CN106512279A - Harmless remediation method and device of electrolytic aluminum waste slag and contaminated soil of electrolytic aluminum waste slag - Google Patents
Harmless remediation method and device of electrolytic aluminum waste slag and contaminated soil of electrolytic aluminum waste slag Download PDFInfo
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- CN106512279A CN106512279A CN201610961603.7A CN201610961603A CN106512279A CN 106512279 A CN106512279 A CN 106512279A CN 201610961603 A CN201610961603 A CN 201610961603A CN 106512279 A CN106512279 A CN 106512279A
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- cyanide
- electrolytic aluminum
- ions
- aluminum waste
- fluoride
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 82
- 239000002699 waste material Substances 0.000 title claims abstract description 78
- 239000002689 soil Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002893 slag Substances 0.000 title claims abstract description 15
- 238000005067 remediation Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 103
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 88
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- -1 fluoride ions Chemical class 0.000 claims description 56
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 50
- 239000007844 bleaching agent Substances 0.000 claims description 45
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 22
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 22
- 239000004571 lime Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011449 brick Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910001610 cryolite Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 7
- 239000002516 radical scavenger Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 3
- 230000007246 mechanism Effects 0.000 claims description 2
- 239000011369 resultant mixture Substances 0.000 claims description 2
- 239000012254 powdered material Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000011109 contamination Methods 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 description 26
- 239000011737 fluorine Substances 0.000 description 26
- 238000002798 spectrophotometry method Methods 0.000 description 10
- 238000001784 detoxification Methods 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 230000001988 toxicity Effects 0.000 description 6
- 231100000419 toxicity Toxicity 0.000 description 6
- GABPOXQOEKZELW-UHFFFAOYSA-N OC(=O)C1=CC=NC=C1.O=C1CC(=O)NC(=O)N1 Chemical compound OC(=O)C1=CC=NC=C1.O=C1CC(=O)NC(=O)N1 GABPOXQOEKZELW-UHFFFAOYSA-N 0.000 description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000007781 pre-processing Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005375 photometry Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000012257 stirred material Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- ISXLKWQYNMXUMH-UHFFFAOYSA-N 1,3-diazinane-2,4,6-trione;pyridine Chemical compound C1=CC=NC=C1.O=C1CC(=O)NC(=O)N1 ISXLKWQYNMXUMH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- AEZLFMQGYJFBAU-UHFFFAOYSA-N pyrazol-3-one;pyridine-4-carboxylic acid Chemical compound O=C1C=CN=N1.OC(=O)C1=CC=NC=C1 AEZLFMQGYJFBAU-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- VGBPIHVLVSGJGR-UHFFFAOYSA-N thorium(4+);tetranitrate Chemical compound [Th+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VGBPIHVLVSGJGR-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/45—Inorganic substances containing nitrogen or phosphorus
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/49—Inorganic substances containing halogen
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/10—Apparatus specially adapted for treating harmful chemical agents; Details thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the field of environment protection, and relates to a soil remediation technology and device, in particular to a harmless remediation treatment technology and device of electrolytic aluminum waste slag and contaminated soil of the electrolytic aluminum waste slag. According to a harmless treatment method of the electrolytic aluminum waste slag and the contaminated soil of the electrolytic aluminum waste slag, cyanide, soluble fluoride and other harmful substances can be removed simply, economically and efficiently, and green harmless treatment of the electrolytic aluminum waste slag and contamination therefore is achieved. According to the harmless treatment device of the electrolytic aluminum waste slag and the contaminated soil of the electrolytic aluminum waste slag, a rotary stirring tank is used as a stirring system for the first time to carry out harmless treatment of the electrolytic aluminum waste slag and the contaminated soil thereof, the walking speed of materials is adjusted by adjusting the tilt angle of the rotary stirring tank, and therefore the mixing effect is adjusted, the design length of the rotary stirring tank is reduced, the device is simple, and the equipment manufacturing cost is greatly reduced.
Description
Technical Field
The invention belongs to the field of environmental protection, relates to a soil remediation technology and a device, and particularly relates to a harmless remediation treatment technology and a device for electrolytic aluminum waste residues and polluted soil thereof.
Background
The main solid waste of the electrolytic aluminum plant is waste residue generated during the overhaul of the electrolytic cell, which is generally called overhaul waste residue. Before the book of national hazardous waste, new at 2016, 8, 1, was officially implemented, most of these wastes were directly landfilled as general industrial solid wastes. Under the normal condition, an electrolytic aluminum plant producing 40 ten thousand tons every year produces about 1.2 ten thousand tons of waste residues every year, the electrolytic aluminum yield in China is thousands of tons every year, the electrolytic aluminum yield is increased year by year at a speed of about 10 percent every year, millions of tons of electrolytic aluminum waste residues are newly added every year, and the existing electrolytic aluminum waste residues are accumulated and piled up, so that a large amount of land is occupied, and soluble fluoride and cyanide contained in the electrolytic aluminum waste residues flow into rivers along with rainwater and permeate into underground polluted soil, underground water and surface water, thereby causing great harm to the surrounding ecological environment, human health and growth of animals and plants.
