CN105884100B - A kind of processing method of heavy metal wastewater thereby - Google Patents

A kind of processing method of heavy metal wastewater thereby Download PDF

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CN105884100B
CN105884100B CN201610405544.5A CN201610405544A CN105884100B CN 105884100 B CN105884100 B CN 105884100B CN 201610405544 A CN201610405544 A CN 201610405544A CN 105884100 B CN105884100 B CN 105884100B
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heavy metal
wastewater
treatment fluid
processing
metal wastewater
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CN105884100A (en
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安俊芳
陈磊
吴勇前
张静
孔令鸟
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浙江奇彩环境科技股份有限公司
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    • C02F1/28Treatment of water, waste water, or sewage by sorption
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    • C02F1/28Treatment of water, waste water, or sewage by sorption
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    • C02F1/48Treatment of water, waste water, or sewage with magnetic or electric fields
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    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
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    • C02F1/72Treatment of water, waste water, or sewage by oxidation
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    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
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    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/76Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
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    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/76Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C02F1/766Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
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    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
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    • C02F2101/20Heavy metals or heavy metal compounds
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    • C02F2101/206Manganese or manganese compounds
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    • C02F2101/10Inorganic compounds
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    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
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    • C02F2305/10Photocatalysts

Abstract

The invention discloses a kind of processing methods of heavy metal wastewater thereby, useless water part organic matter, which is removed, first with the oxidation of oxidant obtains treatment fluid 1, then strong suction-operated of the adsorbent to heavy metal ion in water is utilized, heavy metal in removal treatment fluid 1 obtains treatment fluid 2, remaining organic matter is degraded by light-catalyzed reaction in treatment fluid 2, light-catalyzed reaction can generate the high free radical of many activity, these free radicals have splendid removal effect to organic matter, and the water outlet after photocatalysis treatment can reuse.Processing method processing of the present invention is thorough, without secondary pollution, useful resources can be recycled and be easy to industrialization.

Description

A kind of processing method of heavy metal wastewater thereby

Technical field

The present invention relates to waste water reclaiming recycling fields, and in particular to a kind of processing method of heavy metal wastewater thereby.

Background technique

Heavy metal wastewater thereby refers to that is be discharged in the industrial processes such as mining and metallurgy, machine-building, chemical industry, electronics, instrument contains weight The waste water of metal.The heavy metal pollution of water body has become one of the environment of world today's most serious.

The common technology of heavy metal containing wastewater treatment has at present:

1. chemical method: chemical precipitation method, oxidation-reduction method, solvent extraction and separation.

2. physical-chemical process: ion-exchange, absorption method, membrane separation technique;

3. bioanalysis: phytoremediation, bio-flocculation process, biosorption process.

These traditional treatment process, although can be by the heavy metals removal in waste water, treatment effect be simultaneously unstable, The clear water water quality recycled after processing is still difficult to ensure that stably reaching standard discharges, but also can generate secondary pollution.

Summary of the invention

In order to overcome the above-mentioned defects in the prior art, the present invention provides a kind of processing methods of heavy metal wastewater thereby.

A kind of processing method of heavy metal wastewater thereby, which comprises the following steps:

(1) it aoxidizes: oxidant being added into heavy metal wastewater thereby, oxidation reaction removes useless water part organic matter and handled Liquid 1;Wherein the dosage of oxidant is the 0.05~5% of wastewater quality;

(2) it adsorbs: adsorbent being added into treatment fluid 1 obtained in step (1), treatment fluid 2 is obtained after absorption;Wherein inhale Attached dose of additional amount is the 0.01~3% of wastewater quality;

(3) photochemical catalytic oxidation: light-catalyzed reaction is carried out to treatment fluid 2 obtained in step (2), obtains treatment fluid 3;Wherein Hydrogen peroxide add ratio be wastewater quality 0.5~5%, hydrogen peroxide mass concentration be 25~50%, the reaction time be 0.5~ 5h, light source used in light-catalyzed reaction are low pressure mercury lamp, and power is 300~800W.

