CN108866570A - A kind of method that cyclone electrolytic cell recycles complexing nickel in electroplating wastewater - Google Patents
A kind of method that cyclone electrolytic cell recycles complexing nickel in electroplating wastewater Download PDFInfo
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- CN108866570A CN108866570A CN201810832416.8A CN201810832416A CN108866570A CN 108866570 A CN108866570 A CN 108866570A CN 201810832416 A CN201810832416 A CN 201810832416A CN 108866570 A CN108866570 A CN 108866570A
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- Prior art keywords
- nickel
- electrolytic cell
- electroplating wastewater
- cyclone electrolytic
- complexed
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 239000002351 wastewater Substances 0.000 title claims abstract description 102
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 95
- 238000009713 electroplating Methods 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 65
- 230000000536 complexating effect Effects 0.000 title abstract description 9
- 238000004064 recycling Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 239000001509 sodium citrate Substances 0.000 claims description 45
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 38
- 229910052802 copper Inorganic materials 0.000 claims description 37
- 239000010949 copper Substances 0.000 claims description 37
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims 1
- 239000002699 waste material Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 37
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 23
- 238000004458 analytical method Methods 0.000 description 17
- 238000000691 measurement method Methods 0.000 description 12
- 238000007781 pre-processing Methods 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 241000784732 Lycaena phlaeas Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910000863 Ferronickel Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical group [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UIFOTCALDQIDTI-UHFFFAOYSA-N arsanylidynenickel Chemical compound [As]#[Ni] UIFOTCALDQIDTI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910021652 non-ferrous alloy Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses the methods that nickel is complexed in a kind of cyclone electrolytic cell recycling electroplating wastewater comprising, contact break agent is added in electroplating wastewater and is stirred, aqueous slkali is then added and adjusts wastewater pH=9~10；Contact break is closed into treated the waste water as electrolyte, is placed in swirl electrolysis device, is reacted by control electric current；Product after reaction is washed, is dried, obtains nickel product.The present invention utilizes and is reduced directly to obtain product in swirl electrolysis device inner cathode electrochemistry, complexing nickel is separated in a mild condition, cyclone electrolytic cell enables electrode preferably to contact with solution, liquid eliminates concentration polarization by high speed rotation, so as to obtain high-purity nickel simple substance, and separating effect is more preferable, and obtained nickel simple substance can carry out secondary use well, have very big promotion for the recycling of nickel resources.Resource utilization of the present invention is high, and recovery rate is high, pollution-free, process conditions are mild, at low cost, environmentally friendly and low for equipment requirements.
Description
Technical field
The invention belongs to heavy metal recovery and pollution processing technology fields, and in particular to a kind of cyclone electrolytic cell recycling plating
The method of nickel is complexed in waste water.
Background technique
In recent years, the production and consumption of world's nickel is more steady, and the nickel metal supply-demand situation is not mainly in the world
Rust steel industry development and change and change, with the growth applied in stainless steel industry consumption of nickel metal, nickel iron smelting process has
Greatly progress, high-grade ferronickel yield are improved significantly.China is current global maximum ferronickel production and consumption state, with
The continuous development of economy and steel industry, for nickel resources utilization have very large space.
For nickel resources utilization be mainly used for alloy (such as nickel steel and nickeline) and be used as catalyst (such as Raney nickel, especially
Refer to the catalyst for being used as hydrogenation), plating can prevent from getting rusty on other metals.It can also be used to manufacture stainless steel and other anti-corruption
Alloy is lost, such as nickel steel, nickel-chromium steel and various non-ferrous alloys, the nickeliferous higher corronil of ingredient is not just perishable.Also make
Hydrogenation catalyst and for ceramic, Specialty Chemical vessel, electronic circuit and nickel compound preparation etc..
But simple plating mode nowadays can not be used containing a large amount of complexing nickel in the electroplating wastewater of electronickelling industry
It is separated, so a large amount of nickel ion can not separate in waste water, not only increase the discharge of pollution, also create a large amount of
The wasting of resources, so needing better method processing electroplating wastewater and recycling the nickel in waste water as far as possible.
