CN107338272B - Resource treatment method of arsenic-containing waste residue - Google Patents
Resource treatment method of arsenic-containing waste residue Download PDFInfo
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- CN107338272B CN107338272B CN201710462628.7A CN201710462628A CN107338272B CN 107338272 B CN107338272 B CN 107338272B CN 201710462628 A CN201710462628 A CN 201710462628A CN 107338272 B CN107338272 B CN 107338272B
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- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 68
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000000855 fermentation Methods 0.000 claims abstract description 42
- 230000004151 fermentation Effects 0.000 claims abstract description 42
- COHDHYZHOPQOFD-UHFFFAOYSA-N arsenic pentoxide Chemical compound O=[As](=O)O[As](=O)=O COHDHYZHOPQOFD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000002386 leaching Methods 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000002244 precipitate Substances 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003546 flue gas Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 8
- 238000001694 spray drying Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 230000001954 sterilising effect Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 241000894006 Bacteria Species 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 8
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 abstract description 8
- 229940000488 arsenic acid Drugs 0.000 abstract description 8
- 229960004887 ferric hydroxide Drugs 0.000 abstract description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 abstract description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000084 colloidal system Substances 0.000 abstract description 3
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- -1 iron ions Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000005067 remediation Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000002689 soil Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 206010067125 Liver injury Diseases 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 231100000234 hepatic damage Toxicity 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000008818 liver damage Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000003680 myocardial damage Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
Abstract
The invention relates to a resource treatment method of arsenic-containing waste residues, belonging to the technical field of arsenic residue treatment. The invention mixes the arsenic-containing waste residue and the lichen for fermentation, the organic acid secreted by the lichen reacts with the arsenic in the waste residue to obtain the arsenic acid, then mixing with sodium bicarbonate, the bicarbonate can inhibit the adsorption of the waste residue on arsenic acid, centrifuging to obtain supernatant and precipitate, heating the precipitate to volatilize the volatile substance containing arsenic to obtain arsenic-containing flue gas, leaching the arsenic-containing flue gas, reacting the leachate and the supernatant with ferric chloride, etc., hydrolyzing iron ions to form ferric hydroxide colloid to adsorb arsenic in the solution to form flocculent precipitate, drying, wherein arsenic acid is dehydrated to form arsenic pentoxide, ferric hydroxide is dehydrated to obtain ferric oxide, the mixture of arsenic pentoxide and ferric oxide is dissolved to obtain arsenic pentoxide solution, spray drying is carried out, the arsenic pentoxide can be obtained, and the invention can effectively recycle the arsenic in the waste residue in the form of the arsenic pentoxide.
Description
Technical Field
The invention relates to a resource treatment method of arsenic-containing waste residues, belonging to the technical field of arsenic residue treatment.
Background
With the beginning of industrialization and modernization, the scale of industrial production is continuously enlarged, and the extensive application of arsenic and the disordered stacking disposal of arsenic-containing waste residues cause a great amount of arsenic pollution of soil. Currently, arsenic contamination has become a serious environmental problem. Arsenic pollution is mainly from mining or smelting process wastes of arsenic-containing ores and industrial waste residues of arsenic production enterprises. Arsenic pollution is wide in range, deep in pollution degree and serious in harm in China, arsenic pollution treatment becomes a current urgent priority for environmental treatment, and the treatment technology becomes one of the focus problems concerned in the field of environmental science. Arsenic in the arsenic-containing waste residue can be subjected to physical, chemical or biological conversion under certain conditions, and is harmful to the environment and human health through a food chain approach after being migrated and diffused to surface water, soil and underground water under the drive of environmental factors. Arsenic is used to produce arsenic (As)2O3) The important constituent components of the Chinese herbal medicine are extremely toxic. Arsenic can combine with sulfhydryl-containing enzyme in cell, inhibit cell oxidation process, paralyze blood vessel movement center, and make capillary vessel paralysis, dilation and permeability increase, and long-term exposure to arsenide can cause skin cancer and lung cancer, and severe cases can cause shock, liver damage, and even death from toxic myocardial damage.
