CN106348499A - Treatment method of garbage leachate concentrated solution - Google Patents

Treatment method of garbage leachate concentrated solution Download PDF

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Publication number
CN106348499A
CN106348499A CN201610948814.7A CN201610948814A CN106348499A CN 106348499 A CN106348499 A CN 106348499A CN 201610948814 A CN201610948814 A CN 201610948814A CN 106348499 A CN106348499 A CN 106348499A
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percolate
liquid
concentrates
processing
oxidation
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CN106348499B (en
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成波
成一波
李刚
毛兵
南臻
傅峰
陈磊
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Zhejiang Qicai Eco Technology Co Ltd
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Zhejiang Qicai Eco Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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

Abstract

The invention relates to a treatment method of a garbage leachate concentrated solution. The method comprises the following steps: (1) adding the garbage leachate concentrated solution into a catalyst-A-filled electrocatalytic oxidation device, and carrying out electrocatalytic oxidation reaction for 1-6 hours to obtain a treatment solution I; (2) regulating the pH value of the treatment solution I to 10-11, adding an oxidizer, carrying out oxidation-coagulation reaction, standing for 10-60 minutes, and filtering to obtain a treatment solution II; and (3) regulating the pH value of the treatment solution II to 7-8, enabling the treatment solution II to flow through a solid catalyst bed reactor at the WHSV of 0.5-3 h<-1>, and discharging the effluent. The method can effectively remove COD (chemical oxygen demand), total nitrogen, chroma and heavy metal ions in the concentrated solution, and is simple to operate and low in treatment cost.

Description

A kind of percolate concentrates the processing method of liquid
Technical field
The present invention relates to landfill leachate treatment field, more particularly, to a kind of processing method of percolate concentration liquid.
Background technology
With the growth of population, the raising of industry and Level of Urban Modernization, domestic waste and industrial solid are discarded The yield of thing all rapidly increases.The process of solid waste is directly related with environment, economy, social problem.Solid at present The processing method of garbage typically has sanitary landfills, burning, compost, recycling etc., the municipal refuse of China more than 80% All apply sanitary landfill method.Although the method good economy performance, substantial amounts of percolate can be produced, locate if inappropriate Reason, can cause serious environmental pollution.The processing method of common percolate has biotechnology (anaerobism, aerobic etc.), thing Change technology (flocculation, precipitation, oxidation, absorption, stripping, film process etc.) and land law (mainly including recharge, artificial swamp).
With the execution of " household refuse landfill sites Environmental capacity " (gb16889-2008), increasing percolate Process and increased follow-up NF membrane or reverse osmosis membrane processing unit facility, consequent garbage loading embeading percolation liquid concentrated solution Process increasingly receive publicity.Common percolate concentration liquid treatment technology has following several:
(1) recharge landfill heap body or backflow regulating reservoir
This technique is concentrated solution to be back to front end regulating reservoir reenter processing system, or is poured into landfill by back of pipeline In heap body.The advantage of recharge is good economy performance, and maximum shortcoming is the b/c ratio that a large amount of recharges can lead to percolate for a long time Decline, be unfavorable for biochemistry;
(2) mechanical compress evaporation mvc handling process adopts evaporation treatment process to process concentrated solution, can be by the pollution in water body Thing solidifies.Shortcoming is to produce waste gas and endanger useless;
(3) advanced oxidation
Advanced oxidation processes can produce the hydroxyl radical free radical (ho) with extremely strong oxidisability it is considered to be one kind is preferable The processing method of hardly degraded organic substance.Advantage is efficiently thorough, does not produce secondary pollution, but existing single advanced oxidation Monotechnics processing cost height is it is difficult to reach first discharge standard;
(4) activated carbon adsorption handling process: the adsorption effect to hardly degraded organic substance in concentrated solution for the activated carbon in this technique The size of organic molecule and the matching effect of activated carbon pore size can be controlled by;
(5) composite resin: for existing hydrophobic group in hardly degraded organic substance molecule in concentrated solution, again have more hydrophilic The characteristic of group, can by macroporous resin, hypercrosslinked polymeric resin surface-modification chemistries group formed have adsorption with from The New-type bifunctional resin of sub- exchange interaction.Shortcoming is that resin regeneration is difficult.
