oxidation: conveying the material containing plate 16 to an oxidation area 19, introducing 2L of oxygen into the mixed wet material by using the aeration rake, simultaneously controlling the output power and the microwave frequency of the microwave source, controlling the microwave heating temperature to be 80 ℃, controlling the conveying speed of the conveyor 11, and conveying the mixed wet material in the oxidation area 19 for 0.5 h;
step S5: microwave detoxification: the material containing plate 16 is conveyed to the high heat area 18, the output power and the microwave frequency of the microwave source are controlled at the same time, the microwave heating temperature is controlled to be 105 ℃, the conveying speed of the conveyor 11 is controlled, and the conveying time of the mixed wet material in the high heat area 18 is 0.5 h;
step S6: and (3) cooling: the material containing plate 16 is conveyed to the cooling area 17, cold air is blown into the cooling area 17 through the cooling device, the material subjected to microwave detoxification is cooled to 60 ℃, and the material is taken out for detection again.
Example 2
The embodiment of the present invention is to process the mixture as shown in fig. 1-2, and the specific process is as follows:
step S1: pretreatment of waste materials: adding 100kg of materials into a crusher for crushing, then adding the materials into a grinder for grinding, sieving the powder materials through a sieve with 150 meshes, returning and grinding the materials on the sieve until the granularity of all the powder materials is less than 150 meshes, and preparing the powder materials;
step S2: mixing materials: adding the powder material prepared in the step S1 and 1.95kg of potassium ferrate into a stirrer, controlling the rotating speed to be 180r/min, stirring for 20min to prepare mixed powder, and simultaneously taking sodium bicarbonate, sodium bisulfate, ammonium sulfate, potassium nitrate and ammonium nitrate according to the mass ratio of 1.1: 1.3: 0.7:0.9:0.6, adding tap water, stirring and completely dissolving to prepare a salt solution, wherein the mass fraction of the salt solution is 5.0%, adding 10kg of the salt solution into the mixed powder under the stirring state, and continuously stirring for 10min to prepare a mixed wet material;
step S3: spreading materials: adding the mixed wet material into a bin 12 of microwave equipment, spreading the mixed wet material on a material containing plate 16 through a material spreading plate, setting the thickness of the spread material to be 10cm, and then conveying the spread material into the microwave equipment by a conveyor 11;
step S4: microwave oxidation: the material containing plate 16 is conveyed to an oxidation area 19, 4L of oxygen is introduced into the mixed wet material by the aeration rake, the output power and the microwave frequency of the microwave source are controlled at the same time, the microwave heating temperature is controlled to be 90 ℃, the conveying speed of the conveyor 11 is controlled, and the conveying time of the mixed wet material in the oxidation area 19 is 1.5 hours;
step S5: microwave detoxification: the material containing plate 16 is conveyed to the high heat area 18, the output power and the microwave frequency of the microwave source are controlled at the same time, the microwave heating temperature is controlled to be 220 ℃, the conveying speed of the conveyor 11 is controlled, and the conveying time of the mixed wet material in the high heat area 18 is 4 hours;
step S6: and (3) cooling: the material containing plate 16 is conveyed to the cooling area 17, cold air is blown into the cooling area 17 through the cooling device, the material subjected to microwave detoxification is cooled to 60 ℃, and the material is taken out for detection again.
Example 3
The embodiment of the present invention is to process the mixture as shown in fig. 1-2, and the specific process is as follows:
step S1: pretreatment of waste materials: adding 100kg of materials into a crusher for crushing, then adding the materials into a grinder for grinding, sieving the powder materials through a 300-mesh sieve, returning and grinding the sieved materials until the particle size of all the powder materials is smaller than 300 meshes, and preparing the powder materials;
step S2: mixing materials: adding the powder material prepared in the step S1 and 2.25kg of potassium ferrate into a stirrer, controlling the rotating speed to be 180r/min, stirring for 20min to prepare mixed powder, and simultaneously taking sodium sulfate, sodium sulfite, ammonium nitrate and calcium nitrate according to the mass ratio of 0.2: 0.7: 1.1:0.9, adding tap water, stirring and completely dissolving to prepare a salt solution, wherein the mass fraction of the salt solution is 10.0%, adding 10kg of the salt solution into the mixed powder under the stirring state, and continuously stirring for 10min to prepare a mixed wet material;
step S3: spreading materials: adding the mixed wet material into a bin 12 of microwave equipment, spreading the mixed wet material on a material containing plate 16 through a material spreading plate, setting the thickness of the spread material to be 20cm, and then conveying the spread material into the microwave equipment by a conveyor 11;
step S4: microwave oxidation: conveying the material containing plate 16 to an oxidation area 19, introducing 5L of oxygen into the mixed wet material by using the aeration rake, simultaneously controlling the output power and the microwave frequency of the microwave source, controlling the microwave heating temperature to be 105 ℃, controlling the conveying speed of the conveyor 11, and conveying the mixed wet material in the oxidation area 19 for 3 hours;
step S5: microwave detoxification: the material containing plate 16 is conveyed to the high heat area 18, the output power and the microwave frequency of the microwave source are controlled at the same time, the microwave heating temperature is controlled to be 500 ℃, the conveying speed of the conveyor 11 is controlled, and the conveying time of the mixed wet material in the high heat area 18 is 7 hours;
step S6: and (3) cooling: the material containing plate 16 is conveyed to the cooling area 17, cold air is blown into the cooling area 17 through the cooling device, the material subjected to microwave detoxification is cooled to 60 ℃, and the material is taken out for detection again.
Specific assay data for examples 1-3 are shown in Table 1:
TABLE 1
Figure BDA0003207075200000081
As is clear from table 1, in example 2, the arsenic removal rate of the scrap having a sulfur content of 5.27% and an arsenic content of 18.58% was 96.0%, and the sulfur removal rate was 96.9%, which showed excellent desulfurization and dearsenification effects.
Example 4
The top of the oxidation zone 19, the high heat zone 18 and the cooling zone 17 in the embodiment 1-3 are all provided with exhaust fans 14, exhaust gases are respectively pumped to the sample 1 treatment liquid containing 10.0% of ferric trichloride and 5.5% of calcium hydroxide, the sample 2 treatment liquid containing 15.0% of ferric trichloride and 7% of calcium hydroxide, and the sample 3 treatment liquid containing 20.0% of ferric trichloride and 8% of calcium hydroxide, aeration is carried out, the arsenic and sulfur content in the detected gas all reach the national standard, and finally floc in the treatment liquid is removed by coagulation.
Example 5
Referring to fig. 2, in the treatment process of the mixed wet material, microwave equipment is adopted, the microwave equipment comprises a conveyor 11 and a protective cover arranged outside the conveyor 11, the protective cover is sequentially divided into an oxidation area 19, a high heat area 18 and a cooling area 17 through partition plates, and a plurality of material containing plates 16 are conveyed on the conveyor 11.
The upper side and the lower side of the oxidation zone 19 and the high heat zone 18 are both provided with polar plates 15, the polar plates 15 are distributed above and below the conveyor, one side of the protective cover, which is close to the oxidation zone 19 and is far away from the high heat zone 18, is provided with a stock bin 12, the top of one end of the protective cover, which is close to the stock bin 12, is provided with an air cylinder 13, the output end of the air cylinder 13 penetrates through the polar plate 15 fixedly connected with an aeration rake above the conveyor 11, the air inlet end of the aeration rake is communicated with an oxygen pipeline, the aeration height of the aeration rake is adjusted through the air cylinder 13, and the aeration rake is suitable for aeration with different paving thicknesses.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.

