CN102120663B - Coking wastewater advanced treatment system and process - Google Patents
Coking wastewater advanced treatment system and process Download PDFInfo
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- CN102120663B CN102120663B CN2011100766924A CN201110076692A CN102120663B CN 102120663 B CN102120663 B CN 102120663B CN 2011100766924 A CN2011100766924 A CN 2011100766924A CN 201110076692 A CN201110076692 A CN 201110076692A CN 102120663 B CN102120663 B CN 102120663B
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Abstract
The invention relates to a coking wastewater advanced treatment system, comprising a microwave-assisted catalytic oxidation device, a mixing reaction pool, a sedimentation pool, a manganese sand filter, a precision filter and a frequent electrode reverse electrodialysis device, wherein the microwave-assisted catalytic oxidation device is used for carrying out catalytic oxidation treatment on coking wastewater subjected to A/O (Anoxic/Oxic) biochemical treatment; the mixing reaction pool is connected with the microwave-assisted catalytic oxidation device and the sedimentation pool; the manganese sand filter is connected with the sedimentation pool and the precision filter; and the frequent electrode reverse electrodialysis device is connected with the precision filter. The advanced treatment process provided by the invention can be used for coking wastewater advanced treatment and simultaneously has a high-efficiency pretreatment and economic and proper type desalting system.
Description
Technical field
The present invention relates to the Treatment of Coking Effluent field, be specifically related to a kind of coking advanced waste treatment system and treatment process.
Background technology
Coking chemical waste water is the waste water that contains a large amount of aromatics and heterogeneous ring compound that in coal system coke, gas purification and coke chemicals removal process, produces; Have that quantity discharged is big, organism and characteristics such as ammonia nitrogen concentration is high, biodegradability is poor, organic components complicacy, belong to the organic waste water of difficult for biological degradation.Be containment coking industry low-level duplicate construction and blind expansion trend; Promote industrial structure upgrading; Promote energy-saving and emission-reduction and technical progress; The Ministry of Industry and Information Technology of country revised former " coking industry entry criteria " in 2008, spelt out Treatment of Coking Effluent and will recycle after qualified, must not efflux.
At present; The mode of two stages of treatment is generally adopted in the processing of coking chemical waste water both at home and abroad; The first step be with high density contain phenol and cyanide wastewater carries out pre-treatment such as dephenolize decyanation and ammonia still process air supporting; The second stage is that the pretreated coking chemical waste water of process is carried out biochemical treatment, adopts the A/O technology in the activated sludge process usually.But through after the above-mentioned two stages of treatment, water outlet can't direct reuse in recirculating cooling water system.This is that reuse water wants reuse to do the recirculated cooling water moisturizing because according to " recirculated cooling water is used the reuse water water quality standard " (HG/T 3923-2007), except to COD
Cr, BOD
5Have beyond the strict more regulation Deng the organic pollutant index; Inorganic salt indexs such as total dissolved solid, total hardness, total alkalinity, muriate are also had certain requirement, and the water outlet that after above-mentioned two stages of treatment, obtains can not reach the requirement of " recirculated cooling water is used the reuse water water quality standard " fully.
In order to reach the requirement of " recirculated cooling water is used the reuse water water quality standard ", need carry out advanced treatment once more to the water outlet after above-mentioned two stages of treatment.Coking chemical waste water is carried out the technology of advanced treatment as disclosing a kind of method that adopts catalytic oxidation to combine among the Chinese patent document CN101781039A with membrane separation technique; In this technology; Coking chemical waste water after pre-treatment, A/O biochemical treatment through catalytic oxidation treatment, and then is handled through coagulating sedimentation; After after uf processing and reverse osmosis system handle, promptly can be used as the make up water of circulating water system.
But; The problem that exists in the above-mentioned prior art is, said reverse osmosis desalination system is very harsh to the COD content requirement in the water inlet, and reason is; Organism in the coking chemical waste water can firmly be adsorbed on the surface of reverse osmosis membrane; Bring difficulty for follow-up cleaning, can not only pollute reverse osmosis membrane after the organism of few species is attracted to face in addition in addition, even can also cause the degraded and the degeneration of film.Through our factual survey, different reverse osmosis membrane producers is to water inlet COD
CrRequirement be different, 30mg/L can be described as a higher limit, that is to say into COD in the water
CrContent to be lower than 30mg/L at least; In addition, the producer that also has requires COD
CrBe lower than 15mg/L, the requirement that has is lower than 10mg/L.And the water outlet that the pretreatment technology that adopts above-mentioned catalyzed oxidation+coagulating sedimentation+ultrafiltration obtains, COD
CrThough content can be reduced to below the 80mg/L, long-time running still possibly polluted said reverse osmosis membrane or caused it to stop up, and then the work-ing life of having reduced said reverse osmosis membrane, has increased the running cost of technology.It is thus clear that; The problem that above-mentioned prior art exists in essence; Be to mate inadequately between not high enough pretreatment technology of removal efficient and the reverse osmosis desalination system to cause, and this also is the important factor that limits the coking wastewater deep treatment technical development to the requirement ten minutes harshness of intaking.Therefore, be badly in need of a kind of pre-treatment efficiently and advanced treatment process economic, appropriate type desalting system of having both in the prior art.
Summary of the invention
In order to solve in the catalytic oxidation that uses in the prior art and the advanced treatment process of coking waste water that reverse osmosis technology combines; Owing to remove the not high enough pretreatment technology of efficient and water inlet required between the very harsh reverse osmosis desalination system coupling inadequately, the contaminated or blocking problem of said reverse osmosis membrane meeting during the long-time running that causes.The invention provides a kind of pre-treatment efficiently and advanced treatment process economic, appropriate type desalting system of having both.
