CN1275870C - Method and device for reusing electrolyzed anion cation exchange waste water - Google Patents
Method and device for reusing electrolyzed anion cation exchange waste water Download PDFInfo
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- CN1275870C CN1275870C CN 200410036634 CN200410036634A CN1275870C CN 1275870 C CN1275870 C CN 1275870C CN 200410036634 CN200410036634 CN 200410036634 CN 200410036634 A CN200410036634 A CN 200410036634A CN 1275870 C CN1275870 C CN 1275870C
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Abstract
The present invention relates to a method for reusing electrolyzed anion and cation exchange waste water. In the method, anion and cation exchange waste water is neutralized, removed of hard substances and electrolyzed into acids and alkalis to be used as ion exchange regeneration agents, residual sodium chloride of the electrolyzed waste water is used as a transformation mixed-bed regeneration agent, and the realization flows comprise a raw water transformation flow and a waste water transformation flow. Anion and cation on exchange membranes are alternately arranged in an electrolyzer, wherein between the anion and cation on exchange membrane pairs are respectively an alkali production room, a pure water room, an acid production room, a waste water room, etc. which are circulated, OH<-> type anion resin and H<+> type cation resin are filled in the pure water room, the alkali production room-the pure water room-the acid production room-the waste water room are called as one electrolysis unit, the electrolyzer is formed by the parallel connection of tens to hundreds of electrolysis units, and both outer sides of the electrolyzer are a polar plate and a polar water region. The method and the apparatus can reuse anion and cation exchange waste water, which reduces the use cost and prevents the pollution.
Description
Technical field the invention belongs to the ion exchange technique field, specifically a kind of with cation and anion exchange waste water through neutralization, except hard, be electrolyzed to produce acid and alkali, as the method and apparatus of ion exchange regenerant agent.
In the background technology prior art, adopt ion exchange technique to produce pure water, utilization rate height with water, raw water quality require low, and water quality is good and stablize, reduced investment, but because acid, alkali consumption make the utilization somewhat expensive, in addition, the waste water that produces during cation and anion exchange regeneration all is discharged into sewer, increase water body sodium chloride-containing amount, caused the pollution of environment.For this reason, and the reverse osmosis of increasing or electrodialysis person are arranged before it, but the two investment is big, the utilization ratio of water is low, and the reverse osmosis dispensing of still needing.
Summary of the invention the object of the present invention is to provide a kind of with cation and anion exchange waste water through neutralization, except hard, be electrolyzed to produce acid and alkali, method and apparatus as the ion exchange regenerant agent, thereby reduce the transport expense usefulness of cation and anion exchange technology, alleviate simultaneously industrial wastewater to the pollution of environment.
For achieving the above object, the technical measures taked of the present invention are:
A kind of electrolysis zwitterion exchange waste water reuse method, it is characterized in that with zwitterion exchange waste water through neutralization-remove hard-be electrolyzed to produce acid and alkali, as the ion exchange regenerant agent, the remaining sodium-chlor of waste water is as mixing the bed regenerator transition after electrolysis, and realization flow is divided into two kinds:
The one, front transition, flow process also was called former water flow process transition, namely entered before the yin, yang bed produces water at Yuan Shui, made the transition through the mixed bed that makes the transition earlier, and what agent transition was adopted is sodium chloride, transition mixed bed regenerative wastewater and clean waste water and all drain; Former water is through making the transition mixed bed after transition, and hardness is answered≤0.001mmol/l in the water, and the water after transition goes the sun bed to produce pure water with cloudy again; Behind yin, yang bed efficiency lost resin, regenerate, regenerate used acid and alkali from electrolyzer electrolysis wastewater gained, the sun bed flows into the neutralization pond neutralization with the regenerative wastewater of cloudy bed, sodium chloride concentration in the waste water is 3%～12%, and waste water hardness≤0.08mmol/l, the cleaning waste water of sun bed and cloudy bed is drained, to keep the concentration of regenerative wastewater; Waste water flows out when electrolysis afterchlorinate na concn is down to 1%～3%, as the regenerative agent of mixed bed transition; Entering electrolyzer acid production room and alcaligenes room can be pure water, but better as 1%～3% diluted acid, diluted alkaline to enter concentration, the acid of flowing out from electrolyzer, alkali concn are used as the regenerative agent of negative and positive bed for being 4%～10%.