In processing method of the present invention, it is organic that the useless water part of removing is decomposed first with the oxidation of oxidant Object obtains treatment fluid 1, then utilizes strong suction-operated of the adsorbent to heavy metal ion in water, removes the huge sum of money in treatment fluid 1 Category obtains treatment fluid 2, and remaining organic matter is degraded by light-catalyzed reaction in treatment fluid 2, and light-catalyzed reaction can generate many work Property high free radical, these free radicals have splendid removal effect to organic matter, and the water outlet after photocatalysis treatment can reuse.

Further, the heavy metal wastewater thereby is mercurous (Hg2+), manganese (Mn2+), copper (Cu2+), lead (Pb2+), nickel (Ni2+)、 Chromium (Cr2+) in one or more waste water.

Preferably, oxidation process described in step (1), can cooperate one or both of flocculation and adsorption process, wadding Solidifying or adsorption process can be before oxidation process or after oxidation process.Further preferably, using flocculation and absorption before oxidation process.Flocculation It gets rid of major part heavy metal ion present in waste water first with adsorption process, oxidant can be improved in step (1) to waste water The removal rate of middle organic matter.Flocculant added by flocculation process can be inorganic flocculating agent, organic synthesis high polymer coagulant, natural The mixing of one or more of high polymer coagulant.

Preferably, before step (1) oxidation, flocculation treatment first is carried out to heavy metal wastewater thereby, the flocculant is sulfuric acid Aluminium, aluminium polychloride (PAC), bodied ferric sulfate (PFS), poly aluminium sulfate silicate, polyacrylamide (PAM), polyethyleneimine, One or more of chitosan, modified starch, the dosage of flocculant are 0.01~5%.

Preferably, first carrying out electromagnetism flocculation treatment to heavy metal wastewater thereby before step (1) oxidation;Flocculant is in electricity It is 44.6~89.0mT that magnetized magnetic field strength is carried out in magnetic device, and magnetizing time is 4~10min, and the dosage of flocculant is useless The 0.01~1% of water quality.Flocculation process can remove major part heavy metal ion present in waste water first, reduce heavy metal To the consumption of oxidant, reduce inhibition of the heavy metal to oxidation, to improve in step (1) oxidant to useless Organic substance in water Removal rate.In all identical situation of other conditions, flocculant solution is through electromagnetization compared with the magnetized effect of non-electrical: best Dosage can reduce 1/4-1/2;Meanwhile wadding body forms speed and accelerates, moisture content is low in wadding body, when shortening flocculation and sedimentation Between, reduce the loss of water and the yield of solid waste.

Step (1) oxidant be hydrogen peroxide, ozone, hypochlorite, iodine, Fenton reagent, permonosulphuric acid (also referred to as One or more of oxygen sulfuric acid) or Peracetic acid, the additional amount of oxidant is the 0.1~4% of wastewater quality.Preferably, Oxidant described in step (1) is hydrogen peroxide, and mass concentration is preferably 25~50%, and dosage is preferably wastewater quality 1~3%.

Step (2) adsorbent is in active carbon, diatomite, modified graphene oxide, graphene or carbon nanotube One or more, the additional amount of adsorbent are the 0.01~1% of wastewater quality.

The modified graphene oxide is ethylenediamine tetraacetic acid modified graphene oxide (EDTA-GO), silane-modified oxidation One or more of in the graphene oxide that graphene, chitosan magnetic are modified, additional amount is the 0.02~0.5% of wastewater quality. Further preferably, step (2) adsorbent is EDTA-GO, after adsorbing heavy metal ion, using regeneration of hydrochloric acid graphite oxide Alkene, for the absorption property of the graphene oxide after regeneration without being decreased obviously, the concentration of hydrochloric acid is 0.1~0.5mol/L.

Catalyst is one or more of titanium dioxide, molysite, mantoquita in step (3) photochemical catalytic oxidation.Preferably, Catalyst can be added without.

Preferably, the hydrogen peroxide in step (3) reaction can be substituted with sodium hypochlorite, chlorine dioxide.Hydrogen peroxide dosage Preferably the 1~3% of wastewater quality.

