CN106745551A - The apparatus and method of chlorion in removal industrial circulating water - Google Patents
The apparatus and method of chlorion in removal industrial circulating water Download PDFInfo
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- CN106745551A CN106745551A CN201710005355.3A CN201710005355A CN106745551A CN 106745551 A CN106745551 A CN 106745551A CN 201710005355 A CN201710005355 A CN 201710005355A CN 106745551 A CN106745551 A CN 106745551A
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- 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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- 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
- C02F2001/46133—Electrodes characterised by the material
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- 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
- C02F2101/12—Halogens or halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
Abstract
The device of chlorion in a kind of removal industrial circulating water, including reative cell, control device and power module；It is characterized in that being provided with water inlet, delivery port and sewage draining exit on the reative cell；Discharge duct is housed at the top of reative cell, the exhaust outlet of discharge duct is connected to chlorine collection and treatment device, air exhauster is housed on discharge duct；Reative cell is built with electrode group and level sensor；Electrode group includes at least 1 pair battery lead plate；Electric control valve is equipped with water inlet, delivery port and sewage draining exit；Water inlet is located at the left side of reative cell, and delivery port is located at the top on the right of reative cell, and sewage draining exit is located at the bottom on the right of reative cell；Each group electrode group is sequentially placed along water (flow) direction.The application method of the present apparatus is to open electrode set power supplies switch and exits and entrances valve, and the water to flowing through electrode group is processed；The reacting gas produced in reative cell is exhausted and gas treatment simultaneously；Step 2：Operation carries out flushing pollution discharge after 10~30 days.
Description
Technical field
The technical program is related to water technology, is gone more particularly, to chlorion in the recirculated water in industrial circulating water field
Except technology.
Background technology
During 13, China will be attached most importance to improving environmental quality as core with solving ecological environment field outstanding problem
Point, increases ecological environmental protection dynamics.National policy proposes requirement very high, the circulation of industrial water to enterprise's industrial production
Using extremely urgent with improvement.
Industrial water consumption accounts for more than the 70% of city total water consumption, and strengthens running on for industrial circulating cooling water system
Management, is one of important measures of Industrial Water Saving.Raising recirculated water cycles of concentration is relatively more feasible at present and effectively one kind is saved
Water approach, but while cycles of concentration is improved, various ion concentrations constantly rise in recirculated water, the particularly increasing of chlorion
Plus.
Chlorion is a kind of severe corrosive ion, and ionic radius is small, and penetrability is strong, easily propagates through film layer, replaces oxygen atom
The carrying out of chloride accelerating anode process is formed, accelerates corrosion, be the main cause for causing spot corrosion.In addition it can also be destroyed not
The passivating film on the metal or alloy surfaces such as rust steel and aluminium, the crevice corrosion and stress corrosion for causing metal is destroyed.Currently, to chlorine from
The removal of son does not have particularly effectively method, such as：Chemical precipitation technology, ion exchange technique, traditional electrolyte technology etc..Chemistry
Sedimentation typically uses silver nitrate, stannous chloride method not only high cost, and there is secondary pollution.Ion exchange technique needs
Periodic replacement resin, increased cost.Effect is bad because side reaction is too many for traditional electrolyte technology.
The content of the invention
In order to solve the above-mentioned problems in the prior art, the invention proposes a kind of new chlorion electrochemistry
Minimizing technology and device.
The device of chlorion in a kind of removal industrial circulating water, including reative cell, control device and power module；It is described anti-
Answer and be provided with room water inlet, delivery port and sewage draining exit；
Discharge duct is housed at the top of reative cell, the exhaust outlet of discharge duct is connected to chlorine collection and treatment device, arranges
Air exhauster is housed in feed channel；Reative cell is built with electrode group and level sensor；Electrode group includes at least 1 pair battery lead plate；Enter
Electric control valve (such as magnetic valve, electrical ball valve etc.) is equipped with the mouth of a river, delivery port and sewage draining exit；Water inlet is located at reative cell
The left side, delivery port is located at the top on the right of reative cell, and sewage draining exit is located at the bottom on the right of reative cell；
The electrode group has at least 2 groups；Each group electrode group is sequentially placed along water (flow) direction；
Any electrode group has the multipair battery lead plate being parallel to each other to constitute；The battery lead plate is plate electrode；The material of battery lead plate
Matter is titanium compound (such as titanyl compound can be titanium dioxide etc.), and NACF is covered with electrode plate surface；Electrode
Using the enhanced Ti electrode of carbon fiber surface, titanium has good electric conductivity, and carbon fiber relative area is big, and both increase after combining
Add the relative contact between electrode and raw water to accumulate, lift electrolytic efficiency.
