CN100475320C - Internal electrolyte destruction of scale inhibitor in reverse osmosis concentrate - Google Patents
Internal electrolyte destruction of scale inhibitor in reverse osmosis concentrate Download PDFInfo
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- CN100475320C CN100475320C CNB2006101163073A CN200610116307A CN100475320C CN 100475320 C CN100475320 C CN 100475320C CN B2006101163073 A CNB2006101163073 A CN B2006101163073A CN 200610116307 A CN200610116307 A CN 200610116307A CN 100475320 C CN100475320 C CN 100475320C
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- reverse osmosis
- antisludging agent
- concentrated liquid
- osmosis concentrated
- coagulation
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Abstract
An internal electrolyzing method for destroying the scaling inhibitor in concentrated reverse osmosis liquid for reusing the water features that numerous primary cells formed by the low-potential Fe particle as cathode and the high-potential C particle as anode are used in said concentrated reverse osmosis liquid for generating electrochemical reaction to destroy the scaling inhibitor by reducing, electrolyzing and coagulative adsorbing actions while to educe out the scaling CaCO3.
Description
Technical field
What the present invention relates to is a kind of method of technical field of waste water processing, the internal electrolyte destruction method of antisludging agent in particularly a kind of reverse osmosis concentrated liquid.
Background technology
Counter-infiltration (RO) desalination is widely used in industrial circles such as bitter and desalinization, medicine production, electronics industry high purity water, water for beverages, Chemical Manufacture.Desalination is compared with the way of distillation, and it is low that counter-infiltration has energy consumption, and operation is easy, no regeneration liquid waste discharging, and system's floor space is little, and the operating cost economic dispatch is given prominence to advantage.Along with the improvement of masking technique, the exploitation of energy-recuperation system, the improvement of preconditioning technique and the broad applicability that the height salinity is intake, the reverse osmosis deaslination cost obviously descends year by year, reverse osmosis process constantly strengthens in economical, technical competitiveness, will become one of the leading new and high technology in 21 century desalination field.
In service for a long time at counter-infiltration system, the fouling of film is a very stubborn problem, and its appearance has caused declining to a great extent of reverse osmosis unit aquifer yield, has limited this technology and has used widely.In order to overcome scale problems, general counter-infiltration system all adds antisludging agent in water inlet when operation, the non-scaling incrustation ion is maintained higher degree of supersaturation, thus improved the rate of recovery of water.
After the rate of recovery of counter-infiltration system acquires a certain degree, if continue to improve the rate of recovery again, the incrustation ion in the solution is owing to concentration height supersaturation, and antisludging agent can not maintain it non-scaling state, they will separate out on film in fouling, so the time have only concentrate discharged.Even adopted the concentrate circulating technology that the discharging of final concentrate also will be arranged.To the final relief liquor of counter-infiltration, never utilized well at present.
Find by prior art documents, in " counter-infiltration-membrane technology water chemistry and commercial Application " (Chemical Industry Press, 1999) in the book, the method for disposal of RO concentrate is summarized, typical method comprises surface water discharging, deep-well injection, sprinkling irrigation, thermal evaporation etc.But above method also fails the RO concentrate is utilized well, does not fundamentally reduce the discharging of concentrate, has in fact caused the waste of water resource.Because feed water by reverse osmosis has all passed through strict preliminary treatment, so the water quality of concentrate is also very high, reuse again can not only improve RO system producing water ratio, and can reduce the discharge capacity of refuse.Why concentrate does not obtain reuse, is because contain higher salt, particularly Ca
2+, HCO
3 -Deng CaCO
3Incrustation ion concentration height has bigger scaling tendency, and promptly higher LSI value (bright lattice rel saturation index) is easy to fouling and can not continues to utilize.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, the internal electrolyte destruction method of antisludging agent in a kind of reverse osmosis concentrated liquid is provided, make the scaling tendency of the Coagulation and Adsorption effect reduction reverse osmosis concentrated liquid of its reduction of utilizing Zero-valent Iron in the cast iron filing, the little electrolysis of galvanic cell and process, improve the counter-infiltration system water rate of recovery, realize the concentrate resource reutilization.