The 2nd, rear transition, flow process also was waste water flow process transition, and namely former water makes pure water through sun bed, cloudy bed, regenerates behind the negative and positive bed efficiency lost resin, and regenerative wastewater flows into neutralization pond, and its sodium chloride concentration should be 3%～12%, and the negative and positive bed cleans waste water and then drains; In neutralization pond, add milk of lime tentatively except behind hard, the sedimentation and filtration, hardness should≤2mmol/l, turbidity should≤1 °, precipitation and the waste water that filters are all drained; Tentatively enter mixed of transition except the waste water after hard, hardness is answered≤0.08mmol/l after transition, regenerative wastewater after transition is down to 1%～3% through electrolyzer electrolytic chlorination na concn and is flowed out, and as mixed regenerative agent transition, transition, the regenerative wastewater of mixed bed was all drained with cleaning waste water; For reducing resistance, entering electrolyzer acid production room and alcaligenes room can be pure water, but better as 1%～3% diluted acid, diluted alkaline to enter concentration, the acid when flowing out from electrolyzer, alkali concn are 4%～10%, as negative and positive bed regenerative agent.
A kind of electrolysis cation and anion exchange waste water reuse equipment is electrolyzer, it is by the anion and cation exchange membrane alternative arrangement, distance is between 0.1～1.0cm between the anion and cation exchange membrane, anion and cation exchange membrane between be respectively between alcaligenes room, pure water, acid production room, wastewater room ... so circulation is filled with OH between pure water
-Type negative resin and H
+Type sun resin, the purpose of potting resin is to provide OH for alcaligenes room
-Ion, provide H for acid production room
+Ion reduces the resistance between pure water, OH simultaneously
-, H
+The ion master is if it were not for transmitting in pure water, but transmits in yin and yang resin, thus greatly reduced resistance, under the function of current, wastewater room Na
+Pass cation-exchange membrane and enter alcaligenes room, wastewater room Cl
-Pass anion-exchange membrane and enter acid production room, H between pure water
+Ion passes cation-exchange membrane and enters acid production room, and OH
-Ion then passes anion-exchange membrane and enters alcaligenes room, thereby the acid in the acid production room, alcaligenes room, alkali concn raise, the concentration of sodium chloride reduces in the wastewater room, from the acid of acid production room, alcaligenes room outflow, the regenerative agent that alkali is used as the negative and positive bed, the waste water that contains low concentration chlorination sodium from wastewater room flows out then mixes a bed regenerative agent as making the transition.We with between alcaligenes room-pure water-acid production room-wastewater room is called an electrolysis cells, electrolyzer is to be composed in parallel by dozens of and even hundreds of electrolysis cells, electrolyzer two outsides are pole plate and utmost point pool.
Electrolysis cation and anion exchange method of reutilizing wastewater provided by the invention and equipment thereof can not only reduce transport expense usefulness with the cation and anion exchange waste water reuse, and prevent from polluting.