Plate electrode is parallel with water (flow) direction；
The thickness L1 of battery lead plate is 3mm≤L1≤3.6mm；
The thickness L2 of activated carbon fiber layers is 0.053mm≤L2≤0.058mm；
The area S of battery lead plate is 0.6 square metre≤S≤1.4 square metre；
The scope of any spacing d to battery lead plate is：6mm ＜ d≤10mm；
The battery lead plate quantity n of any one electrode group is：12 couples≤n ＜ 50 couples, or 50 pairs of ＜ n≤72 pair；
It is any to being provided with insulating materials packed layer between battery lead plate；The scope of the thickness D of insulating materials packed layer is：
1.8mm≤D ＜ 2mm；
The power module is powered for control device, level sensor, electrode group, air exhauster and each electric control valve；
The control device includes microcontroller, interface signal change-over circuit, polarity of electrode change-over circuit, analog-to-digital conversion
Device, digital analog converter；
The data-signal and control signal input/output terminal of the microcontroller are outer by the connection of interface signal change-over circuit
The binding post of portion's control device (such as upper industrial computer)；
Each electric control valve control signal output of the microcontroller connects corresponding respectively after digital analog converter
The control signal input of electric control valve；
The air exhauster control signal output of the microcontroller is by connecting corresponding air exhauster after digital analog converter
Control signal input；
The Enable Pin of the polarity of electrode changeover control signal output end connection electrode polarity switching of the microcontroller；
The input of polarity of electrode change-over circuit connects the electrode group feeder ear of power module, and the output end of polarity of electrode change-over circuit connects
Receiving electrode group；
The output end of the level sensor connects the external signal input terminals of microcontroller by analog-digital converter.
Power module becomes industrial-frequency alternating current and is pressed into required voltage, using adapter or inverter etc. according to power device
Can realize.Control device is used for being controlled the signal acquisition and external electrical device of whole machine, in the prior art, adopts
It is to be capable of achieving with programmable logic devices such as single-chip microcomputer (microcontroller) or PLC.
The scope of any spacing d to battery lead plate is：
6mm ＜ d≤7mm：In small distance, the migration rate and fouling ability of ion can all strengthen, go dechlorination from
Sub- effect can reach 90% or so during 7mm ＜ d≤9mm, now may there is larger electrical body due in small distance
Into causing short circuit；
7mm ＜ d≤9mm：This interval Inner electrolysis efficiency is best.Specific removal effect will also regard chloride ion content in water body
And electrode logarithm, the group number being equipped with etc.；
9mm ＜ d≤10mm：Because decomposition voltage is less, only 3.0V, its electrolytic efficiency when pole plate spacing is further increased
Can be lower, the influence of turbidity etc. in plus water, effect only up to reach 65% during 7mm ＜ d≤9mm；
The battery lead plate quantity n scopes of any one electrode group are：12 couples≤n ＜ 35 couples, or 35 couples≤n ＜ 50 couples, or
50 pairs of ＜ n≤60 pair, or 60 pairs of ＜ n≤72 pair；
For same water quality, same treatment amount, electrode pair is The more the better in principle；But it is also necessary to take into account that treatment is effective
Property, it is to avoid cause unnecessary waste.Different quality situation, the electrode pair quantity of use is different, for example：It is to chloride ion content
For the water quality of 500mg/L, the electrode pair quantity of 35≤n ＜ 50 can substantially meet demand, and clearance is up to 70% or so；It is right
For the water quality of 1000mg/L, electrode pair quantity could on an equal basis reach effect for 60 ＜ n≤72.
Electrode pair quantity can not infinitely increase, it is contemplated that fluctuation when power supply, device size and work, maximum is chosen
72 groups of electrodes.
Electrode group has at least 2 groups.
The increase of electrode group quantity is that the chlorine for being electrolysed out in order to further process the chlorion in water, and in water has
A part is redissolved in water, and multi-group electrode need to be used to strengthen efficiency.2 groups are chosen in principle, for chloride ion content
The water quality of 500mg/L, using the battery lead plate of 35 pairs, if at only one group, dechlorination effect is 52% or so, and has 2 groups of timeliness
Fruit is changed into 81% or so at once, and effect is fairly obvious.If increasing to 5 groups, effect now only increases to 86% or so, this be because
Very high by 2 groups for the treatment of removal effects for chloride ion content is not high in water, not only effect is failed to understand to continue increase group number
It is aobvious, and increase cost.
If chloride ion content reaches more than 5000mg/L in water quality, increase group is also needed while electrode logarithm is increased
Number.
The thickness D scopes of insulating materials packed layer are：1.8mm≤D ＜ 1.9mm, or 1.9mm≤D ＜ 2mm.
Fill insulant is used for spaced-apart electrodes to avoiding causing short circuit, and size and the actual production difficulty of its thickness have
Close.
The area S of battery lead plate is：1.0 square metres of 0.6 square metre≤S ＜, or 1.0 square metres≤S≤1.4 square metre.
