CN105600982A - Process for treating polluted acid water in copper smelting by utilizing calcium and magnesium desulfurization sludge - Google Patents

Process for treating polluted acid water in copper smelting by utilizing calcium and magnesium desulfurization sludge Download PDF

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Publication number
CN105600982A
CN105600982A CN201510979910.3A CN201510979910A CN105600982A CN 105600982 A CN105600982 A CN 105600982A CN 201510979910 A CN201510979910 A CN 201510979910A CN 105600982 A CN105600982 A CN 105600982A
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sour water
dirty sour
desulfurization sludge
calcium
technique
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CN105600982B (en
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韩正昌
高亚娟
马军军
崔洪磊
张寅丞
朱伯淞
王云枫
张寿兵
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Nanjing Ge Luote Environmental Engineering Limited-Liability Co
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Nanjing Ge Luote Environmental Engineering Limited-Liability Co
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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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • 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
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Treatment Of Sludge (AREA)

Abstract

The invention discloses a process for treating polluted acid water in copper smelting by utilizing calcium and magnesium desulfurization sludge. The process comprises the steps of (1) directly injecting the polluted acid water under the strong acid condition that the pH value is less than 1 into a catalytic oxidization device with special ferric carbon fillers, and reacting for 10-60 minutes; (2) mixing the polluted acid water after the reaction in the step (1) with concentrated and dehydrated calcium and magnesium desulfurization sludge (based on the water content of 60%) according to a mass ratio of 1 to (0.2-1.2), stirring, reacting for 10-120 minutes, and maintaining the pH value of slurry to be 2-4; (3) adding an oxidizer into the slurry obtained in the step (2) and reacting for 10-120 minutes; (4) performing a neutralization reaction of the slurry obtained in the step (3) and adjusting the pH value of the slurry to be more than 9.2; and (5) precipitating and filtering a solution obtained in the step (4), adjusting the pH value of a filter liquor to be 6-9, and discharging heavy metal by standard. According to the process, the problems in treatment of the calcium and magnesium desulfurization sludge and the polluted acid water can be directly and synchronously solved.

Description

A kind of calcium, magnesium method desulfurization sludge of utilizing processed the technique that copper is smelted dirty sour water
Technical field
The invention belongs to technical field of sewage, be specifically related to one and utilize calcium, magnesium method desulfurization sludge to process copper smeltingThe technique of dirty sour water.
Background technology
The main source of the dirty sour water of copper smelting industry be the flue gas washing of smelting workshop section, off-gas recovery the relieving haperacidity stage andElectrolyte workshop section, the dirty sour water (comprising the dirt acid in relieving haperacidity stage) that this three phases produces accounts for whole smelting and produces acid waste waterMore than 90%. In dirty sour water, contain element, the especially arsenic elements such as a large amount of arsenic, cadmium, lead, zinc, copper, greatly increased dirty sour waterToxicity. Therefore,, processing in the process of dirty sour water, also to remove arsenic and the heavy metal element in dirty sour water simultaneously. Dirty sour water producesThe raw water yield is huge, is highly acid, will have a strong impact on the normal fortune of municipal sewage plant if directly enter municipal wastewater pipe networkOK, enter external environment and will make water quality worsen, intractability is higher, has become at present non-ferrous metal industry and has been difficult to separateA great problem certainly. The physical and chemical index of dirty sour water routine is as shown in table 1.
The physical and chemical index of the conventional dirty sour water of table 1
H2SO4 As Zn Cd Cu Pb
mg/L 48260 12470 350 109 1040 200
Can be found out by the data in table 1, in dirty sour water, the concentration of arsenic has reached 12470mg/L, accounts for 1.2% of solution, concentrationVery high, the constituent contents such as heavy metal element zinc, cadmium, copper are also higher, and fluorine element also significantly exceeds standard. Therefore, dirty sour water belongs to tightThe toxic wastewater of heavily contaminated, directly discharge will certainly cause great destruction to environment, need to process up to standard just can enter into afterwardsIn city planting ductwork or environment water.