The technical scheme of coking advanced waste treatment system of the present invention is:
A kind of coking advanced waste treatment system comprises:
The micro ware auxiliary catalysis oxidizer unit, said micro ware auxiliary catalysis oxidizer unit carries out catalytic oxidation treatment to the coking chemical waste water after the A/O biochemical treatment;
Be connected mixed reaction pond that is provided with and the settling tank that is connected with said mixed reaction pond with said micro ware auxiliary catalysis oxidizer unit;
The filtration with manganese sand device that is connected with said settling tank, and the accurate filter that is connected with said filtration with manganese sand device;
Said coking advanced waste treatment system also comprises the frequently pole-reversing electroosmosis device that is connected with said accurate filter.
Said coking advanced waste treatment system also comprises the dosing agitated pool, and said dosing agitated pool is connected with said micro ware auxiliary catalysis oxidizer unit.
Said coking advanced waste treatment system also comprises the mixing equalizing tank that is connected with said dosing agitated pool;
Between said settling tank and said filtration with manganese sand device, connect the intermediate pool that is provided with, said intermediate pool is provided with aerator.
Said frequently pole-reversing electroosmosis device is provided with two-stage, is respectively:
The one-level frequently pole-reversing electroosmosis device that is connected with said accurate filter;
The secondary frequently pole-reversing electroosmosis device that is connected with said one-level frequently pole-reversing electroosmosis device.
Treatment process based on described coking advanced waste treatment system comprises:
(1) coking chemical waste water after the A/O biochemical treatment; Get into the micro ware auxiliary catalysis oxidizer unit; Adding acid in the coking chemical waste water in said micro ware auxiliary catalysis oxidizer unit regulates below the pH value to 6.0 of said coking chemical waste water; In said coking chemical waste water, add ferrous salt and ydrogen peroxide 50 then and stir, under the effect of microwave field, coking chemical waste water is carried out catalytic oxidation treatment;
The interpolation concentration of said ferrous salt is with Fe
2+The 0.3-0.36 that counts water COD concentration into doubly, the interpolation concentration of said ydrogen peroxide 50 is with H
2O
2The 2.12-2.54 that counts water COD concentration into doubly, the residence time of said coking chemical waste water in said microwave field is 30-60s, the microwave output power of said micro ware auxiliary catalysis oxidizer unit is 20-120kW;
(2) water outlet of said micro ware auxiliary catalysis oxidizer unit gets into said mixed reaction pond, and interpolation pH value regulator transfers to 6.0-9.0 with the pH value of said coking chemical waste water in the coking chemical waste water in said mixed reaction pond; Add coagulant aids again and carry out flocculation reaction, the coking chemical waste water after the completion flocculation reaction is sent into settling tank precipitate;
Said coagulant aids is an anion-polyacrylamide, and the addition of said coagulant aids is 1-20mg/L;
(3) supernatant in the said settling tank is successively sent into the filtration with manganese sand device and accurate filter filters;
The waste water that (4) will pass through after accurate filter filters is sent into the frequently pole-reversing electroosmosis device, and the fresh water that behind said frequently pole-reversing electroosmosis device desalination, obtains promptly can be used as the recirculated cooling water moisturizing.
Said pH value regulator is one or more in sodium hydroxide, sodium hydrogencarbonate, the milk of lime.
In the said step (1); Coking chemical waste water after the A/O biochemical treatment; Get into the dosing agitated pool, add acid in the coking chemical waste water in said dosing agitated pool and regulate below the pH value to 6.0 of said coking chemical waste water, then interpolation ferrous salt and ydrogen peroxide 50 and stirring in said coking chemical waste water; Send into said micro ware auxiliary catalysis oxidizer unit again, under the effect of microwave field, coking chemical waste water is carried out catalytic oxidation treatment.
In the step (1), the coking chemical waste water after the A/O biochemical treatment imports earlier and mixes equalizing tank, again the coking chemical waste water in the said mixing equalizing tank is sent into said dosing agitated pool;
In the said step (3), the supernatant in the said settling tank is introduced into said intermediate pool, after the aerator in the said intermediate pool carries out aeration to said supernatant, again it is successively sent into said filtration with manganese sand device and accurate filter filters.
In the step (4); Waste water through after the accurate filter filtration is sent into one-level frequently pole-reversing electroosmosis device; The strong brine that behind said one-level frequently pole-reversing electroosmosis device desalination, obtains is sent into said secondary frequently pole-reversing electroosmosis device again and is carried out desalination, and the fresh water that behind said one-level electrodialysis unit and secondary electrodialysis unit desalination, obtains promptly can be used as the recirculated cooling water moisturizing.
Advanced treatment process of coking waste water of the present invention; Coking chemical waste water in the step (1) after the A/O biochemical treatment; Get into the micro ware auxiliary catalysis oxidizer unit, the coking chemical waste water in said micro ware auxiliary catalysis oxidizer unit adds acid to be regulated below the pH value to 6.0 of said coking chemical waste water, then interpolation ferrous salt and ydrogen peroxide 50 and stirring in said coking chemical waste water; Under the effect of microwave field, coking chemical waste water is carried out catalytic oxidation treatment; Said ferrous ion and peroxo-Hydrogen Energy generate the hydroxyl radical free radical of strong oxidizing property, and the organism generation organic free radical with difficult degradation in the aqueous solution makes it structure deteriorate, final oxygenolysis.Than traditional catalyzed oxidation step, under the effect of said microwave field heat effect and non-thermal effect, the required time of said catalytic oxidation shortens greatly.Through the catalytic oxidation treatment described in the step (1), effectively removed the organism in the water.
It is 30-60s that the present invention also is provided with the residence time of said coking chemical waste water in said microwave field; Reason is; If it is too short that the said residence time is provided with, also just lower to removal effect of organic matter, thus cause water outlet not reach the requirement of " recirculated cooling water is used the reuse water water quality standard "; If it is long that the said residence time is provided with; Can increase the running cost of said technology again, the present invention is according to the characteristic of said coking chemical waste water, and it is 30-60s that the said residence time is set; Removing significantly the organic while in the water, also reducing the running cost of said technology as far as possible.