Claims (10)

1. A method for industrially treating arsenic-containing materials by microwaves is characterized by comprising the following steps:
step S1: pretreatment of waste materials: detecting the contents of sulfur and arsenic in the materials, crushing and grinding the materials to prepare powder materials;
step S2: mixing materials: uniformly stirring the powder material and potassium ferrate, adding a salt solution, and stirring to prepare a mixed wet material;
step S3: spreading materials: adding the mixed wet material into a storage bin (12) of microwave equipment, spreading the mixed wet material on a material containing plate (16) through a material spreading plate, and conveying the mixed wet material into the microwave equipment by a conveyor (11);
step S4: microwave oxidation: the material containing plate (16) is conveyed to an oxidation zone (19), oxygen is introduced into the mixed wet material by the aeration rake, and microwave heating is carried out at the same time;
step S5: microwave detoxification: the material containing plate (16) is conveyed to a high-heat area (18) and is heated by microwave again to remove oxides containing sulfur and arsenic;
step S6: and (3) cooling: the material containing plate (16) is conveyed to a cooling area (17), heat exchange and temperature reduction are carried out, and the temperature of the material after microwave detoxification is reduced to be lower than 60 ℃.
2. The method for the industrial microwave treatment of arsenic-containing materials as claimed in claim 1, wherein the top of the oxidation zone (19), the high heating zone (18) and the cooling zone (17) are provided with exhaust fans (14) to draw the tail gas to the treatment solution for sedimentation.
3. The method of claim 1, wherein in step S1, the particle size of the powder material is controlled to be 40-300 mesh.
4. The method of claim 1, wherein in step S2, the amount of potassium ferrate added is 1.1-1.5 times the total mass of sulfur and arsenic in the powdered material.
5. The method of claim 1, wherein in step S2, the salt solution is added in an amount of 10.0-20.0% by mass based on the mass of the powder material, and the salt solution is added in an amount of 1.0-10.0% by mass based on the mass of the powder material.
6. The method for microwave industrial treatment of arsenic-containing material as claimed in claim 1, wherein in step S3, the mixed wet material is spread in the material holding plate (16) to a thickness of 1-20 cm.
7. The method of claim 1, wherein the oxygen is added to the wet mixture in an amount of 2-5L/100kg in step S4.
8. The method according to claim 1, wherein the temperature of the microwave heating in the oxidation zone (19) is between 80 and 105 ℃ and the treatment time of the mixed wet material in the oxidation zone (19) is between 0.5 and 3 hours.
9. The method as claimed in claim 1, wherein the microwave heating temperature of the high heat zone (18) is 105 ℃ and 500 ℃, and the treatment time of the mixed wet material in the high heat zone (18) is 0.5-7 h.
10. The method of claim 2, wherein the treatment solution is a mixture of ferric chloride, calcium hydroxide and water, and the mass fraction of ferric chloride is 10.0-20.0%, and the mass fraction of calcium hydroxide is 5.5-8%.
CN202110919854.XA 2021-08-11 2021-08-11 Method for microwave industrial treatment of sulfur-containing and arsenic-containing material Pending CN113617801A (en)

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