Arsenic pollution abatement technology has become one of the key points of research in current environmental remediation technologies. Although the research on arsenic pollution treatment technology is more at home and abroad at present, the more successful commercialized operated practical technology is less. The currently studied soil leaching technology for soil pollution can effectively remove arsenic in arsenic slag, the remediation period is short, but leaching efficiency is continuously reduced along with leaching, the content of arsenic in waste residue after leaching still cannot meet the safety requirement, leaching treatment cost is high, and secondary pollution is easily caused by improper treatment of leaching solution. The phytoremediation technology can safely and effectively remove arsenic pollution in arsenic slag, the technology is mature and high in safety, the remediation cost is low, but the technology is low in remediation efficiency, and the long period of the technology hardly meets the engineering application requirements. Therefore, a new method for treating arsenic-containing waste residue safely and effectively is needed.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the defects that the leaching efficiency is continuously reduced when the arsenic in the arsenic slag is removed by the current leaching technology, the arsenic content in the leached waste slag still can not meet the safety requirement, and secondary pollution is easy to generate, the resource treatment method of the arsenic-containing waste slag is provided.
In order to solve the technical problems, the invention adopts the following technical scheme:
(1) ball-milling 3-5 kg of arsenic-containing waste residue and 1-2 kg of lichen to obtain a mixture, mixing sodium thiosulfate, the mixture and water in a fermentation tank to obtain a fermentation substrate, and adding 10-degree of concentration5cfu/mL of dissimilatory iron reduction bacterium suspension, hermetically fermenting for 12-15 days, after the fermentation is finished, sterilizing the fermentation product at high temperature to obtain a sterilized material, stirring and mixing the sterilized material and 40-50 g of sodium bicarbonate for 1-2 hours, and then performing centrifugal separation to obtain a precipitate and an upper layer liquid respectively;
(2) placing the precipitate in a rotary kiln, calcining for 5-6 h at 700-800 ℃, volatilizing volatile substances in a gaseous form, cooling, recycling by using a cloth bag to obtain arsenic-containing flue gas, and leaching the arsenic-containing flue gas by adding water to obtain a leaching solution;
(3) stirring and reacting the leachate, the supernatant, 1-2L of 25% ferric chloride solution in mass fraction and 100-120 mL of 25% hydrogen peroxide for 40-50 min, adding a pH regulator to regulate the pH to 4.5-4.8, continuously stirring and reacting for 60-90 min, filtering after the reaction is finished to obtain filter residue, placing the filter residue in a tubular furnace, keeping the temperature and heating at 160-180 ℃ for 6-7 h under the protection of nitrogen to obtain a product, mixing the product with 2-3L of water for 30-40 min, filtering to obtain a filtrate, and spray-drying the filtrate to obtain arsenic pentoxide.
The mass ratio of the sodium thiosulfate to the mixture to the water in the step (1) is 1:10: 50.
The adding amount of the dissimilatory iron reducing bacteria bacterial suspension in the step (1) is 8 percent of the mass of the fermentation substrate.
The fermentation temperature in the step (1) is 35-45 ℃.
The amount of the water used in the step (2) is 2-3L.
The temperature during leaching in the step (2) is 60-70 ℃, and the leaching time is 5-6 h.
The pH regulator in the step (3) is hydrochloric acid with the mass fraction of 15%.
Compared with other methods, the method has the beneficial technical effects that:
the invention firstly mixes arsenic-containing waste residue and lichen and then carries out fermentation, organic acid generated by secretion of lichen reacts with arsenic in the waste residue to obtain arsenic acid, then the arsenic acid is mixed with sodium bicarbonate which can promote dissolution of the arsenic acid to inhibit adsorption of the waste residue to the arsenic acid, then the upper liquid and the precipitate are obtained by centrifugal separation, the precipitate is heated to volatilize volatile substances containing arsenic in the precipitate to obtain arsenic-containing flue gas, the arsenic-containing flue gas is leached, the leaching solution is reacted with hydrogen peroxide and ferric chloride, under a certain pH value, ferric ions are hydrolyzed to form ferric hydroxide colloid, the colloid can adsorb the arsenic in the solution to form flocculent precipitate, then the flocculent precipitate is dried, wherein the arsenic acid can be dehydrated to form arsenic pentoxide, the ferric hydroxide is dehydrated to obtain ferric oxide, then the mixture of the arsenic pentoxide and the ferric oxide is mixed with water and then filtered to obtain arsenic pentoxide solution, and spray drying to obtain arsenic pentoxide, which can be effectively recovered in the form of arsenic pentoxide.