Content of the invention
The invention provides a kind of percolate concentrates the processing method of liquid, by electrocatalytic oxidation, oxidation-coagulation, Low temperature wet type oxidation coupling, can effectively remove cod in concentrated solution, total nitrogen, colourity and heavy metal ion, simple to operate, process Low cost.
A kind of percolate concentrates the processing method of liquid, comprising:
(1) percolate is concentrated liquid addition equipped with the electrocatalysis oxidation apparatus of catalyst a, carries out electrocatalytic oxidation, Reaction 1~6h obtains treatment fluid i;
Described catalyst a is the loaded catalyst with activated carbon granule as carrier, and active component is pd, ni, cu, fe At least one in simple substance and its oxide;
(2) the ph value for the treatment of fluid i is adjusted to 10~11, add oxidant, standing 10 after oxidation-coagulation reaction~ 60min, filtration, obtain treatment fluid ii;
(3) the ph value for the treatment of fluid ii is adjusted to 7~8, with mass space velocity for 0.5~3h-1Flow through solid catalyst bed Reactor, Chinese effluent;
Solid catalyst bed reactor is urged built with catalyst b, the support type that catalyst b is carrier for activated carbon granule Agent, active component is at least one in the oxide of pd, ni, au, cu, fe, mn or sulfide.
The present invention carries out degraded heavy metal organic complex by electrocatalytic oxidation to the Organic substance in concentrated solution Carry out contact break conjunction, remove most of total nitrogen and cod in concentrated solution;Act on through oxidation-coagulation again, remove in concentrated solution further Cod and heavy metal ion;Then by the cod in low temperature wet type oxidation depth removal concentrated solution, total nitrogen and colourity, electro-catalysis Oxidation, oxidation-coagulation, the mutual synergism of low temperature wet oxidation, lacking one all can not make concentrated solution reach the requirement of direct discharge.
Heavy metal ion in percolate concentration liquid and content of organics are higher, preferably, the process of the present invention Method also includes pretreatment of flocculating: the ph value that percolate is concentrated liquid is adjusted to 10~11, adds flocculant flocculation, standing Filter after 10~60min, to filtrate execution step (1);
Described flocculant is pam (polyacrylamide), pac (aluminium polychlorid), fecl3、feso4, pfs (polyaluminum sulfate Ferrum) at least one.
By adjusting the ph value of concentrated solution to alkalescence, major part heavy metal ion therein forms precipitation, goes out after filtering Go.
When using, flocculant is configured to solution it is preferred that pam concentration is 1~2g/l, pac concentration is 2~7g/l, fecl3Concentration is 5~15%, feso4Concentration is 5~15%, pfs concentration is 5~20%;
The dosage of flocculant has certain impact to the ph value of system, with the increase of flocculant dosage, its Flocculating effect gradually strengthens, but when flocculant dosage reaches to a certain degree, its flocculating effect keeps dynamic equilibrium substantially, as Preferably, on the basis of the quality that percolate concentrates liquid, the dosage of flocculant is 0.05~2%.
After part heavy metal ion, electrocatalytic oxidation is carried out to concentrated solution in preprocessed removal concentrated solution.
Catalyst a be impact electrocatalytic oxidation property key factor, preferably, the active component of catalyst a be pd, Ni bimetallic or pd, ni bimetallic oxide.Pd, ni or its oxide have higher catalysis activity, and its electrochemistry is steady Qualitative preferably, be resistant to impurity and electrochemical reaction effect and will not poisoning and deactivation quickly.
During electrocatalytic oxidation, tank voltage is the driving force of cell reaction, in the range of suitable tank voltage, concentrates The cod of liquid, colourity have preferable removal effect, preferably, the tank voltage of electrocatalytic oxidation is 6~12v, electric current is 0.3 ~1a.The effect of Electro-catalytic Oxidation Process increases with the increase of tank voltage, but when tank voltage is too high, is easily caused big The generation of amount side reaction, then it is little to the influential effect of Electro-catalytic Oxidation Process to increase voltage.
Electrocatalytic oxidation can remove part cod and most of total nitrogen in concentrated solution, and can make heavy metal ion with organic The complex contact break of thing is closed, and makes heavy metal ion separate out, forms precipitation in the basic conditions, then by follow-up oxidation- Coagulating removes further.