But art methods do not obtain nickel simple substance and products thereof, and the reaction time is longer, some step operations are numerous
Trivial and traditional precipitate recovery process can not carry out large-scale industrial production, for wastewater treatment and heavy metal recovery
Further technology is also needed to develop.
Therefore, this field needs a kind of efficient and high-efficiency environment friendly method, so that the nickel product in electroplating wastewater obtains
It further utilizes, and the waste water of emission request must be reached.And cost is reduced as far as possible, yield is increased and increases economic effect
It answers.
Summary of the invention
The purpose of this section is to summarize some aspects of the embodiment of the present invention and briefly introduce some preferable implementations
Example.It may do a little simplified or be omitted to avoid our department is made in this section and the description of the application and the title of the invention
Point, the purpose of abstract of description and denomination of invention it is fuzzy, and this simplification or omit and cannot be used for limiting the scope of the invention.
In view of above-mentioned technological deficiency, the present invention is proposed.
Therefore, the present invention overcomes the deficiencies in the prior art, provides network in a kind of cyclone electrolytic cell recycling electroplating wastewater
The method for closing nickel.
In order to solve the above technical problems, the present invention provides following technical solutions：A kind of cyclone electrolytic cell recycling electroplating wastewater
The method of middle complexing nickel comprising,
Contact break agent is added in electroplating wastewater to be stirred, aqueous slkali is then added and adjusts wastewater pH=9~10；
Contact break is closed into treated the waste water as electrolyte, is placed in swirl electrolysis device, by control electric current into
Row reaction；
Product after reaction is washed, is dried, obtains nickel product.
A kind of preferred embodiment as the method that nickel is complexed in cyclone electrolytic cell of the present invention recycling electroplating wastewater：It is described
Contact break agent is added in electroplating wastewater to be stirred, wherein the mixing time is in 1h or more.
A kind of preferred embodiment as the method that nickel is complexed in cyclone electrolytic cell of the present invention recycling electroplating wastewater：It is described
Contact break agent is added in electroplating wastewater to be stirred, wherein the contact break agent includes sodium citrate.
A kind of preferred embodiment as the method that nickel is complexed in cyclone electrolytic cell of the present invention recycling electroplating wastewater：It is described
Alkali includes sodium hydroxide or potassium hydroxide.
A kind of preferred embodiment as the method that nickel is complexed in cyclone electrolytic cell of the present invention recycling electroplating wastewater：It is described
Cyclone electrolytic cell, cathode are the copper sheet that high temperature oxidation process has compound hierarchy, and anode is graphite electrode；The copper sheet
Processing method includes,
Copper sheet as electrode is placed on 5~15min of immersion in dilute hydrochloric acid, later the supersound washing 1h in dehydrated alcohol,
It is washed with distilled water；
It is put into 4~6h of standing in 20% hydrogenperoxide steam generator after washing, is put into vacuum oven after being washed with distilled water
It is dry；
It is put into after drying in the tube furnace with gas mixing device and carries out heated oxide, under argon atmosphere, tube furnace is with 5
DEG C/heating rate of min is warming up to 500 DEG C, keeps temperature-resistant, is passed through the oxygen that volume ratio is 10%, keep 10~
30min is down to room temperature under argon atmosphere with the rate of 5 DEG C/min.
A kind of preferred embodiment as the method that nickel is complexed in cyclone electrolytic cell of the present invention recycling electroplating wastewater：It is described
Swirl electrolysis device, including cyclone electrolytic cell slot, wherein the cyclone electrolytic cell slot is normal pressure electrolytic cell, and shape is hollow seal
Cylindrical body.
A kind of preferred embodiment as the method that nickel is complexed in cyclone electrolytic cell of the present invention recycling electroplating wastewater：It is described
It is reacted by controlling electric current, wherein the reaction, temperature are 20~80 DEG C, and the reaction time is greater than 1h.
A kind of preferred embodiment as the method that nickel is complexed in cyclone electrolytic cell of the present invention recycling electroplating wastewater：It is described
It is reacted by controlling electric current, wherein the reaction, temperature are 25~50 DEG C, and the reaction time is 2~4h.
