CN114956390A - Method for removing heavy metal waste acid and reducing red mud solid waste grade by comprehensively utilizing lead smelting - Google Patents
Method for removing heavy metal waste acid and reducing red mud solid waste grade by comprehensively utilizing lead smelting Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 96
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 55
- 239000002910 solid waste Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000003723 Smelting Methods 0.000 title claims abstract description 25
- 239000010814 metallic waste Substances 0.000 title claims abstract description 17
- 239000002699 waste material Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000004073 vulcanization Methods 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- 238000010790 dilution Methods 0.000 claims abstract description 5
- 239000012895 dilution Substances 0.000 claims abstract description 5
- 238000011085 pressure filtration Methods 0.000 claims abstract description 4
- 239000008213 purified water Substances 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 4
- 238000005987 sulfurization reaction Methods 0.000 claims description 4
- 241001062472 Stokellia anisodon Species 0.000 claims 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 239000002920 hazardous waste Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910001570 bauxite Inorganic materials 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 239000011449 brick Substances 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 239000008267 milk Substances 0.000 description 4
- 210000004080 milk Anatomy 0.000 description 4
- 235000013336 milk Nutrition 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 229940079101 sodium sulfide Drugs 0.000 description 4
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 3
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 2
- 238000004131 Bayer process Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- A62D3/36—Detoxification by using acid or alkaline reagents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a method for removing heavy metal waste acid and reducing the solid waste grade of red mud by comprehensively utilizing lead smelting, which comprises the following steps: step one, three-stage vulcanization, namely precipitating and filtering lead smelting waste acid, introducing the lead smelting waste acid into a vulcanization reactor, and continuously carrying out three times of vulcanization reaction to obtain waste acid with heavy metals removed; step two, grinding the red mud; step three, dirty acid dilution, namely adding the dirty acid obtained in the step one after the heavy metals are removed into a reactor, and adding purified water with the volume 4 times that of the dirty acid to obtain dirty acid dilution liquid; and step four, primary neutralization and filtration, namely adding the red mud crushed materials into the polluted acid diluent in batches according to a certain proportion, detecting that the pH value is stable at 6-8, finishing the reaction, and carrying out pressure filtration on the reacted neutral suspension by using a pressure filter, wherein filter residues are I-type common solid waste red mud. The invention directly utilizes the acidity of the waste acid, thereby avoiding the consumption of a large amount of resources and energy sources in the acid extraction process; the red mud is changed from the general solid waste of class II to the general solid waste of class I, which is beneficial to the subsequent storage, transportation and utilization of the red mud.
Description
Technical Field
The invention relates to the technical field, in particular to a method for removing heavy metal waste acid and reducing the solid waste grade of red mud by comprehensively utilizing lead smelting.
Background
The red mud is industrial waste residue discharged in the process of producing alumina from bauxite, and is named as red mud because the bauxite has high iron content and the residue is often like red clay. The chemical composition of red mud depends on the composition of bauxite, the process for producing alumina, the material composition of the additives in the production process, the composition of the newly produced compounds, etc. Usually SiO 2 20 to 25 percent of TiO 2 3-5% of Al 2 O 3 6-25% of Fe 2 O 3 5-12 percent of CaO, 40-50 percent of CaO and Na 2 O is 2-4%, K 2 0.2-0.7 percent of O, 6-14 percent of loss on ignition and about 2 percent of MgO.
The prior invention patent (CN 201410432911.1) named as a method for treating waste acid and wastewater by modified red mud powder has the following defects as the prior art:
1. lime milk is used for adjusting the pH value, so that acid in waste acid is wasted, the effect of changing waste into valuable is not fully achieved, and a large amount of lime milk is consumed;
2. lime milk is used for neutralizing waste acid, a large amount of gypsum precipitate is generated, the precipitate contains a large amount of heavy metals, a large amount of hazardous wastes are newly added, and in the actual operation of a factory, because the gypsum slag is very large in generation amount and belongs to hazardous wastes, the gypsum slag is always a difficult point of environmental protection management of a smelting plant and is difficult to dispose;
3. the lime milk has a certain heavy metal removal effect, but the removal efficiency is limited, so that a large amount of heavy metals are still adsorbed and precipitated by the red mud after the red mud is added;
4. the red mud is general class II solid waste, heavy metals in the waste acid are precipitated and absorbed by the red mud, and a large amount of heavy metals in the waste acid are transferred to the red mud sediments, so that the generated red mud sediments become hazardous waste;
5. the red mud sediment which becomes the dangerous waste is more difficult to store, transport and dispose than the red mud which is the general solid waste of the II class, the technical requirements on the storage, the transport and the disposition are higher by one level, and the required storage, the transport and the disposition costs are also many times higher.