The present invention is achieved by the following technical solutions, the present invention utilizes the potential difference that exists between iron-carbon granule and the numerous trickle galvanic cell effect that forms, in reverse osmosis concentrated liquid, add cast-iron scrap, these trickle batteries become negative electrode with the low iron of current potential, the carbon that current potential is high is done anode, electrochemical reaction takes place in reverse osmosis concentrated liquid, reduction by Zero-valent Iron, the Coagulation and Adsorption effect of little electrolysis of galvanic cell and process, the antisludging agent molecule is destroyed, make the incrustation ion unstability of high degree of supersaturation in the solution, by enhanced coagulation, make the CaCO in the concentrate then
3Scaling salt is separated out and is reduced the scaling tendency of solution, and concentrate is utilized again as water inlet, improves the counter-infiltration system water rate of recovery.
Described reverse osmosis concentrated liquid is meant the dense water section of counter-infiltration wherein to comprise antisludging agent.
Described antisludging agent comprises organic phosphine class, polycarboxylic acid, poly-semi-annular jade pendant acids, polyesters and the copolymer between them thereof, also comprises green scale inhibitor poly-asparagic acid class, molecular structure dendroid class etc.
Described reverse osmosis concentrated liquid is handled, with cast-iron scrap addition 50G/L, stirred, air mass flow is 0.03-0.12m at rotating speed 600rpm
3Sudden and violent gas reacted 30-60 minute down under the/h condition.Through handling, the antisludging agent in the concentrate is destroyed, and the incrustation ion in the height supersaturation concentrate generates crystal grain automatically owing to lost the retardation of antisludging agent and is suspended in the solution.
Described enhanced coagulation after interior electrolysis finishes, adds the polyacrylamide of 0.3% concentration of 0.625% (V/V), carries out coagulation half a minute under 300 rev/mins earlier, and coagulant and solution are fully mixed, and then carries out coagulation 5 minutes under 50 rev/mins.
Described coagulant is meant the commercial polyacrylamide of various molecular weight to comprise anionic, cationic and nonionic.
After enhanced coagulation finished, the alumen ustum of formation was fully grown up, and solution is filtered, and removed the alumen ustum of precipitation, and the reverse osmosis concentrated liquid after promptly obtaining handling, the scaling tendency of this concentrate reduce greatly, and the water inlet that can be used as counter-infiltration system utilizes again.
After enhanced coagulation finishes, the reverse osmosis concentrated liquid after handling is carried out the ion concentration analysis, measure pH, the Ca of solution
2+, HCO
3 -Concentration, and calculate LSI (the bright lattice rel of Langelier saturation index) value, the result shows that the solution scaling tendency reduces greatly, can drop to about LSI=0.6.
The salinity height of the reverse osmosis concentrated liquid that the inventive method adopts, its good conductivity, effective during with Internal Electrolysis Process for Treating.By the little electrolysis of reduction, galvanic cell of Zero-valent Iron in the cast-iron scrap and the Coagulation and Adsorption effect of process, the treatment effeciency height, speed is fast, the antisludging agent in the concentrate can be destroyed, and reduces the scaling tendency of concentrate greatly; Processing procedure need not to add chemical reagent, and is with low cost; The processing procedure environmental friendliness, the discharging of unharmful substance, the concentrate after the processing can be used as into that water utilizes again, realizes the concentrate resource, improves the counter-infiltration system water rate of recovery.
Description of drawings:
Fig. 1 is the result of the embodiment of the invention 1.
Fig. 2 is the result of the embodiment of the invention 2.