In the oxidation-coagulation of step (2) reacts, preferably, described oxidant is 5~10% for effective chlorine density Liquor natrii hypochloritises, the dosage of liquor natrii hypochloritises is the 1~10% for the treatment of fluid i mass.
Preferably, control sodium hypochlorite adds speed, make oxidation-reduction potential orp value in system for 180~ 360v, stirs 20~60min.
Oxidation-coagulation effect removes the cod in concentrated solution further, and heavy metal ion is in alkalescence condition flocculation sediment, mistake Elimination removes, and carries out follow-up CWO to filtrate, and the cod in concentrated solution, total nitrogen and colourity are carried out at depth degradation Reason.
Filtrate, in the presence of catalyst b, carries out low temperature wet oxidation, further the organic contamination in degraded concentrated solution Thing, depth removes cod therein, total nitrogen and colourity.
Preferably, the mass space velocity that treatment fluid ii flows through solid catalyst bed reactor is 0.5~3h-1, solid urges Agent bed reactor temperature is 30~55 DEG C.
Preferably, the active component of catalyst b is at least one in the oxide of cu, fe, mn or sulfide.
Preferably, in step (3), the ph value for the treatment of fluid ii is adjusted to after 7~8 and adds hydrogen peroxide, standing 10~ 60min, control system ph value is 7~8, passes through solid catalyst bed reactor.
Preferably, controlling the dosage of hydrogen peroxide, make h in system2o2Mass percent be 0.1~5%.
Sodium hypochlorite is combined with hydrogen peroxide and is carried out catalysis oxidation, can not only improve the degradation efficiency of low temperature wet oxidation, also Processing cost can be reduced.
Compared with prior art, the invention has the benefit that
(1) present invention by electrocatalytic oxidation the Organic substance in concentrated solution is carried out degraded and heavy metal organic complex Thing carries out contact break conjunction, removes most of total nitrogen and cod in concentrated solution;Act on through oxidation-coagulation again, remove concentrated solution further In cod and heavy metal ion;Then by the cod in low temperature wet type oxidation depth removal concentrated solution, total nitrogen and colourity, electricity is urged Change oxidation, oxidation-coagulation and the mutual synergism of low temperature wet oxidation, make process water outlet water white transparency, cod and total nitrogen reach row Put requirement, and concentration of metal ions is less than refuse landfill sewage first discharge standard, can directly discharge;
(2) processing method of the present invention is simple to operate, and sodium hypochlorite is less expensive with hydrogen peroxide, and processing cost is relatively low.
Brief description
Fig. 1 concentrates the schematic flow sheet of the processing method of liquid for percolate of the present invention.
Specific embodiment
With reference to the accompanying drawings and examples the present invention is described in further detail it should be pointed out that described below is real Apply example to be intended to be easy to the understanding of the present invention, and any restriction effect is not risen to it.
The process chart of the present invention is as shown in Figure 1.
Embodiment 1
Certain percolate concentrates liquid, its cod=2795mg/l, total nitrogen=1140mg/l, ph=6.5, cl-Concentration= 5198.75mg/l, no3 -Concentration=4291mg/l, so4 2-Concentration=3287mg/l, total chromium concn=11.24mg/l, total ni concentration =10mg/l, total cd concentration=4.63mg/l, total concentration of iron=188.4mg/l, mn concentration=14.33mg/l, na+Concentration= 7200mg/l, k+Concentration=5100mg/l.
(1) the naoh solution being 30% using mass fraction adjusts percolate and concentrates the ph value of liquid to 10~11, plus Enter the flocculant pam solution of 1g/l, the dosage of pam concentrates the 0.05% of liquid quality, takes out after standing 30min for percolate Filter;
(2) filtrate is added electrocatalysis oxidation reaction device, with the activated carbon of ni and pd load as catalyst, electrocatalytic oxidation Change 2h, tank voltage u=9.5v, electric current i=0.63a;
(3) the naoh solution being 30% using mass fraction adjusts the ph value of electrocatalytic oxidation water outlet to 10~11.Add Effective chlorine is 10% liquor natrii hypochloritises, on the basis of the quality of electrocatalytic oxidation water outlet, the dosage of liquor natrii hypochloritises For 3%, control sodium hypochlorite adds speed, and the oxidation-reduction potential orp value stabilization making system, in 180~360mv, stirs Stand 30min after 30min, filter;
(4) the ph value of filtrate is adjusted to 7~8 using the concentrated sulphuric acid of 1+1, then by filtrate with mass space velocity as 1.5h-1Flow through Solid catalyst bed reactor, keeps 50 DEG C of constant temperature of reaction;
Catalyst in solid catalyst bed reactor with activated carbon granule as carrier, with fe, cu, ni and its oxide Or sulfide is active component.