In the south, because of the large amount of rainwater, common electrolytic aluminum enterprises perform certain anti-seepage treatment on landfill sites, but the treatment of a large amount of rainwater percolate costs a lot every year, and causes difficulty for government supervision. And the situation that the medium exposes electrolytic aluminum waste residue landfill site which is not well managed brings great harm to the life and property safety of local people emerges endlessly. In northern arid areas, because of the cost problem, many electrolytic aluminum enterprises do not consider the seepage prevention problem, and directly dump the waste residues on the open land without any protective measures. In arid northern areas, the electrolytic aluminum maintenance waste residue field buried according to common industrial solid wastes can become a dangerous source for tens of thousands of years and has the risk of spreading and transferring the dangerous source along with wind and sand (particularly sand storm). It can be said that each slag yard is a continuous source of danger that can bring a huge environmental disaster to local people at any time. Therefore, the development of environment-friendly harmless treatment technology for the electrolytic aluminum waste residues and the polluted soil has important industrial development significance.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a novel method for harmlessly treating electrolytic aluminum waste residues and soil contaminated by the same. The method provided by the invention can simply, economically and efficiently eliminate harmful substances such as cyanide, soluble fluoride and the like, and realize green and harmless treatment of the electrolytic aluminum waste residue and pollution thereof.
The invention also aims to provide a harmless treatment device for the electrolytic aluminum waste residues and the polluted soil thereof. The device uses the rotary stirring tank as a stirring system to carry out harmless treatment on the electrolytic aluminum waste residues and the polluted soil for the first time, and the walking speed of the material is adjusted by adjusting the inclination angle of the rotary stirring tank, so that the mixing effect is adjusted, the design length of the rotary stirring tank is shortened, the device is simple, and the manufacturing cost of the equipment is greatly reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
a harmless restoration method for electrolytic aluminum waste residues and polluted soil thereof comprises the following steps:
(1) crushing: crushing the electrolytic aluminum waste residue into powdery material with the particle size not more than 10 mm;
(2) and (3) harmless treatment: mixing and stirring the powdery material obtained in the step (1), cyanide, a soluble fluoride remover and water;
wherein,
the water is added into the water solution in an amount that the water content of the final mixture obtained by mixing and stirring is 15-18%,
the addition amount of the cyanide and soluble fluoride remover is that cyanide ions and fluoride ions in the electrolytic aluminum waste residue or the polluted soil thereof can be completely removed.
According to the invention, the particle size of the powdery material in the step (1) is 0.01-10mm, and preferably, the particle size of the powdery material in the step (1) is 5-10 mm.
The inventor of the invention finds that when the particle size of the powdery material is larger than 10mm, cyanide and soluble fluoride remover aqueous solution can not infiltrate the interior of the material particles, and the detoxification effect is poor, and experiments show that when the particle size of the powdery material is larger than 10mm, even if the inclination of the tank body of the stirring tank is controlled to be close to 0 degrees, the traveling speed of the material is the slowest, the residue of cyanide ions and fluoride ions in the treated material after 2h reaction is about 100mg/kg, and the residue of fluoride ions is about 200mg/kg, and the detoxification can not be thorough; when the particle size of the powder is not more than 10mm, the cyanide and soluble fluoride remover aqueous solution can completely infiltrate the interior of the material particles, the detoxification effect is good, the cyanide ion residue is not more than 0.05mg/kg, and the fluorine ion residue is not more than 1 mg/kg. If the particle size of the powdery material is further reduced, if the particle size is less than 0.01mm, the detoxification effect is good, but the crushing energy consumption is greatly increased, and the treatment cost is greatly improved.
According to the invention, the electrolytic aluminum waste residue in the step (1) can be pretreated before being crushed, and the pretreatment refers to that the electrolytic aluminum waste residue is firstly subjected to coarse crushing treatment. Preferably, the pretreatment is to sort the electrolytic aluminum waste residues to recover valuable waste materials, and then to perform coarse crushing treatment.
According to the invention, the electrolytic aluminum waste residue in the step (1) can be crushed after being sorted before being crushed to recover valuable waste.
The coarse crushing treatment refers to that large materials are manually or mechanically crushed to enter a hopper of a crushing system, so that the loss of instruments of the crushing system is reduced, and the crushing efficiency is improved. The coarse crushing treatment can be manual or mechanical coarse crushing, such as coarse crushing pretreatment by using a manual impact hammer or a wheel type mechanical impact hammer to enter a hopper of a crushing system.
