CN110342628A - Treatment method of complex copper wastewater - Google Patents
Treatment method of complex copper wastewater Download PDFInfo
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- CN110342628A CN110342628A CN201910510593.9A CN201910510593A CN110342628A CN 110342628 A CN110342628 A CN 110342628A CN 201910510593 A CN201910510593 A CN 201910510593A CN 110342628 A CN110342628 A CN 110342628A
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- 239000010949 copper Substances 0.000 title claims abstract description 46
- 239000002351 wastewater Substances 0.000 title claims abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 19
- 230000000536 complexating effect Effects 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 238000003672 processing method Methods 0.000 claims description 14
- 230000009514 concussion Effects 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- -1 after adjusting pH Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 26
- 150000002500 ions Chemical class 0.000 abstract description 9
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 abstract description 3
- 239000011943 nanocatalyst Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 239000003729 cation exchange resin Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005374 membrane filtration Methods 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000010814 metallic waste Substances 0.000 description 3
- 238000005375 photometry Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical group OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a treatment method of complex copper wastewater, which is characterized in that hydrated ferric oxide is loaded on strong acid cation exchange resin to prepare a loaded HFO-D001 composite nano catalyst, a heterogeneous Fenton-like system generates hydroxyl radical with strong oxidizing property to oxidize complex heavy metal in wastewater, and the complex heavy metal is dissociated from a complex by destroying the stable structure of complex ions, so that the complex is degraded, and meanwhile, the HFO-D001 catalyst adsorbs the dissociated heavy metal ions. The HFO-D001 catalyst Fenton-like system is constructed, the pH value of the wastewater is adjusted through the actual condition of the wastewater in the wastewater treatment, a good treatment effect can be achieved by a one-step method, the catalyst still has good catalytic activity after being repeatedly used, and the wastewater treatment cost can be greatly reduced. Does not need a lot of equipment investment and operation cost, is convenient to obtain materials and simple to operate, and has great environmental and economic benefits.
Description
Technical field
The invention belongs to complexing heavy metal waste water treatment process fields, and in particular to a kind of processing side that copper waste water is complexed
Method.
Background technique
Heavy metal in waste water not only exists in the form of free state, can also be with the ethylenediamine tetra-acetic acid that contains in water body
(EDTA), the complexing agents such as citric acid, tartaric acid form complexing heavy metal.Complexing heavy metal waste water due to source is wide, discharge amount is big,
Complicated component is always the difficult point and hot issue of field of water quality purification.In general, the heavy metal ion of free state can be held
It changes places and is effectively removed from water body by conventional methods such as chemical precipitation, absorption and ion exchanges.But due to metal ion and network
The structure formed between the organic ligands such as carboxyl, amino, phenolic hydroxyl group and sulfydryl in mixture is sufficiently stable, and conventional method is difficult to remove
Complexing heavy metal.
In recent years, many new methods are exploited for the processing of complexing heavy metal waste water, and the basic principle of these methods is all
It is then the heavy metal ion of secondary treatment separate out based on after to complexing heavy metal chemistry contact break, two can be simply divided into
Footwork and single -step method.Typical two-step method is Fenton reagent oxidation-precipitation method, specifically, the ferrous iron in Fenton reagent
Ionic catalysis H2O2The hydroxyl radical free radical (OH) for generating and there is very high redox potential is decomposed, OH can be by complexing heavy metal
Contact break is aoxidized, heavy metal therein is changed into free state heavy metal ion, then alkaline chemical precipitation, heavy metals removal can be realized.
But the operating process of Fenton oxidation method-precipitation method is many and diverse, needs to constantly regulate the pH of system, treatment process Chinese medicine disappears
Consumption is big, is also easy to produce the secondary pollutions such as excess sludge.So far, Zero-valent Iron exchange-precipitation method, TiO2Photocatalytic method, electrochemistry
The single -step methods such as method and photoelectricity oxidizing process processing complexing heavy metal process has obtained giving more sustained attention for researcher.With two-step method phase
Than single -step method can realize simultaneously complexing heavy metal contact break and free heavy metal ion removal in a system, have operation
Easy-to-use advantage.However, some challenges of single -step method in actual application are still in the development for hindering them.Example
Such as, Zero-valent Iron is easily oxidized to ferriferous oxide in water, is unfavorable for its surface and interface and further reacts with complexing heavy metal.