The invention patent (CN 201711178568.2) named as a method for removing various pollutants in copper smelting waste acid by using Bayer process red mud has the following defects as the prior art:
1. the generated ferric arsenate precipitate and the red mud residue cannot be precipitated respectively, so that the arsenic in the ferric arsenate cannot be extracted and comprehensively utilized subsequently;
2. heavy metals in the waste acid are mainly transferred to mixed precipitates formed by ferric arsenate precipitates and red mud residues, so that the red mud is changed from II-type general solid wastes into dangerous wastes, and the problems of storage, transportation and disposal of the dangerous wastes are also faced;
3. because the adsorption and precipitation effects of the red mud on the heavy metals are limited, the formed ferric hydroxide precipitate (which has the effects of flocculation, precipitation and adsorption) contains a certain amount of heavy metals and also belongs to hazardous waste; the obtained iron hydroxide precipitate containing the heavy metals is difficult to comprehensively utilize, the heavy metals are also key objects of current environmental management, and the iron hydroxide containing the heavy metals cannot be easily used in water treatment or other industries so as to avoid introducing the heavy metals into other waste water or substances which do not contain the heavy metals;
4. the red mud is adopted to adjust the pH value of the polluted acid, the acidity of the polluted acid is fully utilized, but the acidity of the polluted acid is very strong (the mass fraction is 10-20%, the concentration of 15% polluted acid hydrogen ions is about 1.7 mol/L), the alkalinity of the red mud attached solution is about pH = 13-14 (the alkalinity is strong, the concentration of hydroxyl is lower than 0.1mol/L, but is lower than the concentration of hydrogen ions in the polluted acid by an order of magnitude), the dosage of the red mud is huge when the pH value of the polluted acid is adjusted by the red mud, so that huge amounts of heavy metal-containing red mud sediments are generated, the heavy metal content of the red mud is extremely low, and after the operation, the heavy metals in the polluted acid are mainly transferred into the red mud, and instead, huge amounts of heavy metal-containing red mud (possibly belonging to dangerous waste) are generated, and the difficulty in treating the red mud is increased.
Therefore, a method for comprehensively utilizing lead smelting to remove heavy metal waste acid and reduce the solid waste grade of red mud is needed to solve the existing problems.
Disclosure of Invention
In view of the above, the invention provides a method for reducing the solid waste grade of red mud by comprehensively utilizing lead smelting to remove heavy metal waste acid, which directly utilizes the acidity of the waste acid, thereby avoiding the consumption of a large amount of resources and energy sources in the processes of distillation concentration and the like; red mud is extracted from
The general solid waste of class I is changed into the general solid waste of class I, and after the alkalinity is removed, the corrosion of equipment can be reduced, thereby being beneficial to the storage, transportation and reutilization of the red mud.
In order to achieve the technical effects, the invention provides a method for removing heavy metal waste acid and reducing the solid waste grade of red mud by comprehensively utilizing lead smelting, which adopts the following technical scheme:
a method for comprehensively utilizing lead smelting to remove heavy metal waste acid and reduce the solid waste grade of red mud comprises the following steps:
step one, three-stage vulcanization, namely precipitating and filtering lead smelting waste acid, introducing the lead smelting waste acid into a vulcanization reactor, slowly adding a vulcanizing agent, controlling the temperature, stirring, reacting and filtering, and continuously carrying out three times of vulcanization reaction in such a way to remove heavy metals to obtain the waste acid with the heavy metals removed;
grinding the red mud, namely taking the red mud in a natural state of a red mud warehouse, and properly grinding the red mud without grinding hard substances in the red mud into fine powder to obtain red mud crushed aggregates;
step three, dirty acid dilution, namely adding the dirty acid obtained in the step one after heavy metal removal into a reactor, adding purified water with the volume 4 times that of the dirty acid, and diluting the original dirty acid to 5 times to obtain dirty acid diluent;
step four, performing primary neutralization filtration, and adding the red mud crushed material obtained in the step two into the contaminated acid diluent obtained in the step three in batches according to a certain proportion to obtain reaction liquid;
the final dosage of the red mud is controlled by detecting the pH value of the reaction liquid, when the pH value of the reaction liquid is stabilized at 6-8, the reaction is finished, the neutral suspension after the reaction is subjected to pressure filtration by a filter press, and filter residues are red mud which is changed into I-type common solid waste and are directly transported outside for comprehensive utilization.