The specific embodiment:
Below in conjunction with accompanying drawing with further describe embodiment.Antisludging agent A is HEDP HEDP among the present invention, antisludging agent B is a 2-phosphonic acids butane-1,2,4-tricarboxylic acids PBTCA, antisludging agent C is Permatreat 190 (a kind of trade name, main component is an organic phospho acid), antisludging agent D is Flocon200 (a kind of trade name, main component is a polyacrylic acid), antisludging agent E is Accumer5000 (a kind of trade name, main component are the acrylic acid polymer), and antisludging agent F is the organic phosphine sulfonate, antisludging agent G is acrylic acid-acrylate-sulfonate terpolymer, and antisludging agent H is olefin(e) acid-acrylate-phosphonic acids-sulfonate quadripolymer.Antisludging agent C is that Permatreat 190 is U.S. GE company product, and antisludging agent D is a U.S. Biolab company product, and antisludging agent E is a U.S. Rohm Haas company product, and all the other antisludging agents are ruddiness chemical plant, changzhou product.Coagulant is the PAMA AP410C of Mitsubishi chemical company among the present invention.
Embodiment 1
Take by weighing 0.72 gram NaHCO
3, 1.18 gram CaCl
2, 0.22 gram MgSO
47H
2O, 0.228 gram NaNO
3, place 800 ml distilled waters, be mixed with concentrate, its initial pH is 7.9, initial LSI
0Be 1.96.Add antisludging agent, antisludging agent concentration is 15mg/L.
The employing cast iron filing experimentizes, and adds the 50g/L cast-iron scrap, is 0.12m in rotating speed 600rpm stirring, air mass flow
3The sudden and violent gas of/h reacted 30 minutes down, carried out interior electrolytic treatments.
Through interior electrolytic treatments, the antisludging agent in the concentrate is destroyed, and the incrustation ion in the height supersaturation concentrate generates crystal grain automatically and is suspended in the solution.In order to remove these suspension fouling particles efficiently, the present invention adopts the method for enhanced coagulation: promptly after interior electrolysis finishes, polyacrylamide (0.3% concentration) AP410C (Mitsubishi chemical company) that adds 0.625% (V/V), under 300 rev/mins, carry out coagulation half a minute earlier, coagulant and solution are fully mixed, then under 50 rev/mins, carried out coagulation 5 minutes.The alumen ustum of formation is fully grown up.
After coagulation finishes, the reverse osmosis concentrated liquid after handling is carried out the ion concentration analysis, measure pH, the Ca of solution
2+, HCO
3 -Concentration, and calculate LSI (the bright lattice rel of Langelier saturation index) value.
8 kinds of different commercial antisludging agents have been carried out interior electrolytic treatments, and these antisludging agents represent with alphabetical A to H that respectively they contain-COOH ,-PO
3H
2,-OH ,-SO
3H ,-COOR isoreactivity group is described in its title and production firm such as the summary of the invention.
Fig. 1 is 8 kinds of results of antisludging agent after interior electrolytic treatments, LSI of concentrate as seen from the figure
fReduce to 0.58, illustrate that antisludging agent is destroyed, and the result of 8 kinds of antisludging agents is basic identical, the efficient height of internal electrolyte destruction antisludging agent is described, do not have selectivity, so the present invention has versatility to the processing of antisludging agent.
Take by weighing 1.712 gram NaHCO
3, 2.458 gram CaCl
2, 0.414 gram MgSO
47H
2O, 0.428 gram NaNO
3, place 800 ml distilled waters, be mixed with concentrate, its initial pH is 8.2, initial LSI
0Be 2.8.Add 3 kinds of antisludging agent A, B and C (described in its title and production firm such as the summary of the invention) respectively and carry out interior electrolysis, its concentration is all 25mg/L.
Adopting the iron filings of cast iron to experimentize, add the 50g/L cast-iron scrap, is 0.12m in rotating speed 600rpm stirring, air mass flow
3The sudden and violent gas of/h reacted 30 minutes down, carried out interior electrolytic treatments.
Through interior electrolytic treatments, the antisludging agent in the concentrate is destroyed, and the incrustation ion in the height supersaturation concentrate generates crystal grain automatically and is suspended in the solution.In order to remove these suspension fouling particles efficiently, the present invention adopts the method for enhanced coagulation: promptly after interior electrolysis finishes, polyacrylamide (0.3% concentration) AP410C (Mitsubishi chemical company) that adds 0.625% (V/V), under 300 rev/mins, carry out coagulation half a minute earlier, coagulant and solution are fully mixed, then under 50 rev/mins, carried out coagulation 5 minutes.The alumen ustum of formation is fully grown up.