In existing treatment technology, the high arsenic-containing waste water that contains generally adopts lime-ferrous sulfate method and sodium sulfide method placeReason. Ferrous sulfate-lime method is that the iron in recycling ferrous sulfate can generate with arsenic the hydrogen-oxygen of difficulty soluble salt, iron with lime neutralizationCompound has the characteristic of powerful Adsorption and flocculation ability, reaches the object of harmful heavy metals such as removing arsenic in dirty acid, cadmium. AdoptThe removal effect of this technology one side arsenic is unstable, wants qualified discharge, needs a large amount of lime and ferrous sulfate, reagent consumptionVery large, cost is very high; The waste residue producing is on the other hand larger, and secondary pollution easily occurs. Sulfuration method is to vulcanize by solubilityThing reacts with heavy metal, generates indissoluble sulfide, and it is removed from dirty acid. The effect that sulfuration method is removed arsenic, cadmium is not too remarkable,What in dirty acid after treatment, the content of arsenic had reaches 100mg/L, far exceedes the limit value of discharge standard. In addition, in the waste residue of generationArsenic element is 3+ arsenic, and toxicity is very big.
In calcium method and magnesium method sweetening process, through spraying for a long time, mud can be formed on bottom, and final mud can be denseClose motor spindle concentrates. The mud that calcium method and the desulfurization of magnesium method produce contains arsenic and heavy metal element, therefore can not arbitrarily stackOr simple process, otherwise can pollute surrounding environment. At present, main for the desulfurization sludge treatment technology of calcium method and the generation of magnesium methodThere are two kinds of processing methods: landfill and to build storehouse temporary. Landfill disposal is mainly using desulfurization sludge as solid waste landfill and dangerLandfill factory gives up. Owing to containing a large amount of arsenic and heavy metal element in desulfurization sludge, its content severe overweight, therefore can not be as oneAs discarded object process, but useless processing of endangering, therefore needed disposal cost is very high; Build place of temporary Ye Shi enterprise, storehouseThe conventional method of reason desulfurization sludge, enterprise by desulfurization sludge concentrate, mummification, reduce volume and the quality of mud, build storehouse temporaryDeposit, treat that technical development processing to can effectively processing these mud when. But desulfurization sludge generation is very large, because ofThis there will be the phenomenon of swell-warehouse. At present, also have some technology, such as desulfurization is carried out to pyrolytic, solid is decomposed into SO2WithContain magnesian solid etc., because cost is higher, and have secondary pollution, its through engineering approaches application is obstructed.
Summary of the invention
The problem existing for above-mentioned prior art, the invention provides one and utilizes calcium, magnesium method desulfurization sludge to process copper smeltingRefine the technique of dirty sour water, can directly synchronously solve the governing problem of calcium, magnesium method desulfurization sludge and dirty sour water.
The present invention relates to the treatment process of the dirty sour water of copper smelting industry and the industrially desulfurized mud of desulfurization, disclosed a kind of profitThe technique of processing dirty sour water with calcium, magnesium method desulfurization sludge, its main contents are as follows:
(1) dirty sour water is directly squeezed under the strong acidic condition of pH < 1 to the catalytic oxidizer that contains special iron carbon filler, reactionTime is 10-60min, is mainly by mainly by As3+Under strong acidic condition, be oxidized to As5+, can produce a certain amount of simultaneouslyFe3+；
(2) calcium after reacted step (1) dirty sour water and thickening, magnesium method desulfurization sludge (in moisture content 60%) are pressedBe that 1:0.2-1.2 ratio is mixed according to mass ratio, stir, the reaction time is 10-120min, maintains the pH of slurries between 2-4;
(3) be liquid oxidizer and/or the gaseous oxidation of 0.1-10% to adding mass fraction in the slurries that obtain in step (2)Agent, the reaction time is 10-120min, makes the As in solution5+Form H2AsO4 -、HAsO4 2-、AsO4 3-；
(4) slurries that step (3) obtained carry out neutralization reaction, regulate the pH of slurries more than 9.2, to make in solutionH2AsO4 -、HAsO4 2-Be converted into AsO4 3-, and with dirty sour water in Cu2+、Pb2+、Zn2+、Cd2+、Hg2+、Mg2+、Ca2+、Fe3+Deng goldBelong to ion and form corresponding arsenate precipitation, the reaction time is 10-120min;
Reaction equation is:
3Cu2++2AsO4 3-→Cu3(AsO4)2↓ its Ksp is 10-44
3Pb2++2AsO4 3-→Pb3(AsO4)2↓ its Ksp is 10-36
3Cd2++2AsO4 3-→Cd3(AsO4)2↓ its Ksp is 10-33
3Zn2++2AsO4 3-→Zn3(AsO4)2↓ its Ksp is 10-28
Fe3++AsO4 3-→FeAsO4↓ its Ksp is 10-21
3Mg2++2AsO4 3-→Mg3(AsO4)2↓ its Ksp is 10-20
3Ca2++2AsO4 3-→Ca3(AsO4)2↓ its Ksp is 10-19
Because Cu2+、Pb2+、Zn2+、Mg2+、Ca2+、Fe3+With AsO4 3-The arsenate salt precipitation that is insoluble in water forming, can be by dirty acidArsenic in water and other heavy metal elements are removed;
In the time that the pH of solution is greater than 9.2, the H in solution2AsO4 -、HAsO4 2-Content reduced micro-rank, arsenic mainly withMainly with AsO4 3-Form exist, therefore arsenic under this pH condition total overall reaction form precipitation, it is gone from the aqueous solutionRemove. In addition, under this pH condition, with Fe3+With OH-Reaction forms Fe (OH)3Precipitation, also has good absorption, wadding to arsenic elementSolidifying effect, promotes the removal of arsenic and other heavy metals more;
(5) solution step (4) being obtained precipitates, filters, and regulates the pH to 6-9 of filtrate, heavy metal qualified discharge.
Preferably, special iron material with carbon element described in step (1), iron, carbon, rare earth element are being greater than the high temperature bar of 980 degreeUnder part, carry out sintering.
Preferably, the special iron carbon filler described in step (1) is iron, charcoal, rare earth ore concentrate, and wherein the mass ratio of iron isThe mass ratio of 50-80%, charcoal is that the mass ratio of 10-20%, rare earth ore concentrate is 10-30%.
Preferably, rare earth element is lanthanum chloride or cerium chloride.
Preferably, in step (1), optimum reacting time is 20-50min.
Preferably, in step (2), dirty sour water and desulfurization sludge (taking moisture content 60%) are 1:0.5-1.2 according to mass ratioRatio is mixed.
Preferably, in step (2), dirty sour water and desulfurization sludge optimum reacting time are 20-60min.
Preferably, in step (3), liquid oxidizer used be a kind of in hydrogen peroxide, clorox, hypochlorous acid orSeveral; Gaseous oxidizer is one or more in air, oxygen, ozone.
Preferably, in step (3), the optimum reacting time of oxidation is 40-60min.
Preferably, in step (4), regulate pH value alkali used for containing calcium oxide and meta-alkali compound, containing na oxideAnd meta-alkali compound, magnesium-containing oxide and meta-alkali compound, containing zinc oxide and meta-alkali compound, containing ba oxide and meta-alkaliCompound, containing one or several of aluminum oxide and meta-alkali compound, oxides-containing iron and meta-alkali compound.
The advantage of patent of the present invention:
1, process dirty sour water and magnesium method desulfurization sludge simultaneously. Patent of the present invention, utilizes two kinds of discarded objects of dirty sour water and desulfurization sludgeFeature, process simultaneously, not only utilize alkaline matter and acidulous material in desulfurization sludge, neutralize the sulphur in dirty sour waterAcid, reduces the needed a large amount of alkali of neutralization reaction, can also utilize Mg a large amount of in desulfurization sludge2+、Ca2+Precipitate dirty sour waterMiddle AsO4 3-Form Mg3(AsO4)2、Ca3(AsO4)2Precipitation, the arsenic ion in the most dirty sour water is removed. Patent of the present invention is abundantUtilize the feature of two kinds of discarded objects, by its associated treatment, saved being processed into of dirty sour water and two kinds of discarded objects of desulfurization sludgeThis, realized that discarded object is innoxious, the processing of greenization.
2, significantly reduced the generation of solid slag. In patent of the present invention, desulfurization sludge is mixed with dirty sour water, in acidUnder property condition, the main component in desulfurization sludge can with dirty acid reaction, desulfurization sludge can be dissolved in dirty acid, therefore by desulfurization dirtThe waste residue of mud is fully cleared up, and it is zero that the waste residue amount of desulfurization sludge is subdued. Mg in desulfurization sludge2+、Ca2+With dirty sour waterArsenic and heavy metal element can generate arsenate precipitation, and this part indissoluble thing can exist with the form of solid waste. But, with desulfurizationMud is comprehensively compared with the solid quantity of slag of processing dirty sour water generation, and the solid quantity of slag that arsenate precipitation produces significantly reduces, too lateOne of percentage originally. Therefore, patent technique of the present invention can significantly reduce the generation of solid waste, the useless expense of processing of dangerAlso be reduced to one of original percentage, economic benefit and obvious environment benefit.