Further, the method also comprises the following steps: step five, secondary neutralization and filtration, wherein the addition amount of the red mud during secondary neutralization is adjusted by detecting and controlling the pH value of the primary filtrate in the step four; when the pH value of the reaction solution is stabilized at 6-8, filtering after the reaction is finished.
Further, in the first step, sodium sulfide aqueous solution is used as the vulcanizing agent.
Further, in the first step, the adding amount of the vulcanizing agent is 1.5 times of the theoretical multiple.
Further, in the first step, the temperature is 30 ℃, and the stirring speed is 600 rpm.
Further, in the first step, the first vulcanization reaction is carried out for 60min, the second vulcanization reaction is carried out for 30min, and the third vulcanization reaction is carried out for 15 min.
Furthermore, in the fourth step, the crushed red mud is added in batches according to the proportion that 19.5g of crushed red mud (with the water content of 14%) is needed for every 10mL of original waste acid.
The technical scheme of the invention at least comprises the following beneficial effects:
1. the acid in the waste acid is comprehensively utilized at low cost, high energy consumption of acid extraction methods such as distillation, air stripping and electrodialysis is avoided, a neutral environment can be created for subsequent advanced treatment of the waste acid, and the resource consumption and cost of a needed neutralizer are reduced;
2. can remove red mud from
Change from general solid waste to solid waste
General solid waste is similar, the grade of the solid waste of the red mud is reduced, the subsequent storage, transportation and comprehensive utilization of the red mud are facilitated, and the environment benefit and the economic benefit are more obvious;
3. the type and the quantity of the hazardous waste are not increased, so that the condition of generating a large amount of hazardous waste in the prior art is avoided;
4. the red mud is subjected to alkaline removal, and then brick firing and cement preparation are carried out, so that the improvement of the product quality of bricks and cement is facilitated, and indirect economic benefits are achieved.
Drawings
FIG. 1 is a flow chart of a method for reducing the solid waste level of red mud by comprehensively utilizing lead smelting to remove heavy metal waste acid in the embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to fig. 1 of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.
Example 1
As shown in figure 1, the method for removing heavy metal waste acid and reducing the solid waste grade of red mud by comprehensively utilizing lead smelting comprises the following steps:
step one, three-stage vulcanization, namely introducing clear liquid obtained after lead smelting waste acid precipitation and filtration into a vulcanization reactor, slowly adding a vulcanizing agent (sodium sulfide aqueous solution), controlling the temperature to be 30 ℃, stirring at the rotating speed of 600rpm, reacting for 60min, and detecting the content of main heavy metals; adding a vulcanizing agent (sodium sulfide aqueous solution) again, wherein the adding amount is 1.5 times of the theoretical multiple, controlling the temperature at 30 ℃, stirring at the rotating speed of 600rpm, and detecting the content of main heavy metals after reacting for 30 min; adding a vulcanizing agent (sodium sulfide aqueous solution) for the third time, wherein the adding amount is 1.5 times of the theoretical multiple, controlling the temperature at 30 ℃, stirring at the rotating speed of 600rpm, and detecting the content of main heavy metals after reacting for 15 min; after three-stage sulfurization reaction, the removal rate of main heavy metals can reach at least 98 percent.
And step two, grinding the red mud, namely taking the red mud in the natural state of the red mud warehouse, properly grinding the red mud (the red mud is not ground deeply in progress because the red mud is a substance with small granularity), and grinding hard substances in the red mud into fine powder to reduce the energy consumption in the treatment process as much as possible, so that the method is closer to the actual application of a factory and obtains the crushed red mud.