Compared with the existing technology, the present invention has following remarkable advantage:

(1) concise in technology of the present invention, short flow, it is easy to operate;

(2) processing method processing of the present invention is thorough, without secondary pollution, useful resources can be recycled and be easy to industry Change.

Specific embodiment

Embodiment 1

Mn containing heavy metal2+Mancozeb waste water, Mn2+Content is 300mg/L, salt content 102044mg/L, COD= 2500mg/L。

(1) it flocculates: adjusting pH value of waste water to 8~9,0.1% polyacrylamide (on the basis of wastewater quality) is added, gathers The concentration of acrylamide is 0.3%, filters after mixing slowly 15min, obtains filtrate.

(2) it adsorbs: 0.3% active carbon (on the basis of wastewater quality), stirring being added in the filtrate obtained to step (1) It is filtered after absorption 1h, measures Mn2+Removal rate is 92.4%.

(3) it aoxidizes: 0.1% hydrogen peroxide (on the basis of wastewater quality) is added, into filtrate to remove the second in waste water Alkene thiocarbamide (ETU), wherein the concentration of hydrogen peroxide is 30%, obtains treatment fluid 1, measures the pH=10 for the treatment of fluid 1, COD= 1324mg/L.In weakly alkaline reaction system, the major oxidation product of ETU is ethylene urea (EU).

(4) adsorb: into treatment fluid 1 be added 0.05% ethylenediamine tetraacetic acid modified graphene oxide (EDTA-GO) (with On the basis of wastewater quality), after adsorbing 1h, obtain treatment fluid 2, COD=870mg/L, Mn2+Removal rate is 99.7%.

(5) photocatalysis: 2% hydrogen peroxide (on the basis of wastewater quality) being added into treatment fluid 2, and the concentration of hydrogen peroxide is 30%, it is placed under low pressure mercury lamp, power 300W, after reacting 2h, obtains treatment fluid 3, COD=51.17mg/L.

(6) be concentrated: treatment fluid 3 is handled through MVR distillation, obtains colorless and transparent condensate liquid, COD=20mg/L, direct emission, Concentrate returns to photocatalytic process, continues cycling through processing, obtained sodium sulphate can achieve national II class qualified product mark after measured Standard, the raw material as industries such as production glass.

Embodiment 2

What is generated during lead-acid storage battery production contains heavy metal Pb2+Waste water, acid content 18.6%, sodium sulphate content For 8%, COD=18740mg/L.

(1) it flocculates: adjusting pH value of waste water to 8~9,0.1% polyacrylamide (on the basis of wastewater quality) is added, gathers The concentration of acrylamide is 0.3%, filters after mixing slowly 15min, obtains filtrate.

(2) it adsorbs: 0.3% active carbon (on the basis of wastewater quality), stirring being added in the filtrate obtained to step (1) It is filtered after absorption 1h, measures Pb2+Removal rate is 90.1%.

(3) it aoxidizes: 0.5% hydrogen peroxide (on the basis of wastewater quality) is added, into filtrate to remove having in waste water Machine object, wherein the concentration of hydrogen peroxide is 30%, obtains treatment fluid 1, measures the pH=10 for the treatment of fluid 1, COD=10253mg/L.

(4) it adsorbs: 0.05% silane-modified graphene oxide (on the basis of wastewater quality) being added into treatment fluid 1, After adsorbing 1h, treatment fluid 2 is obtained, the COD=7983mg/L for the treatment of fluid 2, Pb are measured2+Removal rate is 99.5%.

(5) photocatalysis: adding 1% hydrogen peroxide (on the basis of wastewater quality) into treatment fluid 2, and the concentration of hydrogen peroxide is 30%, it is placed under low pressure mercury lamp, power 800W, after reacting 2h, obtains treatment fluid 3.

(6) be concentrated: treatment fluid 3 is handled through MVR distillation, obtains colorless and transparent condensate liquid, measures condensate liquid COD=75mg/ L, direct emission, concentrate return to photocatalytic process, continue cycling through processing.