3, reduced the toxicity of solid waste. In dirty sour water, contain a large amount of arsenic elements, have+3 valencys of arsenic and+5 valencys point,As3+Toxicity far away higher than As5+, and trivalent arsenic is very unstable, easily surrounding environment is worked the mischief. Adopting sulfuration methodWhile precipitation, main formation is with As3+Be main As2S3Precipitation, its toxicity is larger, and easily oxidized and then to environmentWork the mischief. In patented technology of the present invention, adopt the method for oxidation precipitation, will turn As3+Finally be oxidized to AsO4 3-, and and solutionIn metal cation form arsenate precipitation, the precipitation forming is mainly Mg3(AsO4)2、Zn3(AsO4)2、FeAsO4Deng heavyForm sediment, its for pentavalent arsenic be the deposit of leading, toxicity reduces greatly, and in environment, exists form more stable, alleviates that it is rightThe potential hazard of extraneous ecological environment.
4, greatly reduce the disposal cost of dirty sour water. In the time carrying out dirty acid water processing, while adopting lime method, need to consumeA large amount of alkali, and produce in and the quantity of slag very large, in and the useless processing cost of slag danger also can significantly increase; Adopting the processing of sulfuration methodWhen dirty sour water, As3+With S2-Formation arsenones precipitation, still, along with the interpolation of vulcanized sodium, the pH of solution can raise, along with solutionThe rising of pH, the arsenic element in solution is by As3+Change AsO3 into3-Form, not can with S2-Form precipitation, therefore usingWhen the arsenic removal of sulfuration method, need in solution, add acid, guarantee that the pH of solution is always in acid state, so not only can consume largeVulcanized sodium, the alkaline matter of amount, also will consume a large amount of acid, and its operating cost is approximately 110 yuan/ton. Patent of the present invention is abundantUtilize MgO, MgSO in desulfurization sludge3With CaO, CaSO3Compound, consumes the acidic materials in dirty sour water, in oxidant effectUnder, produce Mg3(AsO4)2And Ca3(AsO4)2Precipitation, does not need to add extra precipitating reagent, is therefore utilizing this PROCESS FOR TREATMENT uselessIn not needing when water and waste residue to add, with medicament and precipitation medicament, operating cost reduces greatly.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of technique of the present invention.
Detailed description of the invention
Embodiment 1
Schematic flow sheet as shown in Figure 1: get the desulfurization that in the dirty sour water of the grand copper industry of Tongling, Anhui Province gold and its factory, the desulfurization of magnesium method producesMud, the pH of dirty sour water is 0.56, the pollution factor wherein containing in dirty sour water has arsenic, copper, zinc, cadmium etc., desulfurization sludge processAfter concentrated, moisture content is reduced to 60% left and right. Dirty sour water is directly entered and contains 10% lanthanum chloride, 80% iron and 10% carbonThe pretreatment reaction device of the special iron carbon filler producing under 990 degree high temperature sinterings, the reaction time is 30min, its water outlet and denseMud (taking moisture content 60%) after contracting is that 1:0.8 mixes according to mass ratio, stirs 40min, the pH that maintains slurries 2-4 itBetween, the key reaction of generation is:
MgSO3+H2SO4→MgSO3+SO2+H2OSO2+H2O→H2SO3
H2SO3+MgO→MgSO3+H2O
Mg(OH)2+H2SO4→MgSO4+2H2O
CaSO3+H2SO4→CaSO3+SO2+H2O
SO2+H2O→H2SO3
H2SO3+CaO→CaSO3+H2O
Mg(OH)2+H2SO4→MgSO4+2H2O
……..
Adding mass fraction is 0.1% oxidant hydrogen peroxide, and stirring reaction 60min adds afterwards calcium oxide and regulates pH to 10 left sideThe right side, adds PAM, and low rate mixing 10min filters the content of measuring pollution factor in supernatant. Determination data is as shown in table 2.