The microwave output power that the present invention also is provided with said micro ware auxiliary catalysis oxidizer unit is 20-120kW; Said microwave output power is that the flooding quantity size according to said advanced treatment system is provided with; Power setting is too small if flooding quantity is big, does not then reach the water outlet effect of expection, and if that the flooding quantity smaller power is provided with is very big; Then can improve the working cost of said micro ware auxiliary catalysis oxidizer unit; Cause unnecessary waste, the present invention is through with reference to the water inlet scope that possibly occur in the reality, and the microwave output power that limits said micro ware auxiliary catalysis oxidizer unit is 20-120kW; As preferred embodiment, the microwave output power that the present invention further limits said micro ware auxiliary catalysis oxidizer unit is 40-60kW;
The present invention also is provided with the interpolation concentration of said ferrous salt with Fe
2+The 0.3-0.36 that counts water COD concentration into doubly, the interpolation concentration of said ydrogen peroxide 50 is with H
2O
2The 2.12-2.54 that counts water COD concentration into doubly.Why be provided with like this,, can cause said micro ware auxiliary catalysis oxidation not reach due catalyzed oxidation effect if be because the addition of ferrous salt and ydrogen peroxide 50 is too small.But as Fe as catalyzer
2+When consumption increases, too much Fe
2+Can consume ydrogen peroxide 50 and form ferric iron, reduce treatment effect.And for ydrogen peroxide 50, excessive H
2O
2Hydroxyl radical free radical in meeting and the water reacts, and said ferrous ion is oxidized to ferric iron, and then reduces the catalytic effect of said medicament, and the excessive running cost that also can improve said technology of pharmaceutical quantities.Therefore only when the addition of molysite and ydrogen peroxide 50 suits, could when minimizing cost, reach best processing efficiency.Step (2) is sent the water outlet of said micro ware auxiliary catalysis oxidizer unit into said mixed reaction pond, and interpolation pH value regulator transfers to 6.0-9.0 with the pH value of said coking chemical waste water in the coking chemical waste water in said mixed reaction pond; Add coagulant aids again and carry out flocculation reaction, the coking chemical waste water after the completion flocculation reaction is sent into settling tank precipitate; The pH value of regulating said coking chemical waste water transfers to 6.0-9.0; Reason is; The water inlet of mixed reaction pond before step (1) in by furnishing acidity; And the tart reuse water is not suitable for as the recirculated cooling water moisturizing, and adding pH value regulator at this can be suitable for said reuse water furnishing to be used as the neutral of recirculated cooling water moisturizing or omit meta-alkalescence water; In addition, through adding pH value regulator, in said waste water, introduced an amount of OH
-Ion, said OH
-Ion combines with iron ion in the waste water, forms bigger flco, has accelerated sedimentary speed.Handle through said coagulating sedimentation, can effectively remove colloidal particle and fine suspension in the waste water, thereby reduce the turbidity and the colourity of said coking chemical waste water.
Supernatant in the said settling tank is successively sent into the filtration with manganese sand device to step (3) and accurate filter filters; Said filtration with manganese sand device and accurate filter, the pigment in the water is removed in the small suspended substance and the absorption that can further filter out in the waste water, and then reduces the turbidity and the colourity of waste water once more.Wherein, Said filtration with manganese sand device also can be removed the ferromanganese ion in the waste water; Reactive group generation irreversible reaction on the ion-exchange membrane that said ferromanganese ion is easy and said electrodialysis unit is interior; Make said ion-exchange membrane receive severe contamination, the present invention is through using said filtration with manganese sand device, for follow-up electrodialysis desalination provides good water inlet condition.
The waste water that said step (4) will be passed through after accurate filter filters is sent into the frequently pole-reversing electroosmosis device, and the fresh water that behind said frequently pole-reversing electroosmosis device desalination, obtains promptly can be used as the recirculated cooling water moisturizing.The desalination rate of the device of frequently pole-reversing electroosmosis described in the present invention is greater than 75%, and said coking chemical waste water approximately can produce the fresh water that accounts for amount of inlet water 75% and 25% strong brine behind said frequently pole-reversing electroosmosis device desalination.Cold open cycle cooling water system between said fresh water can be back in the factory after supercharging if said frequently pole-reversing electroosmosis device is built near the circulation water tower, can consider that also the equipment water outlet directly enters the cooling tower back pool.Said strong brine then can be used for remaining the quenching of coke wet quenching coke oven or sprays the dustproof depositing dust of coal yard.
The advantage of coking advanced waste treatment system of the present invention and treatment process is:
(1) coking advanced waste treatment system of the present invention comprises micro ware auxiliary catalysis oxidizer unit, coagulating sedimentation treatment unit, filtration with manganese sand device, accurate filter and electrodialysis unit.Wide aperture neutral ion exchange membrane in the electrodialysis unit of the present invention has stronger antioxidant, acid and alkali-resistance, anticorrosive, anti-hydrolysis, resistant to pollution ability, is not easy to stop up the long perfomance life of film.Therefore, said frequently pole-reversing electroosmosis device is compared with reverse osmosis unit for the requirement of influent quality and is wanted wide in range many, is usually less than 80mg/L and gets final product.Coking chemical waste water after micro ware auxiliary catalysis oxidizer unit of the present invention is handled, the COD in the water
CrContent can reach below the 80mg/L, and the water outlet that after follow-up coagulating sedimentation+filtration with manganese sand device+accurate filter is handled, obtains again can be satisfied the water inlet requirement of said electrodialysis unit fully.Therefore in the technology of the present invention; Preceding pre-treatment and after electrodialysis desalination plant between can reach the height coupling; Make that said system can steady running, effectively avoided in the prior art blocked easily or pollute maintenance and the high problem of running cost that causes because of the desalting system film.