Description of drawings Fig. 1 is front transition of schematic flow sheet
Fig. 2 is rear transition of schematic flow sheet
Fig. 3 is the electrolyzer schematic diagram
Embodiment
Embodiment 1: front transition flow process
As Fig. 1, shown in Figure 3, water yield Q=50t/h, total salinity 10mmol/l, wherein the former water of hardness 4mmol/l is before entering yin, yang bed product water, mixing bed through making the transition earlier makes the transition, that agent transition is adopted is sodium-chlor (NaCl), former water mixes bed after transition through making the transition, hardness is answered≤0.001mmol/l in the water.Regenerated after mixed bed loses efficacy transition, and regenerative agent sodium chloride needs sodium chloride amount 50 * 4 * 1.4=280mol/h (in the formula: 1.4 is the mixed bed regeneration efficiency) from storage sodium chloride tank, and transition, regenerative wastewater and the cleaning waste water of mixed bed were all drained.Former water enters cation bed and anion bed and produces pure water through after the mixed bed, and from the sour tank of storage and storage alkali tank, needing acid, alkali number is 50 * 10 * 1.2=600mol/h (in the formula: 1.2 are negative and positive bed regeneration efficiency) with acid, alkali for regeneration after cation bed and anion bed lost efficacy, regeneration.During the regeneration of negative and positive bed, earlier extrude the moon with air, the regenerative wastewater of sun bed, make it flow into the neutralization pond neutralization, hardness≤0.08mmol/l, employing concentration is 8% soda acid during regeneration, sodium chloride concentration should be about 12.8% in the sun bed regenerative wastewater, sodium chloride concentration should be about 11.7% in the cloudy bed regenerative wastewater, the water that is actually in the negative and positive bed tank body dilutes, sodium chloride concentration in the regenerative wastewater is about 6%, cloudy bed, sun bed regenerative wastewater sodium chloride-containing amount respectively is 600mol/h, total amount is 1200mol/h, when cleaning the negative and positive bed, cleaning waste water is drained, to guarantee regenerative wastewater concentration, clean waste water and taken away about 20% sodium chloride amount, the actual sodium chloride-containing amount that enters neutralization pond waste water is 1200 * (1-20%)=960mol/h, during the electrolyzer electrolysis wastewater, needing the sodium chloride amount is 600 * 1.1=660mol/h (in the formula: 1.1 are the utilization ratio of electrolytic process sodium chloride), the waste water residue sodium chloride amount that flows out after the electrolysis is 960-660=300mol/h, need sodium chloride amount 280mol/h transition greater than mixed bed, so needn't add sodium chloride.
Electrolyzer in the above-mentioned technology is by yin, yang amberplex alternative arrangement, and apart from being 0.15cm, the effective area of zwitterion film is 8000m between the anion and cation exchange membrane
2, anion and cation exchange membrane between be respectively between alcaligenes room, pure water, acid production room, wastewater room ... so circulation is filled with OH between pure water
-Type negative resin and H
+Type sun resin, the purpose of potting resin is to provide OH for alcaligenes room
-Ion, provide H for acid production room
+Ion reduces the resistance between pure water, OH simultaneously
-, H
+The ion master is if it were not for transmitting in pure water, but transmits in yin and yang resin, so greatly reduced resistance.Under the function of current, wastewater room Na
+Ion passes cation-exchange membrane and enters alcaligenes room, wastewater room Cl
-Ion passes anion-exchange membrane and enters acid production room, H on the middle resin between pure water
+Ion passes cation-exchange membrane and enters acid production room, and OH
-Ion then passes anion-exchange membrane and enters alcaligenes room, thereby the acid in the acid production room, alcaligenes room, alkali concn raises, and the concentration of sodium chloride reduces in the wastewater room.We with between alcaligenes room-pure water-acid production room-wastewater room is called an electrolysis cells, electrolyzer is to be composed in parallel by 80 electrolysis cells, electrolyzer two outsides are pole plate and utmost point pool.
Regenerative wastewater sodium chloride-containing amount after the neutralization is 960mol/h, its concentration was 6% (being equivalent to 1mol/l), the wastewater flow rate that enters between electrolyzer waste water is 960L/h ÷ 1mol/l=960L/h, the sodium chloride concentration that flows out between waste water is 6% * (300 ÷ 960)=1.87%, the waste water that contains lower concentration chlorination sodium flows into storage sodium-chlor jar, as mixing the bed regenerator transition.The acid base concentration 8% that diluted acid, the diluted alkaline concentration that enters electrolyzer acid production room, alcaligenes room is 2%, flows out, the acid, the alkali that flow out from acid production room, alcaligenes room flow into respectively the sour tank of storage, storage alkali tank, as the regenerative agent of negative and positive bed.Acid base concentration rising 6% (concentration is that 6% acid is equivalent to 1.67mol/l, concentration is that 6% alkali is equivalent to 1.5mol/l) in electrolyzer acid production room, alcaligenes room, the diluted alkaline amount that the diluted acid amount that then enters electrolyzer is 600 ÷ 1.67=359L/h, enter electrolyzer is 600 ÷ 1.5=400L/h, the acid of every production 1mol, the water that alkali needs 1mol, electrolyzer is produced acid, the alkali of 600mol/h, the pure water amount that needs is 600mol/h (being equivalent to approximately 11L/h), the pure water that pure water is produced from the negative and positive bed.