Table 2 measured data
Can be found out by the data in table 2, dirty sour water Central Plains water is strongly acid wastewater, and wherein arsenic element severe overweight, has reached8270mg/L, secondly also severe overweight of lead content, has reached 182.30mg/L, and the heavy metal elements such as while cadmium, zinc, copper also have notWith exceeding standard of degree, dirty sour water belongs to highly acid, pollutes very serious waste water, if directly discharge meeting causes environment greatlyHarm. After the technology of the present invention is processed, the arsenic element in dirty sour water has been reduced to 0.35mg/L, and clearance has reached 100%;Zinc concentration has been reduced to 0.24mg/L, and clearance has reached 99.9%; Lead concentration has been reduced to 0.24mg/L, and clearance reaches99.8%; Cadmium concentration has been reduced to 0.02mg/L, and clearance has reached 99.7%; Copper concentration has been reduced to 0.22mg/L, goesExcept rate has reached 95.8%; Mercury concentration has been reduced to 0.02mg/L, and clearance has reached 94.1%.
Can find out the technique in patent of the present invention, utilize calcium method and magnesium method desulfurization sludge to process dirty sour water, can be by dirtArsenic and heavy metal element in sour water are effectively removed, and especially the clearance of arsenic element has reached 100%, other heavy metals fromThe removal efficiency of son has also reached more than 90%. Meanwhile, cleared up the solid slag that desulfurization sludge produces, waste residue amount can subtractArrive less originally 0.01%, significantly, by the low generation of danger wastes, waste water can qualified discharge. The art of this patent processingEffect is good, makes full use of offal treatment discarded object, and operating cost reduces greatly, and technique is simple, easy operating.
Embodiment 2
Schematic flow sheet as shown in Figure 1: get the desulfurization that in the dirty sour water of the grand copper industry of Tongling, Anhui Province gold and its factory, the desulfurization of magnesium method producesMud, the pH of dirty sour water is 0.56, the pollution factor wherein containing in dirty sour water has arsenic, copper, zinc, cadmium etc., desulfurization sludge processAfter concentrated, moisture content is reduced to 60% left and right. By dirty sour water directly enter contained load 30% cerium chloride, 50% iron andThe pretreatment reaction device of the special iron carbon filler that 20% carbon produces under 990 degree high temperature sinterings, the reaction time is 20min, it goes outWater with concentrated after mud (taking moisture content 60%) mixes as 1:1.0 according to mass ratio, stirring 40min, the pH that maintains slurries existsBetween 2-4, adding mass fraction is 10% oxidant hydrogen peroxide, and stirring reaction 90min adds afterwards calcium oxide and regulates pH to 10Left and right, adds PAM, and low rate mixing 10min filters the content of measuring pollution factor in supernatant. Determination data is as shown in table 3.
Table 3 measured data
Can be found out by the data in table 3, dirty sour water Central Plains water is strongly acid wastewater, and wherein arsenic element severe overweight, has reached22245mg/L, secondly also severe overweight of zinc content, has reached 231.90mg/L, and the heavy metal elements such as while cadmium, lead, copper also haveExceeding standard in various degree, dirty sour water belongs to highly acid, pollutes very serious waste water, if directly discharge meeting causes greatly environmentHarm. By utilizing desulfurization sludge to process dirty sour water, and after peroxidating, neutralization, sedimentation and filtration, the arsenic element in dirty sour waterBe reduced to 0.37mg/L, clearance has reached 100%; Zinc concentration has been reduced to 0.45mg/L, and clearance has reached 99.8%;Lead concentration has been reduced to 0.12mg/L, and clearance has reached 96.7%; Cadmium concentration has been reduced to 0.07mg/L, and clearance reaches99.0%; Copper concentration has been reduced to 0.28mg/L, and clearance has reached 94.5%.
Can find out the technique in patent of the present invention, utilize calcium method and magnesium method desulfurization sludge to process dirty sour water, can be by dirtArsenic and heavy metal element in sour water are effectively removed, and especially the clearance of arsenic element has reached 100%, other heavy metals fromThe removal efficiency of son has also reached more than 90%. Meanwhile, clear up the solid slag that desulfurization sludge produces, significantly by low dangerThe generation of danger discarded object, waste water can qualified discharge. The art of this patent treatment effect is good, makes full use of offal treatment uselessGurry, operating cost reduces greatly, and technique is simple, easy operating.

