CN109607872A - A kind of comprehensive utilization of the waste acid containing arsenic and the Safe disposal method of arsenic - Google Patents

A kind of comprehensive utilization of the waste acid containing arsenic and the Safe disposal method of arsenic Download PDF

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CN109607872A
CN109607872A CN201910012852.5A CN201910012852A CN109607872A CN 109607872 A CN109607872 A CN 109607872A CN 201910012852 A CN201910012852 A CN 201910012852A CN 109607872 A CN109607872 A CN 109607872A
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arsenic
heavy
iron
solution
underflow
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CN109607872B (en
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王乾坤
许晓阳
罗婷
方荣茂
林鸿汉
廖元杭
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Zijin Mining Group Co Ltd
Xiamen Zijin Mining and Metallurgy Technology Co Ltd
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Zijin Mining Group Co Ltd
Xiamen Zijin Mining and Metallurgy Technology Co Ltd
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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
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Abstract

The present invention relates to a kind of comprehensive utilization of waste acid containing arsenic and the Safe disposal methods of arsenic, it includes preneutralization: waste acid being mixed with lime stone, preneutralization is to the low acid concentration for not generating arsenic precipitation reaction, and thickened underflow is through filter washing；Oxidation: supernatant and washing lotion aoxidize together after will be dense, are added and contain ferron, control solution iron arsenic molar ratio, and oxidant hydrogen peroxide is added, and control terminal oxidation-reduction potential, trivalent arsenic is made to be fully converted to pentavalent arsenic；One section of heavy arsenic: solution after oxidation is subjected to one section of heavy arsenic, control reaction temperature, initial scorodite seed concentration, solution ph, milk of lime is added during heavy arsenic and reacts heavy arsenic after dense, part scorodite precipitation underflow returns to heavy arsenic slot and makees crystal seed, remaining scorodite precipitation underflow open circuit, adds neutralizer to adjust solution iron arsenic molar ratio, and adjusting can add source of iron, plate compression must meet the crystal form arsenic acid scum that landfill requires；Two sections of heavy arsenic: the supernatant of one section of heavy arsenic is carried out two sections of heavy arsenic stages, and addition milk of lime controls endpoint pH, and arsenic slurry of sinking is dense.It has the advantages that technique is simple and direct, easy to operate, the production quantity of slag is few, slag stability is good, processing cost is low etc., is suitable for non-ferrous metal metallurgy industrial application.

Description

A kind of comprehensive utilization of the waste acid containing arsenic and the Safe disposal method of arsenic
Technical field
The present invention relates to a kind of comprehensive utilization of waste acid containing arsenic and the Safe disposal methods of arsenic, are suitable for non-ferrous metal metallurgy row Industry application.
Background technique
Non-ferrous metal is valuable source needed for industrial development, and China is rich in mineral resources.Due to the arsenic element of nonferrous metals ore Content is high, so in non-ferrous metal pyrometallurgical smelting flue gas acid preparing system and association rare precious metal extraction process, inevitably A large amount of acid waste waters can be generated, acid waste water insider is referred to as waste acid.Waste acid system is complicated, and component is more, concentration is high, main Will the arsenic containing high concentration, sulfate ion, fluorine ion, chloride ion, while also containing the various metals such as copper, zinc, lead, cadmium.With The continuous development of nonferrous smelting technology, it is many about waste acid processing and arsenic-containing waste residue minimizing, stabilisation, harmless treatment Problems demand solves.How economic, green is carried out to non-ferrous metal metallurgy waste acid to handle, it has also become industry facing it is big Project.
Now in the industry to the processing of waste acid mainly for the purpose of arsenic removal, the treatment process of waste acid containing arsenic of use mainly has lime Neutralization precipitation method, lime-iron salt method, sulfurization-precipitation method.Lime precipitation handles waste acid, can generate a large amount of unstable waste residues, Easily cause secondary pollution；Lime-iron salt method handles waste acid, and the additional amount of source of iron needs to meet iron arsenic ratio greater than 3~4, medicament at The quantity of slag of this height, generation is big；Sulfurization-precipitation method handles waste acid, and the arsenic filter cake stability of generation is poor, needs to carry out subsequent stabilisation Dispose to high cost.
