CN109809650A - A kind of cyanide wastewater electrocatalytic oxidation processing method and system - Google Patents
A kind of cyanide wastewater electrocatalytic oxidation processing method and system Download PDFInfo
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- CN109809650A CN109809650A CN201910250903.8A CN201910250903A CN109809650A CN 109809650 A CN109809650 A CN 109809650A CN 201910250903 A CN201910250903 A CN 201910250903A CN 109809650 A CN109809650 A CN 109809650A
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 123
- 239000002351 wastewater Substances 0.000 title claims abstract description 109
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- 230000003647 oxidation Effects 0.000 title claims abstract description 64
- 238000003672 processing method Methods 0.000 title claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 230000005684 electric field Effects 0.000 claims abstract description 5
- 229910001868 water Inorganic materials 0.000 claims description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 77
- 238000012545 processing Methods 0.000 claims description 31
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- BASYJLWAYAUJBW-UHFFFAOYSA-N [Ti].[Ir].[Ru].[Pt] Chemical compound [Ti].[Ir].[Ru].[Pt] BASYJLWAYAUJBW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
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- 229910000679 solder Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 abstract description 13
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- 239000007800 oxidant agent Substances 0.000 abstract description 9
- -1 hydroxyl radical free radical Chemical class 0.000 abstract description 6
- 150000003384 small molecules Chemical class 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
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- 238000004065 wastewater treatment Methods 0.000 description 10
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- 229960004424 carbon dioxide Drugs 0.000 description 7
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- 239000005708 Sodium hypochlorite Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
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- 229910000906 Bronze Inorganic materials 0.000 description 1
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
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- 230000000536 complexating effect Effects 0.000 description 1
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- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- LEKPFOXEZRZPGW-UHFFFAOYSA-N copper;dicyanide Chemical compound [Cu+2].N#[C-].N#[C-] LEKPFOXEZRZPGW-UHFFFAOYSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of cyanide wastewater electrocatalytic oxidation processing method and systems, the inactive metal oxide combination electrode for having catalytic capability is electrode, catalysis forms the intermediate products such as the hydroxyl radical free radical with strong oxidizing property under electric field action, it is reacted with Cyanide in Cyanide Wastewater, it is oxidized as small molecules such as carbon dioxide, nitrogen gas and waters, reaches " broken cyanide " purpose.The present invention has the characteristics that oxidant, reaction condition are mild, cyanide removal is thorough, operating cost is low, system is simple, reliable and stable, high degree of automation without adding.
Description
Technical field
The invention belongs to field of environment engineering, it is related to a kind of cyanide wastewater electrocatalytic oxidation processing method and system.
Background technique
Cyanide wastewater refers to the industrial wastewater containing CN group.Since cyano has strong complexing, there is coloured gold
Belong to the industries such as mineral extraction gold, silver and bronze, cyanide electroplating, chemical industry, coking, heat treatment to be widely used, be discharged in production process
A large amount of cyanide wastewater.Belong to extremely toxic substance containing cyanogen compound, it is high to generate cyaniding in conjunction with ferricytochrome enzyme in human body by CN
Ferricytochrome oxidizing ferment and the transfer function for losing oxygen, cause histanoxia in vivo and suffocate.Cyanide is to the lethal of people
Amount varies with each individual, about in 0.5mg/kg~3.5mg/kg, more to the lethal dose of other toys (such as bird), aquatile
It is small, the life security of people, animal, aquatile will be seriously threatened to cyanide wastewater misfeasance, destroy the ecological balance.Country
It is provided in " discharge standard for electroplating pollutants " GB 21900-2008, territorial development density is higher, environmental bearing capacity starts to subtract
Weak or environmental capacity of water is smaller, ecological environment frailty, is easy to happen serious water environment pollution problem and needs to take special protection
The pollutant emission behavior of strict control facility is answered in the area of measure, is executed Table III standard (≤0.2mg/L).
It is applied to the more extensive technique of cyanide wastewater processing at present and specifically includes that (alkaline chlorination process is acidified back chemical method
Receipts method, sulphur dioxide-air oxidizing process, hydrogen peroxide oxidation process, Ozonation, the precipitating-method of purification), physical-chemical process it is (living
Property carbon adsorption, solvent extraction, ion-exchange, liquid-film method), it is biological treatment (microbial method, membrane bioreactor), high
Press Hydrolyze method, natural degradation method etc., the more extensive method of application is alkaline chlorination process and hydrogen peroxide oxidation process, the former mostly by
Referred to as " second level broken cyanide method ", the latter are referred to as " level-one broken cyanide method " more.