Final process water outlet cod is 84.2mg/l, and total nitrogen is 37mg/l, water white transparency, and ph is 7~8, and total metal ion reaches To city refuse landfill sewage discharge first discharge standard.
Embodiment 2
Compared with Example 1, lack the pretreatment of step (1), other operating conditions are identical.
Final process water outlet cod is 95mg/l, and total nitrogen is 42mg/l, water white transparency, and ph is 7~8, and total metal ion reaches City refuse landfill sewage discharge first discharge standard.
Embodiment 3
Compared with Example 1, difference is in step (2), and tank voltage is 10.5v.
Final process water outlet cod is 73.6mg/l, and total nitrogen is 35mg/l, water white transparency, and ph is 7~8, and total metal ion reaches To city refuse landfill sewage discharge first discharge standard.
Embodiment 4
Compared with Example 1, difference is in step (4), adjusts ph value for after 7~8, adding hydrogen peroxide, total with system On the basis of quality, system h2o2Measure as 1%.
Final process water outlet cod is 75.2mg/l, and total nitrogen is 34mg/l, water white transparency, and ph is 7~8, and total metal ion reaches To city refuse landfill sewage discharge first discharge standard.
Comparative example 1
Compared with Example 1, lack step (2).
Final process water outlet cod is 982mg/l, and total nitrogen is 431mg/l, and ph is 7~8, and total metal ion is too high, does not reach City refuse landfill sewage discharge first discharge standard is it is impossible to directly discharge.
Comparative example 2
Compared with Example 1, lack step (3).
Final process water outlet cod is 695mg/l, and total nitrogen is 276mg/l, and ph is 7~8, and total metal ion is too high, does not reach City refuse landfill sewage discharge first discharge standard is it is impossible to directly discharge.
Comparative example 3
Compared with Example 1, lack step (4).
Final process water outlet cod is 833mg/l, and total nitrogen is 289mg/l, and ph is 7~8, and total metal ion is too high, does not reach City refuse landfill sewage discharge first discharge standard is it is impossible to directly discharge.
From embodiment 1, comparative example 1,2,3, in the processing method of the present invention, electrocatalytic oxidation, oxidation-coagulation, low The mutual synergism of warm wet oxidation, three is indispensable.
Embodiment 5
Certain percolate concentrates liquid, cod=3675mg/l, total nitrogen=956mg/l, ph=7.6, cl-Concentration= 4325mg/l, no3 -Concentration=2237mg/l, 8o4 2-Concentration=2895mg/l, total chromium concn=13.48mg/l, total ni concentration= 9.6mg/l, total cd concentration=5.21mg/l, total concentration of iron=142mg/l, mn concentration=14.3mg/l, na+Concentration= 5420mg/l, k+Concentration=4329mg/l.
(1) the naoh solution being 30% using mass fraction adjusts percolate and concentrates the ph value of liquid to 10~11, plus Enter the flocculant pfs solution that mass fraction is 5%, the dosage of pfs concentrates the 0.05% of liquid quality for percolate, standing Sucking filtration after 30min;
(2) filtrate is added electrocatalysis oxidation reaction device, with the metal oxide supported activated carbon of ni and pd for catalysis Agent, electrocatalytic oxidation 1h, tank voltage u=9.5v, electric current i=0.61a;
(3) the naoh solution being 30% using mass fraction adjusts the ph value of electrocatalytic oxidation water outlet to 10~11, adds Effective chlorine is 10% liquor natrii hypochloritises, on the basis of the quality of electrocatalytic oxidation water outlet, the dosage of liquor natrii hypochloritises For 5%, control sodium hypochlorite adds speed, and the oxidation-reduction potential orp value stabilization making system, in 180~360mv, stirs Stand 30min after 30min, filter;
(4) the ph value adjusting filtrate using the concentrated sulphuric acid of 1+1, to 7~8, adds hydrogen peroxide, on the basis of system gross mass, System h2o2Measure as 1%, then by filtrate with mass space velocity as 2h-1Flow through solid catalyst bed reactor, keep reaction constant temperature 55℃;
Catalyst in solid catalyst bed reactor with activated carbon granule as carrier, with fe, cu, ni and its oxide Or sulfide is active component.