(2) coking advanced waste treatment system of the present invention; The micro ware auxiliary catalysis oxidizer unit that adopts has the advantage that floor space is little, the reagent consumption amount is low, the treatment time is short; And reaction does not receive the influence of ambient temperature, Pollutant levels; Flexibility is strong, and treatment of organic matters of organic efficient also is far longer than traditional catalytic oxidation.The more important thing is; Said micro ware auxiliary catalysis oxidizer unit has relaxed the requirement to water inlet pH value; The pH value of said water inlet is reduced to below 6.0 and gets final product; Need the pH value of water inlet be reduced to the consumption that way below 4.0 has reduced sour reagent than the conventional catalyst oxidation style, reduce the running cost of said technology; And said micro ware auxiliary catalysis oxidizer unit is being handled the organic effect that also can play sterilization, algae removal simultaneously, so the technology among the present invention do not need extra interpolation sterilant again, has further reduced the running cost of technology.
(3) coking advanced waste treatment system of the present invention; Selection is provided with said frequently pole-reversing electroosmosis device and carries out the desalination processing; Overcome the problem that traditional electrodialysis unit is easy to generate concentration polarization; The equipment scaling phenomenon that causes because of concentration polarization, stable and reliable operation have effectively been prevented.
(4) coking advanced waste treatment system of the present invention, said micro ware auxiliary catalysis oxidizer unit comprise dosing agitated pool and the micro ware auxiliary catalysis oxidizer unit that is connected with said dosing agitated pool.Through said dosing agitated pool is set, made that before getting into the micro ware auxiliary catalysis oxidizer unit said coking chemical waste water and ferrous salt, ydrogen peroxide 50 can thorough mixing, improved said micro ware auxiliary catalysis oxidizer unit to treatment of organic matters of organic efficient.
(5) coking advanced waste treatment system of the present invention also is connected with intermediate pool between said settling tank and said filtration with manganese sand device, said intermediate pool is provided with aerator.The advantage that is provided with like this is, said intermediate pool precipitates once more the supernatant of said settling tank and clarifies, and prevents that the throw out in the said settling tank from getting into said filtration with manganese sand device, has effectively avoided manganese sand treater phenomenon of blocking; In addition, be provided with aerator in the said intermediate pool, through said aerator aeration in said intermediate pool; Can waste water remaining ferrous ion after the micro ware auxiliary catalysis oxide treatment be oxidized to ferric iron, said ferric iron normally exists with the colloidal form, in follow-up filtration treatment, is removed more easily; Simultaneously; Because the said ferric iron colloid that obtains itself is exactly a coagulating agent, therefore be equivalent in intermediate pool, carry out second coagulation, can remove the suspended substance in anhydrating better.In addition, through said aerator aeration in said intermediate pool, also can be with H residual in the waste water
2O
2Stripping is removed, and prevents H
2O
2Hardware to follow-up causes oxidation corrosion.
(6) coking advanced waste treatment system of the present invention, said coking advanced waste treatment system also comprise the mixing equalizing tank that is connected with said dosing agitated pool.Coking chemical waste water after the A/O biochemical treatment imports earlier and mixes equalizing tank, again the coking chemical waste water in the said mixing equalizing tank is sent into said dosing agitated pool.Through said mixing equalizing tank is set, can effectively prevent the water yield and the water quality generation big ups and downs of said coking chemical waste water, the unsettled phenomenon of processing efficiency of the advanced treatment that has effectively prevented to cause because of flooding quantity and influent quality big ups and downs.
Description of drawings
For content of the present invention is more clearly understood, below in conjunction with specific embodiment and accompanying drawing content of the present invention is done further detailed explanation, wherein
Fig. 1 is the structure iron of coking advanced waste treatment system of the present invention;
Fig. 2 is the structure iron of the convertible mode of coking advanced waste treatment system of the present invention.
Embodiment
Among the following embodiment 1-4, the concentration of COD is 305mg/L described in the coking chemical waste water after the A/O biochemical treatment.
Embodiment 1
Coking advanced waste treatment system described in the present embodiment is as shown in Figure 1, comprising:
The micro ware auxiliary catalysis oxidizer unit, said micro ware auxiliary catalysis oxidizer unit carries out catalytic oxidation treatment to the coking chemical waste water after the A/O biochemical treatment;
Be connected mixed reaction pond that is provided with and the settling tank that is connected with said mixed reaction pond with said micro ware auxiliary catalysis oxidizer unit;
The filtration with manganese sand device that is connected with said settling tank, and the accurate filter that is connected with said filtration with manganese sand device;
Said coking advanced waste treatment system also comprises the frequently pole-reversing electroosmosis device that is connected with said accurate filter.
Treatment process based on the coking advanced waste treatment system described in the present embodiment is:
(1) coking chemical waste water after the A/O biochemical treatment is with 1200m
3The flooding quantity of/d gets into said micro ware auxiliary catalysis oxidizer unit; Add acid in the coking chemical waste water in said micro ware auxiliary catalysis oxidizer unit and regulate the pH value to 5.0 of said coking chemical waste water; In said coking chemical waste water, add ferrous salt and ydrogen peroxide 50 then and mix, under the effect of microwave field, coking chemical waste water is carried out catalytic oxidation treatment;
The interpolation concentration of ferrous salt described in the present embodiment is with Fe
2+Counting 91.5 mg/L, is 0.3 times of said COD concentration; The interpolation concentration of said ydrogen peroxide 50 is with H
2O
2Counting 646.6 mg/L, is 2.12 times of water COD concentration into, and the residence time of said coking chemical waste water in said microwave field is 60s; The microwave output power of the oxidizer unit of micro ware auxiliary catalysis described in the present embodiment is 20kW.