Calculate for the electrician below:
By the electrolyzer that 80 electrolysis cells compose in parallel, the useful area of zwitterion film is 8000m
2, intermembranous apart from 0.15cm
1. total current: (600 * 26.8) ÷ 80=201A
In the formula: the electric current that per hour producing the acid, alkali of 1mol needs is 26.8A
2. current strength 201 ÷ 8000=0.025A
| Wastewater room | Acid production room | Alcaligenes room | Between pure water | |
| Calculating concentration (mg/l) | 35600 | 43280 | 43280 | |
| Resistivity (Ω) | 33 | 21 | 28 | 700 |
In the table: 700 Ω are the resistivity behind the filling yin and yang resin between pure water, and pure water can suitably be heated when entering and is no more than 70 ℃, to reduce resistance.
3. elemental area resistance: (33+21+28+700) * 1.7 * 1.2 * 0.15=239 Ω cm
2
In the formula: 1.7 is the water layer specific resistance; 1.2 be the membrane resistance coefficient
4. cell voltage: 239 * 0.025=5.98V
5. total voltage: in 80 * 5.98+15=493.4V formula: 15V is a pole tension
6. hour power consumption: (201 * 493.4) ÷ 1000=99.2kw
7. ton water power consumption: 99.2 ÷ 50=2.0 degree/tons
Embodiment 2: flow process afterwards makes the transition
Former water is with embodiment 1, and former water makes pure water through cloudy bed and sun bed, regenerates behind the negative and positive bed efficiency lost resin, required acid, alkali number are 600mol/h, during the regeneration of negative and positive bed, extrude regenerative wastewater with air earlier, regenerative wastewater flows into neutralization pond, and the cleaning waste water of negative and positive bed is drained, to guarantee regenerative wastewater concentration.Employing concentration is 8% soda acid during regeneration, sodium chloride concentration should be 12.8% in the sun bed regenerative wastewater, sodium chloride concentration should be 11.7% in the cloudy bed regenerative wastewater, the water that is actually in the negative and positive bed tank body dilutes, sodium chloride concentration is about 6%, content is 1200-50 * 4=1000mmol (50 * 4 are the hardness total amount in the waste water), the negative and positive bed cleans waste water and takes away about 20% sodium chloride amount, the actual sodium chloride-containing amount that enters neutralization pond waste water is 1000 * (1-20%)=800mol/h, tentatively remove hard in neutralization pond neutralization and adding milk of lime, needing amount of lime is (50 * 4 * 74) ÷ 1000=14.8kg/h (in the formula: 74 are the molecular weight of lime), after in neutralization pond, stirring precipitation, entering filter filters, hardness is answered≤2mmol/l, and turbidity is answered≤1 °, and precipitation and the waste water that filters are all drained; Enter then the mixed bed that makes the transition, hardness is answered≤0.08mmol/l after transition; Enter then the electrolyzer electrolysis, needing the sodium chloride amount is 660mol/h, the waste water residue sodium chloride amount that flows out from the electrolyzer wastewater room is 800-660=140mol/h, the sodium chloride-containing amount was 800mol/h when regenerative wastewater entered the electrolyzer wastewater room, sodium chloride concentration was 6% (being equivalent to 1mol/l), the wastewater flow rate that enters so the electrolyzer wastewater room is 800 ÷ 1=800l/h=0.8t/h, the sodium chloride that need when mixed bed is regenerated transition is from storage sodium chloride tank, its amount is 0.8 * 2 * 1.8 ≈ 2.88mol/h (in the formula: 1.8 are mixed bed efficient transition), flow out the waste water that enters storage sodium chloride tank from the electrolyzer wastewater room, residue sodium chloride amount 140mol/h, greater than needing sodium chloride amount 2.88mol/h mixed of transition, so needn't add in addition sodium chloride, in addition, transition, the regenerative wastewater of mixed bed was all drained with cleaning waste water.