Elites In The Trades are made great efforts towards economic, green waste acid containing arsenic stabilizes, method for innocent treatment direction is visited It begs for.Research finds that scorodite rate containing arsenic is high, needs iron few, and Leaching is low, and stability is high, small in size, also has crystal structure, Easily clarification, filtering and separation the advantages that, and store that expense is low, and scorodite is acknowledged as being most suitable for stockpiling or landfill disposal at present Gu arsenic compound.About the existing many reports of method for consolidating arsenic with scorodite precipitation: (1) Chinese Academy of Sciences Shenyang is ground using ecology Study carefully institute patent CN102531236B and disclose " processing method of arsenic in a kind of waste acid ", calcium oxide first is added into waste acid containing arsenic, Be separated by solid-liquid separation to obtain gypsum, then into supernatant after separation of solid and liquid plus molysite and oxidant, lower Fe/As molar ratio (0.8~ 1.2:1) and under the conditions of certain pH value (1.8~4) arsenic in waste acid is first made to form amorphous precipitated ferric arsenate, precipitation slag adds again Acid is returned molten and is heated (80~95 DEG C), and separation of solid and liquid obtains the mixed precipitation of gypsum and scorodite.Supernatant after separation of solid and liquid Be added after trivalent iron salt and calcium oxide carry out deeply removing arsenic and reach discharge standard, but in this method amorphous ferric arsenate acid adding return it is molten And scorodite precipitation, the problem of being not directed to pH value control, reaction time and addition crystal seed, that there are transformation efficiencies is not high, conversion The arsenic process needs that not exclusively and twice sink are separated by solid-liquid separation twice, and the supernatant after being separated by solid-liquid separation twice also needs deeply removing arsenic Processing, process flow is complicated and the deficiencies of not mentioning the transformation efficiency of scorodite；(2) Kunming University of Science and Technology's patent CN107459166A is disclosed " curing method of sour resource utilization and arsenic in a kind of waste acid ", this method be by arsenic flue dust and Waste acid is sized mixing, and is then passed to air or oxygen and is carried out Oxidation Leaching, endpoint pH 0~1.0, arsenic leaching solution are leached in control By the way that ferrous sulfate is added, simultaneously blowing air progress normal pressure scorodite consolidates arsenic, and there are ferrous iron and trivalent arsenic oxidation are endless for this method Entirely, heavy arsenic low efficiency, cannot ensure the deficiencies of arsenic precipitates completely in the form of crystal form ferric arsenate；(3) Central South University's patent CN102674526B discloses " a method of from arsenic containing solution sink the steady arsenic of arsenic ", used in liquor sodii arsenatis ferrous salt as Heavy arsenical, under mild acid conditions, by air oxidation process by ferrous oxidation at ferric iron, ferric iron is reacted with arsenic, is generated and is stablized Property the low sediment of high, arsenic Leaching, in pH4-6,70-95 DEG C of temperature, iron arsenic molar ratio 1-1.5, air mass flow 120- 200L/h, under the conditions of reaction time 5-7 hour, the sediment of generation is ferric arsenate crystalline compounds-scorodite crystals FeAsO4·2H2O, the Leaching concentration of the sediment arsenic are 1-2mg/L, are lower than " hazardous waste judging standard-Leaching Identify " limit value of (GB 5085.3-2007), the innoxious and stabilization processes of arsenic containing solution are able to achieve, but this method is in pH4 Under the conditions of~6, if ferrous addition and oxidation control is improper will form ferric iron and unformed ferric arsenate, precipitation slag is influenced The stability that toxicity leaches；(4) Otto Thailand patent CN100558918C discloses " one kind recycling valuable metal and arsenic from solution Method ", valuable metal is recycled from solution first, then send solution to two stages arsenic removal, wherein in the first stage with suitable In the scorodite FeAsO of storage4·2H2The form of O precipitates arsenic, and the solution after precipitating is sent to the second precipitate phase, heavy second In the shallow lake stage, remaining arsenic is with unsetting ferric arsenate FeAsO4Form precipitate and be recycled to the first precipitate phase, terminate second The arsenic concentration of the aqueous solution of precipitate phase is 0.01-0.2mg/L, and the underflow part of the first precipitate phase of this method returns, remaining Underflow is with scorodite FeAsO4·2H2The form of O stores, and shortcoming is that first stage scorodite precipitation acidity is high, needs to wash Just it is suitable for storage or landfill after clean, thus a large amount of acid wash waters can be generated and need to handle, increases the treating capacity of system, the Two precipitate phases need to add source of iron adjustment iron arsenic ratio and are greater than 3, and it is heavy that the indefinite form precipitated ferric arsenate of generation is all back to first In the shallow lake stage, reagent cost is high and the gypsum of generation, the scorodite mixing quantity of slag are big, and storage or landfill stabilization are costly, the nothing of return If ferric arsenate of being formed is anti-molten incomplete in the first precipitate phase, and then the Leaching for influencing the mixing arsenic slag for entering landfill yard is steady It is qualitative.