Comparative example 1

As different from Example 2 in step (4), adsorbent is 0.05% active carbon (on the basis of wastewater quality), is obtained To treatment fluid 2, COD=9800mg/L, Pb2+Removal rate is 91.8%.

Known to the result of comparative example 2 and comparative example 1: the adsorption effect of active carbon is obviously not so good as modified graphite oxide Alkene.

Comparative example 2

As different from Example 2 in step (6), treatment fluid 3 is handled through air-distillation, condensate liquid COD=125mg/L.

From 2 result of embodiment 2 and comparative example: air-distillation effect is good not as good as MVR.

Embodiment 3

By the ethylenediamine tetraacetic acid modified graphene oxide (EDTA-GO) in 1 step of embodiment (4), zeolite regeneration is again For the absorption of heavy metal ion, this Mn2+Removal rate be 98.2%.

Elution process: 0.45 μm of millipore filter of the adsorbent material adsorbed is filtered, is washed with deionized and sloughs not The metal ion being adsorbed, is then added in the hydrochloric acid of 0.1mol/L, and 1h is vibrated on shaking table, with 0.45 μm of millipore filter mistake Filter with the salt acid elution of 0.1mol/L, then is washed with deionized.

Embodiment 4

By the silane-modified graphene oxide adsorbent in 2 step of embodiment (4), zeolite regeneration be reused for heavy metal from The absorption of son, this Pb2+Removal rate be 98.3%.

Elution process: 0.45 μm of millipore filter of the adsorbent material adsorbed is filtered, is washed with deionized and sloughs not The metal ion being adsorbed, is then added in the hydrochloric acid of 0.1mol/L, and 1h is vibrated on shaking table, with 0.45 μm of millipore filter mistake Filter with the salt acid elution of 0.1mol/L, then is washed with deionized.

Embodiment 5

Containing heavy metal Cu2+Acid electroplating waste water, acid content 17.6%, sodium sulphate content 8%, COD= 15730mg/L。

(1) it aoxidizes: 0.5% hydrogen peroxide (on the basis of wastewater quality) is added, into industrial wastewater to remove in waste water Organic matter, wherein the concentration of hydrogen peroxide be 30%, obtain treatment fluid 1, measure the COD=9253mg/L for the treatment of fluid 1.

(2) it adsorbs: 0.05% silane-modified graphene oxide (on the basis of wastewater quality) being added into treatment fluid 1, It is filtered after absorption 1h, obtains treatment fluid 2, measure the COD=4215mg/L for the treatment of fluid 2, Pb2+Removal rate is 99.5%.

(3) photocatalysis: adding 1% hydrogen peroxide (on the basis of wastewater quality) into treatment fluid 2, and the concentration of hydrogen peroxide is 30%, it is placed under low pressure mercury lamp, power 800W, after reacting 2h, obtains treatment fluid 3, measure the COD=590mg/L for the treatment of fluid 3

(4) be concentrated: treatment fluid 3 is handled through MVR distillation, obtains colorless and transparent condensate liquid, COD=65mg/L, direct emission, Concentrate returns to photocatalytic process, continues cycling through processing.

Embodiment 6

Containing heavy metal Cu2+Acid electroplating waste water, acid content 17.6%, sodium sulphate content 8%, COD= 15730mg/L。

(1) electromagnetism flocculates: adjusting pH value of waste water to 8~9, the flocculant poly aluminium chloride handled through electromagnetization is added (PAC).It is 60.5mT, magnetizing time 6min, the use of flocculant that flocculant carries out magnetized magnetic field strength in calutron Amount is the 0.05% of wastewater quality.It is filtered after mixing slowly 10min, obtains filtrate.

(2) it aoxidizes: 0.5% hydrogen peroxide (on the basis of wastewater quality) is added, into filtrate to remove having in waste water Machine object, wherein the concentration of hydrogen peroxide is 30%, obtains treatment fluid 1, measures the COD=5123mg/L for the treatment of fluid 1.

(3) it adsorbs: 0.05% silane-modified graphene oxide (on the basis of wastewater quality) being added into treatment fluid 1, It is filtered after absorption 1h, obtains treatment fluid 2, measure the COD=3286mg/L for the treatment of fluid 2, Pb2+Removal rate is 99.8%.