And step three, dirty acid dilution, namely adding the dirty acid obtained in the step one after heavy metal removal into a reactor, adding purified water with the volume 4 times that of the dirty acid, and diluting the original dirty acid to 5 times to obtain dirty acid diluent.
Step four, performing primary neutralization and filtration, and adding the red mud crushed aggregates obtained in the step two into the polluted acid diluent obtained in the step three in batches according to the proportion of 19.5g of the red mud crushed aggregates obtained in the step two (the water content is about 14%)/10 mL of original polluted acid to obtain reaction liquid; the final dosage of the red mud is controlled by detecting the pH value of the reaction liquid, when the pH value of the reaction liquid is stabilized at 6-8, the reaction is finished, the neutral suspension after the reaction is subjected to pressure filtration by a filter press, and filter residues are red mud which is changed into I-type common solid waste and are directly transported outside for comprehensive utilization.
Step five, secondary neutralization and filtration, wherein in order to ensure the neutralization effect, a secondary neutralization and filtration process is arranged, and the addition amount of the red mud crushed aggregates during secondary neutralization is adjusted by detecting and controlling the pH value of the primary filtrate in the step four; when the pH value of the reaction solution is stabilized at 6-8, filtering is carried out after the reaction is finished. The filtrate after the neutralization reaction is neutral, and favorable pH conditions are created for subsequent treatment.
The method comprehensively utilizes the acid in the waste acid at low cost, avoids high energy consumption of acid extraction methods such as distillation, air stripping, electrodialysis and the like, and simultaneously can create a neutral environment for subsequent advanced treatment of the waste acid, thereby reducing the resource consumption and the cost of the needed neutralizer; the invention can remove red mud from
Change from general solid waste to solid waste
General solid waste is similar, the grade of the solid waste of the red mud is reduced, the subsequent storage, transportation and comprehensive utilization of the red mud are facilitated, and the environment benefit and the economic benefit are more obvious; the invention does not increase the variety and the quantity of the hazardous waste, thereby avoiding the condition of generating a large amount of hazardous waste in the prior art; the red mud is used for baking bricks and producing cement after being subjected to alkaline removal, is favorable for improving the product quality of the bricks and the cement, and has indirect economic benefit.
Test example 1
First, basic data
The red mud is industrial waste residue discharged in the process of producing alumina by using bauxite, and is named as red mud because the bauxite has high iron content and the residue is often like red clay; the chemical composition of red mud depends on the composition of bauxite, the process for producing alumina, the material composition of the additives in the production process, the composition of the newly produced compounds, etc. Usually SiO 2 20 to 25 percent of TiO 2 3-5% of Al 2 O 3 6-25% of Fe 2 O 3 5-12 percent of CaO, 40-50 percent of CaO and Na 2 O is 2-4%, K 2 0.2-0.7 percent of O, 6-14 percent of loss on ignition and about 2 percent of MgO.
Second, the experimental subject
1. Red mud from domestic ores of a large-scale alumina plant in Henan province;
2. the waste acid generated in the acid making process of a large lead-zinc smelting plant in Henan province.
Third, related detection of experimental object
1. Placing 20g of red mud into a conical flask, adding water, mixing, diluting, and uniformly stirring to 250 mL. Fully stirring and dissolving for 10min, and then detecting the pH value of the aqueous solution, wherein the pH value is between 13 and 14, and the aqueous solution belongs to the II-class common solid wastes.
2. ICP and an ion chromatograph are adopted to detect the components of various pollutants in the waste acid, and the detection results of all the components are as follows:
TABLE 1 detection results of cations in contaminated acids
As shown in table 1, since the content of some heavy metal elements is very small, the elements with low content are not analyzed in the subsequent analysis, and only the main heavy metal is analyzed.
TABLE 2 detection results of anions in contaminated acids
According to SO, as shown in Table 2 4 2- The content is estimated, and the mass fraction of the sulfuric acid in the waste acid is about 16-17%.
Fourth, experiment and result of using waste acid to reduce solid waste grade of red mud
1. Neutralization of red mud
100g of red mud in a natural state is taken and ground properly (because the red mud is a substance with small particle size), and the hard substances in the red mud are not ground into fine powder any more.
The supernatant after the filtration of the waste acid tertiary vulcanization reaction was transferred to a 250mL Erlenmeyer flask with a 10mL pipette and diluted to 100mL with distilled water.