For this purpose, needing to research and develop a kind of comprehensive utilization of the waste acid containing arsenic of green economy and the Safe disposal method of arsenic just seems It is especially urgent.
Summary of the invention
The task of the present invention is for overcome the deficiencies in the prior art, provide the non-ferrous metal smelting for developing a kind of green economy The comprehensive utilization of the waste acid containing arsenic and the Safe disposal method of arsenic are refined, it had not only been able to achieve the comprehensive utilization of waste acid, but also was able to achieve arsenic Harmlessness disposing is stabilized, the yield of waste residue is reduced while reducing production cost, reduces the disposal costs of waste residue.
The task of the present invention is by the following technical programs to complete:
A kind of comprehensive utilization of the waste acid containing arsenic and the Safe disposal method of arsenic, successively by following processing step and condition into Row:
(1) preneutralization: waste acid being mixed with the thickened underflow that two sections of heavy arsenic processes return, lime stone is added to carry out preneutralization, It is 10-20g/L H to the low acid concentration for not generating arsenic precipitation reaction2SO4, preneutralization slurry enters thickening pond, obtains supernatant and dense Close underflow, combination of the thickened underflow through filtration washing, multi-stage countercurrent washing or both, obtains washing lotion and meets cement additive standard Qualified gypsum tailings, sell outside gypsum tailings；
(2) aoxidize: supernatant after dense and washing lotion aoxidized together, control 40~90 DEG C of solution temperature, be added with Ferrous sulfate or ferric sulfate etc. are source of iron containing ferron, control the iron arsenic molar ratio 1.0~1.5 in solution, and it is double that oxidant is added Oxygen water, control terminal oxidation-reduction potential keep trivalent arsenic complete in 550~700mV using an interstage section or multistage continuous oxidation It is converted into pentavalent arsenic, solution after must aoxidizing；
(3) one sections of heavy arsenic: entering heavy arsenic slot for solution after oxidation and carry out one section of heavy arsenic, 85~100 DEG C of reaction temperature of control, just Any neutralizer or addition can be not added in beginning 50~300g/L of scorodite seed concentration, solution ph 0.6~1.5, heavy arsenic in the process Milk of lime is reacted heavy arsenic, the underflow for obtaining clear liquid and precipitating with scorodite form, part scorodite for 4~8 hours after dense Precipitating underflow returns to heavy arsenic slot and makees crystal seed, remaining scorodite precipitation underflow open circuit adds one or more levels alkali tune of neutralizer to be neutralized to Terminal pH7.0~10.0, the iron arsenic molar ratio in alkali tune and in solution contained by underflow are lower than 1.5, can add during alkali tune Source of iron obtains filtrate and slag through plate compression, and slag can be directly entered landfill yard；
(4) two sections of heavy arsenic: the dense rear supernatant of one section of heavy arsenic is carried out two sections of heavy arsenic stages, addition milk of lime controls terminal PH value 5.5~9.0, arsenic slurry feeding concentrator progress of sinking is dense, obtains two sections of heavy arsenic supernatants and thickened underflow.