The sorting and recycling of valuable waste materials comprises sorting and recycling of anode and cathode carbon blocks, iron blocks, aluminum blocks, sintered cryolite blocks, silicon carbide refractory bricks and other materials, so that the environmental pollution is reduced, and the waste recycling is realized, and the economic value is increased.
According to the invention, in step (2), cyanide and soluble fluoride remover can be dissolved in water and then mixed with the powdery material in step (1).
According to the present invention, the amount of water added to the aqueous solution of a cyanide/soluble fluoride-eliminating agent in the step (2) is such that the water content of the resultant mixture is 15 to 18%.
The present inventors found that when the water content of the final mixture obtained by stirring is higher than 18%, the stirring resistance is large, and even if the mixture adheres to the wall of the tank and is not stirred, the mixture cannot be sufficiently mixed; when the water content of the final mixture obtained by mixing and stirring is lower than 15%, the wetting effect of the material particles is poor, and when the water content of the final mixture obtained by mixing and stirring is 15-18%, particularly when the water content is 16-17%, the wetting effect of the material particles is good, and the stirring resistance is appropriate.
According to the invention, the cyanide and soluble fluoride scavenger of step (2) is selected from bleaching powder or a mixture of bleaching powder and lime. Preferably, the cyanide, soluble fluoride scavenger is bleach.
According to the invention, the cyanide and soluble fluoride remover in the step (2) is preferably used in an amount of the highest limit capable of completely removing cyanide ions and fluoride ions in the electrolytic aluminum waste residue or the soil polluted by the electrolytic aluminum waste residue.
The cyanide and soluble fluoride remover are used for harmless treatment of electrolytic aluminum waste residues and polluted soil thereof according to the following principle:
the cyanide detoxification chemical reaction formula is:
4NaCN+5Ca(ClO)2+4H2O——2N2↑+2Ca(HCO3)2+3CaCl2+4NaCl
2CN-+5ClO-+2H2O——N2↑+2HCO3 -+5Cl-
the chemical reaction formula of the soluble fluoride ion detoxification is as follows:
2F-+Ca2+——CaF2↓
theoretically, 104g of cyanide ion (CN) should be removed-) The toxicity of (2) requires 715g of calcium hypochlorite, i.e. 1g of cyanide ion (CN)-) 6.875g of calcium hypochlorite is required for toxicity of (2). If the content of calcium hypochlorite is about 56.6% calculated on commercial bleaching powder with a high available chlorine content of 28%, 1g of cyanide ions (CN)-) The toxicity of bleaching powder, 12.14g is required; or 1g of bleaching powder can remove 0.082g of cyanide ions (CN)-) Toxicity of (2).
The bleaching powder is cheap and easy to obtain, and has little influence on the environment, so the total calcium content in the bleaching powder is calculated by adopting a conservative estimation method. Bleaching powders are relatively complex in composition and include calcium hypochlorite (Ca (ClO))2) Calcium chloride (CaCl)2) Calcium hydroxide (Ca (OH)2) Etc., wherein calcium hypochlorite (Ca (ClO))2) Calcium content of 27.87%, calcium chloride (CaCl)2) Calcium content 36.04%, calcium hydroxide (Ca (OH)2) Contains 54.05% of calcium. Thus, 1g of fluoride ion was removedSon (F)-) The maximum consumption of bleaching powder was 3.78g, estimated by conservative estimates of calcium hypochlorite, i.e. 1g of bleaching powder removed 0.265g of fluoride ions (F)-) Toxicity of (2).
Namely, each gram of bleaching powder with the high performance price ratio and the effective chlorine content of 28 percent can simultaneously remove 0.082g of cyanide ions (CN)-) And 0.265g of fluoride ion (F)-) Toxicity of (2).
When calculating the dosage principle of bleaching powder, the dosage of bleaching powder is added to simultaneously remove cyanide ions (CN)-) And fluorine ion (F)-) The maximum amount of bleaching powder is the principle, namely the dosage of bleaching powder can be further enlarged to 120-150% on the basis of the maximum theoretical dosage. Namely, when the mass ratio of cyanide ions to fluorine ions in the electrolytic aluminum waste residues or the polluted soil thereof is not less than 1:3.2, the using amount of the cyanide and soluble fluoride remover in the step (2) is added according to the proportion of removing 0.082g of cyanide ions by 1g-1.5g of bleaching powder, and when the mass ratio of cyanide ions to fluorine ions in the electrolytic aluminum waste residues or the polluted soil thereof is less than 1:3.2, the using amount of the cyanide and soluble fluoride remover in the step (2) is added according to the proportion of removing 0.265g of fluorine ions by 1g-1.5g of bleaching powder. Of course, when the mass ratio of cyanide ions to fluorine ions in the electrolytic aluminum waste residues or the polluted soil thereof is less than 1:3.2, the cyanide and soluble fluoride remover in the step (2) is added according to the ratio of removing cyanide ions of 0.082g by using bleaching powder of 1g-1.5g, and simultaneously, the surplus fluorine ions can be removed by using lime with lower price (the chemical reaction formula is Ca (OH))2+2NaF——CaF2↓ +2NaOH), adding lime according to the proportion of 1g lime for curing 0.51g fluoride ion, and curing the excessive fluoride ion.
