CN110921787A - Method for removing free chlorine from nickel chloride electrodeposition anolyte - Google Patents

Method for removing free chlorine from nickel chloride electrodeposition anolyte Download PDF

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Publication number
CN110921787A
CN110921787A CN201911230049.5A CN201911230049A CN110921787A CN 110921787 A CN110921787 A CN 110921787A CN 201911230049 A CN201911230049 A CN 201911230049A CN 110921787 A CN110921787 A CN 110921787A
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China
Prior art keywords
anolyte
nickel chloride
free chlorine
chlorine
chloride electrodeposition
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CN201911230049.5A
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Chinese (zh)
Inventor
张晗
郁洪波
郭金权
席海龙
张建玲
王书友
高晓婷
陈彩霞
李全
王钦
路思阳
马天飞
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Jinchuan Group Co Ltd
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Jinchuan Group Co Ltd
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Priority to CN201911230049.5A priority Critical patent/CN110921787A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/12Halogens or halogen-containing compounds

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

A method for removing free chlorine from nickel chloride electrodeposition anolyte comprises the following processes: under the action of a forced force field, the nickel chloride electrodeposition anolyte is fully dripped to form liquid drops with the radius of 1-3mm, the liquid drops are in cross flow contact with a certain amount of air, and the equilibrium reaction of free chlorine in the solution is carried out towards the analytic direction according to the principle of gas-liquid interface equilibrium concentration, so that the concentration of the free chlorine in the nickel chloride electrodeposition anolyte is reduced, and the purpose of removing the free chlorine from the nickel chloride electrodeposition anolyte is achieved. The concentration of the chlorine in the anolyte after the chlorine is removed is below 6ppm, the dechlorination effect in the whole process is good, the removal rate of free chlorine is above 98.5%, the removal rate of the free chlorine in the anolyte is improved, the chlorine content of the anolyte is low, chlorine odor is avoided, the requirement of recycling the anolyte is met, the dechlorinated anolyte is in an ideal state for recycling, and the aim of clean and friendly environment in field operation is met.