In theory, the bigger effects of area S are better, because area is bigger, the water quality for the treatment of can be more in the unit interval.Actual measurement
In, typically under equal conditions 1.0 square metres or so effects preferably, at 0.6 square metre effect be only its 75%；1.4 square metres
Shi Xiaoguo for its 80% because the more big stability for being difficult to ensure that all parts of area, there is a possibility that fluctuation
Bigger, the possibility that electrolysis removes other ions is higher, such as：OH-。
The thickness L1 of battery lead plate is：3mm≤L1≤3.6mm.
Electrode plate thickness and the convenience being fixedly connected, and operation when stability it is relevant, it is bigger that electrode area does,
Electrode plate thickness is corresponding thick.It has to be noted here that thickness is not increased always, the thicker energy loss for causing of thickness is more
Seriously, such as：The electrode efficiency that 5.0mm is only has 70% during 3.6mm.
The thickness L2 of activated carbon fiber layers is 0.053mm≤L2≤0.058mm.
Battery lead plate is titanium-based material, and on plated surface is NACF, and thickness is more thick better, but in view of attachment difficulty
And cost of manufacture, have chosen above-mentioned value.
The wall of the reative cell is the thick PP plastics of 15mm, and reative cell inner chamber is cubic shaped.
Also include numerical-control direct-current voltage regulator；The input of numerical-control direct-current voltage regulator connects the output of power module
End, the output end of numerical-control direct-current voltage regulator is used as electrode group feeder ear；The control signal of numerical-control direct-current voltage regulator is defeated
Enter the polar plate voltage value control signal output of the end connection microcontroller.
The polarity of electrode change-over circuit includes two groups of on-off circuits；The polarity of electrode changeover control signal of microcontroller is defeated
Go out end and connect two groups of Enable Pins of on-off circuit respectively；
One group of on-off circuit includes two on-off circuits, wherein：The input and output end of one on-off circuit connect respectively
First pole plate of the direct current "+" of receiving electrode group feeder ear extremely and in paired electrode plate；The input of another on-off circuit
Second pole plate in and paired electrode plate extreme with the direct current "-" of output end difference connection electrode group feeder ear；
Another group of on-off circuit includes two on-off circuits, wherein：Input and the output end difference of one on-off circuit
Second pole plate of the direct current "+" of connection electrode group feeder ear extremely and in paired electrode plate；The input of another on-off circuit
First pole plate of the direct current "-" of end and output end difference connection electrode group feeder ear extremely and in paired electrode plate.
On-off circuit can select power tube according to demanded power output, or the switching device such as relay is core
Circuit.The enable of two on-off circuits is controlled using microcontroller, you can realize dipole inversion.
Also include filter and descaler；The delivery port of filter connects the water inlet of descaler, the delivery port of descaler
Connect the water inlet of the closed container；
The filter is quartz filter, cellulose filter or self-cleaning filter；The descaler is electricity
Chemical cleaning equipment or ion-exchange unit.
The method for removing chlorion in industrial circulating water of the device of chlorion, step bag in above-mentioned removal industrial circulating water
Include：
Step 1：Electrode set power supplies switch and exits and entrances valve are opened, the water to flowing through electrode group is processed；It is simultaneously right
The reacting gas produced in reative cell is exhausted and gas treatment；
Because the standard electrolytic current potential of chlorion is Φ0=+1.3595V, the actual electrolytic potential of water is 1.6V, based on reality
With property, the current potential between coordination electrode plate is 3.0V；
Because water body has dissolved carbon dioxide, bicarbonate ion is generated, water shows faintly acid, and the reaction on battery lead plate is such as
Under：
1) reaction on positive plate
Anion includes chlorion and sulfate ion in circulating water body；During logical direct current, anion is to anode movement, electricity
Solution chlorion and water：
Generation side reaction generates a small amount of ozone, hydrogen peroxide, hydrogen ion, hypochlorite ion and chlorition；Cause
For the residence time is short, they can quickly react and disappear：
2) reaction on minus plate
Because recirculated water shows faintly acid, when leading to direct current, the hydrogen ion contained in water is sent out to movable cathode in cathode surface
Raw cell reaction generation hydrogen effusion：
Hydroxide ion in water has the carbonate for promoting fouling ability by the reaction generation with bicarbonate ion
Ion, generates magnesium hydroxide and precipitation of calcium carbonate：
3) in running, every 1~3 hour polarity of reverse battery lead plate；After former minus plate polarity, battery lead plate table
The dirty layer in face is dissolved into water, is reacted as follows：
Step 2：Operation carries out flushing pollution discharge after 10~30 days, and import, sewage draining exit valve are opened during blowdown, closes delivery port
Valve, washing time is 10~30min；After the completion of flushing, return to step 1.