Preferably, when the mass ratio of cyanide ions to fluorine ions in the electrolytic aluminum waste residues or the polluted soil thereof is not less than 1:3.2, the using amount of the cyanide and soluble fluoride remover in the step (2) is added according to the ratio of 1.2g to 1.5g of bleaching powder to remove 0.082g of cyanide ions, and when the mass ratio of cyanide ions to fluorine ions in the electrolytic aluminum waste residues or the polluted soil thereof is less than 1:3.2, the using amount of the cyanide and soluble fluoride remover in the step (2) is added according to the ratio of 1.2g to 1.5g of bleaching powder to remove 0.265g of fluorine ions. Of course, when the mass ratio of cyanide ions to fluoride ions in the electrolytic aluminum waste residues or the polluted soil thereof is less than 1:3.2, the cyanide and soluble fluoride remover in the step (2) is added according to the ratio of 1.2g-1.5g of bleaching powder to remove 0.082g of cyanide ions, and simultaneously, the lime with lower price can be considered to remove the redundant fluoride ions, for example, the lime is added according to the ratio of 1g of lime to solidify 0.51g of fluoride ions to solidify the redundant fluoride ions.
According to the present invention, the amount of water added to the aqueous solution of a cyanide, soluble fluoride scavenger in step (2) is calculated by: and (4) subtracting the water content obtained by testing the raw material from the final water content of the mixed material of 15-18% to calculate the required water addition amount.
The test method of cyanide ions in the electrolytic aluminum waste residues or the polluted soil thereof comprises an isonicotinic acid pyrazolone photometry, a pyridine barbituric acid photometry, an electrode method and the like. Preferably, the test method of cyanide ions in the electrolytic aluminum waste residues or the polluted soil thereof is an isonicotinic acid barbituric acid spectrophotometry.
The method for testing the fluoride ions in the electrolytic aluminum waste residues or the polluted soil thereof comprises a fluoride ion selective electrode method, a fluorine reagent colorimetric method, an alizarin zirconium sulfonate colorimetric method, a thorium nitrate titration method and the like. Preferably, the test of the fluoride ions in the electrolytic aluminum waste residues or the polluted soil thereof adopts the national standard of determination of water quality fluoride-fluorine reagent spectrophotometry (GB/T7483-1987).
According to the invention, the mixing and stirring in the step (2) are preferably carried out so that the water content of the mixture obtained by mixing and stirring is 15-18%, and the simplest detection method is that the mixture is agglomerated by hand and is immediately crumbled by touch.
In some specific embodiments, the invention provides a harmless remediation method for electrolytic aluminum waste residues and polluted soil thereof, comprising the following steps:
(1) crushing: crushing the electrolytic aluminum waste residue into powdery material with the particle size not more than 10 mm;
(2) and (3) detection: detecting the content and the water content of cyanide ions and fluoride ions in the powdery material;
(3) and (3) harmless treatment: and (2) calculating the using amount and water consumption of the cyanide and the soluble fluoride remover and the ratio of the medicament to the water consumption, mixing and stirring the powdery material obtained in the step (1) with the cyanide, the soluble fluoride remover and water, wherein the water consumption is 15-18% of the water content of the finally mixed and stirred material, and subtracting the water content of the raw material.
Preferably, the cyanide and soluble fluoride removing agent are dissolved in water according to the calculated proportion and then mixed and stirred with the powdery material in the step (1).
In other specific embodiments, the present invention provides a method for harmlessly restoring electrolytic aluminum waste residues and contaminated soil thereof, comprising the following steps:
(1) coarse crushing: performing manual or mechanical coarse crushing treatment on the large materials, wherein the coarse crushing treatment can be manual or mechanical coarse crushing, for example, performing coarse crushing by using a manual impact hammer or a wheel type mechanical impact hammer until the large materials can enter a charging opening of a crushing system;
(2) crushing: crushing the electrolytic aluminum waste residue into powdery material with the particle size not more than 10 mm;
(3) and (3) detection: detecting the content and the water content of cyanide ions and fluoride ions in the powdery material;
(4) and (3) harmless treatment: and (3) calculating the using amount and water consumption of the cyanide and the soluble fluoride remover, uniformly mixing the cyanide and the soluble fluoride remover with water, and then mixing and stirring the mixture with the powdery material in the step (2).