Then still " level-one broken cyanide method " regardless of " second level broken cyanide method ", treatment process is required to add oxidant, as follows
Sodium chlorate, hydrogen peroxide etc., strong to medicament dependence, processing cost is high.As environmentally friendly dynamics continues to increase, each chemical raw material
Price is rising steadily, and the traditional treatment method cost dependent on chemical agent is also higher and higher.According to national Ministry of Industry and Information
Specific equipment Development major fields illustrate in 2017 " about the instructions for accelerating that environmentally friendly equipment manufacture is promoted to develop "
" emphasis is tackled key problems the oxidation technologies equipment such as Anammox technical equipment and catalytic and oxidative electrolysis technology, supercritical oxidation dress, research and development life
Object strengthens and the advanced membrane technology and component of low-energy-consumption high-efficiency, carries out drinking water trace toxic pollutant process technology dress
It is standby to wait basic research ", electrochemically Treatment of Cyanide-containing Wastewater, is a kind of more green, cleaning, while being also a kind of low cost
Novel treatment Technology of Cyanide Wastewater.
Summary of the invention
Goal of the invention: the purpose of the present invention is to solve deficiency in the prior art, a kind of cyanide wastewater electricity is provided and is urged
Change oxidation treatment method and system, under electric field action, the Strong oxdiative of cyanide wastewater and the generation of electrocatalysis oxidation reaction device anode
Property intermediate product reaction, CN group is oxidized to the small molecules such as carbon dioxide, nitrogen gas and water, completes electrocatalytic oxidation process.Electricity is urged
Change the waste water after aoxidizing to enter in coagulating case, to form a huge sum of money by reacting with milk of lime or liquid alkaline, coagulant, flocculation aid
Belong to sediment, the isolated heavy metal sewage sludge of clarified device and clear water, clear water, which enters, further to be gone to decontaminate in biochemical reaction device
Object is contaminated, final outflow water meets GB 21900-2008 " discharge standard for electroplating pollutants " Table III standard.
Technical solution:
A kind of cyanide wastewater electrocatalytic oxidation processing method, specific steps are as follows:
1) cyanide wastewater is conveyed to electrocatalysis oxidation reaction device；
2) in electrocatalysis oxidation reaction device, electrocatalytic oxidation is carried out to cyanide wastewater；
3) enter in coagulating case, carry out neutralization reaction；
4) enter clarifier) in, it is clarified；
5) enter in biochemical treatment apparatus, carry out biochemical treatment.
In order to which the present embodiment is explained further, it should be noted that
In step 1), cyanide wastewater is entered from the inlet in pipe-line mixer, after being mixed with recycling waste water in circulation pipe, from
Circulation water inlet enters in the reactor cabinet of electrocatalysis oxidation reaction device；
In step 2), electrocatalysis oxidation reaction is carried out under the action of anode and cathode, lacks portion after the completion of electrocatalytic oxidation
Waste water is divided to flow out from water outlet, most of waste water enters in circulation pipe from circulating water outlet, continues cycling through in the case where recycling pumping action,
Carbon dioxide, the nitrogen of generation are flowed out from gas outlet；
In step 3), free heavy metal is converted sediment by feeding lime cream or liquid alkaline, coagulant, flocculation aid.
A kind of cyanide wastewater electrocatalytic oxidation processing system, including delivery pump, electrocatalysis oxidation reaction device, coagulating
Case, clarifier, biochemical treatment apparatus；
Delivery pump is connected, for conveying cyanide wastewater with electrocatalysis oxidation reaction device；
Electrocatalysis oxidation reaction device is connected with coagulating case, for carrying out electrocatalytic oxidation to cyanide wastewater；
Coagulating case, is connected with clarifier, for that will be dissociated by investment milk of lime or liquid alkaline, coagulant, flocculation aid
Heavy metal convert sediment for heavy metal；
Clarifier is connected with biochemical treatment apparatus, for obtaining clear water by clarification；
Biochemical treatment apparatus obtains water up to standard for handling by microorganism the water after clarification.
In order to which the present embodiment is explained further, it should be noted that
Electrocatalysis oxidation reaction device by reactor cabinet, reactor sealing plate, anode, cathode, power supply, cable, circulation pipe,
Pipe-line mixer, circulating pump composition；
One water inlet is set on circulation pipe, is connected with delivery pump；
One water outlet is set on reactor cabinet, on the upper end side wall of reactor cabinet, with coagulating case phase
Even；
One circulation water inlet, is set on reactor cabinet, is connected with circulation pipe, for the waste water in circulation pipe to be delivered to
In reactor cabinet；
One circulating water outlet is set on reactor cabinet, is connected with circulation pipe, for the waste water in reactor cabinet is defeated
It send to circulation pipe；
One gas outlet is set on reactor cabinet, on the upper end side wall of reactor cabinet, for conveying generate two
Carbonoxide, nitrogen；
One sewage draining exit, the ejected wash water generated when being cleaned for discharging to equipment；
Circulating pump is set on circulation pipe；
Gas outlet is set to the top of water outlet；
Reactor sealing plate is set to the top of reactor cabinet；
Anode, cathode are set in reactor cabinet；
Power supply is electrically connected with anode, cathode by cable.
A further improvement of the present invention is that reactor cabinet is bolted with reactor sealing plate, reactor
Sealing ring is set between cabinet and reactor sealing plate.