Compared with the prior art, the present invention has the following advantages and effect:
(1) all tests carry out in atmospheric conditions, and reaction condition is mild.
(2) it utilizes to mix containing scum with waste acid and size mixing, the preneutralization stage produces the gypsum tailings that can make cement retarder, i.e., It realizes the comprehensive utilization of waste acid and reduces the waste residue yield during subsequent solid arsenic.
(3) one sections of heavy arsenic thickened underflows open circuits, alkali tune sink arsenic slag into landfill yard after neutralizing, one section of heavy arsenic thickened underflow is consolidated Body portion is stable scorodite precipitation object, and the arsenic quantity of slag into landfill yard that highest arsenic content is generated up to 32.5% is few；It opens PH value can be improved in the neutralization of road underflow alkali tune, and the solvent portions institute iron-bearing water solution in underflow generates the oxyhydroxide of iron, passes through suction Co-precipitation mechanism is echoed, the Leaching stability of scorodite arsenic slag can be further enhanced；After underflow alkali tune of opening a way neutralizes, Arsenic concentration in aqueous solution is lower than 0.5mg/L, and scorodite arsenic slag filter cake does not need to wash, and can be sent directly into landfill yard.
After (4) one sections of heavy arsenic supernatants are cooling plus neutralizer milk of lime carries out two sections of heavy arsenic, and the slurry of two sections of heavy arsenic is passed through The preneutralization stage is all back to after dense, arsenic concentration is low in supernatant after two sections of heavy arsenic are dense, may be used as recycle-water, can make Supplement water and preneutralization gypsum tailings washing water are washed for flue gas during smelting, keeps wastewater zero discharge and systematic water balance；Two sections of heavy arsenic Neutralizer milk of lime is added to adjust pH, the mixture of iron hydroxide, gypsum and indefinite form ferric arsenate is back to pre- in dense rear slurry Neutralization stage, iron hydroxide and indefinite form ferric arsenate are anti-molten, into solution iron as one section of scorodite sink arsenic source of iron supplement, Gypsum improves the performance of preneutralization precipitating as crystal seed；Dense slurry is all back to the preneutralization stage, and unreacted is complete in slurry Neutralizer can improve the utilization rate of neutralizer in the preneutralization stage with the reaction was continued；The gypsum tailings of output can other than sell or As general solidification disposal of waste, reduce the quantity of slag into arsenic slag landfill yard.
(5) sheet containing scum is nonferrous metallurgy mine solid waste, need to occupy Tailings Dam storage capacity, can contain scum and take as source of iron For lime stone, while playing the role of neutralizing regulator and reactant, not only turn waste into wealth, comprehensive utilization of resources, and reduce Production cost, alleviates Tailings Dam storage capacity pressure.
In short, present invention process is simple and direct, low in cost, high treating effect, environmental pollution risk are small, the comprehensive of acid is realized It closes and utilizes, while being the stabilisation harmless treatment of arsenic, provide a kind of method of disposal of green economy safety, have wide Application prospect.
Detailed description of the invention
Fig. 1 is a kind of comprehensive utilization of waste acid containing arsenic of the invention and the Safe disposal method process flow chart of arsenic.
Explanation is described in further detail below in conjunction with attached drawing.
