CN102701496A - Method and process for treating high-concentration organic wastewater difficult to degrade - Google Patents
Method and process for treating high-concentration organic wastewater difficult to degrade Download PDFInfo
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Abstract
The invention relates to a method and a process for treating high-concentration organic wastewater difficult to degrade. The method and the process sequentially comprises the steps of regulating homogenization, coagulating sedimentation, pulse electrolytic oxidation, centrifugal separation, three-dimensional electrode-electric Fenton oxidation, flocculating sedimentation, ozone oxidation and filtration treatment, and realize stable and standard (in COD<Cr> and chromaticity) treatment of the high-concentration organic wastewater difficult to degrade. Ozone tail gas is led in a pulse electrolytic oxidation tank to enhance the electrolytic oxidation treatment effect, so as to realize the comprehensive utilization of the ozone tail gas; and sludge produced by a system is dehydrated through a press filter, a filter liquor enters a regulating homogenization tank, and a filter cake is dried for brick manufacture or is subjected to solidification treatment. Impulse current and electrolytic oxidation are combined so as to greatly improve the electrolysis efficiency and reduce concentration polarization and power consumption; the coupling of a three dimensional electrode and an electric Fenton method enlarges the surface area of a working electrode, improves the mass transfer effect and greatly improves the current efficiency and the unit space time yield, and no secondary pollution is caused; and the ozone oxidation treatment ensures the stability of the effluent quality.
Description
One, technical field
The present invention relates to a kind of method and technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby, belong to the treatment of Organic Wastewater field.
Two, background technology
High concentration hard-degraded organic waste water mainly is the waste water that produces in the industry production processes such as petrochemical complex, coking, printing and dyeing, papermaking, pharmacy, and the water quality and quantity fluctuation of waste water is big, composition is complicated, COD
CrConcentration is high, saltiness is high, the poisonous and harmful hard-degraded substance is many, the pH value changes greatly, biodegradability is poor, and part waste water nitrogen and phosphorus content is high.According to Chinese environmental situation in 2011, Chinese COD year total emission volumn be 1238.1 ten thousand tons.The high COD of waste water
CrBrought baptism for the biochemical treatment of high concentration hard-degraded organic waste water with low biodegradability; The poisonous and harmful hard-degraded substance that in addition exists in the waste water; Like heavy metal substances such as polycyclic aromatic hydrocarbons, halohydrocarbon, heterocyclic compound, organic phenolic compound, organophosphorus pesticide, tensio-active agent, organic dye and arsenic, mercury; This pollutant is very difficult effectively to be handled, and is prone to enrichment in vivo, also becomes the potential pollution source of water body easily.
Because the high concentrated organic wastewater intractability is big, initial cost is high, working cost is high; And effective and more sophisticated treatment technology is difficult to seek; A lot of industrial and mining enterprises do not take effective treatment measures; But a large amount of untreated high-concentration hardly-degradable organic pollutants are directly entered water body environment, this certainly will cause greatly water ecological environment influence, even possibly threaten human health.Simultaneously; Technology Standards Division of national environmental protection portion constantly reformulates and revises the industry wastewater discharge standard; Emission standard is also more and more stricter, makes the processing of high concentration hard-degraded organic waste water also therefore become a present stage difficult problem needing to be resolved hurrily of water-treatment technology field.
The main method of treatment of high concentration organic wastewater with difficult degradation thereby has solvent extration, absorption method, wet oxidation process, catalytic wet air oxidation, supercritical water oxidation method, chemical oxidization method, biochemical treatment process and burning method etc. at present.These treatment processs more or less have certain limitation, and are saturated easily like the sorbent material of absorption method, and the regeneration of sorbent material or replacing bother, expense is higher, cause secondary pollution easily; High temperature resistant, the high pressure, corrosion-resistant of equipment and materials palpus of wet oxidation, and one-time investment is high; The catalyzer of catalytic wet air oxidation is prone to inactivation and stripping brings secondary pollution; Supercritical water oxidation method needs under the operational condition of HTHP, to carry out, and is strict to equipment material; The biological treatment floor space is big, complex management, and is low to colourity and COD clearance, and under the environmental requirement of increasingly stringent, single biochemical process is handled the requirement that also is difficult to satisfy printing and dyeing wastewater to reach standard discharging and reuse; The matched restriction of boiler of the water yield that burning method is handled waste water, processing cost is higher relatively.Therefore; Water quality to high concentrated organic wastewater removes to select proper treatment process with the pollution characteristic; Carry out the optimum combination of technology according to the advantage of each water technology; Could realize efficient, the economic treatment of high concentrated organic wastewater, the resource utilization of realization waste water and innoxious, thus obtain bigger economic benefit, environmental benefit and social benefit.