Above in chemical formula, ClO2 -It is an electronegative ClO2Molecule.
Often run 1~2 year, change battery lead plate.
Step 1 and step 2 also include step：Water inlet to reative cell is pre-processed；
Preprocess method is, first using filter method reduction turbidity, to reach the turbidity≤5NTU of water to the water inlet of reative cell,
Again using calcium, the concentration of magnesium ion in descaler reduction water, the total hardness≤300mg/L of water is reached；
Water feeding reative cell after the completion of pretreatment removes removing chloride.
The technical program using a set of equipment can realize removal industrial circulating water in chlorion, it is simple and easy to do, dechlorinate effect
It is good.
Brief description of the drawings
Fig. 1 is the principle schematic diagram. of the present apparatus；
In figure：1-shell；2-the first group electrode；3-outlet pipe；4-air exhauster；5-the second group electrode；6-go out
The mouth of a river；7-water inlet；The arrow of 8-expression water (flow) direction；9-reative cell；10-sewage draining exit.
Specific embodiment
It is further described below with specific embodiment correlation technique scheme below in conjunction with the accompanying drawings：
Such as Fig. 1, the device of chlorion in a kind of removal industrial circulating water, including reative cell, control device and power module；
Water inlet, delivery port and sewage draining exit are provided with the reative cell；
Discharge duct is housed at the top of reative cell, the exhaust outlet of discharge duct is connected to chlorine collection and treatment device, arranges
Air exhauster is housed in feed channel；Reative cell is built with electrode group and level sensor；Electrode group includes at least 1 pair battery lead plate；Enter
Electric control valve is equipped with the mouth of a river, delivery port and sewage draining exit；Water inlet is located at the left side of reative cell, and it is right that delivery port is located at reative cell
The top on side, sewage draining exit is located at the bottom on the right of reative cell；
The electrode group has at least 2 groups；Each group electrode group is sequentially placed along water (flow) direction；
Any electrode group has the multipair battery lead plate being parallel to each other to constitute；The battery lead plate is plate electrode；The material of battery lead plate
Matter is titanium compound, and NACF is covered with electrode plate surface；
Plate electrode is parallel with water (flow) direction；
The thickness L1 of battery lead plate is 3mm≤L1≤3.6mm；
The thickness L2 of activated carbon fiber layers is 0.053mm≤L2≤0.058mm；
The area S of battery lead plate is 0.6 square metre≤S≤1.4 square metre；
The scope of any spacing d to battery lead plate is：6mm ＜ d≤10mm；
The battery lead plate quantity n of any one electrode group is：12 couples≤n ＜ 50 couples, or 50 pairs of ＜ n≤72 pair；
It is any to being provided with insulating materials packed layer between battery lead plate；The scope of the thickness D of insulating materials packed layer is：
1.8mm≤D ＜ 2mm；
The power module is powered for control device, level sensor, electrode group, air exhauster and each electric control valve；
The control device includes microcontroller, interface signal change-over circuit, polarity of electrode change-over circuit, analog-to-digital conversion
Device, digital analog converter；
The data-signal and control signal input/output terminal of the microcontroller are outer by the connection of interface signal change-over circuit
The binding post of portion's control device；
Each electric control valve control signal output of the microcontroller connects corresponding respectively after digital analog converter
The control signal input of electric control valve；
The air exhauster control signal output of the microcontroller is by connecting corresponding air exhauster after digital analog converter
Control signal input；
The Enable Pin of the polarity of electrode changeover control signal output end connection electrode polarity switching of the microcontroller；
The input of polarity of electrode change-over circuit connects the electrode group feeder ear of power module, and the output end of polarity of electrode change-over circuit connects
Receiving electrode group；
The output end of the level sensor connects the external signal input terminals of microcontroller by analog-digital converter.
The scope of any spacing d to battery lead plate is：6mm ＜ d≤7mm, or 7mm ＜ d≤9mm, or 9mm ＜ d≤
10mm；
The battery lead plate quantity n scopes of any one electrode group are：12 couples≤n ＜ 35 couples, or 35 couples≤n ＜ 50 couples, or
50 pairs of ＜ n≤60 pair, or 60 pairs of ＜ n≤72 pair；
Electrode group has at least 2 groups；
The thickness D scopes of insulating materials packed layer are：1.8mm≤D ＜ 1.9mm, or 1.9mm≤D ＜ 2mm；
The area S of battery lead plate is：1.0 square metres of 0.6 square metre≤S ＜, or 1.0 square metres≤S≤1.4 square metre；
The thickness L1 of battery lead plate is：3mm≤L1≤3.6mm；
The thickness L2 of activated carbon fiber layers is 0.053mm≤L2≤0.058mm.
The wall of the reative cell is the thick PP plastics of 15mm, and reative cell inner chamber is cubic shaped.