Specific embodiment
As shown in Figure 1, a kind of comprehensive utilization of waste acid containing arsenic of the invention and the Safe disposal method of arsenic, successively by as follows Processing step and condition carry out:
(1) preneutralization: waste acid being mixed with the thickened underflow that two sections of heavy arsenic processes return, lime stone is added to carry out preneutralization, It is 10-20g/L H to the low acid concentration for not generating arsenic precipitation reaction2SO4, preneutralization slurry enters thickening pond, obtains supernatant and dense Close underflow, combination of the thickened underflow through filtration washing, multi-stage countercurrent washing or both, obtains washing lotion and meets cement additive standard Qualified gypsum tailings, sell outside gypsum tailings；
(2) aoxidize: supernatant after dense and washing lotion aoxidized together, control 40~90 DEG C of solution temperature, be added with Ferrous sulfate or ferric sulfate etc. are source of iron containing ferron, control the iron arsenic molar ratio 1.0~1.5 in solution, and it is double that oxidant is added Oxygen water, control terminal oxidation-reduction potential keep trivalent arsenic complete in 550~700mV using an interstage section or multistage continuous oxidation It is converted into pentavalent arsenic, solution after must aoxidizing；
(3) one sections of heavy arsenic: entering heavy arsenic slot for solution after oxidation and carry out one section of heavy arsenic, 85~100 DEG C of reaction temperature of control, just Any neutralizer or addition can be not added in beginning 50~300g/L of scorodite seed concentration, solution ph 0.6~1.5, heavy arsenic in the process Milk of lime is reacted heavy arsenic, the underflow for obtaining clear liquid and precipitating with scorodite form, part scorodite for 4~8 hours after dense Precipitating underflow returns to heavy arsenic slot and makees crystal seed, remaining scorodite precipitation underflow open circuit adds one or more levels alkali tune of neutralizer to be neutralized to Terminal pH7.0~10.0, the iron arsenic molar ratio in alkali tune and in solution contained by underflow are lower than 1.5, can add during alkali tune Source of iron obtains filtrate and slag through plate compression, and slag can be directly entered landfill yard；
(4) two sections of heavy arsenic: the dense rear supernatant of one section of heavy arsenic is carried out two sections of heavy arsenic stages, addition milk of lime controls terminal PH value 5.5~9.0, arsenic slurry feeding concentrator progress of sinking is dense, obtains two sections of heavy arsenic supernatants and thickened underflow.
Technique of the invention may furthermore is that:
It can be contained scum with slag or smelting scum etc. in mine acid wastewater before step (1) preneutralization and substitute part lime Stone, in advance plus part waste acid is tuned into slurry and enters back into preneutralization process, with using the acid dissolution in waste acid containing in scum iron or Other acid consumpting substances provide source of iron containing scum simultaneously and part neutralize, and can supplement in oxidation operation depending on feelings and source of iron is added, meet iron Arsenic is than requiring.
(4) two sections of heavy arsenic thickened underflows of the step are all back to step (1) preneutralization reuse.
Filtrate is used as recycle-water after (4) two sections of heavy arsenic supernatants of the step and one section of heavy arsenic plate compression, returns existing System supplements water or preneutralization gypsum tailings slurry as flue gas washing.
The specific embodiment of the invention is further illustrated combined with specific embodiments below.
Embodiment 1
Preneutralization, by a certain amount of waste acid (H2SO4160g/L, As 25.7g/L, Cu 55.3mg/L, current potential 455mv) injection It in stirred tank, is slowly added into reactive tank in lime stone and part free acid, makes endpoint pH 1.0, be stirred to react 3h obtains qualified gypsum tailings after being separated by solid-liquid separation washing；It aoxidizes the filtered wash solution of supernatant and dense slurry dense after preneutralization It is transferred in stirred tank together, ferric sulfate is added as source of iron, meets Fe/As molar ratio about 1.1 in solution, controls solution temperature 60 DEG C of degree, adds dioxygen water management terminal oxidation-reduction potential in the section 650mV, trivalent arsenic is made all to be oxidized to pentavalent arsenic, iron is equal For ferric iron；Solution after oxidation is warming up to 90 DEG C by one section of heavy arsenic, and crystal seed 300g/L is added, and heavy arsenic process adds milk of lime Control pH value of solution about 1.1, be stirred to react 4 hours, after be separated by solid-liquid separation through concentrator, underflow part is back to one section of heavy arsenic and starts Stage adds milk of lime alkali tune to be neutralized to pH 9.5 as crystal seed, remaining underflow open circuit, is then fed into plate and frame filter press and carries out solid-liquid Separation, filter-press residues enter landfill yard；Toxicity characteristic leaching procedure, leachate pH9.6, arsenic concentration are carried out to the slag for entering landfill yard 0.52mg/L meets national standard of landfill (GB18598-2001 hazard waste landfill contamination control standard), into landfill yard Quantity of slag 6.5t/t arsenic；Two sections of heavy arsenic, one section of heavy dense supernatant arsenic content about 0.3g/L of arsenic add milk of lime to control solution terminal pH 9.0, arsenic is precipitated in the form of indefinite form ferric arsenate, the solid mixtures such as ferric arsenate, iron hydroxide and calcium sulfate of generation pass through After concentrator is separated by solid-liquid separation, it is all back to the preneutralization stage, arsenic concentration 0.055mg/L in solution after two sections of heavy arsenic, two sections heavy Filtrate is used as recycle-water return existing system after arsenic supernatant and one section of heavy arsenic plate compression.