A further improvement of the present invention is that the nonactive electrode of anode system inertia, it can be compound for titanium-based metal oxide
Electrode contains one of metals such as titanium platinum ruthenium iridium slicker solder or a variety of in titanium-based metal oxide combination electrode.
A further improvement of the present invention is that reactor cabinet, reactor sealing plate, circulation pipe, pipe-line mixer, circulation
Pump insulate between each other with anode, cathode, power supply, cable, that is, connects or there is insulating layer at the place of being closer；Power supply is that low-voltage is high
Electric current high-power DC power supply.
A further improvement of the present invention is that power supply is powered by cable to anode and cathode, to distribute in anti-
Answer the intracorporal electric field of device case.
A further improvement of the present invention is that cable is that copper bar or aluminium are arranged.
A further improvement of the present invention is that anode and cathode is arranged by the mode of being alternately arranged, insulate, is only capable of each other
Pass through waste water conduction.
Cyanide wastewater electrocatalytic oxidation processing technique of the invention, including following procedure:
(1) cyanide wastewater delivers into pipe-line mixer by delivery pump, mixed with waste water in circulation pipe it is latter with into
Enter in electrocatalysis oxidation reaction device, due to using big flow endless form, reduces waste water quality fluctuation, mainly cryanide ion
The fluctuation of content, the impact to electrocatalytic oxidation processing system；
(2) after waste water enters electrocatalysis oxidation reaction device, after reactor anode and waste water, it is anti-to carry out direct oxidation
It answers or indirect oxidation reaction, direct oxidation reaction process is as follows:
CN-+2OH--2e-—→CNO-+H2O
2CNO-+4OH--6e-—→2CO2↑+N2↑+2H2O
Or:
2CN-+8OH--10e-—→2CO2↑+N2↑+4H2O
Indirect oxidation reaction process includes hydroxyl radical free radical indirect oxidation, hypochlorite indirect oxidation etc., hydroxyl radical free radical
Indirect oxidation reaction process is as follows:
OH--e-—→·OH
CN-+2·OH—→CNO-+H2O
2CNO-+6·OH—→2CO2↑+N2↑+2H2O+2OH-
Or:
OH--e-—→·OH
2CN-+10·OH—→2CO2↑+N2↑+4H2O+2OH-
Sodium hypochlorite indirect oxidation reaction process is as follows:
2Cl--2e-—→Cl2(liq)
OH--e-—→·OH
2Cl-+2·OH—→Cl2(liq)+2OH-
Cl2(liq)+2OH-—→Cl-+ClO-+H2O
CN-+ClO-+H2O—→CNCl+2OH-
CNCl+2OH-—→CNO-+H2O+Cl-
2CNO-+3ClO-+H2O—→CO2↑+N2↑+3Cl-+2OH-
Several oxidation process are synchronous to be carried out, and is rapidly the small molecules such as carbon dioxide, nitrogen by CN radical oxidation in waste water, together
When heavy metal with the coordination of CN group, such as copper synchronous will be changed into free state by complex state, and cyanide wastewater is " broken to complete
Cyanogen " process.
(3) cyanide wastewater that completes " broken cyanide " process is flowed out from electrocatalysis oxidation reaction device, is pumped up or entrance of flowing automatically
In coagulating case, coagulating case is occurred by alkaline reagents such as feeding lime cream or liquid alkaline with free state heavy metal ion
Reaction forms heavy metal hydroxide precipitating, forms big wadding body under coagulant, flocculation aid effect, adds into clarifier
With separation, isolated sludge is heavy metal sewage sludge, and can entrust outer processing, and clear water is then flowed out from clarifier top.
(4) clarifier top clear water is basically completed the removal of CN group and heavy metal, and remaining pollutant includes COD, total
Nitrogen, total phosphorus etc., into after processing removal COD, total nitrogen, total phosphorus in biochemical treatment apparatus, water outlet meets GB 21900-2008 " electricity
Plate pollutant emission standard " Table III standard.
As environmental requirement is constantly promoted, cyanide wastewater processing water outlet executes GB 21900-2008 " plating pollutant emission
Standard " Table III standard is extremely urgent, and majority electroplating enterprises, plating garden, PCB manufacturing enterprise etc. still contain cyanogen in use at present
Waste water treatment process is " second level broken cyanide method " or " level-one broken cyanide method " etc., and the present invention is directed to cyanide wastewater, is provided a kind of containing cyanogen
Wastewater by Electric catalytic oxidation treatment technology, without add oxidant, medicament dependence is low, operating cost is low, cyanide removal thoroughly,
System is simple, stable and reliable operation, while can suitably reduce the salt content of final outflow water.