Also include numerical-control direct-current voltage regulator；The input of numerical-control direct-current voltage regulator connects the output of power module
End, the output end of numerical-control direct-current voltage regulator is used as electrode group feeder ear；The control signal of numerical-control direct-current voltage regulator is defeated
Enter the polar plate voltage value control signal output of the end connection microcontroller.
The polarity of electrode change-over circuit includes two groups of on-off circuits；The polarity of electrode changeover control signal of microcontroller is defeated
Go out end and connect two groups of Enable Pins of on-off circuit respectively；
One group of on-off circuit includes two on-off circuits, wherein：The input and output end of one on-off circuit connect respectively
First pole plate of the direct current "+" of receiving electrode group feeder ear extremely and in paired electrode plate；The input of another on-off circuit
Second pole plate in and paired electrode plate extreme with the direct current "-" of output end difference connection electrode group feeder ear；
Another group of on-off circuit includes two on-off circuits, wherein：Input and the output end difference of one on-off circuit
Second pole plate of the direct current "+" of connection electrode group feeder ear extremely and in paired electrode plate；The input of another on-off circuit
First pole plate of the direct current "-" of end and output end difference connection electrode group feeder ear extremely and in paired electrode plate.
Also include filter and descaler；The delivery port of filter connects the water inlet of descaler, the delivery port of descaler
Connect the water inlet of the closed container；
The filter is quartz filter, cellulose filter or self-cleaning filter；The descaler is electricity
Chemical cleaning equipment or ion-exchange unit.
The method for removing chlorion in industrial circulating water of the device of chlorion, step in a kind of removal industrial circulating water
Suddenly include：
Step 1：Electrode set power supplies switch and exits and entrances valve are opened, the water to flowing through electrode group is processed；It is simultaneously right
The reacting gas produced in reative cell is exhausted and gas treatment；
Because the standard electrolytic current potential of chlorion is Φ0=+1.3595V, the actual electrolytic potential of water is 1.6V, based on reality
With property, the current potential between coordination electrode plate is 3.0V；
Because water body has dissolved carbon dioxide, bicarbonate ion is generated, water shows faintly acid, and the reaction on battery lead plate is such as
Under：
1) reaction on positive plate
Anion includes chlorion and sulfate ion in circulating water body；During logical direct current, anion is to anode movement, electricity
Solution chlorion and water：
Generation side reaction generates a small amount of ozone, hydrogen peroxide, hydrogen ion, hypochlorite ion and chlorition；Cause
For the residence time is short, they can quickly react and disappear：
2) reaction on minus plate
Because recirculated water shows faintly acid, when leading to direct current, the hydrogen ion contained in water is sent out to movable cathode in cathode surface
Raw cell reaction generation hydrogen effusion：
Hydroxide ion in water has the carbonate for promoting fouling ability by the reaction generation with bicarbonate ion
Ion, generates magnesium hydroxide and precipitation of calcium carbonate：
3) in running, every 1~3 hour polarity of reverse battery lead plate；After former minus plate polarity, battery lead plate table
The dirty layer in face is dissolved into water, is reacted as follows：
Step 2：Operation carries out flushing pollution discharge after 10~30 days, and import, sewage draining exit valve are opened during blowdown, closes delivery port
Valve, washing time is 10~30min；After the completion of flushing, return to step 1.
Often run 1~2 year, change battery lead plate.
Also include step between step 1 and step 2：Water inlet to reative cell is pre-processed；
Preprocess method is, first using filter method reduction turbidity, to reach the turbidity≤5NTU of water to the water inlet of reative cell,
Again using calcium, the concentration of magnesium ion in descaler reduction water, the total hardness≤300mg/L of water is reached；
Water feeding reative cell after the completion of pretreatment removes removing chloride.
The technical program can automatic conversion anode and cathode to remove removing chloride, it is specific as follows：
The technical program uses titanium-based carbon fiber surface enhanced electrode, and electrode spacing is controlled in 6~10mm.To protect
Card operating efficiency should ensure that and for 12~72 pairs of battery lead plates be arranged into one group, and set two groups along the direction of current, every group anti-with insulation
Oxidation material polypropylene plastics PP is fixed together and avoids the generation of short circuit, and battery lead plate connects same power supply, when running one section
Between after, change anode and cathode automatically, strengthen efficiency.Because the standard electrolytic current potential of chlorion is Φ0=+1.3595V, the reality of water
Border electrolytic potential is generally 1.6V, it is contemplated that extraneous factor during real work, and the current potential between coordination electrode plate is 3.0V.Due to following
Contain CO in ring water3 2—、HCO3 —, can be in alkalescent plus constantly circulation, the reaction on electrode is as follows：
1) reaction on anode
During logical direct current, to anode movement, anion is mainly chlorion, sulfate ion to anion in circulating water body,
Wherein sulfate ion will not be electrolysed, and mainly be electrolysed chlorion, while can also be electrolysed a small amount of water.