(2) said mixed reaction pond is sent in the water outlet of said micro ware auxiliary catalysis oxidizer unit, interpolation sodium hydroxide regulator transfers to 6.0 with the pH value of said coking chemical waste water in the coking chemical waste water in said mixed reaction pond; Add anion-polyacrylamide again and carry out flocculation reaction, the coking chemical waste water after the completion flocculation reaction is sent into settling tank precipitate;
The addition of said anion-polyacrylamide is 1mg/L;
The hydraulic detention time of mixed reaction pond described in the present embodiment is 10 minutes;
The hydraulic detention time of said settling tank is 10 hours;
(3) supernatant in the said settling tank is successively sent into the filtration with manganese sand device and accurate filter filters;
The filtrate of the device of filtration with manganese sand described in the present embodiment adopts natural manganese sand, and thickness of filter bed is 700mm; Adopt silica sand as bed course, cushion thickness is 200mm, and said filtration with manganese sand device design filtering velocity is 5m/h;
The waste water that (4) will pass through after accurate filter filters is sent into the frequently pole-reversing electroosmosis device, and the fresh water that behind said frequently pole-reversing electroosmosis device desalination, obtains gets into reuse pool and promptly can be used as the recirculated cooling water moisturizing.
The desalination rate of the device of frequently pole-reversing electroosmosis described in the present embodiment is 80%; The intake pressure of said frequently pole-reversing electroosmosis device is 0.2MPa.
Embodiment 2
Coking advanced waste treatment system described in the present embodiment is identical with embodiment 1.
Treatment process based on the coking advanced waste treatment system described in the present embodiment is:
(1) coking chemical waste water after the A/O biochemical treatment is with 4800m
3The flooding quantity of/d gets into said micro ware auxiliary catalysis oxidizer unit; Add acid in the coking chemical waste water in said micro ware auxiliary catalysis oxidizer unit and regulate the pH value to 5.0 of said coking chemical waste water; In said coking chemical waste water, add ferrous salt and ydrogen peroxide 50 then and mix, under the effect of microwave field, coking chemical waste water is carried out catalytic oxidation treatment;
The interpolation concentration of ferrous salt described in the present embodiment is with Fe
2+Counting 91.5 mg/L, is 0.3 times of said COD concentration; The interpolation concentration of said ydrogen peroxide 50 is with H
2O
2Counting 646.6 mg/L, is 2.12 times of water COD concentration into, and the residence time of said coking chemical waste water in said microwave field is 60s; The microwave output power of the oxidizer unit of micro ware auxiliary catalysis described in the present embodiment is 40kW.
(2) said mixed reaction pond is sent in the water outlet of said micro ware auxiliary catalysis oxidizer unit, interpolation sodium hydroxide regulator transfers to 6.0 with the pH value of said coking chemical waste water in the coking chemical waste water in said mixed reaction pond; Add anion-polyacrylamide again and carry out flocculation reaction, the coking chemical waste water after the completion flocculation reaction is sent into settling tank precipitate; The addition of said anion-polyacrylamide is 1mg/L;
The hydraulic detention time of mixed reaction pond described in the present embodiment is 8 minutes;
The hydraulic detention time of said settling tank is 6 hours;
(3) supernatant in the said settling tank is successively sent into the filtration with manganese sand device and accurate filter filters;
The filtrate of the device of filtration with manganese sand described in the present embodiment adopts natural manganese sand, and thickness of filter bed is 800mm; Silica sand is as bed course, and cushion thickness is 300mm, and the design filtering velocity is 8m/h;
The waste water that (4) will pass through after accurate filter filters is sent into the frequently pole-reversing electroosmosis device, and the fresh water that behind said frequently pole-reversing electroosmosis device desalination, obtains gets into reuse pool and promptly can be used as the recirculated cooling water moisturizing.
The desalination rate of the device of frequently pole-reversing electroosmosis described in the present embodiment is 78%; The intake pressure of said frequently pole-reversing electroosmosis device is 0.3MPa.
Embodiment 3
Coking advanced waste treatment system described in the present embodiment is as shown in Figure 2, comprising:
Mix equalizing tank; Be connected the dosing agitated pool that is provided with said mixing equalizing tank; And the micro ware auxiliary catalysis oxidizer unit that is connected with said dosing agitated pool, said micro ware auxiliary catalysis oxidizer unit carries out catalytic oxidation treatment to the coking chemical waste water after the A/O biochemical treatment;
Be connected the mixed reaction pond that is provided with said micro ware auxiliary catalysis oxidizer unit, and the settling tank that is connected with said mixed reaction pond, being connected with intermediate pool with said settling tank, said intermediate pool is provided with aerator;
The filtration with manganese sand device that is connected with said intermediate pool, and the accurate filter that is connected with said filtration with manganese sand device;
Said coking advanced waste treatment system also comprises the frequently pole-reversing electroosmosis device that is connected with said accurate filter; The device of frequently pole-reversing electroosmosis described in the present embodiment is provided with two-stage; Be respectively: the one-level frequently pole-reversing electroosmosis device that is connected with said accurate filter, the secondary frequently pole-reversing electroosmosis device that is connected with said one-level frequently pole-reversing electroosmosis device.
Treatment process based on the coking advanced waste treatment system described in the present embodiment is:
(1) coking chemical waste water after the A/O biochemical treatment is with 8000m
3The flooding quantity of/d gets into and mixes equalizing tank, and the hydraulic detention time that mixes equalizing tank described in the present embodiment is 6 hours;
(2) waste water that from said mixing equalizing tank, comes out gets into said dosing agitated pool; Add acid in the coking chemical waste water in said dosing agitated pool and regulate the pH value to 3.0 of said coking chemical waste water; In said coking chemical waste water, add ferrous salt and ydrogen peroxide 50 then and stir; Send into said micro ware auxiliary catalysis oxidizer unit again, under the effect of microwave field, coking chemical waste water is carried out catalytic oxidation treatment.