Compared with prior art, a kind of cyanide wastewater electrocatalytic oxidation processing system provided by the invention, at least realizes
It is following the utility model has the advantages that
Compared with traditional " second level broken cyanide method ":
(1) reaction condition is mild, does not need strong acid or basic conditions, waste water, which does not need adjusting pH, can be directly entered electricity
Catalyst oxidation reactor, and carry out broken cyanide reaction；
(2) does not need consumption oxidizing agent sodium hypochlorite, does not need to consume the soda acid that frequently adjusting pH is added, adds medicine
Dosage is few, reduces wastewater treatment to the dependence of medicament；
(3) process is simple, electrocatalysis oxidation reaction device can a step realize " broken cyanide ", directly convert CO for CN group2With
N2Etc. small molecules；
(4) electrocatalysis oxidation reaction device replaces chemical agent with electricity, due to not needing to add a large amount of medicaments, wastewater treatment
Cost substantially reduces；
(5) the control variable of the core equipment electrocatalysis oxidation reaction device of electrocatalytic oxidation processing technique is few, control process
Simply, it is easy to accomplish automation.
Compared with traditional " level-one broken cyanide method ":
(1) reaction condition is mild, does not need strong acid or basic conditions, waste water, which does not need adjusting pH, can be directly entered electricity
Catalyst oxidation reactor, and carry out broken cyanide reaction；
(2) does not need consumption oxidant hydrogen peroxide, adds that pharmaceutical quantities are few, reduces wastewater treatment to the dependence of medicament；
(3) broken cyanide is thorough, and CN group in waste water only can be down to 0.5mg/L hereinafter, can not expire by traditional " level-one broken cyanide method "
Sufficient GB 21900-2008 " discharge standard for electroplating pollutants " Table III standard requirements, electrocatalytic oxidation processing technique can be by CN groups
It is down to 0.2mg/L, meets Table III standard requirements.
(4) electrocatalysis oxidation reaction device replaces chemical agent with electricity, due to not needing to add a large amount of medicaments, wastewater treatment
Cost substantially reduces；
(5) the control variable of the core equipment electrocatalysis oxidation reaction device of electrocatalytic oxidation processing technique is few, control process
Simply, it is easy to accomplish automation.
Certainly, not specific needs are implemented any of the products of the present invention while reaching all the above technical effect.
By referring to the drawings to the detailed description of exemplary embodiment of the present invention, other feature of the invention and its
Advantage will become apparent.
Detailed description of the invention
Fig. 1 is a kind of cyanide wastewater electrocatalytic oxidation processing technique schematic diagram of the present invention；
Fig. 2 is electrocatalysis oxidation reaction device structure principle chart；
In figure: 1- delivery pump, 2- electrocatalysis oxidation reaction device, 3- coagulating case, 4- clarifier, 5- biochemical treatment dress
It sets, 201- reactor cabinet, 202- reactor sealing plate, 203- anode, 204- cathode, 205- power supply, 206- cable, 207- is followed
Endless tube, 208- pipe-line mixer, 209- circulating pump, 210- water inlet, 211- water outlet, 212- recycle water inlet, 213- circulation
Water out, the gas outlet 214-, 215- sewage draining exit.
Specific embodiment
The existing various exemplary embodiments of detailed description of the present invention.It should also be noted that unless specifically stated otherwise, otherwise at this
Component described in a little embodiments and the positioned opposite of step, numerical expression and numerical value do not limit the scope of the invention.
Be to the description only actually of at least one exemplary embodiment below it is illustrative, never as to the present invention
And its application or any restrictions used.
Technology, method and apparatus known to person of ordinary skill in the relevant may be not discussed in detail, but suitable
In the case of, the technology, method and apparatus should be considered as part of specification.
It is shown here and discuss all examples in, any occurrence should be construed as merely illustratively, without
It is as limitation.Therefore, other examples of exemplary embodiment can have different values.
Embodiment 1,
As shown in Figure 1, 2, a kind of cyanide wastewater electrocatalytic oxidation processing method, specific steps are as follows:
1) cyanide wastewater is conveyed to electrocatalysis oxidation reaction device 2；
2) in electrocatalysis oxidation reaction device 2, electrocatalytic oxidation is carried out to cyanide wastewater；
3) enter in coagulating case 3, carry out neutralization reaction；
4) enter in clarifier 4, clarified；
5) enter in biochemical treatment apparatus 5, carry out biochemical treatment.
In order to which the present embodiment is explained further, it should be noted that
In step 1), cyanide wastewater enters in pipe-line mixer 208 from water inlet 210, with recycling waste water in circulation pipe 207
After mixing, enter in the reactor cabinet 201 of electrocatalysis oxidation reaction device 2 from circulation water inlet 212；
In step 2), electrocatalysis oxidation reaction is carried out under the action of anode 203 and cathode 204, electrocatalytic oxidation is completed
Small part waste water is flowed out from water outlet 211 afterwards, and most of waste water enters in circulation pipe 207 from circulating water outlet 213, in circulating pump
It is continued cycling through under 209 effects, carbon dioxide, the nitrogen of generation are flowed out from gas outlet 214；
In step 3), free heavy metal is converted sediment by feeding lime cream or liquid alkaline, coagulant, flocculation aid.