It is quick compound due to light induced electron and hole, TiO is used on a large scale2Photocatalysis carrys out Simultaneous Oxidation contact break and reduction is free out
The heavy metal ion come, to realize the efficient removal of complexing heavy metal, it is also necessary to further research and discussion.High energy consumption and sun
Pole passivation phenomenon annoyings electrochemical wastewater treatment process always, therefore it is particularly important to develop new processing method and technique.
Summary of the invention
It is an object of the invention to a kind of processing method that copper waste water is complexed is provided to improve the deficiencies in the prior art.
The technical solution of the present invention is as follows: first adjusting the pH of copper-containing wastewater, HFO-D001 catalyst and hydrogen peroxide are added, is set
In concussion bed, so that the complex copper contact break in the waste water is converted into free copper ion and organic matter, be able to be adsorbed and degrade.
The specific technical proposal of the invention is: a kind of processing method that copper waste water is complexed, the specific steps of which are as follows:
1) hydrated ferric oxide-resin D001 (HFO-D001) catalyst is prepared:
Macroreticular resin D001 is added to the FeCl of 1mol/L3In solution, after magnetic agitation reacts 10~12h, washing,
It is dry, it is then added in sodium hydroxide solution, electric stirring reacts 10~12h, and washing, vacuum drying obtain HFO-D001 and urge
Agent；The mass ratio that wherein quality of fe accounts for vector resin D001 in prepared HFO-D001 catalyst is 9~12%；
2) the HFO-D001 catalyst of step 1) preparation is added into waste water containing EDTA-Cu, after adjusting pH, is added 30% pair
Oxygen water is subsequently placed in concussion bed, 4~6h of concussion reaction at 200~300rpm.
Preferred steps 1) in macroreticular resin D001 be added to FeCl3Quality and FeCl in solution3The volume ratio of solution be 10~
20g/L。
Preferred steps 1) described in sodium hydroxide and FeCl3Molar ratio be 1~4:1.
Preferred steps 1) described in macroreticular resin D001 using it is preceding by processing: by the macroreticular resin of purchase according to routine
Pretreatment mode processing after, cross 60 meshes it is spare.
Preferred steps 2) described in HFO-D001 catalyst addition quality with complexing copper waste water volume ratio be 1~
4g/L。
Preferred steps 2) described in adjusting pH range be 2~6；PH is carried out using the hydrochloric acid of 0.05~0.15mol/L
It adjusts.
Preferred steps 2) described in hydrogen peroxide be mass concentration 30% hydrogen peroxide, 30% hydrogen peroxide of mass concentration and network
The volume ratio for closing copper waste water is 1 ‰~4 ‰: 1.
It detects the removal rate of method Cu and COD provided by the invention: being 0.45um water system by the waste water via hole diameter after reaction
Membrane filtration measures the concentration of the Cu and COD in liquid, and the removal rate of measurement result Cu can reach 85.2-95.8% respectively,
COD removal rate reaches 89.6-98.2%；Wherein COD uses atom using potassium dichromate method measurement (GB/71191421989), Cu
Absorptiometry (GB11912-89) measurement.
Supernatant is outwelled, with catalyst 5 times of pH=1 hydrochloric acid clean and reuse repeatedly, then 70 DEG C of vacuum ovens is placed in and dries
It does to weight；Amount, the complexing copper waste water of same catalyst is added, waits a tangent condition identical as previous run, carries out circulation examination
It tests 5 times；The removal rate of measurement result Cu can reach 72.5-83.6% respectively；The removal rate 56.4-70.2% of COD.
In the present invention, hydrated ferric oxide-resin D001 (HFO-D001) composite nano-catalyst is generated in Fenton-like
Hydroxyl radical free radical (OH) is to the contact break reaction key factor of EDTA-Cu waste water in the Innovation Mechanism of the following aspects:
(1) it is generated in the surface particle HFO-D001 active group rich in and hydrated ferric oxide stable containing active group
Divide the complex compound of iron, the stability and recycling number of catalyst are significantly improved；
(2) oxygen-containing functional group abundant especially sulfonic group in the surface HFO-D001 has good adsorption effect to heavy metal；
(3) heterogeneous activation of the active component iron of the complex state in HFO-D001 structure to hydrogen peroxide.