Description

Method for removing free chlorine from nickel chloride electrodeposition anolyte
Technical Field
The invention belongs to the technical field of nickel chlorination electrodeposition processes, and particularly relates to a method for removing free chlorine from nickel chlorination electrodeposition anolyte.
Background
At present, the common dechlorination methods for light salt brine at home and abroad comprise a blast dechlorination method, a vacuum dechlorination method, a chemical dechlorination method and the like.
The air blast dechlorination method can generally remove free chlorine in the light salt brine to 5-6ppm, but the purity of the removed chlorine is poor and the chlorine cannot enter a chlorine main pipe. The NaClO is generally prepared after being absorbed by NaOH, because the amount of the removed chlorine is large, a large amount of caustic soda is consumed to absorb the removed chlorine, and the market of the prepared sodium hypochlorite is also considered. The vacuum dechlorination method can remove free chlorine in the dilute brine to below 50ppm (30 ppm) generally, and the removed chlorine has high concentration and can be directly returned to a chlorine manifold. Chemical dechlorination is generally carried out by adjusting the solution to alkaline after vacuum dechlorination, and adding a reagent such as sodium sulfite to the solution to cause a chemical reaction.
At present, the anode liquor of the nickel chlorination electrodeposition production system is not dechlorinated thoroughly, and the content of free chlorine in the new feed liquor is high. Although the anode of the nickel chlorination electrowinning cell has good chlorine gas sealing effect and no chlorine gas leakage, if the content of free chlorine in the fresh feed liquid is high, the improvement of the nickel chlorination electrowinning cell on the operating environment is greatly reduced. In order to improve the operating environment and ensure that no chlorine gas overflows on the operating site, the nickel chlorination electrodeposition tank needs to be additionally provided with an anolyte dechlorination system, so that the anolyte dechlorination effect is improved. Therefore, it is necessary to develop a method for removing free chlorine from anolyte with high efficiency.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for removing free chlorine from nickel chloridized electrodeposition anolyte, which is simple to operate, low in cost and high in efficiency, aiming at the defects of poor dechlorination effect of the anolyte, poor operation environment of a production site and the like in the traditional nickel chloridized electrodeposition process.
The technical scheme is as follows for solving the technical problem of the invention:
a method for removing free chlorine from nickel chloride electrodeposition anolyte comprises the following processes: under the action of a forced force field, the nickel chloride electrodeposition anolyte is fully dripped to form liquid drops with the radius of 1-3mm, the liquid drops are in cross flow contact with a certain amount of air, and the equilibrium reaction of free chlorine in the solution is carried out towards the analytic direction according to the principle of gas-liquid interface equilibrium concentration, so that the concentration of the free chlorine in the nickel chloride electrodeposition anolyte is reduced, and the purpose of removing the free chlorine from the nickel chloride electrodeposition anolyte is achieved.
The method for removing the free chlorine from the nickel chloride electrodeposition anolyte comprises the following specific processes:
a) forming liquid drops with the radius of 1-3mm by nickel chloride electrodeposition anolyte under the action of a forced force field;
b) the liquid drop of the nickel chloride electrodeposition anolyte is contacted with air in a cross flow manner;
c) carrying out gas-water separation on the dechlorinated tail gas, combining the separated aqueous phase with nickel chloride electrodeposition anolyte, and enabling the tail gas to enter a tail gas absorption treatment device;
d) the nickel chloride electrodeposition anode liquid drops releasing free chlorine are collected to be dechlorinated liquid and enter the subsequent working procedures.
The temperature of the nickel chloride electrodeposition anolyte in the step a) is 70-80 ℃, the pH value is 1.0-2.5, and the concentration of free chlorine is 400-500 ppm.
In the step b), the volume of air is 10-50 times of the total volume of the nickel chloride electrodeposition anode liquid drops when the nickel chloride electrodeposition anode liquid drops are in cross flow contact with the air.
The invention controls the anode liquid to be forced to be liquid-dropped to form liquid drops with the radius of 1-3mm through the forced force field, enlarges the specific surface area of the liquid phase, leads the liquid drops of the anode liquid to be fully contacted with the blown air in a cross flow way, and more completely finishes the mass transfer process of chlorine from the liquid phase to the gas phase. The concentration of the chlorine in the anolyte after the chlorine is removed is below 6ppm, the dechlorination effect in the whole process is good, the removal rate of free chlorine is above 98.5%, the removal rate of the free chlorine in the anolyte is improved, the chlorine content of the anolyte is low, chlorine odor is avoided, the requirement of recycling the anolyte is met, the dechlorinated anolyte is in an ideal state for recycling, and the aim of clean and friendly environment in field operation is met.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention relates to a method for removing free chlorine from nickel chloride electrodeposition anolyte, which has the advantages that the anolyte is dripped under the action of a forced force field, and the anolyte is in cross flow full mixing contact with introduced air to transfer chlorine in the anolyte to the air, so that the free chlorine in the anolyte is removed.
The process of the invention is further illustrated by the following non-limiting examples, which are intended to aid the understanding of the invention and its advantages, but are not intended to limit the scope of the invention, which is defined by the claims.
Example 1
A method for removing free chlorine from nickel chloride electrodeposition anolyte comprises the following specific implementation processes: the reaction solution was heated at 80 ℃ with a free chlorine concentration of 400ppm, a pH of 1.2 and a volume of 1m3The nickel chloride electrodeposition anolyte is forcedly dripped into droplets with the radius of 1mm, and the droplets of the nickel chloride electrodeposition anolyte are introduced into a container with the diameter of 10m3The air cross flow is fully mixed and contacted with the anolyte liquid drops, and the air carrying chlorine escapes and then flows into the gas-water separation deviceAnd (3) combining the separated aqueous phase with the nickel chloride electrodeposition anolyte, introducing the dechlorinated liquid into the subsequent process, analyzing and detecting to obtain the free chlorine concentration of the dechlorinated liquid of 6ppm, and calculating to obtain the free chlorine removal rate of 98.5%.
Example 2
A method for removing free chlorine from nickel chloride electrodeposition anolyte comprises the following specific implementation processes: the reaction mixture was heated at 80 ℃ with a free chlorine concentration of 413ppm, a pH of 2.0 and a volume of 1.2m3The nickel chloride electrodeposition anolyte is forcedly dripped into droplets with the radius of 2mm, and the droplets of the nickel chloride electrodeposition anolyte are introduced into the droplet with the diameter of 20m3The air cross flow is fully mixed and contacted with the anolyte liquid drops, air carrying chlorine escapes to enter a gas-water separation device, a separated aqueous phase and the nickel chloride electrodeposition anolyte are combined for treatment, the dechlorinated liquid enters a subsequent process, the chlorine concentration of the dechlorinated liquid is 5.5ppm through analysis and detection, and the removal rate of free chlorine is calculated to be 98.7%.
Example 3
A method for removing free chlorine from nickel chloride electrodeposition anolyte comprises the following specific implementation processes: the temperature was 80 ℃, the free chlorine concentration was 448ppm, the pH was 2.2, and the volume was 1.5m3The nickel chloride electrodeposition anolyte is forcedly dripped into droplets with the radius of 3mm, and the droplets of the nickel chloride electrodeposition anolyte are introduced into a chamber with the diameter of 50m3The air cross flow is fully mixed and contacted with the anolyte liquid drops, air carrying chlorine escapes to enter a gas-water separation device, a separated aqueous phase and the nickel chloride electrodeposition anolyte are combined for treatment, the dechlorinated liquid enters a subsequent process, the chlorine concentration of the dechlorinated liquid is 4.5ppm through analysis and detection, and the removal rate of free chlorine is 99% through calculation.
Example 4
A method for removing free chlorine from nickel chloride electrodeposition anolyte comprises the following specific implementation processes: the reaction mixture was heated at 70 ℃ with a free chlorine concentration of 490ppm, a pH of 2.50 and a volume of 1.1m3The nickel chloride electrodeposition anolyte is forcibly dripped into droplets with the radius of 2mm, and the droplets of the nickel chloride electrodeposition anolyte are introduced into a chamber with the diameter of 55m3The air cross flow is fully mixed and contacted with the anolyte liquid drops, the air carrying chlorine escapes to a gas-water separation device, the separated aqueous phase is combined with the nickel chloride electrodeposition anolyte for treatment, and the dechlorinated liquid entersAnd (4) performing subsequent procedures, analyzing and detecting that the chlorine concentration of the dechlorinated liquid is 5ppm, and calculating to obtain that the removal rate of free chlorine is 99%.