Cyanide wastewater electrocatalytic oxidation processing technique of the invention, including following procedure:
(1) cyanide wastewater delivers into pipe-line mixer by delivery pump, mixed with waste water in circulation pipe it is latter with into
Enter in electrocatalysis oxidation reaction device, due to using big flow endless form, reduces waste water quality fluctuation, mainly cryanide ion
The fluctuation of content, the impact to electrocatalytic oxidation processing system；
(2) after waste water enters electrocatalysis oxidation reaction device, after reactor anode and waste water, it is anti-to carry out direct oxidation
It answers or indirect oxidation reaction, direct oxidation reaction process is as follows:
CN-+2OH--2e-—→CNO-+H2O
2CNO-+4OH--6e-—→2CO2↑+N2↑+2H2O
Or:
2CN-+8OH--10e-—→2CO2↑+N2↑+4H2O
Indirect oxidation reaction process includes hydroxyl radical free radical indirect oxidation, hypochlorite indirect oxidation etc., hydroxyl radical free radical
Indirect oxidation reaction process is as follows:
OH--e-—→·OH
CN-+2·OH—→CNO-+H2O
2CNO-+6·OH—→2CO2↑+N2↑+2H2O+2OH-
Or:
OH--e-—→·OH
2CN-+10·OH—→2CO2↑+N2↑+4H2O+2OH-
Sodium hypochlorite indirect oxidation reaction process is as follows:
2Cl--2e-—→Cl2(liq)
OH--e-—→·OH
2Cl-+2·OH—→Cl2(liq)+2OH-
Cl2(liq)+2OH-—→Cl-+ClO-+H2O
CN-+ClO-+H2O—→CNCl+2OH-
CNCl+2OH-—→CNO-+H2O+Cl-
2CNO-+3ClO-+H2O—→CO2↑+N2↑+3Cl-+2OH-
Several oxidation process are synchronous to be carried out, and is rapidly the small molecules such as carbon dioxide, nitrogen by CN radical oxidation in waste water, together
When heavy metal with the coordination of CN group, such as copper synchronous will be changed into free state by complex state, and cyanide wastewater is " broken to complete
Cyanogen " process.
(3) cyanide wastewater that completes " broken cyanide " process is flowed out from electrocatalysis oxidation reaction device, is pumped up or entrance of flowing automatically
In coagulating case, coagulating case is occurred by alkaline reagents such as feeding lime cream or liquid alkaline with free state heavy metal ion
Reaction forms heavy metal hydroxide precipitating, forms big wadding body under coagulant, flocculation aid effect, adds into clarifier
With separation, isolated sludge is heavy metal sewage sludge, and can entrust outer processing, and clear water is then flowed out from clarifier top.
(4) clarifier top clear water is basically completed the removal of CN group and heavy metal, and remaining pollutant includes COD, total
Nitrogen, total phosphorus etc., into after processing removal COD, total nitrogen, total phosphorus in biochemical treatment apparatus, water outlet meets GB 21900-2008 " electricity
Plate pollutant emission standard " Table III standard.
As environmental requirement is constantly promoted, cyanide wastewater processing water outlet executes GB 21900-2008 " plating pollutant emission
Standard " Table III standard is extremely urgent, and majority electroplating enterprises, plating garden, PCB manufacturing enterprise etc. still contain cyanogen in use at present
Waste water treatment process is " second level broken cyanide method " or " level-one broken cyanide method " etc., and the present invention is directed to cyanide wastewater, is provided a kind of containing cyanogen
Wastewater by Electric catalytic oxidation treatment technology, without add oxidant, medicament dependence is low, operating cost is low, cyanide removal thoroughly,
System is simple, stable and reliable operation, while can suitably reduce the salt content of final outflow water.
Embodiment 2,
As shown in Figure 1, 2, a kind of cyanide wastewater electrocatalytic oxidation processing system, including delivery pump 1, electrocatalysis oxidation reaction
Device 2, coagulating case 3, clarifier 4, biochemical treatment apparatus 5；
Delivery pump 1 is connected, for conveying cyanide wastewater with electrocatalysis oxidation reaction device 2；
Electrocatalysis oxidation reaction device 2 is connected with coagulating case 3, for carrying out electrocatalytic oxidation to cyanide wastewater；
Coagulating case 3 is connected with clarifier 4, for that will be swum by investment milk of lime or liquid alkaline, coagulant, flocculation aid
From heavy metal convert sediment for heavy metal；
Clarifier 4 is connected with biochemical treatment apparatus 5, for obtaining clear water by clarification；
Biochemical treatment apparatus 5 obtains water up to standard for handling by microorganism the water after clarification.