A kind of preferred embodiment as the method that nickel is complexed in cyclone electrolytic cell of the present invention recycling electroplating wastewater：It is described
It is reacted by controlling electric current, wherein the reaction, electric current are 250~450A/m2。
A kind of preferred embodiment as the method that nickel is complexed in cyclone electrolytic cell of the present invention recycling electroplating wastewater：It is described
It is reacted by controlling electric current, wherein the reaction, electric current 350A/m2
Beneficial effects of the present invention：It is to be utilized that the method for nickel, which is complexed, in cyclone electrolytic cell recycling electroplating wastewater of the present invention
It is reduced directly to obtain product in swirl electrolysis device inner cathode electrochemistry, which can in a mild condition separate complexing nickel
It comes, since cyclone electrolytic cell enables electrode preferably to contact with solution, liquid eliminates concentration polarization by high speed rotation, thus
High-purity nickel simple substance can be obtained, and separating effect is more preferable, obtained nickel simple substance can carry out secondary use well, for nickel
The recycling of resource has very big promotion.The method of the present invention resource utilization is high, recovery rate is high, pollution-free, process conditions mildly, at
This is low, environmentally friendly and low for equipment requirements.The present invention carries out the pretreatment of electroplating wastewater using sodium citrate, will strengthen
The broken complexing of the recycling of nickel in waste water, sodium citrate has good effect, and sodium citrate for waste water of the invention
Ecological environment is not adversely influenced.In the method for the present invention, used cathode is to have again by high temperature oxidation process
Activation copper sheet layered is closed, copper sheet surface has extra specific surface area, have through overactivation in fine and close stacking reticular structure
Have stronger absorption property, with traditional cyclone electrolytic cell used in compared with stainless steel substrates and common copper sheet, can preferably divide
From with absorption nickel product, obtain the nickel of high-purity, there has also been significantly promoted for yield.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill of field, without any creative labor, it can also be obtained according to these attached drawings other
Attached drawing.Wherein：
Fig. 1 is that cyclone electrolytic cell of the present invention recycles the processing technological flow figure that nickel is complexed in electroplating wastewater.
Fig. 2 is the Recovery curve of nickel product at any time.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, right combined with specific embodiments below
A specific embodiment of the invention is described in detail.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, but the present invention can be with
Implemented using other than the one described here other way, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by the specific embodiments disclosed below.
Secondly, " one embodiment " or " embodiment " referred to herein, which refers to, may be included at least one realization side of the invention
A particular feature, structure, or characteristic in formula." in one embodiment " that different places occur in the present specification not refers both to
The same embodiment, nor the individual or selective embodiment mutually exclusive with other embodiments.
Swirl electrolysis device cathode of the present invention is the copper sheet that high temperature oxidation process has compound hierarchy, and anode is graphite
Electrode.
Cathode copper sheet oxidation step of the present invention is：
1, the copper sheet as electrode is placed on 5~15min of immersion in dilute hydrochloric acid, then copper sheet is placed in dehydrated alcohol and is surpassed
Sound washs 1h, is then washed with distilled water for several times.
2, copper sheet is placed on 4~6h of standing in 20% hydrogenperoxide steam generator, is put into after being then washed with distilled water for several times
It is dry in vacuum oven.
3, copper sheet is put into the tube furnace with gas mixing device and carries out heated oxide, under argon atmosphere, tube furnace is with 5
DEG C/heating rate of min is warming up to 500 DEG C, it then keeps temperature-resistant, is passed through the oxygen that volume ratio is 10%, keep
Then 20min is down to room temperature under argon atmosphere with the rate of 5 DEG C/min, obtain cathode electrode used in cyclone electrolytic cell.
Embodiment 1：
(1) ingredient：Electroplating wastewater 5L, sodium citrate 50g, sodium hydroxide solution, are added sodium citrate in waste water first
It is stirred 2h, then adjusts pH=9.5 with sodium hydroxide solution, the treated electroplating wastewater is standby as electrolyte
With.
(2) will be processed that electroplating wastewater is fitted into cyclone electrolytic cell slot, 25 DEG C are adjusted the temperature to, cyclone electrolytic cell equipment is opened
Circulating pump, current density is adjusted to 350A/m2, reacted, reaction time 2h.Cathode can be recycled after reaction
Product on copper sheet.Swirl electrolysis device cathode of the present invention is the copper sheet that high temperature oxidation process has compound hierarchy, anode
For graphite electrode.