Between producing acid from electrolyzer, produce effusive acid between alkali, alkali and flow into storage acid jar, storage alkali jar respectively, as the regenerator of negative and positive bed.The pure water that the pure water that electrolyzer acid, alkali need is produced from the yin, yang bed.
Working condition when electrolyzer is produced acid, alkali is substantially the same manner as Example 1, no longer narration.
Claims (3)
1, a kind of electrolysis cation and anion exchange method of reutilizing wastewater, it is characterized in that with cation and anion exchange waste water through neutralization-except hard-be electrolyzed to produce acid and alkali, as the ion exchange regenerant agent, remaining common salt mixes a bed regenerative agent in the waste water as making the transition after electrolysis, realization flow is front transition of flow process, also be called former water flow process transition, namely before Yuan Shui enters yin, yang bed product water, make the transition through the mixed bed that makes the transition earlier, what make the transition the agent employing is sodium chloride, and transition, the regenerative wastewater of mixed bed was all drained with cleaning waste water; Former water is through making the transition mixed bed after transition, and hardness is answered≤0.001mmol/l in the water, and the water after transition goes the sun bed to produce pure water with cloudy again; Regenerate behind yin, yang bed efficiency lost resin, regenerate used acid and alkali are from electrolyzer electrolysis wastewater gained; The sun bed flows into the neutralization pond neutralization with the regenerative wastewater of cloudy bed, and the sodium chloride concentration in the waste water is 3%～12%, and waste water hardness≤0.08mmol/l, the cleaning waste water of sun bed and cloudy bed is drained, to keep the concentration of regenerative wastewater; Waste water flows out when electrolysis afterchlorinate na concn is down to 1%～3%, as mixed bed regenerative agent transition; What enter electrolyzer acid production room and alcaligenes room is that concentration is 1%～3% diluted acid, diluted alkaline or pure water, and the acid, the alkali concn that flow out from electrolyzer are 4%～10%, as the regenerative agent of negative and positive bed.
2, a kind of electrolysis cation and anion exchange method of reutilizing wastewater, it is characterized in that with cation and anion exchange waste water through neutralization-except hard-be electrolyzed to produce acid and alkali, as the ion exchange regenerant agent, remaining sodium chloride mixes a bed regenerative agent in the waste water as making the transition after electrolysis, realization flow is rear transition of flow process, also be waste water flow process transition, be that former water is through sun bed, cloudy bed, make pure water, regenerate behind the negative and positive bed efficiency lost resin, regenerative wastewater flows into neutralization pond, and its sodium chloride concentration should be 3%～12%, and the negative and positive bed cleans waste water and then drains; In neutralization pond, add milk of lime tentatively except behind hard, the sedimentation and filtration, hardness should≤2mmol/l, turbidity should≤1 °, precipitation and the waste water that filters are all drained; Tentatively enter mixed of transition except the waste water after hard, hardness is answered≤0.08mmol/l after transition, regenerative wastewater after transition is down to 1%～3% through electrolyzer electrolytic chlorination na concn and is flowed out, and as mixed regenerative agent transition, transition, the regenerative wastewater of mixed bed was all drained with cleaning waste water; What enter electrolyzer acid production room and alcaligenes room is that concentration is 1%～3% diluted acid, diluted alkaline or pure water, and the acid, the alkali concn that flow out from electrolyzer are 4%～10%, as negative and positive bed regenerative agent.
3, used electrolyzer in a kind of as claimed in claim 1 or 2 method, it is characterized in that it is to be arranged by the anion and cation exchange membrane exchange, distance is between 0.1～1.0cm between the anion and cation exchange membrane, be followed successively by between alcaligenes room, pure water between every a pair of anion and cation exchange membrane, acid production room and wastewater room, between pure water, be filled with OH
-Type negative resin and H
+Type sun resin, between described alcaligenes room-pure water-acid production room-wastewater room is called as an electrolysis cells, and electrolyzer is to be composed in parallel by dozens of and even hundreds of electrolysis cells, and the electrolyzer both sides are pole plate and utmost point pool.
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