In order to which the present embodiment is explained further, it should be noted that
Electrocatalysis oxidation reaction device 2 is by reactor cabinet 201, reactor sealing plate 202, anode 203, cathode 204, power supply
205, cable 206, circulation pipe 207, pipe-line mixer 208, circulating pump 209 form；
One water inlet 210 is set on circulation pipe 207, is connected with delivery pump 1；
One water outlet 211 is set on reactor cabinet 201, on the upper end side wall of reactor cabinet 201, with coagulation
Reaction chamber 3 is connected；
One circulation water inlet 212, is set on reactor cabinet 201, is connected with circulation pipe 207, being used for will be in circulation pipe 207
Waste water be delivered in reactor cabinet 201；
One circulating water outlet 213 is set on reactor cabinet 201, is connected with circulation pipe 207, is used for reactor cabinet
Waste water in 201 is delivered in circulation pipe 207；
One gas outlet 214 is set on reactor cabinet 201, on the upper end side wall of reactor cabinet 201, for defeated
Send carbon dioxide, the nitrogen of generation；
One sewage draining exit 215, the ejected wash water generated when being cleaned for discharging to equipment；
Circulating pump 209 is set on circulation pipe 207；
Gas outlet 214 is set to the top of water outlet 211；
Reactor sealing plate 202 is set to the top of reactor cabinet 201；
Anode 203, cathode 204 are set in reactor cabinet 201；
Power supply 205 is electrically connected with anode 203, cathode 204 by cable 206.
In order to which the present embodiment is explained further, it should be noted that
Reactor cabinet 201 is bolted with reactor sealing plate 202, reactor cabinet 201 and reactor it is close
Sealing ring is set between sealing plate 202.
In order to which the present embodiment is explained further, it should be noted that
Anode 203 is the nonactive electrode of inertia, can be titanium-based metal oxide combination electrode, and titanium-based metal oxide is multiple
Contain one of metals such as titanium platinum ruthenium iridium slicker solder or a variety of in composite electrode.
In order to which the present embodiment is explained further, it should be noted that
Reactor cabinet 201, reactor sealing plate 202, circulation pipe 207, pipe-line mixer 208, circulating pump 209 and anode
203, cathode 204, power supply 205, cable 206 insulate between each other, that is, connect or there is insulating layer at the place of being closer；Power supply 205 is
Low voltage and high current high-power DC power supply.
In order to which the present embodiment is explained further, it should be noted that
Power supply 205 is powered by cable 206 to anode 203 and cathode 204, to distribute in reactor cabinet 201
Interior electric field.
In order to which the present embodiment is explained further, it should be noted that
Cable 206 is that copper bar or aluminium are arranged.
In order to which the present embodiment is explained further, it should be noted that
Anode 203 and cathode 204 are arranged by the mode of being alternately arranged, and are insulated each other, are only capable of through waste water conduction.
Embodiment 3,
As shown in Figure 1, 2, a kind of cyanide wastewater electrocatalytic oxidation processing method, cyanide wastewater are that cyanide copper plating process is manual
Production line waste water, CN radical concentration 400mg/L, total copper 165mg/L, pH are between 9~10, and COD is in 1000mg/L or so, total nitrogen
250mg/L, total phosphorus 30mg/L, 5000 μ S/cm of conductivity.Cyanide wastewater is delivered in pipe-line mixer 208 by delivery pump 1,
Enter in electrocatalysis oxidation reaction device 2 after being mixed with recirculated water along circulation water inlet 212, recirculated water flow of inlet water ratio 8:1, control
Voltage carries out electrocatalysis oxidation reaction between 6.5V~7.5V, and CN radical concentration is down within 0.2mg/L in reactor, complete
It is flowed out at the waste water of " broken cyanide " process from water outlet 211.
The waste water flowed out from water outlet 211 is buffered through buffer pool, then is delivered in coagulating case 3 by pump, feeding lime
Cream or liquid alkaline control pH in Cu2+And Cu+Sedimentation pH or more, Cu is changed into Cu (OH)2And CuOH, then in coagulant and help
Under the action of solidifying agent, sediment wadding body increases, and into being separated by solid-liquid separation in clarifier, obtains the sludge and clear water rich in copper.Due to
Cu2+And Cu+It is largely removed, Cu of the solution in clear water2+And Cu+Total concentration meets GB 21900-2008 within 0.3mg/L
" discharge standard for electroplating pollutants " Table III standard.
" drop copper " of " broken cyanide " and coagulation clarification link by electrocatalysis oxidation reaction device, remaining pollutant in waste water
Predominantly COD, total nitrogen, total phosphorus etc., the part is by biochemical treatment apparatus, i.e., controllable water outlet COD is within 50mg/L, total nitrogen
Within 15mg/L, within total phosphorus 0.5mg/L, i.e. GB 21900-2008 " discharge standard for electroplating pollutants " Table III standard requirements.
Embodiment 4,
As shown in Figure 1, 2, a kind of cyanide wastewater electrocatalytic oxidation processing method, cyanide wastewater are that cyanide zinc plating wastewater technique is automatic
Production line waste water, CN radical concentration 200mg/L, total zinc 90mg/L, pH are between 9~10, and COD is in 1000mg/L or so, total nitrogen
150mg/L, total phosphorus 100mg/L, 15000 μ S/cm of conductivity.Cyanide wastewater is delivered to pipe-line mixer 208 by delivery pump 1
In, enter in electrocatalysis oxidation reaction device 2 after being mixed with recirculated water along circulation water inlet 212, recirculated water flow of inlet water ratio 4:1,
Control voltage carries out electrocatalysis oxidation reaction between 5.0V~5.5V, CN radical concentration be down in reactor 0.2mg/L with
Interior, the waste water for completing " broken cyanide " process is flowed out from water outlet 211.