1.5g of the red mud is added step by step, the mixture is stirred for 1min, then the red mud is continuously added, the pH of the reaction solution is monitored, the addition is stopped when the pH is neutral, and the operation is carried out for 5 times.
In 5 experiments, the average red mud dosage was 19.5 g.
2. Sulfurizing to remove heavy metals
At present, the removal of heavy metals by means of a sulfiding agent is still the most efficient method.
Therefore, the three-stage vulcanization measure is adopted for treating the waste acid in the experiment.
The experimental vulcanizing agent adopts sodium sulfide nonahydrate or sodium hydrosulfide, and through orthogonal experimental comparison analysis, the treatment effect of the sodium sulfide nonahydrate on the waste acid is generally superior to that of the sodium hydrosulfide. Therefore, sodium sulfide nonahydrate is used as a vulcanizing agent in all subsequent experiments.
Setting an orthogonal experiment according to 4 factors of theoretical multiple, stirring speed, time and temperature, designing 16 sample points in total, and obtaining the optimal treatment conditions after all reactions are finished as follows: the addition of the vulcanizing agent is 1.5 times of theoretical multiple, the temperature is 30 ℃, the stirring speed is 600rpm, and the reaction is carried out for 60 minutes. Taking arsenic as an example, the single-stage treatment efficiency of arsenic can reach 98%.
After the contaminated acid stock solution is subjected to three-stage vulcanization precipitation treatment, the concentrations of main heavy metal pollutants are as follows:
TABLE 3 detection results of contaminated acids after three-stage vulcanization
TABLE 4 two-stage red mud neutralized filtrate test results
As can be seen from Table 3, after the lead smelting waste acid is subjected to three-stage vulcanization, the content of main heavy metals does not reach the industrial emission standard, but is very low, and the invention adopts two-stage red mud neutralization, mainly utilizes the alkalinity of the red mud to neutralize the acidity of the waste acid;
as can be seen from Table 4, the lead smelting waste acid is subjected to three-stage vulcanization and two-stage red mud neutralization, so that the content of main heavy metals is reduced, and the red mud has certain adsorbability and flocculation property besides alkalinity; however, the adsorption and flocculation effects are not particularly pronounced since the content of heavy metal contaminants is already low. After two-stage red mud neutralization, advanced treatment measures are further adopted to ensure that the waste acid and wastewater reaches the standard and is discharged (out of the scope of the invention).
According to the actual operation effect of three-stage vulcanization in a contaminated acid treatment station of a large-scale lead-zinc smelting plant in Henan province, the contaminated acid subjected to three-stage vulcanization is treated by using carbide slag as a neutralization precipitator, and the generated neutralized slag of the contaminated acid belongs to common solid waste through identification.
The foregoing is a preferred embodiment of the present invention, and it should be noted that it would be apparent to those skilled in the art that various modifications and enhancements can be made without departing from the principles of the invention, and such modifications and enhancements are also considered to be within the scope of the invention.
Claims (7)
1. A method for comprehensively utilizing lead smelting to remove heavy metal waste acid and reduce the solid waste grade of red mud is characterized by comprising the following steps:
step one, three-stage vulcanization, namely precipitating and filtering lead smelting waste acid, introducing the lead smelting waste acid into a vulcanization reactor, slowly adding a vulcanizing agent, controlling the temperature, stirring, reacting and filtering, and continuously carrying out three times of vulcanization reaction in such a way to remove heavy metals to obtain the waste acid with the heavy metals removed;
grinding the red mud, namely taking the red mud in a natural state of a red mud warehouse, and properly grinding the red mud without grinding hard substances in the red mud into fine powder to obtain red mud crushed aggregates;
step three, dirty acid dilution, namely adding the dirty acid obtained in the step one after heavy metal removal into a reactor, adding purified water with the volume 4 times that of the dirty acid, and diluting the original dirty acid to 5 times to obtain dirty acid diluent;
step four, primary neutralization and filtration, namely adding the red mud crushed aggregates obtained in the step two into the waste acid diluent obtained in the step three in batches according to a certain proportion to obtain reaction liquid;
the final dosage of the red mud is controlled by detecting the pH value of the reaction liquid, when the pH value of the reaction liquid is stabilized at 6-8, the reaction is finished, the neutral suspension after the reaction is subjected to pressure filtration by a filter press, and filter residues are red mud which is changed into I-type common solid waste and are directly transported outside for comprehensive utilization.