Coagulant sedimentation be point to add in the waste water certain or certain type can play in the coagulating agent of colloidal grain surface electric charge; And compression double electric layer, electrically neutralization, net catch build bridge and effect such as absorption winding under; Make colloidal solid take off steady and polymerization each other; Generate bigger flco and be precipitated out, thus the purpose of realization mud-water separation.Coagulant sedimentation can effectively reduce turbidity, the colourity of waste water and remove part dissolved organic matter and inorganics.Coagulating agent at present commonly used mainly contains inorganic coagulant (like traditional molysite, aluminum salt, inorganic polymer coagulant), organic coagulating agent (comprise natural with two kinds of synthetic) and compound coagulant (mainly being microbial flocculant) three major types.Discover preferred and the composite highly effective coagulation of realizing high concentration hard-degraded organic waste water of coagulating agent.
The pulse electrolysis oxidation style is that electrolytic oxidation groove and the pulse power are connected to form electrolysis system and the electrolytic acid cleaning oxydation process that carries out; It with electronics as reagent; Electric field energy is a reaction power; Generally need not add chemical reagent, can avoid too much secondary pollution, also have effects such as air supporting, flocculation, oxidation and sterilization and disinfection simultaneously concurrently.The electrode reaction of pulse electrolysis oxidation is the same with the direct current solution, makes organic pollutant that Direct Electrochemistry reaction take place on electrode or utilizes electrode surface to produce strong active oxide material (like hydroxyl radical free radical, hypochlorite, H
2O
2, O
3, oxidation state metal ion and ClO
2, O
2With O etc.) with the reaction of pollutent generation indirect electrolytic oxidation, with those macromole hardly degraded organic substances in the waste water be broken into small organic molecule or thoroughly mineralising be water and carbonic acid gas.In addition, because pulse electrolysis is one and constantly repeats the electrolytic process of " power supply-outage-power supply ", make electrolytic efficiency obtain raising significantly.The conduction time of pulse electrolysis oxidation, the reaction on the electrode helped diffusion off and on, reduces concentration polarization, thereby has reduced power consumption less than the electrolysis total reaction time.
Three-diemsnional electrode-Fenton method is a kind of emerging advanced oxidation water technology that three-diemsnional electrode method and Fenton method are coupled.Wherein three-diemsnional electrode is granular or other clastic materials of filling between the traditional two-dimensional electrode; And under the galvanic action that main electrode is supplied with, make the working electrode material surface charging of filling; Become new electrode (being third electrode); It has overcome the shortcoming that two-dimensional flat plate electrode mass transfer effect is poor, current efficiency is low, energy consumption is high, has increased the long-pending electrode surface area of unit cell body, and need not to add a large amount of ionogen and reduced processing cost; And the Fenton method mainly is to utilize the carbon cathode in-situ hydrogen peroxide, is adding under the situation of ferrous ion, generates hydroxyl radical free radical and oxidative degradation takes place.Through in Fenton system, introducing effective coupling that granule electrode can be realized three-diemsnional electrode method and Fenton method; It has the advantage of three-diemsnional electrode and Fenton method concurrently; Can fully utilize the indirect oxidation effect of anodic direct oxidation effect, anode generation hydroxyl radical free radical and the indirect oxidation effect that negative electrode produces hydrogen peroxide; Not only increase the surface-area of working electrode and improved mass transfer effect, also greatly improved current efficiency and unit space-time yield, and non-secondary pollution.In recent years, Chinese scholars adopt three-diemsnional electrode-Fenton method at waste water from dyestuff, wash aspects such as glue waste water, CTMP waste water, percolate, phenolic waste water and obtained the good treatment effect.
The ozone oxidation method is a kind of of water treatment high-level oxidation technology.Ozone is the strongest a kind of oxygenant of oxidation capacity in the water treatment, and ozone can decompose very strong hydroxyl radical free radical (OH), the superoxide ion (O of generation oxidation capacity in the aqueous solution
2-), antozone (O) etc.; Especially the OH that produces; It has very strong chemically reactive and oxidation capacity, and OH can react with multiple inorganic and organism in the waste water or functional group, with the hardly degraded organic substance matter Degradation and Transformation in the waste water become small molecules be prone to degradation material or thoroughly mineralising become CO
2And H
2O can effectively realize decolouring, the biodegradability of deodorizing, sterilization and disinfection, oxidation of organic compounds, raising waste water and improve purpose such as flocculating settling effect, and the ozone in the processed waste water is prone to decompose, and does not produce secondary pollution.
Three, summary of the invention
The objective of the invention is to propose a kind of method and technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby, it has overcome the problem that background technology exists, effluent quality (COD after treatment
CrAnd colourity) can reach national sewage comprehensive discharge primary standard.