After coagulation finishes, the reverse osmosis concentrated liquid after handling is carried out the ion concentration analysis, measure pH, the Ca of solution
2+, HCO
3 -Concentration, and calculate LSI (the bright lattice rel of Langelier saturation index) value.
Interior electrolysis result as shown in Figure 2.As seen from the figure, the LSI of concentrate
fReduce to 0.62, scaling tendency LSI value has reduced by 76%, and treatment effect is obvious, and the result of 3 kinds of antisludging agents is basic identical.The efficient height do not have selectivity, so the inventive method had universal when this further specified internal electrolysis destruction antisludging agent.
Embodiment 3
Take by weighing 0.72 gram NaHCO
3, 1.18 gram CaCl
2, 0.22 gram MgSO
47H
2O, 0.228 gram NaNO
3, place 800 ml distilled waters, be mixed with concentrate, its initial pH is 7.8, initial LSI
0Be 1.86.Add antisludging agent B (described in its title and production firm such as the summary of the invention), get 3 kinds of concentration and carry out electrolysis, be respectively 10,25 and 35mg/L.
Adopting the iron filings of cast iron to experimentize, add the 50g/L cast-iron scrap, is 0.12m in rotating speed 600rpm stirring, air mass flow
3The sudden and violent gas of/h reacted 30 minutes down, carried out interior electrolytic treatments.
Through interior electrolytic treatments, the antisludging agent in the concentrate is destroyed, and the incrustation ion in the height supersaturation concentrate generates crystal grain automatically and is suspended in the solution.In order to remove these suspension fouling particles efficiently, the present invention adopts the method for enhanced coagulation: promptly after interior electrolysis finishes, polyacrylamide (0.3% concentration) AP410C (Mitsubishi chemical company) that adds 0.625% (V/V), under 300 rev/mins, carry out coagulation half a minute earlier, coagulant and solution are fully mixed, then under 50 rev/mins, carried out coagulation 5 minutes.The alumen ustum of formation is fully grown up.
After coagulation finishes, the reverse osmosis concentrated liquid after handling is carried out the ion concentration analysis, measure pH, the Ca of solution
2+, HCO
3 -Concentration, and calculate LSI (the bright lattice rel of Langelier saturation index) value.
Through the solion analysis, calculate the LSI that handles the back concentrate
fReduce to 0.57,0.60 and 0.63 respectively, illustrate that the scaling tendency of solution descends greatly.The influential effect of the internal electrode processing of the variation of antisludging agent concentration is little as can be known simultaneously, and electrolytic process destroys the very capable of antisludging agent in illustrating.
Embodiment 4
Take by weighing 0.72 gram NaHCO
3, 1.18 gram CaCl
2, 0.22 gram MgSO
47H
2O, 0.228 gram NaNO
3, place 800 ml distilled waters, be mixed with concentrate, its initial pH is 7.8, initial LSI
0Be 1.86.The adding antisludging agent is C (described in its title and production firm such as the summary of the invention), and concentration is 8mg/L.
Adopting the iron filings of cast iron to experimentize, add the 50g/L cast-iron scrap, is 0.03m in rotating speed 600rpm stirring, air mass flow
3The sudden and violent gas of/h is reaction down, carries out interior electrolytic treatments.Do twice experiment, once sudden and violent solid/liquid/gas reactions 30 minutes, the sudden and violent solid/liquid/gas reactions of another time 60 minutes.
Through interior electrolytic treatments, the antisludging agent in the concentrate is destroyed, and the incrustation ion in the height supersaturation concentrate generates crystal grain automatically and is suspended in the solution.In order to remove these suspension fouling particles efficiently, the present invention adopts the method for enhanced coagulation: promptly after interior electrolysis finishes, polyacrylamide (0.3% concentration) AP410C (Mitsubishi chemical company) that adds 0.625% (V/V), under 300 rev/mins, carry out coagulation half a minute earlier, coagulant and solution are fully mixed, then under 50 rev/mins, carried out coagulation 5 minutes.The alumen ustum of formation is fully grown up.