In other specific embodiments, the present invention provides a method for harmlessly restoring electrolytic aluminum waste residues and contaminated soil thereof, comprising the following steps:
(1) sorting and recycling: sorting and recovering anode and cathode carbon blocks, iron blocks, aluminum blocks, sintered cryolite blocks, silicon carbide refractory bricks and other materials in the electrolytic aluminum waste slag;
(2) coarse crushing: carrying out manual or mechanical coarse crushing treatment on the sorted and recovered electrolytic aluminum waste residues and large materials in the polluted soil of the electrolytic aluminum waste residues, wherein the manual or mechanical coarse crushing treatment can be manual or mechanical coarse crushing, for example, the coarse crushing treatment is carried out by applying a manual impact hammer or a wheel type mechanical impact hammer, and the crushed materials can enter a charging opening of a crushing system;
(3) crushing: crushing the electrolytic aluminum waste residue into powdery material with the particle size not more than 10 mm;
(4) and (3) detection: detecting the content and the water content of cyanide ions and fluoride ions in the powdery material;
(5) and (3) harmless treatment: and (3) calculating the using amount and water consumption of the cyanide and the soluble fluoride remover, uniformly mixing the cyanide and the soluble fluoride remover with water according to a proportion, and then mixing and stirring the mixture with the powdery material in the step (2).
The invention also provides a harmless treatment device for the electrolytic aluminum waste residues and the polluted soil thereof, which comprises a material crushing system ⑩, a material conveyor belt, a rotary tank stirrer and a dosing tankThe four parts are formed, the material feeding belt machine of the material conveying beltOne end of the rotary tank mixer is connected with a discharge hole of the crushing system, and the other end of the rotary tank mixer is connected with a feeding hopper of the rotary tank mixerConnected with each other and a dosing boxFeeding hole of rotary tank stirrerAre connected.
Crushing system (r) be the broken system of portable two-stage type that jaw breaker and impact crusher constitute, this kind of broken system has great advantage than single-section type, syllogic in operating efficiency and running cost.
The material conveying belt is provided with a self-propelled mechanism capable of being lowered without powerCan make the conveying system better communicate with the discharge port and the feeding hopper of the crushing systemThe feed ports are well connected.
The material conveying belt can be divided into a plurality of sections, so that materials can be conveyed to different directions conveniently, and inclination change of different conveying belts can be adapted.
The rotary tank stirrer can be driven by a driving mechanismThe drive is arranged on the driven supporting seatUpward angle adjusting deviceAdjusting rotary stirring tank bodyThereby adjusting the tank body of the rotary stirring tankThe materials in the container travel at a speed to achieve the degree of uniform mixing, i.e. the materials are conglobated by holding with hands and are crumbled by touching.
The harmless treatment device for the electrolytic aluminum waste residues and the polluted soil thereof provided by the invention is simple and convenient to operate, realizes uninterrupted continuous operation, has large treatment capacity, small equipment investment and low operation cost, can completely realize no pollution residue of the treated soil, and has remarkable economic benefit and social benefit.
The harmless treatment device for the electrolytic aluminum waste residues and the polluted soil thereof provided by the invention can also be used for repairing other large-scale soil adopting solidification and detoxification.
Drawings
FIG. 1 is a schematic view of a harmless treatment apparatus for electrolytic aluminum waste residues and soil polluted by the same according to the present invention.
Detailed Description
The present invention is described below with reference to specific embodiments, and it should be noted that, for those skilled in the art, variations or modifications can be made without departing from the principle of the present invention, and the present invention should also be considered as falling within the protection scope of the present invention.