In order to reach catalyzed oxidation effect preferably, the agitated pool of dosing described in the present embodiment is divided into 2 sections usually: add sour adjust pH at the 1st section agitated pool front end, and add ferrous salt simultaneously, hydraulic detention time is 20 minutes; Add ydrogen peroxide 50 at the 2nd section agitated pool front end, hydraulic detention time is 25 minutes; The stirring velocity of the whisking appliance in the agitated pool of dosing described in the present embodiment is 60 rev/mins; As selectable embodiment, said dosing agitated pool also can not segmentation, and said ferrous salt and ydrogen peroxide 50 can add simultaneously;
The interpolation concentration of ferrous salt described in the present embodiment is with Fe
2+Counting 109.8mg/L, is 0.36 times of said COD concentration; The interpolation concentration of said ydrogen peroxide 50 is with H
2O
2Counting 774.7 mg/L, is 2.54 times of water COD concentration into, and the residence time of said coking chemical waste water in said microwave field is 30s; The microwave output power of the oxidizer unit of micro ware auxiliary catalysis described in the present embodiment is 60kW.
(2) said mixed reaction pond is sent in the water outlet of said micro ware auxiliary catalysis oxidizer unit, interpolation sodium hydrogencarbonate regulator transfers to 9.0 with the pH value of said coking chemical waste water in the coking chemical waste water in said mixed reaction pond; Add anion-polyacrylamide again and carry out flocculation reaction, the coking chemical waste water after the completion flocculation reaction is sent into settling tank precipitate;
The addition of said anion-polyacrylamide is 20mg/L;
The hydraulic detention time of mixed reaction pond described in the present embodiment is 7 minutes; Mixed reaction pond described in the present embodiment also is provided with whisking appliance, and the stirring velocity of said whisking appliance is 30 rev/mins;
The hydraulic detention time of said settling tank is 5 hours;
(3) supernatant in the said settling tank is introduced into said intermediate pool, after the aerator in the said intermediate pool carries out aeration to said supernatant, again it is successively sent into said filtration with manganese sand device and accurate filter filters.
The hydraulic detention time of intermediate pool described in the present embodiment is 60 minutes; The GWR of the aeration rate of said aerator is 1;
The filtrate of the device of filtration with manganese sand described in the present embodiment adopts natural manganese sand, and thickness of filter bed is 800mm; Silica sand is as bed course, and cushion thickness is 300mm, and the design filtering velocity of said filtration with manganese sand device is 8m/h;
(4) send into one-level frequently pole-reversing electroosmosis device through the waste water after the accurate filter filtration; The strong brine that behind said one-level frequently pole-reversing electroosmosis device desalination, obtains is sent into said secondary frequently pole-reversing electroosmosis device again and is carried out desalination, and the fresh water that obtains behind said one-level electrodialysis unit and the secondary electrodialysis unit desalination gets into reuse pool and promptly can be used as the recirculated cooling water moisturizing.
The desalination rate of the device of frequently pole-reversing electroosmosis described in the present embodiment is 77%; The intake pressure of said frequently pole-reversing electroosmosis device is 0.3MPa.
Embodiment 4
Coking advanced waste treatment system described in the present embodiment is identical with embodiment 3.
Treatment process based on the coking advanced waste treatment system described in the present embodiment is:
(1) coking chemical waste water after the A/O biochemical treatment is with 13000m
3The flooding quantity of/d gets into and mixes equalizing tank, and the hydraulic detention time that mixes equalizing tank described in the present embodiment is 2 hours;
(2) waste water that from said mixing equalizing tank, comes out gets into said dosing agitated pool; Add acid in the coking chemical waste water in said dosing agitated pool and regulate the pH value to 3.0 of said coking chemical waste water; In said coking chemical waste water, add ferrous salt and ydrogen peroxide 50 then and stir; Send into said micro ware auxiliary catalysis oxidizer unit again, under the effect of microwave field, coking chemical waste water is carried out catalytic oxidation treatment.
The agitated pool of dosing described in the present embodiment is divided into 2 sections usually: add sour adjust pH at the 1st section agitated pool front end, and add ferrous salt simultaneously, hydraulic detention time is 18 minutes; Add ydrogen peroxide 50 at the 2nd section agitated pool front end, hydraulic detention time is 23 minutes; The stirring velocity of the whisking appliance in the agitated pool of dosing described in the present embodiment is 60 rev/mins;
The interpolation concentration of ferrous salt described in the present embodiment is with Fe
2+Counting 109.8mg/L, is 0.36 times of said COD concentration; The interpolation concentration of said ydrogen peroxide 50 is with H
2O
2Counting 774.7 mg/L, is 2.54 times of water COD concentration into, and the residence time of said coking chemical waste water in said microwave field is 30s; The microwave output power of the oxidizer unit of micro ware auxiliary catalysis described in the present embodiment is 120kW.
(2) said mixed reaction pond is sent in the water outlet of said micro ware auxiliary catalysis oxidizer unit, interpolation sodium hydrogencarbonate regulator transfers to 9.0 with the pH value of said coking chemical waste water in the coking chemical waste water in said mixed reaction pond; Add anion-polyacrylamide again and carry out flocculation reaction, the coking chemical waste water after the completion flocculation reaction is sent into settling tank precipitate;
The addition of said anion-polyacrylamide is 20mg/L;
The hydraulic detention time of mixed reaction pond described in the present embodiment is 5 minutes; Mixed reaction pond described in the present embodiment also is provided with whisking appliance, and the stirring velocity of said whisking appliance is 50 rev/mins;
The hydraulic detention time of said settling tank is 2 hours;
(3) supernatant in the said settling tank is introduced into said intermediate pool, after the aerator in the said intermediate pool carries out aeration to said supernatant, again it is successively sent into said filtration with manganese sand device and accurate filter filters.
The hydraulic detention time of intermediate pool described in the present embodiment is 20 minutes; The GWR of the aeration rate of said aerator is 2;
The filtrate of the device of filtration with manganese sand described in the present embodiment adopts natural manganese sand, and thickness of filter bed is 1000mm; Silica sand is as bed course, and cushion thickness is 400mm; The design filtering velocity is 10m/h;
(4) send into one-level frequently pole-reversing electroosmosis device through the waste water after the accurate filter filtration; The strong brine that behind said one-level frequently pole-reversing electroosmosis device desalination, obtains is sent into said secondary frequently pole-reversing electroosmosis device again and is carried out desalination, and the fresh water that obtains behind said one-level electrodialysis unit and the secondary electrodialysis unit desalination gets into reuse pool and promptly can be used as the recirculated cooling water moisturizing.