The waste water flowed out from water outlet 211 is buffered through buffer pool, then is delivered in coagulating case 3 by pump, feeding lime
Cream or liquid alkaline control pH in Zn2+Sedimentation pH or more, Zn is changed into Zn (OH)2, then in the effect of coagulant and flocculation aid
Under, sediment wadding body increases, and into being separated by solid-liquid separation in clarifier, obtains the sludge and clear water rich in copper.Due to Zn2+Largely gone
It removes, Zn of the solution in clear water2+Concentration meets GB 21900-2008 " discharge standard for electroplating pollutants " table within 1.0mg/L
III standard.
" drop zinc " of " broken cyanide " and coagulation clarification link by electrocatalysis oxidation reaction device, remaining pollutant in waste water
Predominantly COD, total nitrogen, total phosphorus etc., the part is by biochemical treatment apparatus, i.e., controllable water outlet COD is within 50mg/L, total nitrogen
Within 15mg/L, within total phosphorus 0.5mg/L, i.e. GB 21900-2008 " discharge standard for electroplating pollutants " Table III standard requirements.
Through the foregoing embodiment it is found that a kind of cyanide wastewater electrocatalytic oxidation processing system provided by the invention, at least in fact
Showed it is following the utility model has the advantages that
The present invention without add oxidant, medicament dependence is low, operating cost is low, cyanide removal thoroughly, system it is simple,
Stable and reliable operation, while can suitably reduce the salt content of final outflow water.
Compared with traditional " second level broken cyanide method ":
(1) reaction condition is mild, does not need strong acid or basic conditions, waste water, which does not need adjusting pH, can be directly entered electricity
Catalyst oxidation reactor, and carry out broken cyanide reaction；
(2) does not need consumption oxidizing agent sodium hypochlorite, does not need to consume the soda acid that frequently adjusting pH is added, adds medicine
Dosage is few, reduces wastewater treatment to the dependence of medicament；
(3) process is simple, electrocatalysis oxidation reaction device can a step realize " broken cyanide ", directly convert CO for CN group2With
N2Etc. small molecules；
(4) electrocatalysis oxidation reaction device replaces chemical agent with electricity, due to not needing to add a large amount of medicaments, wastewater treatment
Cost substantially reduces；
(5) the control variable of the core equipment electrocatalysis oxidation reaction device of electrocatalytic oxidation processing technique is few, control process
Simply, it is easy to accomplish automation.
Compared with traditional " level-one broken cyanide method ":
(1) reaction condition is mild, does not need strong acid or basic conditions, waste water, which does not need adjusting pH, can be directly entered electricity
Catalyst oxidation reactor, and carry out broken cyanide reaction；
(2) does not need consumption oxidant hydrogen peroxide, adds that pharmaceutical quantities are few, reduces wastewater treatment to the dependence of medicament；
(3) broken cyanide is thorough, and CN group in waste water only can be down to 0.5mg/L hereinafter, can not expire by traditional " level-one broken cyanide method "
Sufficient GB 21900-2008 " discharge standard for electroplating pollutants " Table III standard requirements, electrocatalytic oxidation processing technique can be by CN groups
It is down to 0.2mg/L, meets Table III standard requirements.
(4) electrocatalysis oxidation reaction device replaces chemical agent with electricity, due to not needing to add a large amount of medicaments, wastewater treatment
Cost substantially reduces；
(5) the control variable of the core equipment electrocatalysis oxidation reaction device of electrocatalytic oxidation processing technique is few, control process
Simply, it is easy to accomplish automation.
Although some specific embodiments of the invention are described in detail by example, the skill of this field
Art personnel it should be understood that example above merely to being illustrated, the range being not intended to be limiting of the invention.The skill of this field
Art personnel are it should be understood that can without departing from the scope and spirit of the present invention modify to above embodiments.This hair
Bright range is defined by the following claims.
Claims (10)
1. a kind of cyanide wastewater electrocatalytic oxidation processing method, which is characterized in that specific steps are as follows:
1) cyanide wastewater is conveyed to electrocatalysis oxidation reaction device (2)；
2) in electrocatalysis oxidation reaction device (2), electrocatalytic oxidation is carried out to cyanide wastewater；
3) enter in coagulating case (3), carry out neutralization reaction；
4) enter in clarifier (4), clarified；
5) enter in biochemical treatment apparatus (5), carry out biochemical treatment.