Claims (10)

1. utilize calcium, magnesium method desulfurization sludge to process a technique for dirty sour water, it is characterized in that, comprise following content:
(1) dirty sour water is directly squeezed under the strong acidic condition of pH < 1 to the catalytic oxidizer that contains special iron carbon filler, reactionTime is 10-60min;
(2) by the calcium that after reacted step (1) dirty sour water and thickening, moisture content is 60%, magnesium method desulfurization sludge according to matterAmount, than mixing for 1:0.2-1.2 ratio, stirs, and the reaction time is 10-120min, maintains the pH of slurries between 2-4;
(3) be liquid oxidizer and/or the gaseous oxidation of 0.1-10% to adding mass fraction in the slurries that obtain in step (2)Agent, the reaction time is 10-120min, makes the As in solution5+Form H2AsO4 -、HAsO4 2-、AsO4 3-；
(4) slurries that step (3) obtained carry out neutralization reaction, regulate the pH of slurries more than 9.2, to make in solutionH2AsO4 -、HAsO4 2-Be converted into AsO4 3-, and forming corresponding arsenate precipitation with the metal ion in dirty sour water, the reaction time is10-120min；
(5) solution step (4) being obtained precipitates, filters, and regulates the pH to 6-9 of filtrate, heavy metal qualified discharge.
2. the technique of utilizing calcium, magnesium method desulfurization sludge to process dirty sour water according to claim 1, is characterized in that step(1) material with carbon element of special iron described in is that iron, carbon, rare earth element carry out sintering and form under the hot conditions that is greater than 980 degree.
3. the technique of utilizing calcium, magnesium method desulfurization sludge to process dirty sour water according to claim 2, is characterized in that, described inSpecial iron carbon filler be iron, charcoal, rare earth ore concentrate, wherein the mass ratio of iron is that the mass ratio of 50-80%, charcoal is 10-20%, rare earthThe mass ratio of concentrate is 10-30%.
4. the technique of utilizing calcium, magnesium method desulfurization sludge to process dirty sour water according to claim 2, is characterized in that rare earthElement is lanthanum chloride or cerium chloride.
5. the technique of utilizing calcium, magnesium method desulfurization sludge to process dirty sour water according to claim 1, is characterized in that step(1), in, the reaction time is 20-50min.
6. the technique of utilizing calcium, magnesium method desulfurization sludge to process dirty sour water according to claim 1, is characterized in that step(2), in, dirty sour water is that 1:0.5-1.2 ratio is mixed with desulfurization sludge according to mass ratio.
7. the technique of utilizing calcium, magnesium method desulfurization sludge to process dirty sour water according to claim 1, is characterized in that step(2), in, dirty sour water and desulfurization sludge reaction time are 20-60min.
8. the technique of utilizing calcium, magnesium method desulfurization sludge to process dirty sour water according to claim 1, is characterized in that step(3), in, liquid oxidizer used is one or several in hydrogen peroxide, clorox, hypochlorous acid; Gaseous oxidizer is emptyOne or more in gas, oxygen, ozone.
9. the technique of utilizing calcium, magnesium method desulfurization sludge to process dirty sour water according to claim 1, is characterized in that step(3), in, the optimum reacting time of oxidation is 40-60min.
10. the technique of utilizing calcium, magnesium method desulfurization sludge to process dirty sour water according to claim 1, is characterized in that step(4), in, regulate pH value alkali used for containing calcium oxide and meta-alkali compound, contain na oxide and meta-alkali compound, containing magnesiaCompound and meta-alkali compound, containing zinc oxide and meta-alkali compound, containing ba oxide and meta-alkali compound, containing aluminum oxide and partiallyOne or several of alkali cpd, oxides-containing iron and meta-alkali compound.
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Cited By (2)

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CN106862235A (en) * 2017-02-14 2017-06-20 深圳市能源环保有限公司 A kind of on-line checking heavy metal solid waste method for innocent treatment
CN111035882A (en) * 2019-11-21 2020-04-21 扬州杰嘉工业固废处置有限公司 Method for the synergistic treatment of arsenic-containing waste and barium-containing waste for stabilization and solidification

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