(4) photocatalysis: adding 1% hydrogen peroxide (on the basis of wastewater quality) into treatment fluid 2, and the concentration of hydrogen peroxide is 30%, it is placed under low pressure mercury lamp, power 800W, after reacting 2h, obtains treatment fluid 3, measure the COD=320mg/L for the treatment of fluid 3

(5) be concentrated: treatment fluid 3 is handled through MVR distillation, obtains colorless and transparent condensate liquid, COD=25mg/L, direct emission, Concentrate returns to photocatalytic process, continues cycling through processing.

Claims (7)

1. a kind of processing method of heavy metal wastewater thereby, which comprises the following steps:
(1) it aoxidizes: being added oxidant into heavy metal wastewater thereby, oxygenolysis is given up water part organic matter, and treatment fluid 1 is obtained;Its The dosage of middle oxidant is the 0.05~5% of wastewater quality;The heavy metal wastewater thereby is mercurous (Hg2+), manganese (Mn2+), copper (Cu2+), lead (Pb2+), nickel (Ni2+), chromium (Cr2+) in one or more of waste water;
(2) it adsorbs: adsorbent is added into the resulting treatment fluid 1 of step (1), treatment fluid 2 is obtained after absorption;Wherein adsorbent Additional amount is the 0.01~3% of wastewater quality;
(3) photochemical catalytic oxidation: light-catalyzed reaction is carried out to treatment fluid 2 obtained in step (2), obtains treatment fluid 3;Wherein dioxygen Water adds 0.5~5% that ratio is wastewater quality, and hydrogen peroxide mass concentration is 25~50%, and the reaction time is 0.5~5h, light Catalysis reaction light source used is low pressure mercury lamp, and power is 300~800W;
Before step (1) oxidation, flocculation treatment first is carried out to heavy metal wastewater thereby, the flocculant is aluminum sulfate, polyaluminium Aluminium (PAC), bodied ferric sulfate (PFS), poly aluminium sulfate silicate, polyacrylamide (PAM), polyethyleneimine, chitosan, modification One or more of starch, the flocculation are that electromagnetism flocculates;Flocculant carries out magnetized magnetic field strength in calutron 44.6~89.0mT, magnetizing time are 4~10min, and the dosage of flocculant is the 0.01~1% of wastewater quality.
2. the processing method of heavy metal wastewater thereby according to claim 1, which is characterized in that step (1) described oxidant is One or more of hydrogen peroxide, ozone, hypochlorite, iodine, Fenton reagent, chlorine dioxide, permonosulphuric acid or Peracetic acid, The additional amount of oxidant is the 0.1~4% of wastewater quality.
3. the processing method of heavy metal wastewater thereby according to claim 1, which is characterized in that step (2) described adsorbent is The additional amount of one or more of active carbon, diatomite, modified graphene oxide, graphene or carbon nanotube, adsorbent is The 0.01~1% of wastewater quality.
4. the processing method of heavy metal wastewater thereby according to claim 3, which is characterized in that the modified graphene oxide is The oxidation stone that ethylenediamine tetraacetic acid modified graphene oxide (EDTA-GO), silane-modified graphene oxide, chitosan magnetic are modified One or more of in black alkene, additional amount is the 0.02~0.5% of wastewater quality.
5. the processing method of heavy metal wastewater thereby according to claim 1, which is characterized in that in step (3) photochemical catalytic oxidation Catalyst is one or more of titanium dioxide, molysite, mantoquita.
6. the processing method of heavy metal wastewater thereby according to claim 5, which is characterized in that the hydrogen peroxide in reaction is replaceable For sodium hypochlorite, chlorine dioxide.
7. the processing method of heavy metal wastewater thereby according to claim 1, which is characterized in that dioxygen described in step (3) Water dosage is the 1~3% of wastewater quality.
CN201610405544.5A 2016-06-08 2016-06-08 A kind of processing method of heavy metal wastewater thereby CN105884100B (en)

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