Due to operating voltage very little, it may occur that minimal amount of side reaction, a small amount of ozone, hydrogen peroxide, hypochlorous acid is produced
Root plasma, these ions because the residence time it is very short, and will soon react with certain sterilization algae removal ability and
Disappear.
2) reaction on negative electrode
Recirculated water shows alkalescent mostly, and in the presence of additional power source, negative electrode Direct Electrolysis water produces hydrogen
Anode can a small amount of hydroxide ion OH of electrolysis water production during electrolysis-, by with bicarbonate ion
Reaction generation have promote fouling ability carbanion, generate a small amount of magnesium hydroxide, precipitation of calcium carbonate, have following
Side reaction：
The incrustation scale of generation can be attached to electrode surface, by prolonged operation after can form one layer in cathode surface
Dirt, reduces and even eliminates electrolytic efficiency.Therefore, by the way of 1-3 hours reverse electrode, carry out guard electrode, preferably protection
Electrode extends its service life.Negative electrode originally is inverted to a small amount of dirty layer in surface after anode can be dissolved into water, and electrode is anti-
Should be as follows：
The present apparatus such as Fig. 1, water inlet, delivery port, sewage draining exit are connected with flange, and valve can use electrical ball valve, if
Operation is controlled using switch board during standby work, it is specific as follows：
1) prepare, water inlet valve opens water inlet and device interior is once cleaned, sewage draining exit is opened after full of water
Valve, water is all put clean；
2) bring into operation, close sewage draining exit valve, open water inlet valve and outlet valve, wait current normally steady
It is fixed from delivery port out when open electrode set power supplies switch, while starting air exhauster；
3) in running, after automatic conversion both positive and negative polarity after work 1-3 hours, (it is true that specific time setting regards original water hardness
Fixed, hardness is higher, and the conversion both positive and negative polarity time is shorter)；
4) blowdown process, (setting value, to prevent dirt from accumulating) closes outlet valve after running 10-30 days, the row of opening
Dirty mouth valve, 10-30min of constant flushing of intaking；
5) after the completion of rinsing, sewage draining exit valve is closed, opens outlet valve, normal work is started again.
Battery lead plate can be because of the extension of working time, and fixed insulation material PP can be deposited between electrode surface carbon fiber layer, electrode
In destruction, therefore, work 1-2 years ensures equipment with maximum, it is necessary to electrode is taken out again into coated carbon fibers with PP plastics are changed
Operating efficiency operation.
The technical program has certain requirement for influent quality, especially turbidity and calcium, the concentration of magnesium ion, it is proposed that turbid
Degree≤5NTU, carbonate hardness (in terms of CaCO3)≤300mg/L, in order to avoid because the too high fouling of calcium ions and magnesium ions is serious damage electrode,
Reduce service efficiency, if water quality is not up to standard, it is proposed that use pre-processing device, can be used quartz filter, cellulose filter,
Self-cleaning filter reduces turbidity, and electrochemical descaling equipment, ion-exchange unit reduction calcium, magnesium ion concentration can be used.
Voltage during work between every group of battery lead plate is only 3.0V, can greatly guard electrode material.
Using the enhanced Ti electrode of carbon fiber surface, titanium has good electric conductivity to electrode, and carbon fiber relative area is big,
Both increased the relative contact product between electrode and raw water after combining, lift electrolytic efficiency.To ensure enough efficiency, stop
Time should be as long as possible, and flow velocity is up to 0.3m/s, generally 0.1m/s.
This technology due to frequent reverse electrode, theoretically from the point of view of can't cause secondary pollution, but in running
Still a small amount of pollutant can be produced, therefore, every 10~30 days automatic pollution discharges once, each 10-30min of blowdown.Electrolysis is anti-
Answer room using 15mm thick PP plastics, reative cell is rendered as cubic.
Electrolysis chlorion generation chlorine, electrolysis water generation hydrogen, oxygen are raising electrolytic efficiency above electrode reaction room
One air exhauster (rotating speed 2400r/min, power 18w) is installed, the chlorine of generation, hydrogen and a small amount of oxygen are discharged in time, plus
Fast electrolytic process；Meanwhile, the mechanism of air exhauster can mix rapidly the chlorine, hydrogen, the oxygen that generate with air, reduce
There is dangerous possibility.
Present apparatus processing cycle water is 20~200t/h, typically takes bypass and is arranged in circulation.