The utility model has the advantages that
Compared with prior art, hydrated ferric oxide is supported on macroreticular resin D001 in the present invention, support type is made
HFO-D001 composite nano-catalyst, heterogeneous Fenton-like generate the network in the hydroxyl radical free radical oxidized waste water of strong oxidizing property
State heavy metal is closed, by destroying the rock-steady structure of complex ion, to make heavy metal separate out from complex compound, complex compound is obtained
With degradation, while HFO-D001 catalyst adsorbs free heavy metal ion.The present invention constructs HFO-D001 catalyst
Fenton-like, adjusts the pH value of waste water by waste water actual conditions in the treatment of waste water, and one-step method can reach good place
Effect is managed, catalyst still has preferable catalytic activity after reusing, can substantially reduce cost for wastewater treatment.It does not need very
More equipment investments and operating cost, materials facilitate operation simple, have great environment and economic benefit.
Specific embodiment
Embodiment 1:
A kind of processing method that copper waste water is complexed, includes the following steps
1) with commercially available general macroreticular resin D001,60 meshes are crossed after pretreatment；15gD001 is added to the 1mol/L of 1L
In ferric chloride solution, after magnetic agitation reacts 10h, washing, drying are then added in the 2mol/L sodium hydroxide solution of 1L, electricity
Dynamic to be stirred to react 12h, washing, vacuum drying obtain HFO-D001 catalyst, the content of fe accounts in HFO-D001 catalyst
The mass ratio of vector resin D001 is 9.5%；
2) the HFO-D001 catalyst of 1g is added in the EDTA-Cu waste water of 250mL, n copper=10mmol/L in waste water,
NEDTA=10mmol/L after 0.5mL30% hydrogen peroxide is added, will react after adjusting pH to 4.0 with the HCl solution of 0.1mol/L
Test tube is placed in concussion bed, and concussion rate is 200rpm, reaction to 4h time；
It is 0.45um water system membrane filtration that the waste water after answering, which is negated, with aperture；The concentration of the COD and Cu in supernatant are measured,
The removal rate of measurement result Cu and COD can reach 95.8% and 98.2% respectively, and wherein Atomic absorption point is respectively adopted in Cu and COD
Light photometry and potassium dichromate method, outwell supernatant, with catalyst 5 times of pH=1 hydrochloric acid clean and reuse repeatedly, then are placed in 70 DEG C
Vacuum oven is dried to weight；Be added same catalyst amount, complexing copper waste water, wait a tangent condition with previous run phase
Together, it carries out cyclic test 5 times；The removal rate of measurement result Cu can reach 83.6%；The removal rate 70.2% of COD.
Embodiment 2:
A kind of processing method that copper waste water is complexed, includes the following steps
1) with commercially available general macroreticular resin D001,60 meshes are crossed after pretreatment；20gD001 is added to the 1mol/L of 2L
In ferric chloride solution, after magnetic agitation reacts 12h, washing, drying are then added in the 1mol/L sodium hydroxide solution of 2L, electricity
Dynamic to be stirred to react 11h, washing, vacuum drying obtain HFO-D001 catalyst, the content of fe accounts in HFO-D001 catalyst
The mass ratio of vector resin D001 is 12%；
2) the HFO-D001 catalyst of 0.5g is added in the EDTA-Cu waste water of 250mL, n copper=8mmol/ in waste water
L, nEDTA=8mmol/L, will be anti-after 0.6mL30% hydrogen peroxide is added after adjusting pH to 6.0 with the HCl solution of 0.05mol/L
Test tube is answered to be placed in concussion bed, concussion rate is 250rpm, reaction to 5h time；
It is 0.45um water system membrane filtration that the waste water after answering, which is negated, with aperture；The concentration of the COD and Cu in supernatant are measured,
The removal rate of measurement result Cu and COD can reach 85.2% and 89.6% respectively, and wherein Atomic absorption point is respectively adopted in Cu and COD
Light photometry and potassium dichromate method, outwell supernatant, with catalyst 5 times of pH=1 hydrochloric acid clean and reuse repeatedly, then are placed in 70 DEG C
Vacuum oven is dried to weight；Be added same catalyst amount, complexing copper waste water, wait a tangent condition with previous run phase
Together, it carries out cyclic test 5 times；The removal rate of measurement result Cu can reach 72.5%；The removal rate 56.4% of COD.