Example 1 method for harmlessly repairing electrolytic aluminum waste residues and polluted soil thereof
Step 1: sorting out easily-identified massive materials with recycling value, including anode and cathode carbon blocks, iron blocks, aluminum blocks, sintered cryolite blocks with dissolved alumina, silicon carbide and silicon nitride refractory bricks and the like;
step 2: the method comprises the following steps of (1) crushing and preprocessing large materials which cannot directly enter a hopper of a crushing system into small materials which can enter the crushing system by using a manual impact hammer or a wheel type mechanical impact hammer;
and step 3: conveying the coarsely crushed material obtained in the step 2 into a crushing system by using a conveyor belt for crushing, wherein the crushed particle size is less than or equal to 10 mm;
and 4, step 4: uniformly and multipoint sampling a crude sample, grinding, intercepting a test sample by a multi-time round cake quartering method, weighing 100g, adding 100ml of water, stirring, filtering, and taking filtrate for analysis; detecting the content of cyanide ions to be 0.216g/kg by adopting an isonicotinic acid barbituric acid spectrophotometry; detecting the content of the fluorine ions to be 12g/kg by adopting a national standard of determination of water quality fluoride-fluorine reagent spectrophotometry (GB/T7483-1987);
taking another 100g of sample, drying and dehydrating at 105 ℃, and determining the water content of the material to be 5.5%;
and 5: as the mass ratio of cyanide ions to fluorine ions is less than 3.2, bleaching powder is added according to the proportion that 1.2g of bleaching powder is solidified and 0.265g of fluorine ions is solidified, namely 54kg of industrial-grade bleaching powder with 28 percent of effective chlorine content and 125kg of water are added to treat 1 ton of materials, the agents are fully and uniformly mixed with the materials after being added with water and blended, and the materials are preferably held by a discharging hand to be agglomerated and then are crushed by one touch.
After the materials are treated for 2 hours, the content of cyanide ions and the content of fluorine ions in the mixed and stirred materials are detected to be 0.04mg/kg and 0.82 mg/kg.
Example 2 harmless remediation method for electrolytic aluminum waste residues and polluted soil thereof
Step 1: sorting out easily-identified massive materials with recycling value, including anode and cathode carbon blocks, iron blocks, aluminum blocks, sintered cryolite blocks with dissolved alumina, silicon carbide and silicon nitride refractory bricks and the like;
step 2: the method comprises the following steps of (1) crushing and preprocessing large materials which cannot directly enter a hopper of a crushing system into small materials which can enter the crushing system by using a manual impact hammer or a wheel type mechanical impact hammer;
and step 3: conveying the coarsely crushed material obtained in the step 2 into a crushing system by using a conveyor belt for crushing, wherein the crushed particle size is less than or equal to 10 mm;
and 4, step 4: uniformly and multipoint sampling a crude sample, grinding, intercepting a test sample by a multi-time round cake quartering method, weighing 100g, adding 100ml of water, stirring, filtering, and taking filtrate for analysis; detecting the content of cyanide ions to be 0.216g/kg by adopting an isonicotinic acid barbituric acid spectrophotometry; detecting the content of the fluorine ions to be 12g/kg by adopting a national standard of determination of water quality fluoride-fluorine reagent spectrophotometry (GB/T7483-1987);
taking another 100g of sample, drying and dehydrating at 105 ℃, and determining the water content of the material to be 5.5%;
and 5: because the mass ratio of cyanide ions to fluoride ions in the material is far less than 3.2, the adding amount of bleaching powder is calculated according to the ratio of 0.082g of cyanide ions solidified by 1.2g of bleaching powder, namely 3.16kg of industrial-grade bleaching powder with the effective chlorine content of 28 percent is added for treating 1 ton of material; 105 kg of water and 125kg of water are required for treating one ton of materials; 0.7kg of fluoride ions can be removed after 3.16kg of bleaching powder is used in 1 ton of materials, the rest 11.3kg of fluoride ions are eliminated by adding lime, and 29.5kg of lime with the purity of 90 percent is added to 11.3kg of fluoride ions according to the calculation of treating 0.51g of fluoride ions by 1.2g of lime.
Step 6: 3.16kg of industrial bleaching powder with the effective chlorine content of 28 percent, 29.5kg of industrial lime with the calcium hydroxide content of 90 percent and 125kg of water are added into 1 ton of materials to be treated, the medicament and the water are uniformly stirred, the medicament and the materials are fully and uniformly mixed, and the materials are preferably kneaded by a discharging hand and are crushed by one touch.
After the materials are treated for 2 hours, the content of cyanide ions and the content of fluorine ions in the materials obtained by mixing and stirring are detected to be 0.048mg/kg and 0.95mg/kg respectively.