(3) product that step (2) obtains is washed and is dried in vacuo, the solution after taking a small amount of reaction carries out ICP survey
Examination analysis, the rate of recovery for calculating nickel is 99%.
If pre-processing in the embodiment without using sodium citrate, remaining step is constant, is obtained using identical measurement method
The rate of recovery of nickel is 10%.
Embodiment 2：
(1) ingredient：Electroplating wastewater 5L, sodium citrate 10g, sodium hydroxide solution, are added sodium citrate in waste water first
It is stirred 2h, then adjusts pH=9.5 with sodium hydroxide solution, the treated electroplating wastewater is standby as electrolyte
With.
(2) will be processed that electroplating wastewater is fitted into cyclone electrolytic cell slot, 45 DEG C are adjusted the temperature to, cyclone electrolytic cell equipment is opened
Circulating pump, current density is adjusted to 350A/m2, reacted, reaction time 2h.Cathode can be recycled after reaction
Product on copper sheet.Swirl electrolysis device cathode of the present invention is the copper sheet that high temperature oxidation process has compound hierarchy, anode
For graphite electrode.
(3) product that step (2) obtains is separated, washed and is dried in vacuo, the solution after taking a small amount of reaction carries out
ICP test analysis, the rate of recovery for calculating nickel is 75%.
If pre-processing in the embodiment without using sodium citrate, remaining step is constant, is obtained using identical measurement method
The rate of recovery of nickel is 11%.
Embodiment 3：
(1) ingredient：Electroplating wastewater 5L, sodium citrate 50g, sodium hydroxide solution, are added sodium citrate in waste water first
It is stirred 2h, then adjusts pH=9.5 with sodium hydroxide solution, the treated electroplating wastewater is standby as electrolyte
With.
(2) will be processed that electroplating wastewater is fitted into cyclone electrolytic cell slot, 25 DEG C are adjusted the temperature to, cyclone electrolytic cell equipment is opened
Circulating pump, current density is adjusted to 350A/m2, reacted, reaction time 2h.Cathode can be recycled after reaction
Product on copper sheet.Swirl electrolysis device cathode of the present invention is the copper sheet that high temperature oxidation process has compound hierarchy, anode
For graphite electrode.
(3) product that step (2) obtains is separated, washed and is dried in vacuo, the solution after taking a small amount of reaction carries out
ICP test analysis, the rate of recovery for calculating nickel is 92%.
If pre-processing in the embodiment without using sodium citrate, remaining step is constant, is obtained using identical measurement method
The rate of recovery of nickel is 8%.
Embodiment 4：
(1) ingredient：Electroplating wastewater 5L, sodium citrate 50g, sodium hydroxide solution, are added sodium citrate in waste water first
It is stirred 2h, then adjusts pH=9.5 with sodium hydroxide solution, the treated electroplating wastewater is standby as electrolyte
With.
(2) will be processed that electroplating wastewater is fitted into cyclone electrolytic cell slot, 45 DEG C are adjusted the temperature to, cyclone electrolytic cell equipment is opened
Circulating pump, current density is adjusted to 250A/m2, reacted, reaction time 2h.Cathode can be recycled after reaction
Product on copper sheet.Swirl electrolysis device cathode of the present invention is the copper sheet that high temperature oxidation process has compound hierarchy, anode
For graphite electrode.
(3) product that step (2) obtains is separated, washed and is dried in vacuo, the solution after taking a small amount of reaction carries out
ICP test analysis, the rate of recovery for calculating nickel is 89%.
If pre-processing in the embodiment without using sodium citrate, remaining step is constant, is obtained using identical measurement method
The rate of recovery of nickel is 6%.
Embodiment 5：
(1) ingredient：Electroplating wastewater 5L, sodium citrate 50g, sodium hydroxide solution, are added sodium citrate in waste water first
It is stirred 2h, then adjusts pH=12 with sodium hydroxide solution, the treated electroplating wastewater is spare as electrolyte.