Using the test data of this electrochemical dechlorination technology：
Recirculated water using this electrochemical dechlorination equipment respectively at different chloride ion contents is tested, chloride ion content every
Every detection in 10 days once, data such as following table：
Machine monitoring data unit：mg/L
| Sequence number | 0d | 10d | 20d | 30d | 40d |
| 1 | 280.5 | 196.9 | 141.7 | 86.2 | 81.7 |
| 2 | 415.3 | 298.0 | 205.2 | 132 | 148.4 |
| 3 | 1350 | 692.5 | 447.6 | 319 | 320.5 |
| 4 | 2910 | 1811.8 | 920 | 616 | 603 |
| 5 | 5012 | 2876 | 1753 | 890.6 | 698.2 |
In upper table, the data of 0d are the original amount of chlorion.
Equipment dechlorination effect is obvious as seen from the above table.With 30d as standard, every group of clearance difference of recirculated water chlorion
For：69.27%th, 68.19%, 76.37%, 78.83%, 82.23%, data display, raw water chloride ion content removal effect higher
Fruit can be better.
Claims (9)
1. a kind of device for removing chlorion in industrial circulating water, including reative cell, control device and power module；It is characterized in that
Water inlet, delivery port and sewage draining exit are provided with the reative cell；
Discharge duct is housed at the top of reative cell, the exhaust outlet of discharge duct is connected to chlorine collection and treatment device, blast pipe
Air exhauster is housed on road；Reative cell is built with electrode group and level sensor；Electrode group includes at least 1 pair battery lead plate；Water inlet,
Electric control valve is equipped with delivery port and sewage draining exit；Water inlet is located at the left side of reative cell, and delivery port is located on the right of reative cell
Top, sewage draining exit is located at the bottom on the right of reative cell；
The electrode group has at least 2 groups；Each group electrode group is sequentially placed along water (flow) direction；
Any electrode group has the multipair battery lead plate being parallel to each other to constitute；The battery lead plate is plate electrode；The material of battery lead plate is
Titanium compound, NACF is covered with electrode plate surface；
Plate electrode is parallel with water (flow) direction；
The thickness L1 of battery lead plate is 3mm≤L1≤3.6mm；
The thickness L2 of activated carbon fiber layers is 0.053mm≤L2≤0.058mm；
The area S of battery lead plate is 0.6 square metre≤S≤1.4 square metre；
The scope of any spacing d to battery lead plate is：6mm ＜ d≤10mm；
The battery lead plate quantity n of any one electrode group is：12 couples≤n ＜ 50 couples, or 50 pairs of ＜ n≤72 pair；
It is any to being provided with insulating materials packed layer between battery lead plate；The scope of the thickness D of insulating materials packed layer is：1.8mm≤D
＜ 2mm；
The power module is powered for control device, level sensor, electrode group, air exhauster and each electric control valve；
The control device includes microcontroller, interface signal change-over circuit, polarity of electrode change-over circuit, analog-digital converter, number
Weighted-voltage D/A converter；
The data-signal and control signal input/output terminal of the microcontroller are by the outside control of interface signal change-over circuit connection
The binding post of control equipment；
Each electric control valve control signal output of the microcontroller connects corresponding automatically controlled respectively after digital analog converter
The control signal input of valve；
The air exhauster control signal output of the microcontroller is by connecting the control of corresponding air exhauster after digital analog converter
Signal input part；
The Enable Pin of the polarity of electrode changeover control signal output end connection electrode polarity switching of the microcontroller；Electrode
The input of polarity switching connects the electrode group feeder ear of power module, the output end connection electricity of polarity of electrode change-over circuit
Pole group；
The output end of the level sensor connects the external signal input terminals of microcontroller by analog-digital converter.
2. in removal industrial circulating water according to claim 1 chlorion device, it is characterized in that any to battery lead plate
The scope of spacing d is：6mm ＜ d≤7mm, or 7mm ＜ d≤9mm, or 9mm ＜ d≤10mm；
The battery lead plate quantity n scopes of any one electrode group are：12 couples≤n ＜ 35 couples, or 35 couples≤n ＜ 50 couples, or 50 pairs
＜ n≤60 pair, or 60 pairs of ＜ n≤72 pair；
Electrode group has at least 2 groups；
The thickness D scopes of insulating materials packed layer are：1.8mm≤D ＜ 1.9mm, or 1.9mm≤D ＜ 2mm；
The area S of battery lead plate is：1.0 square metres of 0.6 square metre≤S ＜, or 1.0 square metres≤S≤1.4 square metre；
The thickness L1 of battery lead plate is：3mm≤L1≤3.6mm；
The thickness L2 of activated carbon fiber layers is 0.053mm≤L2≤0.058mm.
3. it is according to claim 1 removal industrial circulating water in chlorion device, it is characterized in that the wall of the reative cell
It is the thick PP plastics of 15mm, reative cell inner chamber is cubic shaped.