Detailed Description
Firstly weighing 3-5 kg of arsenic-containing waste residues and 1-2 kg of lichen, adding the arsenic-containing waste residues and 1-2 kg of lichen into a ball mill, carrying out ball milling for 40-50 min to obtain a mixture, adding sodium thiosulfate, the mixture and water into a fermentation tank according to the mass ratio of 1:10:50, stirring and mixing for 3-5 min to obtain a fermentation substrate, adding the fermentation substrate into the fermentation tank, wherein the concentration of 8% of the fermentation substrate is 105Sealing cfu/mL dissimilatory iron reducing bacteria suspension at 35-45 DEG CFermenting for 12-15 days, after fermentation, placing a fermentation product in a high-temperature sterilization box, performing high-temperature sterilization for 15-20 min at the temperature of 125-135 ℃ to obtain a sterilized material, adding 40-50 g of sodium bicarbonate into the sterilized material, stirring and mixing for 1-2 h, then pouring into a centrifuge, performing centrifugal separation for 10-15 min at the rotating speed of 4000-5000 r/min to respectively obtain a precipitate and an upper layer liquid, placing the precipitate in a rotary kiln, calcining for 5-6 h at the temperature of 700-800 ℃ to volatilize volatile matters in a gaseous state, then cooling, recovering by using a cloth bag to obtain arsenic-containing flue gas, leaching the arsenic-containing flue gas by adding 2-3L of water, controlling the leaching temperature to be 60-70 ℃ and the leaching time to be 5-6 h to obtain a leachate, mixing the leachate with the upper layer liquid to obtain a mixed solution, adding 1-2L of 25 mass percent ferric chloride solution and 100-120 mL of hydrogen peroxide into the mixed solution, stirring and reacting for 40-50 min, adding 15% hydrochloric acid by mass, adjusting the pH value to 4.5-4.8, continuing stirring and reacting for 60-90 min, after the reaction is finished, filtering the reaction product to obtain filter residue, placing the filter residue in a tubular furnace, introducing nitrogen into the tubular furnace, controlling the nitrogen introduction rate to be 10-15 mL/min, keeping the temperature and heating for 6-7 h at 160-180 ℃ under the protection of nitrogen, obtaining a product, adding the product into a beaker containing 2-3L of water, stirring and mixing for 30-40 min, filtering to obtain filtrate, and spray-drying to obtain a dried product, namely arsenic pentoxide.
Example 1
Firstly weighing 5kg of arsenic-containing waste residue and 2kg of lichen, adding the arsenic-containing waste residue and the lichen into a ball mill, carrying out ball milling for 50min to obtain a mixture, adding sodium thiosulfate, the mixture and water into a fermentation tank according to the mass ratio of 1:10:50, stirring and mixing for 5min to obtain a fermentation substrate, adding the fermentation substrate into the fermentation tank, wherein the concentration of 8% of the fermentation substrate is 105Sealing and fermenting cfu/mL dissimilatory iron reducing bacteria suspension at 45 ℃ for 15 days until fermentation is finished, placing a fermentation product in a high-temperature sterilization box, sterilizing at 135 ℃ for 20min to obtain a sterilized material, adding 50g of sodium bicarbonate into the sterilized material, stirring and mixing for 2h, pouring into a centrifuge, centrifugally separating at the rotating speed of 5000r/min for 15min to respectively obtain a precipitate and an upper layer liquid, placing the precipitate in a rotary kiln, calcining at 800 ℃ for 6 daysh, volatilizing volatile matters in a gaseous state, cooling, recovering by using a cloth bag to obtain arsenic-containing flue gas, adding 3L of water into the arsenic-containing flue gas to extract, controlling the leaching temperature to be 70 ℃ and the leaching time to be 6h to obtain a leaching solution, mixing the leaching solution with an upper layer solution to obtain a mixed solution, adding 2L of 25% ferric chloride solution and 120mL of 25% hydrogen peroxide solution by mass fraction into the mixed solution, stirring and reacting for 50min, adding 15% hydrochloric acid by mass fraction to adjust the pH to be 4.8, continuing stirring and reacting for 90min, filtering a reaction product after the reaction is finished to obtain filter residue, placing the filter residue into a tubular furnace, introducing nitrogen into the tubular furnace, controlling the nitrogen introduction rate to be 15mL/min, keeping the temperature and heating at 180 ℃ for 7h under the protection of the nitrogen to obtain a product, adding the product into a beaker containing 3L of water, stirring and mixing for 40min, filtering to obtain filtrate, and spray drying to obtain dried product, namely arsenic pentoxide.