Final process water outlet cod is 152mg/l, and total nitrogen is 78mg/l, water white transparency, and ph is 7~8, and total metal ion reaches To city refuse landfill sewage discharge first discharge standard.

Claims (10)

1. a kind of percolate concentrates the processing method of liquid it is characterised in that including:
(1) percolate is concentrated the electrocatalysis oxidation apparatus equipped with catalyst a for the liquid addition, carry out electrocatalytic oxidation, react 1 ~6h obtains treatment fluid i;
Described catalyst a is the loaded catalyst with activated carbon granule as carrier, and active component is pd, ni, cu, fe simple substance With at least one in its oxide;
(2) the ph value for the treatment of fluid i is adjusted to 10~11, add oxidant, standing 10~60min, mistake after oxidation-coagulation reaction Filter, obtains treatment fluid ii;
(3) the ph value for the treatment of fluid ii is adjusted to 7~8, with mass space velocity for 0.5~3h-1Flow through the reaction of solid catalyst bed Device, Chinese effluent;
Solid catalyst bed reactor is the supported catalyst of carrier built with catalyst b, catalyst b for activated carbon granule Agent, active component is at least one in the oxide of pd, ni, au, cu, fe, mn or sulfide.
2. percolate according to claim 1 concentrates the processing method of liquid it is characterised in that also including pre- place of flocculating Reason: the ph value that percolate is concentrated liquid is adjusted to 10~11, adds flocculant flocculation, filters after standing 10~60min, right Filtrate execution step (1);
Described flocculant is pam, pac, fecl3、feso4, at least one in pfs.
3. percolate according to claim 1 concentrates the processing method of liquid it is characterised in that the activity of catalyst a Composition is pd, ni bimetallic or pd, ni bimetallic oxide.
4. percolate according to claim 1 concentrates the processing method of liquid it is characterised in that in step (1), electricity is urged The tank voltage changing oxidation is 6~12v, and electric current is 0.3~1a.
5. percolate according to claim 1 concentrates the processing method of liquid it is characterised in that in step (2), described Oxidant be 5~10% for effective chlorine density liquor natrii hypochloritises, the dosage of liquor natrii hypochloritises is treatment fluid i mass 1~10%.
6. percolate according to claim 5 concentrates the processing method of liquid it is characterised in that controlling sodium hypochlorite Add speed, make the oxidation-reduction potential orp value in system be 180~360v, stir 20~60min.
7. percolate according to claim 1 concentrates the processing method of liquid it is characterised in that in step (3), will locate The ph value of reason liquid ii adjusts and adds hydrogen peroxide to after 7~8, stands 10~60min, control system ph value is 7~8, passes through solid Body catalyst bed reactor.
8. percolate according to claim 7 concentrates the processing method of liquid it is characterised in that controlling the throwing of hydrogen peroxide Dosage, makes h in system2o2Mass percent be 0.1~5%.
9. percolate according to claim 1 concentrates the processing method of liquid it is characterised in that treatment fluid ii flows through admittedly The mass space velocity of body catalyst bed reactor is 0.5~3h-1, solid catalyst bed temperature of reactor be 30~55 DEG C.
10. percolate according to claim 1 concentrates the processing method of liquid it is characterised in that the activity of catalyst b Composition is at least one in the oxide of cu, fe, mn or sulfide.
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CN107098513A (en) * 2017-04-28 2017-08-29 浙江奇彩环境科技股份有限公司 A kind of processing method of high concentration morpholine waste water
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CN107098513A (en) * 2017-04-28 2017-08-29 浙江奇彩环境科技股份有限公司 A kind of processing method of high concentration morpholine waste water
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