(2) will be processed that electroplating wastewater is fitted into cyclone electrolytic cell slot, 45 DEG C are adjusted the temperature to, cyclone electrolytic cell equipment is opened
Circulating pump, current density is adjusted to 350A/m2, reacted, reaction time 2h.Cathode can be recycled after reaction
Product on copper sheet.Swirl electrolysis device cathode of the present invention is the copper sheet that high temperature oxidation process has compound hierarchy, anode
For graphite electrode.
(3) product that step (2) obtains is separated, washed and is dried in vacuo, the solution after taking a small amount of reaction carries out
ICP test analysis, the rate of recovery for calculating nickel is 98%.
If pre-processing in the embodiment without using sodium citrate, remaining step is constant, is obtained using identical measurement method
The rate of recovery of nickel is 12%.
Embodiment 6：
(1) ingredient：Electroplating wastewater 5L, sodium citrate 50g, sodium hydroxide solution, are added sodium citrate in waste water first
It is stirred 2h, then adjusts pH=9.5 with sodium hydroxide solution, the treated electroplating wastewater is standby as electrolyte
With.
(2) will be processed that electroplating wastewater is fitted into cyclone electrolytic cell slot, 45 DEG C are adjusted the temperature to, cyclone electrolytic cell equipment is opened
Circulating pump, current density is adjusted to 350A/m2, reacted, reaction time 1.5h.Yin can be recycled after reaction
Product on the copper sheet of pole.Swirl electrolysis device cathode of the present invention is the copper sheet that high temperature oxidation process has compound hierarchy, sun
Extremely graphite electrode.
(3) product that step (2) obtains is separated, washed and is dried in vacuo, the solution after taking a small amount of reaction carries out
ICP test analysis, the rate of recovery for calculating nickel is 95%.
If pre-processing in the embodiment without using sodium citrate, remaining step is constant, is obtained using identical measurement method
The rate of recovery of nickel is 7%.
Embodiment 7：
(1) ingredient：Electroplating wastewater 5L, sodium citrate 30g, sodium hydroxide solution, are added sodium citrate in waste water first
It is stirred 2h, then adjusts pH=9.5 with sodium hydroxide solution, the treated electroplating wastewater is standby as electrolyte
With.
(2) will be processed that electroplating wastewater is fitted into cyclone electrolytic cell slot, 55 DEG C are adjusted the temperature to, cyclone electrolytic cell equipment is opened
Circulating pump, current density is adjusted to 350A/m2, reacted, reaction time 3h.Cathode can be recycled after reaction
Product on copper sheet.Swirl electrolysis device cathode of the present invention is the copper sheet that high temperature oxidation process has compound hierarchy, anode
For graphite electrode.
(3) product that step (2) obtains is separated, washed and is dried in vacuo, the solution after taking a small amount of reaction carries out
ICP test analysis, the rate of recovery for calculating nickel is 97%.
If pre-processing in the embodiment without using sodium citrate, remaining step is constant, is obtained using identical measurement method
The rate of recovery of nickel is 11%.
Embodiment 8：
(1) ingredient：Electroplating wastewater 5L, sodium citrate 40g, sodium hydroxide solution, are added sodium citrate in waste water first
It is stirred 2h, then adjusts pH=9.5 with sodium hydroxide solution, the treated electroplating wastewater is standby as electrolyte
With.
(2) will be processed that electroplating wastewater is fitted into cyclone electrolytic cell slot, 25 DEG C are adjusted the temperature to, cyclone electrolytic cell equipment is opened
Circulating pump, current density is adjusted to 400A/m2, reacted, reaction time 2h.Cathode can be recycled after reaction
Product on copper sheet.Swirl electrolysis device cathode of the present invention is the copper sheet that high temperature oxidation process has compound hierarchy, anode
For graphite electrode.
(3) product that step (2) obtains is separated, washed and is dried in vacuo, the solution after taking a small amount of reaction carries out
ICP test analysis, the rate of recovery for calculating nickel is 94%.
If pre-processing in the embodiment without using sodium citrate, remaining step is constant, is obtained using identical measurement method
The rate of recovery of nickel is 8%.
Embodiment 9：
(1) ingredient：Electroplating wastewater 5L, sodium citrate 50g, sodium hydroxide solution, are added sodium citrate in waste water first
It is stirred 2h, then adjusts pH=9.5 with sodium hydroxide solution, the treated electroplating wastewater is standby as electrolyte
With.