Example 2
Firstly weighing 3kg of arsenic-containing waste residue and 1kg of lichen, adding the arsenic-containing waste residue and the lichen into a ball mill, carrying out ball milling for 40min to obtain a mixture, adding sodium thiosulfate, the mixture and water into a fermentation tank according to the mass ratio of 1:10:50, stirring and mixing for 3min to obtain a fermentation substrate, adding the fermentation substrate into the fermentation tank, wherein the concentration of 8% of the fermentation substrate is 105cfu/mL dissimilatory iron reducing bacteria suspension, hermetically fermenting for 12 days at 35 ℃, after fermentation is finished, putting a fermentation product into a high-temperature sterilization box, sterilizing at the high temperature of 125 ℃ for 15min to obtain a sterilized material, adding 40g of sodium bicarbonate into the sterilized material, stirring and mixing for 1h, pouring into a centrifuge, centrifugally separating at the rotating speed of 4000r/min for 10min to respectively obtain a precipitate and an upper layer liquid, putting the precipitate into a rotary kiln, calcining at 700 ℃ for 5h to volatilize volatile matters in a gaseous state, cooling, recycling by using a cloth bag to obtain arsenic-containing flue gas, adding 2L of water into the arsenic-containing flue gas to extract, controlling the extraction temperature to be 60 ℃, extracting for 5h to obtain an extract, mixing the extract with the upper layer liquid to obtain a mixed liquid, adding 1L of 25 mass percent ferric chloride solution and 100mL of 25 mass percent hydrogen peroxide into the mixed liquid, stirring for reaction for 40min, adding 15% hydrochloric acid to adjust pH to 4.5, and stirring for reaction for 60 minAnd min, after the reaction is finished, filtering a reaction product to obtain filter residue, placing the filter residue in a tubular furnace, introducing nitrogen into the tubular furnace, controlling the introduction rate of the nitrogen to be 10mL/min, keeping the temperature and heating at 160 ℃ for 6h under the protection of the nitrogen to obtain a product, adding the product into a beaker filled with 2L of water, stirring and mixing for 30min, filtering to obtain filtrate, and spray-drying to obtain a dried product, namely arsenic pentoxide.
Example 3
Firstly weighing 4kg of arsenic-containing waste residue and 1kg of lichen, adding the arsenic-containing waste residue and the lichen into a ball mill, ball-milling for 45min to obtain a mixture, adding sodium thiosulfate, the mixture and water into a fermentation tank according to the mass ratio of 1:10:50, stirring and mixing for 4min to obtain a fermentation substrate, adding the fermentation substrate into the fermentation tank, wherein the concentration of 8% of the fermentation substrate is 105cfu/mL dissimilatory iron reducing bacteria suspension, hermetically fermenting for 13 days at 40 ℃, after the fermentation is finished, putting a fermentation product into a high-temperature sterilization box, sterilizing at 130 ℃ for 17min to obtain a sterilized material, adding 45g of sodium bicarbonate into the sterilized material, stirring and mixing for 2h, pouring into a centrifuge, centrifugally separating at the rotating speed of 4500r/min for 12min to respectively obtain a precipitate and a supernatant, putting the precipitate into a rotary kiln, calcining at 750 ℃ for 6h to volatilize volatile matters in a gaseous state, cooling, recycling by using a cloth bag to obtain arsenic-containing flue gas, adding 2L of water into the arsenic-containing flue gas to extract, controlling the extraction temperature to be 65 ℃, extracting for 5h to obtain an extract, mixing the extract with the supernatant to obtain a mixed solution, adding 2L of 25 mass percent ferric chloride solution and 110mL of 25 mass percent hydrogen peroxide into the mixed solution, stirring and reacting for 45min, adding 15% hydrochloric acid by mass, adjusting the pH value to 4.7, continuously stirring and reacting for 80min, after the reaction is finished, filtering the reaction product to obtain filter residue, placing the filter residue in a tubular furnace, introducing nitrogen into the tubular furnace, controlling the introduction rate of the nitrogen to be 12mL/min, keeping the temperature and heating at 170 ℃ for 6h under the protection of the nitrogen to obtain a product, adding the product into a beaker filled with 2L of water, stirring and mixing for 35min, filtering to obtain filtrate, and spray-drying to obtain a dried substance, namely arsenic pentoxide.