2. a kind of cyanide wastewater electrocatalytic oxidation processing method according to claim 1, which is characterized in that
In the step 1), cyanide wastewater enters in pipe-line mixer (208) from water inlet (210), and follows in circulation pipe (207)
After the mixing of ring waste water, from the reactor cabinet (201) that circulation water inlet (212) enters electrocatalysis oxidation reaction device (2)；
In the step 2), electrocatalysis oxidation reaction, electrocatalytic oxidation are carried out under the action of anode (203) and cathode (204)
Small part waste water is flowed out from water outlet (211) after the completion, and most of waste water enters circulation pipe (207) from circulating water outlet (213)
In, it is continued cycling through under circulating pump (209) effect, carbon dioxide, the nitrogen of generation are flowed out from gas outlet (214)；
In the step 3), free heavy metal is converted sediment by feeding lime cream or liquid alkaline, coagulant, flocculation aid.
3. a kind of cyanide wastewater electrocatalytic oxidation processing system according to claim 1, which is characterized in that including delivery pump
(1), electrocatalysis oxidation reaction device (2), coagulating case (3), clarifier (4), biochemical treatment apparatus (5)；
The delivery pump (1) is connected, for conveying cyanide wastewater with the electrocatalysis oxidation reaction device (2)；
The electrocatalysis oxidation reaction device (2) is connected with the coagulating case (3), urges for carrying out electricity to cyanide wastewater
Change oxidation；
The coagulating case (3), is connected with the clarifier (4), for by putting into milk of lime or liquid alkaline, coagulant, helping
Solidifying agent converts sediment for heavy metal for free heavy metal；
The clarifier (4), is connected with the biochemical treatment apparatus (5), for obtaining clear water by clarification；
The biochemical treatment apparatus (5) obtains water up to standard for handling by microorganism the water after clarification.
4. a kind of cyanide wastewater electrocatalytic oxidation processing system according to claim 3, which is characterized in that
The electrocatalysis oxidation reaction device (2) is by reactor cabinet (201), reactor sealing plate (202), anode (203), cathode
(204), power supply (205), cable (206), circulation pipe (207), pipe-line mixer (208), circulating pump (209) composition；
One water inlet (210) is set on the circulation pipe (207), is connected with the delivery pump (1)；
One water outlet (211) is set on the reactor cabinet (201), is located at the upper end side wall of the reactor cabinet (201)
On, it is connected with the coagulating case (3)；
One circulation water inlet (212), is set on the reactor cabinet (201), is connected with the circulation pipe (207), and being used for will
Waste water in the circulation pipe (207) is delivered in the reactor cabinet (201)；
One circulating water outlet (213) is set on the reactor cabinet (201), is connected with the circulation pipe (207), and being used for will
Waste water in the reactor cabinet (201) is delivered in the circulation pipe (207)；
One gas outlet (214) is set on the reactor cabinet (201), is located at the upper end side wall of the reactor cabinet (201)
On, for conveying the carbon dioxide generated, nitrogen；
One sewage draining exit (215), the ejected wash water generated when being cleaned for discharging to equipment；
The circulating pump (209) is set on circulation pipe (207)；
The gas outlet (214) is set to the top of water outlet (211)；
The reactor sealing plate (202) is set to the top of reactor cabinet (201)；
The anode (203), cathode (204) are set in reactor cabinet (201)；
The power supply (205) is electrically connected with anode (203), cathode (204) by cable (206).
5. a kind of cyanide wastewater electrocatalytic oxidation processing system according to claim 4, which is characterized in that
The reactor cabinet (201) is bolted with reactor sealing plate (202), the reactor cabinet (201)
Sealing ring is set between reactor sealing plate (202).
6. a kind of cyanide wastewater electrocatalytic oxidation processing system according to claim 4, which is characterized in that
The anode (203) is the nonactive electrode of inertia, can be titanium-based metal oxide combination electrode, the titanium-based metal oxygen
Contain one of titanium platinum ruthenium iridium slicker solder metal or a variety of in compound combination electrode.
7. a kind of cyanide wastewater electrocatalytic oxidation processing system according to claim 4, which is characterized in that
The reactor cabinet (201), reactor sealing plate (202), circulation pipe (207), pipe-line mixer (208), circulating pump
(209) it insulate between each other with anode (203), cathode (204), power supply (205), cable (206), that is, connects or be closer place
There is insulating layer；The power supply (205) is low voltage and high current high-power DC power supply.
8. a kind of cyanide wastewater electrocatalytic oxidation processing system according to claim 4, which is characterized in that
The power supply (205) is powered by cable (206) to anode (203) and cathode (204), to distribute in reactor
Electric field in cabinet (201).
9. a kind of cyanide wastewater electrocatalytic oxidation processing system according to claim 4, which is characterized in that
The cable (206) is that copper bar or aluminium are arranged.
10. a kind of cyanide wastewater electrocatalytic oxidation processing system according to claim 4, which is characterized in that
The anode (203) and cathode (204) are arranged by the mode of being alternately arranged, and are insulated each other, are only capable of through waste water conduction.
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| CN116212941A (en) * | 2022-12-08 | 2023-06-06 | 湖南大学 | Preparation method and application of catalyst |
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Application publication date: 20190528 |