(2) will be processed that electroplating wastewater is fitted into cyclone electrolytic cell slot, 25 DEG C are adjusted the temperature to, cyclone electrolytic cell equipment is opened
Circulating pump, current density is adjusted to 350A/m2, reacted, reaction time 2h.Cathode can be recycled after reaction
Product on copper sheet.Swirl electrolysis device cathode of the present invention is the copper sheet that high temperature oxidation process has compound hierarchy, anode
For graphite electrode.
(3) product that step (2) obtains is separated, washed and is dried in vacuo, the solution after taking a small amount of reaction carries out
ICP test analysis, the rate of recovery for calculating nickel is 98%.
If pre-processing in the embodiment without using sodium citrate, remaining step is constant, is obtained using identical measurement method
The rate of recovery of nickel is 10%.
Embodiment 10：
(1) ingredient：Electroplating wastewater 5L, sodium citrate 30g, sodium hydroxide solution, are added sodium citrate in waste water first
It is stirred 2h, then adjusts pH=9.5 with sodium hydroxide solution, the treated electroplating wastewater is standby as electrolyte
With.
(2) will be processed that electroplating wastewater is fitted into cyclone electrolytic cell slot, 65 DEG C are adjusted the temperature to, cyclone electrolytic cell equipment is opened
Circulating pump, current density is adjusted to 400A/m2, reacted, reaction time 2h.Cathode can be recycled after reaction
Product on copper sheet.Swirl electrolysis device cathode of the present invention is the copper sheet that high temperature oxidation process has compound hierarchy, anode
For graphite electrode.
(3) product that step (2) obtains is separated, washed and is dried in vacuo, the solution after taking a small amount of reaction carries out
ICP test analysis, the rate of recovery for calculating nickel is 94%.
If pre-processing in the embodiment without using sodium citrate, remaining step is constant, is obtained using identical measurement method
The rate of recovery of nickel is 9%.
Comparative example 1：
In addition to the sodium citrate in step (1) is replaced with hydrogen peroxide, remaining is same as Example 1.
Solution after reaction is subjected to icp analysis, the rate of recovery that nickel is calculated is 8%.
Comparative example 2：
In addition to the sodium citrate in step (1) is replaced with calcium oxide, remaining is same as Example 1.
Solution after reaction is subjected to icp analysis, the rate of recovery that nickel is calculated is only 6%, and can be obtained certain
Sediment.
Comparative example 3：
In addition to the sodium citrate in step (1) is replaced with barium chloride, remaining is same as Example 1.
Solution after reaction is subjected to icp analysis, the rate of recovery that nickel is calculated is 5%, and processed waste water obtains centainly
Precipitated product.
Comparative example 4：
In addition to the sodium citrate in step (1) is replaced with calcium oxide and barium chloride, remaining is same as Example 1.
Solution after reaction is subjected to icp analysis, the rate of recovery that nickel is calculated is 12%, and is occurred in experiment wastewater
Certain sediment.
Comparative example 5：
By high temperature oxidation process will there is the copper sheet of compound hierarchy to replace with untreated common copper sheet, ruler
Very little thickness is all identical, remaining is identical as step (1).
Solution after reaction is subjected to icp analysis, the rate of recovery that nickel is calculated is 78%.
If pre-processing in the embodiment without using sodium citrate, remaining step is constant, is obtained using identical measurement method
The rate of recovery of nickel is only 2%.
Comparative example 6：
By high temperature oxidation process will there is the copper sheet of compound hierarchy to replace with 316L stainless steel substrates, dimensional thickness is all
Identical, remaining is identical as step (1).
Solution after reaction is subjected to icp analysis, the rate of recovery that nickel is calculated is 70%.
If pre-processing in the embodiment without using sodium citrate, remaining step is constant, is obtained using identical measurement method
The rate of recovery of nickel is 3%.
Comparative example 7：
In addition to the cyclone electrolytic cell reaction in step (2) is replaced with general electrolytic, remaining is same as Example 1.
Solution after reaction is subjected to icp analysis, the rate of recovery that nickel is calculated is 48%.