The desalination rate of the device of frequently pole-reversing electroosmosis described in the present embodiment is 75%; The intake pressure of said frequently pole-reversing electroosmosis device is 0.4MPa.
In the above-described embodiments; The specific configuration of said micro ware auxiliary catalysis oxidizer unit comprises microwave source, microwave reaction chamber, microwave cooling system, pipeline, circuit and robot control system(RCS), and wherein robot control system(RCS) comprises PLC, housing, frequency transformer, COD on-line detector, pH on-line detector, under meter, liquidometer etc.; As selectable embodiment, the configuration of said micro ware auxiliary catalysis oxidizer unit can be carried out different designs according to the needs of practical situation, no longer gives exhaustive at this.In addition, in the above-described embodiments, said accurate filter all adopts 5 μ m filter cores, and as selectable embodiment, said accurate filter also can adopt other filter cores commercially available arbitrarily, that specification is suitable.
In the above-described embodiments, in " adding the pH value that said coking chemical waste water is regulated in acid in the coking chemical waste water in said dosing agitated pool ", said acid can be such as in the acid such as sulfuric acid, hydrochloric acid, nitric acid any one or multiple.The selection of this acid is to well known to a person skilled in the art technology, there is no need to give exhaustive at this again.Equally as selectable embodiment, the pH value regulator described in the foregoing description can be in milk of lime or other commercially available arbitrarily pH value regulator one or more, like lime, yellow soda ash etc.
Said frequently pole-reversing electroosmosis device in the foregoing description is the commercially available prod, and the membrane material of said frequently pole-reversing electroosmosis device is an anti-pollution type ion-exchange composite membranes, and the water recovery of said frequently pole-reversing electroosmosis device is all more than 75%; Said frequently pole-reversing electroosmosis device to the requirement of influent quality is: 5 ~ 40 ℃ of water temperatures, pH value 6 ~ 9, turbidity＜3NTU, COD
Cr＜80mg/L, free chlorine＜0.3mg/L, total iron＜0.3mg/L, manganese＜0.1mg/L, oil＜1mg/L.
Water quality situation before and after handling
In order to further specify the technique effect of coking advanced waste treatment system of the present invention; Below in conjunction with " recirculated cooling water is used the reuse water water quality standard " (HG/T 3923-2007), the water quality situation before and after handling through coking advanced waste treatment system of the present invention is described:
Can find out that from The above results the coking chemical waste water after coking advanced waste treatment system of the present invention is handled meets the requirement of " recirculated cooling water is used the reuse water water quality standard " fully.
Obviously, the foregoing description only be for explanation clearly done for example, and be not qualification to embodiment.For the those of ordinary skill in affiliated field, on the basis of above-mentioned explanation, can also make other multi-form variation or change.Here need not also can't give to all embodiments exhaustive, and the conspicuous variation of being extended out thus or the change still be among the protection domain of the invention.
Claims (9)
1. coking advanced waste treatment system comprises:
The micro ware auxiliary catalysis oxidizer unit, said micro ware auxiliary catalysis oxidizer unit carries out catalytic oxidation treatment to the coking chemical waste water after the A/O biochemical treatment;
Be connected mixed reaction pond that is provided with and the settling tank that is connected with said mixed reaction pond with said micro ware auxiliary catalysis oxidizer unit;
The filtration with manganese sand device that is connected with said settling tank, and the accurate filter that is connected with said filtration with manganese sand device;
Said coking advanced waste treatment system also comprises the frequently pole-reversing electroosmosis device that is connected with said accurate filter.
2. coking advanced waste treatment system according to claim 1; It is characterized in that; Said coking advanced waste treatment system also comprises the dosing agitated pool, and said dosing agitated pool is arranged on before the said micro ware auxiliary catalysis oxidizer unit, is connected with said micro ware auxiliary catalysis oxidizer unit.
3. coking advanced waste treatment system according to claim 2 is characterized in that, said coking advanced waste treatment system also comprises the mixing equalizing tank that is connected with said dosing agitated pool, and said mixing equalizing tank is arranged on before the said dosing agitated pool;
Between said settling tank and said filtration with manganese sand device, connect the intermediate pool that is provided with, said intermediate pool is provided with aerator.
4. according to claim 1 or 2 or 3 described coking advanced waste treatment systems, it is characterized in that said frequently pole-reversing electroosmosis device is provided with two-stage, is respectively:
The one-level frequently pole-reversing electroosmosis device that is connected with said accurate filter;
The secondary frequently pole-reversing electroosmosis device that is connected with said one-level frequently pole-reversing electroosmosis device.
5. treatment process based on the described coking advanced waste treatment system of claim 1 comprises:
(1) coking chemical waste water after the A/O biochemical treatment; Get into the micro ware auxiliary catalysis oxidizer unit; Adding acid in the coking chemical waste water in said micro ware auxiliary catalysis oxidizer unit regulates below the pH value to 6.0 of said coking chemical waste water; In said coking chemical waste water, add ferrous salt and ydrogen peroxide 50 then and stir, under the effect of microwave field, coking chemical waste water is carried out catalytic oxidation treatment;
The interpolation concentration of said ferrous salt is with Fe
2+The 0.3-0.36 that counts water COD concentration into doubly, the interpolation concentration of said ydrogen peroxide 50 is with H
2O
2The 2.12-2.54 that counts water COD concentration into doubly, the residence time of said coking chemical waste water in said microwave field is 30-60s, the microwave output power of said micro ware auxiliary catalysis oxidizer unit is 20-120kW;
(2) water outlet of said micro ware auxiliary catalysis oxidizer unit gets into said mixed reaction pond, and interpolation pH value regulator transfers to 6.0-9.0 with the pH value of said coking chemical waste water in the coking chemical waste water in said mixed reaction pond; Add coagulant aids again and carry out flocculation reaction, the coking chemical waste water after the completion flocculation reaction is sent into settling tank precipitate;
Said coagulant aids is an anion-polyacrylamide, and the addition of said coagulant aids is 1-20mg/L;
(3) supernatant in the said settling tank is successively sent into the filtration with manganese sand device and accurate filter filters;
The waste water that (4) will pass through after accurate filter filters is sent into the frequently pole-reversing electroosmosis device, and the fresh water that behind said frequently pole-reversing electroosmosis device desalination, obtains promptly can be used as the recirculated cooling water moisturizing.