Comparative example: and recovering arsenic-containing waste residues by adopting a leaching method.
The arsenic pentoxide recovered in examples 1 to 3 and the comparative example was measured, and the results are shown in table 1.
TABLE 1
As is clear from Table 1, the recovery rate and purity of arsenic in the recovery treatment technique of the present invention were high.
Claims (1)
1. A resource treatment method of arsenic-containing waste residue is characterized by comprising the following specific preparation steps:
(1) ball-milling 3-5 kg of arsenic-containing waste residue and 1-2 kg of lichen to obtain a mixture, mixing sodium thiosulfate, the mixture and water in a fermentation tank to obtain a fermentation substrate, and adding 10-degree of concentration5cfu/mL of dissimilatory iron reduction bacterium suspension, hermetically fermenting for 12-15 days, after the fermentation is finished, sterilizing the fermentation product at high temperature to obtain a sterilized material, stirring and mixing the sterilized material and 40-50 g of sodium bicarbonate for 1-2 hours, and then performing centrifugal separation to obtain a precipitate and an upper layer liquid respectively; the mass ratio of the sodium thiosulfate to the mixture to the water is 1:10: 50; the addition amount of the dissimilatory iron reducing bacteria suspension is 8 percent of the mass of the fermentation substrate; the fermentation temperature is 35-45 ℃;
(2) placing the precipitate in a rotary kiln, calcining for 5-6 h at 700-800 ℃, volatilizing volatile substances in a gaseous form, cooling, recycling by using a cloth bag to obtain arsenic-containing flue gas, and leaching the arsenic-containing flue gas by adding water to obtain a leaching solution; the temperature during leaching is 60-70 ℃, and the leaching time is 5-6 h; the amount of the water is 2-3L;
(3) stirring and reacting the leachate, the supernatant, 1-2L of 25% ferric chloride solution and 100-120 mL of 25% hydrogen peroxide for 40-50 min, and then adding a pH regulator to regulate the pH to 4.5-4.8, wherein the pH regulator is hydrochloric acid with the mass fraction of 15%; and continuously stirring and reacting for 60-90 min, filtering after the reaction is finished to obtain filter residue, placing the filter residue in a tubular furnace, keeping the temperature and heating at 160-180 ℃ for 6-7 h under the protection of nitrogen to obtain a product, mixing the product with 2-3L of water for 30-40 min, filtering to obtain a filtrate, and spray-drying the filtrate to obtain the arsenic pentoxide.
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| GB372189A (en) * | 1930-09-09 | 1932-05-05 | Norddeutsche Affinerie | Process for the recovery of arsenic from arseniferous metallurgical intermediate products and by-products |
| CN101954370B (en) * | 2010-09-06 | 2012-12-05 | 同济大学 | Method for recycling arsenic-containing waste residues |
| CN102139919B (en) * | 2011-02-21 | 2012-09-05 | 湖南辰州矿业股份有限公司 | Method for reducing arsenic and lead in production of antimonous oxide by wet process |
| CN105540973B (en) * | 2015-12-28 | 2017-12-15 | 中南大学 | High arsenic acid water purification and the method recycled |
| CN106834707B (en) * | 2016-12-21 | 2019-03-26 | 中南大学 | A kind of method that arsenic-containing material synthetical recovery and arsenic resource utilize |
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