After coagulation finishes, the reverse osmosis concentrated liquid after handling is carried out the ion concentration analysis, measure pH, the Ca of solution
2+, HCO
3 -Concentration, and calculate LSI (the bright lattice rel of Langelier saturation index) value.
Must handle the LSI of back concentrate as calculated
fReduce to 0.59 and 0.60 respectively, illustrate that the scaling tendency of solution descends greatly.Electrolysis time is little to the influence of antisludging agent execution in simultaneously visible, and declarative procedure destroys the very capable of antisludging agent, finishes the destruction reaction to antisludging agent in 30 minutes substantially.
Claims (3)
1, the internal electrolyte destruction method of antisludging agent in a kind of reverse osmosis concentrated liquid, it is characterized in that, utilize the potential difference that exists between iron-carbon granule and the numerous trickle galvanic cell effect that forms, in comprising the reverse osmosis concentrated liquid of antisludging agent, add cast-iron scrap, these trickle batteries become negative electrode with the low iron of current potential, the carbon that current potential is high is done anode, electrochemical reaction takes place in reverse osmosis concentrated liquid, reduction by Zero-valent Iron, the Coagulation and Adsorption effect of little electrolysis of galvanic cell and process, the antisludging agent molecule is destroyed, make the incrustation ion unstability of high degree of supersaturation in the solution, by enhanced coagulation, make the CaCO in the concentrate then
3Scaling salt is separated out and is reduced the scaling tendency of solution, and concentrate is utilized again as water inlet, improves the counter-infiltration system water rate of recovery; Specifically comprise the steps:
1. adopting internal electrolysis to add the 50g/L cast-iron scrap in containing the reverse osmosis concentrated liquid of antisludging agent, is 0.03-0.12m in rotating speed 600rpm stirring, air mass flow
3Under/the h sudden and violent solid/liquid/gas reactions 30-60 minute;
2. interior electrolysis is carried out enhanced coagulation after finishing, and adds the polyacrylamide of 0.3% concentration of percent by volume 0.625%, carries out coagulation half a minute under 300 rev/mins earlier, and coagulant and solution are fully mixed, and then carries out coagulation 5 minutes under 50 rev/mins;
3. after enhanced coagulation finishes, solution is filtered, the reverse osmosis concentrated liquid after promptly obtaining handling carries out the ion concentration analysis to the reverse osmosis concentrated liquid after handling, and measures pH, the Ca of solution
2+, HCO
3 -Concentration is calculated the bright lattice rel of Langelier saturation index value, obtains handling the LSI=0.6 of back reverse osmosis concentrated liquid.
2, the internal electrolyte destruction method of antisludging agent in the reverse osmosis concentrated liquid according to claim 1, it is characterized in that, described antisludging agent, comprise organic phosphine class, polycarboxylic acid, poly-semi-annular jade pendant acids, polyesters and the copolymer between them thereof, also comprise green scale inhibitor poly-asparagic acid class, molecular structure dendroid class.
3, the internal electrolyte destruction method of antisludging agent in the reverse osmosis concentrated liquid according to claim 1 is characterized in that, described coagulant comprises anionic, cationic and nonionic.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101163073A CN100475320C (en) | 2006-09-21 | 2006-09-21 | Internal electrolyte destruction of scale inhibitor in reverse osmosis concentrate |
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|---|---|---|---|
| CNB2006101163073A CN100475320C (en) | 2006-09-21 | 2006-09-21 | Internal electrolyte destruction of scale inhibitor in reverse osmosis concentrate |
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| CN100475320C true CN100475320C (en) | 2009-04-08 |
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| CN105016569B (en) * | 2014-04-25 | 2017-04-26 | 宝山钢铁股份有限公司 | Processing system and method for cold rolling reverse osmosis strong brine |
| CN104261598B (en) * | 2014-09-23 | 2015-10-28 | 扬州佳境环境科技股份有限公司 | A kind of printed circuit board developing waste water zero discharge treatment process and device |
| CN115215493A (en) * | 2021-04-20 | 2022-10-21 | 国家能源投资集团有限责任公司 | Method and device for treating scale inhibitor in membrane concentrated solution |
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