Embodiment 2
Preneutralization, by a certain amount of waste acid (H2SO455g/L, As 5.4g/L, Cu 452mg/L, current potential 462mv) injection stirring It in reactive tank, is slowly added into reactive tank in neutralizer lime stone and part free acid, makes endpoint pH 1.0, stirring is instead 3h is answered, obtains qualified gypsum tailings after being separated by solid-liquid separation washing；Oxidation, by the filtration washing of supernatant and dense slurry dense after preneutralization Liquid is transferred in stirred tank together, and ferrous sulfate is added as source of iron, meets Fe/As molar ratio about 1.0 in solution, controls molten Liquid temperature 70 C adds dioxygen water management terminal oxidation-reduction potential in the section 570mV, trivalent arsenic is made all to be oxidized to pentavalent arsenic, Iron is ferric iron；Solution after oxidation is warming up to 95 DEG C by one section of heavy arsenic, and crystal seed 150g/L is added, and heavy arsenic process adds stone Grey cream control pH value of solution about 1.1, is stirred to react 6 hours, after be separated by solid-liquid separation through concentrator, underflow part is back to one section of heavy arsenic Incipient stage adds ferrous sulfate as crystal seed, remaining underflow open circuit, the iron in solution contained by the open circuit underflow for neutralizing alkali tune Arsenic adds milk of lime alkali tune to be neutralized to pH7.5 than 4.0, is then fed into plate and frame filter press and is separated by solid-liquid separation, and filter-press residues enter landfill ?；Toxicity characteristic leaching procedure is carried out to the slag for entering landfill yard, leachate pH7.4, arsenic concentration 0.15mg/L meet country's landfill mark Quasi- (GB18598-2001 hazard waste landfill contamination control standard), into the quantity of slag 6.2t/t arsenic of landfill yard；Two sections of heavy arsenic, one The heavy dense supernatant arsenic content about 0.5g/L of arsenic of section, adds milk of lime to control solution terminal pH 6.8, by arsenic with indefinite form ferric arsenate Form precipitating, the solid mixtures such as ferric arsenate, iron hydroxide and calcium sulfate of generation all return after concentrator is separated by solid-liquid separation It is back to the preneutralization stage, arsenic concentration is lower than 0.05mg/L, two sections of heavy arsenic supernatants and one section of heavy arsenic plate in solution after two sections of heavy arsenic Filtrate is used as recycle-water return existing system after frame filters pressing.