If remaining step is constant, is applicable in identical test method and obtains without using sodium citrate and processing in the embodiment
The rate of recovery to nickel is 3%.
To sum up, the method for nickel being complexed in cyclone electrolytic cell recycling electroplating wastewater of the present invention is to be utilized to fill in cyclone electrolytic cell
It sets inner cathode electrochemistry to be reduced directly to obtain product, which can in a mild condition separate complexing nickel, due to rotation
Galvanic electricity solution enables electrode preferably to contact with solution, and liquid eliminates concentration polarization by high speed rotation, high-purity so as to obtain
Nickel simple substance is spent, and separating effect is more preferable, obtained nickel simple substance can carry out secondary use, the recycling for nickel resources well
There is very big promotion.The method of the present invention resource utilization is high, recovery rate is high, pollution-free, process conditions are mild, it is at low cost, to ring
Border is friendly and low for equipment requirements.
It is noted that used cathode is by high temperature oxidation process with composite layered in the method for the present invention
The activation copper sheet of structure, copper sheet surface have extra specific surface area in fine and close stacking reticular structure, have through overactivation stronger
Absorption property, with traditional cyclone electrolytic cell used in compared with stainless steel substrates and common copper sheet, preferably can separate and inhale
Attached nickel product obtains the nickel of high-purity, and there has also been significantly promoted for yield.
The method that nickel is complexed in cyclone electrolytic cell recycling electroplating wastewater provided by the invention uses atmospheric operation, and reaction temperature can
Down to 25 DEG C, reaction temperature is reduced compared with traditional technique, to reduce energy consumption.
The method of the present invention is not introduced into for fear of isolated impurity from reaction medium, in system, is convenient for product following process
It utilizes；Used alkali concentration is greatly lowered, and alkaline consumption greatly reduces down to 0.1M in minimum alkali concentration, increases production
Out, cost is saved.
The method of the present invention is added to a small amount of auxiliary material for obtaining better separating effect, but the dosage of auxiliary material
It is comparable few, and any side effect will not be generated to electrolysis, secondary wastewater will not be caused to pollute, this is compared to traditional work
Skill, not only yield increases 30%, but also can reduce by 90% waste water, has great side for the recycling of waste water
It helps.
It is noted that the present invention carries out the pretreatment of electroplating wastewater using sodium citrate, nickel in waste water will be strengthened
Recycling, the broken complexing of sodium citrate has good effect for waste water of the invention, and sodium citrate is for ecological ring
Border is not adversely influenced.
The method of the present invention cyclone electrolytic cell operation is simple, reduces human input, operates, can bring convenient for high-volume
Good economic benefit and social benefit, have a good application prospect.The method of the present invention utilizes contact break conjunction and cyclone electrolytic cell side
Method is recycled, and obtained product is a kind of powder with metallic luster, for it is subsequent application with processing have it is good
Plasticity facilitates subsequent use.
The method that nickel is complexed in cyclone electrolytic cell recycling electroplating wastewater provided by the invention is carried out further using electroplating wastewater
Nickel separation, the electroplating wastewater of the prior art carries out electro-deposition again cannot achieve, but processing method through the invention, Ke Yijin
One step obtains nickel product, can also be further processed waste water simultaneously, reach discharge standard.
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferable
Embodiment describes the invention in detail, those skilled in the art should understand that, it can be to technology of the invention
Scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered in this hair
In bright scope of the claims.
Claims (10)
1. the method for nickel is complexed in a kind of cyclone electrolytic cell recycling electroplating wastewater, it is characterised in that：Including,
Contact break agent is added in electroplating wastewater to be stirred, aqueous slkali is then added and adjusts wastewater pH=9~10；
Contact break is closed into treated the waste water as electrolyte, is placed in swirl electrolysis device, is carried out instead by control electric current
It answers；
Product after reaction is washed, is dried, obtains nickel product.
2. the method for nickel is complexed in cyclone electrolytic cell recycling electroplating wastewater as described in claim 1, it is characterised in that：It is described in electricity
Contact break agent is added in waste electroplating to be stirred, wherein the mixing time is in 1h or more.
3. the method for nickel is complexed in cyclone electrolytic cell recycling electroplating wastewater as claimed in claim 1 or 2, it is characterised in that：It is described
Contact break agent is added in electroplating wastewater to be stirred, wherein the contact break agent includes sodium citrate.