4. it is according to claim 1 to remove the device of chlorion in industrial circulating water, it is characterized in that also including numerical-control direct-current
Voltage regulator；The input of numerical-control direct-current voltage regulator connects the output end of power module, numerical-control direct-current voltage regulator
Output end as electrode group feeder ear；The control signal input of numerical-control direct-current voltage regulator connects the microcontroller
Polar plate voltage value control signal output.
5. it is according to claim 1 removal industrial circulating water in chlorion device, it is characterized in that the polarity of electrode turn
Changing circuit includes two groups of on-off circuits；The polarity of electrode changeover control signal output end of microcontroller connects two groups of switch electricity respectively
The Enable Pin on road；
One group of on-off circuit includes two on-off circuits, wherein：The input and output end of one on-off circuit connect electricity respectively
First pole plate of the direct current "+" of pole group feeder ear extremely and in paired electrode plate；The input of another on-off circuit and defeated
Go out second pole plate of the direct current "-" of end difference connection electrode group feeder ear extremely and in paired electrode plate；
Another group of on-off circuit includes two on-off circuits, wherein：The input and output end of one on-off circuit are connected respectively
Second pole plate of the direct current "+" of electrode group feeder ear extremely and in paired electrode plate；The input of another on-off circuit and
First pole plate of the direct current "-" of output end difference connection electrode group feeder ear extremely and in paired electrode plate.
6. it is according to claim 1 removal industrial circulating water in chlorion device, it is characterized in that also include filter and
Descaler；The delivery port of filter connects the water inlet of descaler, and the delivery port of descaler connects the water inlet of the closed container
Mouthful；
The filter is quartz filter, cellulose filter or self-cleaning filter；The descaler is electrochemistry
Descaling equipment or ion-exchange unit.
7. in a kind of any removal industrial circulating water of claim 1~6 in the removal industrial circulating water of the device of chlorion
The method of chlorion, its feature is comprised the following steps：
Step 1：Electrode set power supplies switch and exits and entrances valve are opened, the water to flowing through electrode group is processed；Simultaneously to reaction
The reacting gas of indoor generation is exhausted and gas treatment；
Because the standard electrolytic current potential of chlorion is Φ0=+1.3595V, the actual electrolytic potential of water is 1.6V, based on practicality,
Current potential between coordination electrode plate is 3.0V；
Because water body has dissolved carbon dioxide, bicarbonate ion is generated, water shows faintly acid, and the reaction on battery lead plate is as follows：
1) reaction on positive plate
Anion includes chlorion and sulfate ion in circulating water body；During logical direct current, anion is to anode movement, electrolytic chlorine
Ion and water：
Generation side reaction generates a small amount of ozone, hydrogen peroxide, hydrogen ion, hypochlorite ion and chlorition；Because stopping
Stay the time short, they can quickly react and disappear：
2) reaction on minus plate
Because recirculated water shows faintly acid, when leading to direct current, the hydrogen ion contained in water occurs to movable cathode in cathode surface
Cell reaction generation hydrogen effusion：
Hydroxide ion in water have by the reaction generation with bicarbonate ion promote the carbonate of fouling ability from
Son, generates magnesium hydroxide and precipitation of calcium carbonate：
3) in running, every 1~3 hour polarity of reverse battery lead plate；After former minus plate polarity, electrode plate surface
Dirty layer be dissolved into water, react it is as follows：
Step 2：Operation carries out flushing pollution discharge after 10~30 days, and import, sewage draining exit valve are opened during blowdown, closes water outlet valve
Door, washing time is 10~30min；After the completion of flushing, return to step 1.
8. method according to claim 7, it is characterized in that often running 1~2 year, changes battery lead plate.
9. method according to claim 7, it is characterized in that the water inlet to reative cell is pre-processed；
Preprocess method is, first using filter method reduction turbidity, to reach the turbidity≤5NTU of water, then adopt to the water inlet of reative cell
With the concentration of calcium, magnesium ion in descaler reduction water, the purpose of the total hardness≤300mg/L of water is reached；
Water feeding reative cell after the completion of pretreatment removes removing chloride.
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| CN108439553A (en) * | 2018-04-20 | 2018-08-24 | 武汉大学 | A kind of Electrochemical oxidation device for removing chlorion in water removal |
| CN108502985A (en) * | 2018-06-01 | 2018-09-07 | 山东深信节能环保科技有限公司 | A kind of the combined electrical chemical system and processing method of scale removal dechlorination |
| CN110143774A (en) * | 2019-05-29 | 2019-08-20 | 中实泰广(北京)环保科技有限公司 | Sea sand purification system |
| CN111072112A (en) * | 2020-01-09 | 2020-04-28 | 河北超绿节能环保科技有限公司 | Wastewater treatment method and system for zero discharge of desulfurization wastewater |
| CN112393966A (en) * | 2021-01-18 | 2021-02-23 | 湖南久钰电子有限公司 | Ion enrichment device in water and ion concentration monitoring system in water |
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