Embodiment 3
Preneutralization will be in mine acid wastewater and slag (Fe 10.18%, Ca 23.90%, As 0.048% and Cu 0.10%) With (the H of waste acid containing arsenic2SO481.6g/L, As 17.7g/L, Cu 33.5mg/L, current potential 472mv) it is mixed in a certain ratio and sizes mixing, make The molar ratio 1.2 of arsenic content in the iron and waste acid of dissolution, is stirred to react 30 minutes at normal temperature, sizes mixing object to the mixing after reaction Expect in stirred tank, is added in lime stone with part free acid, is stirred to react 3 hours, makes endpoint pH 0.9, be separated by solid-liquid separation, wash It obtains after washing and is sold outside qualified gypsum tailings；Oxidation, the filtered wash solution of supernatant dense after preneutralization and dense slurry is transferred to together In stirred tank, source of iron is supplemented as needed, meets Fe/As molar ratio about 1.2 in solution, is controlled 50 DEG C of solution temperature, is added Dioxygen water management terminal oxidation-reduction potential makes trivalent arsenic all be oxidized to pentavalent arsenic in the section 690mV, and iron is ferric iron； Solution after oxidation is warming up to 95 DEG C by one section of heavy arsenic, and crystal seed 50g/L is added, and heavy arsenic process adds milk of lime control pH value of solution About 0.9, be stirred to react 8 hours, after be separated by solid-liquid separation through concentrator, underflow part is back to one section of heavy arsenic incipient stage as brilliant Kind, remaining underflow open circuit adds milk of lime alkali tune to be neutralized to pH 7.5, is then fed into plate and frame filter press and is separated by solid-liquid separation, filters pressing Slag enters landfill yard；Toxicity characteristic leaching procedure is carried out to the slag for entering landfill yard, leachate pH7.4, arsenic concentration 0.21mg/L meet National standard of landfill (GB18598-2001 hazard waste landfill contamination control standard), into the quantity of slag 6.4t/t arsenic of landfill yard； Two sections of heavy arsenic, one section of heavy dense supernatant arsenic content about 0.23g/L of arsenic, add milk of lime control solution terminal pH 6.5, by arsenic with Indefinite form ferric arsenate form precipitating, the solid mixtures such as ferric arsenate, iron hydroxide and calcium sulfate of generation pass through concentrator solid-liquid After separation, it is all back to the preneutralization stage.Arsenic concentration is less than 0.5mg/L in solution after two sections of heavy arsenic.Two sections of heavy arsenic supernatants It is used as recycle-water with filtrate after one section of heavy arsenic plate compression and returns to existing system.
Embodiment 4
Preneutralization, by Copper making flotation tailings (Fe 44.7%, Si14.5%, Ca 1.32%, As 0.04% and Cu 0.2%) with (H of waste acid containing arsenic2SO4280g/L, As 9.3g/L, Cu 86.2mg/L, current potential 485mv) it is mixed in a certain ratio tune Slurry makes the molar ratio 1.4 of arsenic content in the iron and waste acid of dissolution, is stirred to react at normal temperature 1 hour, to the mixing tune after reaction It starches in material stirring slot, is added in lime stone with part free acid, is stirred to react 2 hours, so that pH value is maintained at about 1.2, solid-liquid Separation is obtained after washing and is sold outside qualified gypsum tailings；Oxidation, by the filtered wash solution one of supernatant dense after preneutralization and dense slurry And be transferred in stirred tank, source of iron is supplemented as needed, meets Fe/As molar ratio about 1.4 in solution, controls solution temperature 70 DEG C, add dioxygen water management terminal oxidation-reduction potential in the section 600mV, trivalent arsenic is made all to be oxidized to pentavalent arsenic, iron is three Valence iron；Solution after oxidation is warming up to 85 DEG C, crystal seed 200g/L is added by one section of heavy arsenic, and milk of lime is not added in one section of heavy arsenic stage, Be stirred to react 6 hours, after be separated by solid-liquid separation through concentrator, underflow part is back to one section of heavy arsenic incipient stage as crystal seed, Remaining underflow open circuit, adds milk of lime alkali tune to be neutralized to pH 8.5, is then fed into plate and frame filter press and is separated by solid-liquid separation, filter-press residues enter Landfill yard；Toxicity characteristic leaching procedure is carried out to the slag for entering landfill yard, leachate pH8.5, arsenic concentration 0.085mg/L meet country Standard of landfill (GB18598-2001 hazard waste landfill contamination control standard), into the quantity of slag 3.3t/t arsenic of landfill yard；Two sections Heavy arsenic, one section of heavy dense supernatant arsenic content about 0.8g/L of arsenic add milk of lime to control solution terminal pH 7.5, by arsenic with indefinite form Ferric arsenate form precipitating, the solid mixtures such as ferric arsenate, iron hydroxide and calcium sulfate of generation after concentrator is separated by solid-liquid separation, All it is back to the preneutralization stage.Arsenic concentration is less than 0.5mg/L in solution after two sections of heavy arsenic.Two sections of heavy arsenic supernatants and one section are heavy Filtrate is used as recycle-water return existing system after arsenic plate compression.