4. the method for nickel is complexed in cyclone electrolytic cell recycling electroplating wastewater as claimed in claim 1 or 2, it is characterised in that：It is described
Alkali includes sodium hydroxide or potassium hydroxide.
5. the method for nickel is complexed in cyclone electrolytic cell recycling electroplating wastewater as claimed in claim 1 or 2, it is characterised in that：It is described
Cyclone electrolytic cell, cathode are the copper sheet that high temperature oxidation process has compound hierarchy, and anode is graphite electrode；The copper sheet
Processing method includes,
Copper sheet as electrode is placed on 5~15min of immersion in dilute hydrochloric acid, later the supersound washing 1h in dehydrated alcohol, with steaming
Distilled water washing；
It is put into 4~6h of standing in 20% hydrogenperoxide steam generator after washing, is put into after being washed with distilled water in vacuum oven dry；
It is put into after drying in the tube furnace with gas mixing device and carries out heated oxide, under argon atmosphere, tube furnace is with 5 DEG C/min
Heating rate be warming up to 500 DEG C, keep temperature-resistant, be passed through the oxygen that volume ratio is 10%, 10~30min is kept, in argon
Atmosphere with the rate of 5 DEG C/min is down to room temperature under enclosing.
6. the method for nickel is complexed in cyclone electrolytic cell recycling electroplating wastewater as claimed in claim 1 or 2, it is characterised in that：It is described
Swirl electrolysis device, including cyclone electrolytic cell slot, wherein the cyclone electrolytic cell slot is normal pressure electrolytic cell, and shape is hollow seal
Cylindrical body.
7. the method for nickel is complexed in cyclone electrolytic cell recycling electroplating wastewater as claimed in claim 1 or 2, it is characterised in that：It is described
It is reacted by controlling electric current, wherein the reaction, temperature are 20~80 DEG C, and the reaction time is greater than 1h.
8. the method for nickel is complexed in cyclone electrolytic cell recycling electroplating wastewater as claimed in claim 7, it is characterised in that：It is described to pass through
Control electric current is reacted, wherein the reaction, temperature are 25~50 DEG C, and the reaction time is 2~4h.
9. the method that nickel is complexed in the cyclone electrolytic cell recycling electroplating wastewater as described in any in claim 1,2,8, feature exist
In：It is described to be reacted by controlling electric current, wherein the reaction, electric current are 250~450A/m2。
10. the method for nickel is complexed in cyclone electrolytic cell recycling electroplating wastewater as claimed in claim 9, it is characterised in that：It is described logical
It crosses control electric current to be reacted, wherein the reaction, electric current 350A/m2。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1533399A2 (en) * | 2003-11-24 | 2005-05-25 | Walter Hillebrand GmbH & Co. Galvanotechnik | Method for obtaining a waste-water-low alkali zinc-nickel bath |
| CN107364985A (en) * | 2016-05-13 | 2017-11-21 | 禾华环保科技（上海）有限公司 | A kind of method of complexation heavy metal ion in removal water body |
| CN107651733A (en) * | 2016-07-26 | 2018-02-02 | 中国科学院生态环境研究中心 | A kind of method that rotating cathode strengthens photoelectrocatalysioxidization oxidization processing complex state heavy metal wastewater thereby and negative electrode recovery heavy metal |
-
2018
- 2018-07-26 CN CN201810832416.8A patent/CN108866570A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1533399A2 (en) * | 2003-11-24 | 2005-05-25 | Walter Hillebrand GmbH & Co. Galvanotechnik | Method for obtaining a waste-water-low alkali zinc-nickel bath |
| CN107364985A (en) * | 2016-05-13 | 2017-11-21 | 禾华环保科技（上海）有限公司 | A kind of method of complexation heavy metal ion in removal water body |
| CN107651733A (en) * | 2016-07-26 | 2018-02-02 | 中国科学院生态环境研究中心 | A kind of method that rotating cathode strengthens photoelectrocatalysioxidization oxidization processing complex state heavy metal wastewater thereby and negative electrode recovery heavy metal |
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Application publication date: 20181123 |