Claims (4)

1. A method for removing free chlorine from nickel chloride electrodeposition anolyte is characterized by comprising the following steps: under the action of a forced force field, the nickel chloride electrodeposition anolyte is fully dripped to form liquid drops with the radius of 1-3mm, the liquid drops are in cross flow contact with a certain amount of air, and the equilibrium reaction of free chlorine in the solution is carried out towards the analytic direction according to the principle of gas-liquid interface equilibrium concentration, so that the concentration of the free chlorine in the nickel chloride electrodeposition anolyte is reduced, and the purpose of removing the free chlorine from the nickel chloride electrodeposition anolyte is achieved.
2. The method for removing free chlorine from nickel chloride electrowinning anolyte as claimed in claim 1, characterized by comprising the following specific processes:
a) forming liquid drops with the radius of 1-3mm by nickel chloride electrodeposition anolyte under the action of a forced force field;
b) the liquid drop of the nickel chloride electrodeposition anolyte is contacted with air in a cross flow manner;
c) carrying out gas-water separation on the dechlorinated tail gas, combining the separated aqueous phase with nickel chloride electrodeposition anolyte, and enabling the tail gas to enter a tail gas absorption treatment device;
d) the nickel chloride electrodeposition anode liquid drops releasing free chlorine are collected to be dechlorinated liquid and enter the subsequent working procedures.
3. The method for removing free chlorine from the nickel chloride electrodeposition anolyte as claimed in claim 2, characterized in that: the temperature of the nickel chloride electrodeposition anolyte in the step a) is 70-80 ℃, the pH value is 1.0-2.5, and the concentration of free chlorine is 400-500 ppm.
4. The method for removing free chlorine from the nickel chloride electrowinning anolyte as claimed in claim 2 or 3, characterized in that: in the step b), the volume of air is 10-50 times of the total volume of the nickel chloride electrodeposition anode liquid drops when the nickel chloride electrodeposition anode liquid drops are in cross flow contact with the air.
CN201911230049.5A 2019-12-04 2019-12-04 Method for removing free chlorine from nickel chloride electrodeposition anolyte Pending CN110921787A (en)

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CN110407357A (en) * 2019-07-23 2019-11-05 个旧兴华锌业有限公司 The solution chloride ion minimizing technology of waste acid containing chlorine
CN110498484A (en) * 2019-07-25 2019-11-26 西安交通大学 A kind of electrochemistry aeration dechlorination device and method
CN110482506A (en) * 2019-10-10 2019-11-22 昆明理工大学 A kind of process intensification removes the device and method of hydrogen sulfide in industrial phosphoric acid

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