2. The method for comprehensively utilizing lead to smelt and remove heavy metal waste acid to reduce the solid waste grade of red mud according to claim 1, which is characterized by further comprising the following steps: step five, secondary neutralization and filtration, wherein the addition amount of the red mud during secondary neutralization is adjusted by detecting and controlling the pH value of the primary filtrate in the step four; when the pH value of the reaction solution is stabilized at 6-8, filtering is carried out after the reaction is finished.
3. The method for comprehensively utilizing lead smelting to remove heavy metal waste acid and reduce the solid waste grade of red mud according to claim 1, wherein in the first step, a vulcanizing agent is an aqueous solution of sodium sulfide.
4. The method for comprehensively utilizing lead to smelt and remove heavy metal waste acid to reduce the solid waste grade of red mud according to claim 1, wherein in the step one, the addition amount of a vulcanizing agent is 1.5 times of the theoretical multiple.
5. The method for comprehensively utilizing lead to smelt to remove heavy metal waste acid and reduce the solid waste grade of red mud according to claim 1, wherein in the first step, the temperature is 30 ℃, and the stirring speed is 600 rpm.
6. The method for comprehensively utilizing lead to smelt to remove heavy metal waste acid and reduce the solid waste grade of red mud according to claim 1, wherein in the first step, the first sulfurization reaction is performed for 60min, the second sulfurization reaction is performed for 30min, and the third sulfurization reaction is performed for 15 min.
7. The method for comprehensively utilizing lead to smelt and remove heavy metal waste acid to reduce the grade of red mud solid waste according to claim 1, wherein in the fourth step, the red mud crushed aggregates are added in batches according to the proportion that 19.5g of red mud crushed aggregates (with the water content of 14%) are needed for every 10mL of original waste acid.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003554A (en) * | 2014-06-04 | 2014-08-27 | 武汉飞博乐环保工程有限公司 | Waste acid purifying device and process |
| JP2017213507A (en) * | 2016-05-31 | 2017-12-07 | 住友金属鉱山株式会社 | Waste acid treatment method |
| CN109078962A (en) * | 2018-08-30 | 2018-12-25 | 西北矿冶研究院 | Combined treatment method of arsenic-containing acidic wastewater, red mud and carbide slag |
| CN110451680A (en) * | 2019-07-27 | 2019-11-15 | 济源豫光有色冶金设计研究院有限公司 | A kind of processing method of nonferrous smelting waste acid |
| CN113430380A (en) * | 2021-06-23 | 2021-09-24 | 中南大学 | Clean and efficient smelting waste acid treatment method |
-
2022
- 2022-07-06 CN CN202210789648.6A patent/CN114956390A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003554A (en) * | 2014-06-04 | 2014-08-27 | 武汉飞博乐环保工程有限公司 | Waste acid purifying device and process |
| JP2017213507A (en) * | 2016-05-31 | 2017-12-07 | 住友金属鉱山株式会社 | Waste acid treatment method |
| CN109078962A (en) * | 2018-08-30 | 2018-12-25 | 西北矿冶研究院 | Combined treatment method of arsenic-containing acidic wastewater, red mud and carbide slag |
| CN110451680A (en) * | 2019-07-27 | 2019-11-15 | 济源豫光有色冶金设计研究院有限公司 | A kind of processing method of nonferrous smelting waste acid |
| CN113430380A (en) * | 2021-06-23 | 2021-09-24 | 中南大学 | Clean and efficient smelting waste acid treatment method |
Non-Patent Citations (4)
| Title |
|---|
| 卢治旭: "赤泥处理含砷污酸技术研究", 《中国优秀硕士学位论文全文数据库 工程科技I缉》, pages 3 - 4 * |
| 卢治旭: "赤泥处理含砷污酸技术研究", 中国优秀硕士学位论文全文数据库 工程科技I缉, pages 3 - 4 * |
| 夏胜文等: "冶炼污酸高效强化处理新工艺及工业化应用", 《世界有色金属》, pages 16 * |
| 赵洪贵等: "有色冶炼污酸综合处理及废水回用技术研究", 《硫酸工业》, pages 39 * |
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