6. advanced treatment process of coking waste water according to claim 5 is characterized in that, said pH value regulator is one or more in sodium hydroxide, sodium hydrogencarbonate, the milk of lime.
7. advanced treatment process of coking waste water according to claim 6; It is characterized in that; In the said step (1), the coking chemical waste water after the A/O biochemical treatment gets into the dosing agitated pool; Adding acid in the coking chemical waste water in said dosing agitated pool regulates below the pH value to 6.0 of said coking chemical waste water; In said coking chemical waste water, add ferrous salt and ydrogen peroxide 50 then and stir, send into said micro ware auxiliary catalysis oxidizer unit again, under the effect of microwave field, coking chemical waste water is carried out catalytic oxidation treatment.
8. advanced treatment process of coking waste water according to claim 7 is characterized in that, in the step (1), the coking chemical waste water after the A/O biochemical treatment imports earlier and mixes equalizing tank, again the coking chemical waste water in the said mixing equalizing tank is sent into said dosing agitated pool;
In the said step (3), the supernatant in the said settling tank is introduced into intermediate pool, after the aerator in the said intermediate pool carries out aeration to said supernatant, again it is successively sent into said filtration with manganese sand device and accurate filter filters.
9. advanced treatment process of coking waste water according to claim 6; It is characterized in that; In the step (4); Waste water through after the accurate filter filtration is sent into one-level frequently pole-reversing electroosmosis device, and the strong brine that behind said one-level frequently pole-reversing electroosmosis device desalination, obtains is sent into secondary frequently pole-reversing electroosmosis device again and carried out desalination, and the fresh water that behind said one-level electrodialysis unit and secondary electrodialysis unit desalination, obtains promptly can be used as the recirculated cooling water moisturizing.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11855324B1 (en) | 2022-11-15 | 2023-12-26 | Rahul S. Nana | Reverse electrodialysis or pressure-retarded osmosis cell with heat pump |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086549B (en) * | 2011-11-01 | 2014-11-05 | 中国石油化工股份有限公司 | Wastewater deep processing method |
| CN102659269A (en) * | 2012-04-19 | 2012-09-12 | 北京美通科技发展有限公司 | Efficient and stable coking wastewater advanced treatment process and treatment system |
| CN103787532A (en) * | 2012-11-02 | 2014-05-14 | 通用电气公司 | System and method for reducing fluid chemical oxygen demand |
| CN103332812A (en) * | 2013-07-23 | 2013-10-02 | 中国海洋石油总公司 | Method for refining circulating cooling sewage water and reusing water by electroosmosis desalination treatment |
| CN104556313A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Method for desalinizing oil-field wastewater with electrodialysis method |
| CN104030523B (en) * | 2014-05-30 | 2015-09-23 | 石家庄开发区德赛化工有限公司 | A kind of deep treatment method of coking chemical waste water |
| CN104478045B (en) * | 2014-12-11 | 2016-10-05 | 中国科学院过程工程研究所 | A kind of efficient electric Dialytic desalination apparatus for coking chemical waste water and method |
| CN105884093A (en) * | 2016-06-15 | 2016-08-24 | 杭州蓝然环境技术有限公司 | High-alkalinity PTA reclaimed water reuse process |
| US11502322B1 (en) | 2022-05-09 | 2022-11-15 | Rahul S Nana | Reverse electrodialysis cell with heat pump |
| US11502323B1 (en) | 2022-05-09 | 2022-11-15 | Rahul S Nana | Reverse electrodialysis cell and methods of use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001092607A1 (en) * | 2000-05-25 | 2001-12-06 | Mykrolis Corporation | Regeneration of plating baths |
| CN101037244A (en) * | 2007-04-23 | 2007-09-19 | 北京市百村环保科技开发有限公司 | Treatment method of high-concentration ammonia nitrogenous wastewater and double-phase isolation film and preparation method thereof |
| CN101955282A (en) * | 2010-10-18 | 2011-01-26 | 江苏省环境科学研究院 | Method for realizing zero emission of dyeing wastewater with high salinity in printing and dyeing enterprises |
| CN202016923U (en) * | 2011-03-29 | 2011-10-26 | 北京惟泰安全设备有限公司 | Coking wastewater advanced treatment system |
-
2011
- 2011-03-29 CN CN2011100766924A patent/CN102120663B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001092607A1 (en) * | 2000-05-25 | 2001-12-06 | Mykrolis Corporation | Regeneration of plating baths |
| CN101037244A (en) * | 2007-04-23 | 2007-09-19 | 北京市百村环保科技开发有限公司 | Treatment method of high-concentration ammonia nitrogenous wastewater and double-phase isolation film and preparation method thereof |
| CN101955282A (en) * | 2010-10-18 | 2011-01-26 | 江苏省环境科学研究院 | Method for realizing zero emission of dyeing wastewater with high salinity in printing and dyeing enterprises |
| CN202016923U (en) * | 2011-03-29 | 2011-10-26 | 北京惟泰安全设备有限公司 | Coking wastewater advanced treatment system |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11855324B1 (en) | 2022-11-15 | 2023-12-26 | Rahul S. Nana | Reverse electrodialysis or pressure-retarded osmosis cell with heat pump |
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