Embodiment 3:
A kind of processing method that copper waste water is complexed, includes the following steps
1) with commercially available general macroreticular resin D001,60 meshes are crossed after pretreatment；30gD001 is added to 1.5L's
In 1mol/L ferric chloride solution, after magnetic agitation reacts 11h, washing, drying are then added to the 4mol/L sodium hydroxide solution of 1L
In, electric stirring reacts 10h, and washing, vacuum drying obtain HFO-D001 catalyst, fe in HFO-D001 catalyst
The mass ratio that content accounts for vector resin D001 is 9%；
2) the HFO-D001 catalyst of 0.25g is added in the EDTA-Cu waste water of 250mL, n copper in waste water=
1mL30% hydrogen peroxide is added after adjusting pH to 2.0 with the HCl solution of 0.15mol/L in 12mmol/L, nEDTA=12mmol/L
Afterwards, reaction tube is placed in concussion bed, concussion rate is 300rpm, reaction to 5h time；
It is 0.45um water system membrane filtration that the waste water after answering, which is negated, with aperture；The concentration of the COD and Cu in supernatant are measured,
The removal rate of measurement result Cu and COD can reach 90.2% and 96.4% respectively, and wherein Atomic absorption point is respectively adopted in Cu and COD
Light photometry and potassium dichromate method, outwell supernatant, with catalyst 5 times of pH=1 hydrochloric acid clean and reuse repeatedly, then are placed in 70 DEG C
Vacuum oven is dried to weight；Be added same catalyst amount, complexing copper waste water, wait a tangent condition with previous run phase
Together, it carries out cyclic test 5 times；The removal rate of measurement result Cu can reach 79.6%；The removal rate 63.2% of COD.
Claims (7)
1. a kind of processing method that copper waste water is complexed, the specific steps of which are as follows:
1) hydrated ferric oxide-resin D001 catalyst is prepared:
Macroreticular resin D001 is added to FeCl3In solution, after magnetic agitation reacts 10~12h, washing, drying are then added to
In sodium hydroxide solution, electric stirring reacts 10~12h, and washing, vacuum drying obtain HFO-D001 catalyst；It is wherein made
It is 9~12% that the quality of fe, which accounts for the mass ratio of vector resin D001, in standby HFO-D001 catalyst；
2) the HFO-D001 catalyst of step 1) preparation is added into waste water containing EDTA-Cu, after adjusting pH, hydrogen peroxide is added, so
It is placed in concussion bed, 4~6h of concussion reaction at 200~300rpm.
2. processing method according to claim 1, it is characterised in that macroreticular resin D001 is added to FeCl in step 1)3It is molten
Quality and FeCl in liquid3The volume ratio of solution is 10~20g/L.
3. processing method according to claim 1, it is characterised in that sodium hydroxide described in step 1) and FeCl3Rub
You are than being 1~4:1.
4. processing method according to claim 1, it is characterised in that macroreticular resin D001 described in step 1) crosses 60 mesh
Sieve.
5. processing method according to claim 1, it is characterised in that HFO-D001 catalyst described in step 2) adds
Entering quality with the volume ratio of complexing copper waste water is 1~4g/L.
6. processing method according to claim 1, it is characterised in that the range for adjusting pH described in step 2) is 2~6；
PH adjusting is carried out using the hydrochloric acid of 0.05~0.15mol/L.
7. processing method according to claim 1, it is characterised in that hydrogen peroxide described in step 2) is mass concentration
The volume ratio of 30% hydrogen peroxide, 30% hydrogen peroxide of mass concentration and complexing copper waste water is 1 ‰~4 ‰: 1.
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