As described above, the present invention can be better realized.Above-described embodiment is only the optimal embodiment of the present invention, but this The embodiment of invention is simultaneously not restricted to the described embodiments, what other were done without departing from the spirit and principles of the present invention Change, modification, replacement, combination, simplify, should be equivalent substitute mode, be included in protection scope of the present invention.

Claims (4)

1. a kind of comprehensive utilization of waste acid containing arsenic and the Safe disposal method of arsenic, it is characterised in that successively by following processing step and Condition carries out:
(1) preneutralization: waste acid is mixed with the thickened underflow that two sections of heavy arsenic processes return, adds lime stone to carry out preneutralization, until not The low acid concentration for generating arsenic precipitation reaction is 10-20g/L H2SO4, preneutralization slurry enters thickening pond, obtains supernatant and dense bottom Stream, combination of the thickened underflow through filtration washing, multi-stage countercurrent washing or both, obtains washing lotion and meets the conjunction of cement additive standard Lattice gypsum tailings, gypsum tailings are sold outside；
(2) aoxidize: supernatant and washing lotion aoxidize together after will be dense, control 40~90 DEG C of solution temperature, are added with sulfuric acid Ferrous or ferric sulfate etc. is source of iron containing ferron, controls the iron arsenic molar ratio 1.0~1.5 in solution, and oxidant hydrogen peroxide is added, Controlling terminal oxidation-reduction potential converts trivalent arsenic completely using an interstage section or multistage continuous oxidation in 550~700mV For pentavalent arsenic, solution after must aoxidizing；
(3) one sections of heavy arsenic: entering heavy arsenic slot for solution after oxidation and carry out one section of heavy arsenic, 85~100 DEG C of reaction temperature of control, initial smelly Any neutralizer can be not added in the process or lime is added for 50~300g/L of green onion stone seed concentration, solution ph 0.6~1.5, heavy arsenic Cream is reacted heavy arsenic, the underflow for obtaining clear liquid and precipitating with scorodite form, part scorodite precipitation for 4~8 hours after dense Underflow returns to heavy arsenic slot and makees crystal seed, remaining scorodite precipitation underflow open circuit adds one or more levels alkali tune of neutralizer to neutralize to terminal PH7.0~10.0 can add iron when the iron arsenic molar ratio in alkali tune and in solution contained by underflow is lower than 1.5 during alkali tune Source obtains filtrate and slag through plate compression, and slag can be directly entered landfill yard；
(4) two sections of heavy arsenic: the dense rear supernatant of one section of heavy arsenic is carried out two sections of heavy arsenic stages, addition milk of lime controls endpoint pH 5.5~9.0, arsenic slurry feeding concentrator progress of sinking is dense, obtains two sections of heavy arsenic supernatants and thickened underflow.
2. the method as described in claim 1, it is characterized in that before the step (1) preneutralization can in mine acid wastewater and slag or It smelts scum etc. and substitutes part lime stone containing scum, in advance plus part waste acid is tuned into slurry and enters back into preneutralization process, to utilize Acid dissolution in waste acid provides source of iron containing scum simultaneously and part neutralizes containing the iron or other acid consumpting substances in scum, can depending on feelings It is supplemented in oxidation operation and source of iron is added, meet iron arsenic than requiring.
3. it is method according to claim 1 or 2, it is characterized in that (4) two sections of heavy arsenic thickened underflows of the step are all back to Step (1) preneutralization reuse.
4. it is method according to claim 1 or 2, it is characterized in that (4) two sections of heavy arsenic supernatants of the step and one section of heavy arsenic plate Filtrate is used as recycle-water after frame filters pressing, returns to existing system as flue gas washing and supplements water or preneutralization gypsum tailings slurry.
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CN112897730A (en) * 2021-01-07 2021-06-04 易门铜业有限公司 System and method for treating and recycling high-arsenic high-fluorine waste acid
CN112897730B (en) * 2021-01-07 2023-01-06 易门铜业有限公司 System and method for treating and recycling high-arsenic high-fluorine waste acid
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CN113620464A (en) * 2021-08-12 2021-11-09 楚雄滇中有色金属有限责任公司 Processing method of colored smelting waste acid for forming amorphous ferric arsenate
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