Example 3 harmless remediation method of electrolytic aluminum waste residues and polluted soil thereof
Step 1: sorting out easily-identified massive materials with recycling value, including anode and cathode carbon blocks, iron blocks, aluminum blocks, sintered cryolite blocks with dissolved alumina, silicon carbide and silicon nitride refractory bricks and the like;
step 2: the method comprises the following steps of (1) crushing and preprocessing large materials which cannot directly enter a hopper of a crushing system into small materials which can enter the crushing system by using a manual impact hammer or a wheel type mechanical impact hammer;
and step 3: conveying the coarsely crushed material obtained in the step 2 into a crushing system by using a conveyor belt for crushing, wherein the crushed particle size is less than or equal to 10 mm;
and 4, step 4: uniformly and multipoint sampling a crude sample, grinding, intercepting a test sample by a multi-time round cake quartering method, weighing 100g, adding 100ml of water, stirring, filtering, and taking filtrate for analysis; detecting the content of cyanide ions to be 0.216g/kg by adopting an isonicotinic acid barbituric acid spectrophotometry; detecting the content of the fluorine ions to be 12g/kg by adopting a national standard of determination of water quality fluoride-fluorine reagent spectrophotometry (GB/T7483-1987);
taking another 100g of sample, drying and dehydrating at 105 ℃, and determining the water content of the material to be 5.5%;
and 5: as the mass ratio of cyanide ions to fluorine ions is less than 3.2, bleaching powder is added according to the proportion that 1.5g of bleaching powder is solidified and 0.265g of fluorine ions is solidified, namely 68kg of industrial-grade bleaching powder with 28 percent of effective chlorine content is required to be added for treating 1 ton of materials, 105 kg of water is added, the agent is fully and uniformly mixed with the materials after being added with water and blended, and the agent is preferably kneaded by a discharging hand and then is crushed by one touch.
After the materials are treated for 2 hours, the content of cyanide ions and the content of fluorine ions in the materials obtained by mixing and stirring are detected to be 0.038mg/kg and 0.8 mg/kg.
Example 4 harmless remediation method for electrolytic aluminum waste residues and polluted soil thereof
Step 1: sorting out easily-identified massive materials with recycling value, including anode and cathode carbon blocks, iron blocks, aluminum blocks, sintered cryolite blocks with dissolved alumina, silicon carbide and silicon nitride refractory bricks and the like;
step 2: the method comprises the following steps of (1) crushing and preprocessing large materials which cannot directly enter a hopper of a crushing system into small materials which can enter the crushing system by using a manual impact hammer or a wheel type mechanical impact hammer;
and step 3: conveying the coarsely crushed material obtained in the step 2 into a crushing system by using a conveyor belt for crushing, wherein the crushed particle size is less than or equal to 10 mm;
and 4, step 4: uniformly and multipoint sampling a crude sample, grinding, intercepting a test sample by a multi-time round cake quartering method, weighing 100g, adding 100ml of water, stirring, filtering, and taking filtrate for analysis; detecting the content of cyanide ions to be 0.216g/kg by adopting an isonicotinic acid barbituric acid spectrophotometry; detecting the content of the fluorine ions to be 12g/kg by adopting a national standard of determination of water quality fluoride-fluorine reagent spectrophotometry (GB/T7483-1987);
taking another 100g of sample, drying and dehydrating at 105 ℃, and determining the water content of the material to be 5.5%;
and 5: as the mass ratio of cyanide ions to fluoride ions in the material is far less than 3.2, the adding amount of bleaching powder is calculated according to the proportion of 0.082g of cyanide ions solidified by 1.5g of bleaching powder, namely 3.95kg of industrial-grade bleaching powder with 28 percent of effective chlorine is required to be added for treating 1 ton of material; 105 kg of water and 125kg of water are required for treating one ton of materials; 0.7kg of fluoride ions can be removed after 3.95kg of bleaching powder is used in 1 ton of materials, the rest 11.3kg of fluoride ions are eliminated by adding lime, 33.2kg of lime is required to be added into 11.3kg of fluoride ions according to the calculation of treating 0.51g of fluoride ions by 1.5g of lime, and 36.9kg of industrial-grade lime is required if the content of calcium hydroxide of the industrial-grade lime is 90 percent.
Step 6: 3.95kg of industrial bleaching powder with the effective chlorine content of 28 percent, 36.9kg of industrial lime with the calcium hydroxide content of 90 percent and 125kg of water are added into 1 ton of materials to be treated, the medicament and the water are uniformly stirred, the medicament and the materials are fully and uniformly mixed, and the materials are preferably kneaded by a discharging hand and are crushed by one touch.
After the materials are treated for 2 hours, the content of cyanide ions and the content of fluorine ions in the materials obtained by mixing and stirring are detected to be 0.047mg/kg and 0.9mg/kg respectively.
The invention is suitable for the electrolytic aluminum factory to carry out soil remediation on the overhaul slag yard which is buried without detoxification treatment before 2016, 8, 1 and can also be suitable for carrying out harmless treatment on newly generated final waste slag which cannot be reused.
The method provided by the invention fully considers the relationship among the electric power cost, the medicament cost, the labor cost and the detoxification effect in the crushing link, has low operation cost, can completely realize no pollution residue of the treated soil, and has remarkable economic and social benefits.
Claims (10)
1. A harmless restoration method for electrolytic aluminum waste residues and polluted soil thereof comprises the following steps:
(1) crushing: crushing the electrolytic aluminum waste residue into powdery material with the particle size not more than 10 mm;
(2) and (3) harmless treatment: mixing and stirring the powdery material obtained in the step (1), cyanide, a soluble fluoride remover and water;
wherein,
the water is added in an amount such that the water content of the resultant mixture obtained by final mixing and stirring is 15 to 18%,
the addition amount of the cyanide and soluble fluoride remover is that cyanide ions and fluoride ions in the electrolytic aluminum waste residue or the polluted soil thereof can be completely removed.
2. The innocent repair method of claim 1, further comprising the steps of: and detecting the content and the water content of cyanide ions and fluoride ions in the powdery material.
3. The innocent restoration method according to claim 1 or 2, further comprising the steps of: coarse crushing, wherein large materials are manually or mechanically coarse crushed to enter a feed inlet of a crushing system.
4. The innocent restoration method according to any one of claims 1 to 3, further comprising the steps of: sorting and recovering, namely sorting and recovering anode and cathode carbon blocks, iron blocks, aluminum blocks, sintered cryolite blocks, silicon carbide refractory bricks and other materials in the electrolytic aluminum waste slag.
5. The innocent restoration method according to any one of claims 1 to 4, wherein the particle size of the powdery material in the step (1) is 0.01 to 10mm, preferably, the particle size of the powdery material in the step (1) is 5 to 10 mm.
6. The harmless remediation method of any one of claims 1 to 4 wherein in step (2) the cyanide, soluble fluoride scavenger is dissolved in water and mixed with the powdered material of step (1).
7. The innocent restoration method of any one of claims 1-4 wherein the cyanide, soluble fluoride scavenger of step (2) is selected from bleaching powder or a mixture of bleaching powder and lime.
8. The innocent repair method of any one of claims 1 to 4 wherein the cyanide, soluble fluoride scavenger of step (2) is used in an amount of: when the mass ratio of cyanide ions to fluoride ions in the electrolytic aluminum waste residues or the polluted soil is not less than 1:3.2, the using amount of the cyanide and soluble fluoride remover in the step (2) is added according to the proportion of removing 0.082g of cyanide ions by 1g-1.5g of bleaching powder; when the mass ratio of cyanide ions to fluoride ions in the electrolytic aluminum waste residues or the polluted soil thereof is less than 1:3.2, adding the cyanide and soluble fluoride remover in the step (2) according to the proportion that 0.265g of fluoride ions are removed by 1g-1.5g of bleaching powder or adding the cyanide and soluble fluoride remover according to the proportion that 0.082g of cyanide ions are removed by 1g-1.5g of bleaching powder, and simultaneously adding lime according to the proportion that 0.51g of fluoride ions are solidified by 1g of lime to solidify redundant fluoride ions; preferably, when the mass ratio of cyanide ions to fluoride ions in the electrolytic aluminum waste residues or the polluted soil thereof is not less than 1:3.2, the usage amount of the cyanide and soluble fluoride remover in the step (2) is added according to the ratio of 1.2g to 1.5g of bleaching powder to remove 0.082g of cyanide ions; when the mass ratio of cyanide ions to fluoride ions in the electrolytic aluminum waste residues or the polluted soil thereof is less than 1:3.2, the using amount of the cyanide and soluble fluoride remover in the step (2) is added according to the proportion that 0.265g of fluoride ions are removed by 1.2g-1.5g of bleaching powder or added according to the proportion that 0.082g of cyanide ions are removed by 1.2g-1.5g of bleaching powder, and lime is added according to the proportion that 0.51g of fluoride ions are solidified by 1.2g-1.5g of lime to solidify redundant fluoride ions.
9. The innocent restoration method according to any one of claims 1 to 4, wherein the required water addition amount is calculated by subtracting the water content of the raw material from the final water content of the mixed material of 15 to 18% in the water solution.
10. A harmless treatment device for electrolytic aluminum waste residues and polluted soil thereof is composed of a material crushing system ⑩, a material conveying belt, a rotary tank stirrer and a dosing tankThe four parts are formed, the material feeding belt machine of the material conveying beltOne end of the rotary tank mixer is connected with a discharge hole of the crushing system, and the other end of the rotary tank mixer is connected with a feeding hopper of the rotary tank mixerConnected with each other and a dosing boxFeeding hole of rotary tank stirrerAnd a movable two-section crushing system ⑩ consisting of jaw crusher and impact crusher, wherein the material conveyer belt is provided with a self-propelled mechanism capable of lowering powerThe multi-section conveying belt can ensure that the conveying system is better communicated with the discharge port and the feeding hopper of the crushing systemThe feed inlets are well connected, and the rotary tank stirrer can be driven by a driving mechanismThe drive is arranged on the driven supporting seatUpward angle adjusting deviceAdjusting rotary stirring tank bodyThereby adjusting the tank body of the rotary stirring tankThe walking speed of the materials in the container.
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