The objective of the invention is to realize through following technical scheme:
A kind of method and technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby that the present invention proposes is characterized in that: comprise the following steps:
⑴ regulate homogenizing and handle: the adjusting and the homogenizing of organic waste water being carried out water quality, the water yield;
⑵ coagulating sedimentation is handled: the waste water after step ⑴ is handled carries out coagulating sedimentation to be handled, and adds efficient composite coagulant, basifier and coagulant aids successively, and reaction pH is 8～10, and the coagulation churning time is 10～20 minutes, and the ST is more than 30 minutes;
⑶ pulse electrolysis oxide treatment: the waste water after the step ⑵ processing is carried out the pulse electrolysis oxide treatment, and current/voltage is 5～20 V, and current density is 30～60 mA/cm
2, pulse-repetition is 5 000～12 000 Hz, and reaction pH is 7～11, and the reaction times is 30～60 minutes;
⑷ spinning is handled: the waste water after step ⑶ is handled carries out spinning to be handled, and use vitriol oil adjusting wastewater pH is 3～5;
⑸ three-diemsnional electrode-Fenton oxide treatment: the waste water after the step ⑷ processing is carried out three-diemsnional electrode-Fenton oxide treatment, and add ferrous sulfate, consumption is 0.5～3.0 mg/L, and current/voltage is 10～20 V, and current density is 30～60 mA/cm
2, oxidizing reaction pH is 3～5, the reaction times is 10～60 minutes;
⑹ flocculation sediment is handled: the waste water after step ⑸ is handled carries out flocculation sediment to be handled, and under agitation condition, adds basifier and flocculation agent successively, and the adjustment wastewater pH is 8～10, and flocculation time is 0.5～2 minute, and the ST is more than 30 minutes;
⑺ ozone Oxidation Treatment: if detect step ⑹ treat effluent COD
CrWhen 150～330 mg/L are above, waste water is carried out ozone Oxidation Treatment; Otherwise step ⑹ treat effluent is directly carried out step ⑻ filtration treatment; Concentration of ozone gas is 70～90 mg/L in the ozone Oxidation Treatment; Ozone gas flow is 6～9 L/h, and using basifier conditioned reaction pH is 11～11.5, and the reaction times is 30～80 minutes;
⑻ filter process: the waste water after step ⑺ handles discharges or reuse after the strainer filtration treatment;
⑼ the mud that system produces is through the pressure filter dehydration, and filtrating entering is regulated balancing reservoir, filter cake mummification brickmaking.
Described efficient composite coagulant is one or more the mixture in rapid precipitation agent flyash or gac or powdery slag and coagulating agent ferrous sulfate, bodied ferric sulfate, the Poly aluminum Chloride (PAC); The mass ratio of rapid precipitation agent and coagulating agent is (0.05～0.15): 1, and total consumption is 3～30 g/L.
Described basifier is a kind of in unslaked lime, white lime, sodium hydroxide, Youxiaolin and the Losantin.
Described coagulant aids is SEPIGEL 305 or active silicic acid or partially hydrolyzed polyacrylamide, and consumption is 50～120 mg/L.
Described pulse electrolysis oxide treatment, adopting iron plate or stainless steel plate is the anodic-cathodic plate, interpole gap is 1.5～3.0 cm.
Described three-diemsnional electrode-Fenton oxide treatment, adopting solubility iron plate is the positive electricity pole plate, and stainless steel plate is the negative electricity pole plate, and interpole gap is 1.5～3.0 cm, and the granule electrode material is a columnar activated carbon, aeration intensity is 600～800 L/h.
The dosing method of described ferrous sulfate is continuous dosing method.
Described flocculation agent is SEPIGEL 305 or polymer NSG, and consumption is 30～80 mg/L.
Ozone tail gas in the described ozone Oxidation Treatment gets into the pulse electrolysis oxidation trough, in order to strengthen the treatment effect of pulse electrolysis oxidation to waste water, realizes the comprehensive utilization of ozone tail gas.
The present invention has following beneficial effect:
⑴ the present invention is directed to the actual water quality situation of high concentration hard-degraded organic waste water, implemented above-mentioned treatment step successively, waste water after treatment, water outlet COD
CrAll reached national sewage comprehensive discharge primary standard with colourity.
⑵ a kind of method and technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby that the present invention proposes is particularly useful for well-drilling waste water, gathers and drive oil extraction waste water, fld and shale gas field pressure break and return high-concentration hardly-degradable waste waters such as effluent, coking chemical waste water and handle project.
⑶ a kind of method and technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby that the present invention proposes can ensure the water outlet standard discharge or satisfy the reuse requirement.This treatment process capacity of resisting impact load is strong, processing efficiency is high, mass transfer effect good, system stability is high, power consumption is low and non-secondary pollution.
Above-mentioned treatment process also can be according to actual water quality situation, expense and the time of high concentration hard-degraded organic waste water; After coagulating sedimentation is handled; Do not carry out pulse electrolysis oxide treatment and spinning and handle, just directly carry out three-diemsnional electrode-Fenton oxide treatment, flocculation sediment processing and ozone Oxidation Treatment successively, or do not carry out three-diemsnional electrode-Fenton oxide treatment and flocculation sediment processing; Just directly carry out ozone Oxidation Treatment; Such treating processes as long as suitably increase the three-diemsnional electrode-time of Fenton oxide treatment or the time of ozone Oxidation Treatment, also can realize (the COD up to standard of high concentration hard-degraded organic waste water
CrAnd colourity) discharging.For example, for well-drilling waste water, after coagulating sedimentation is handled; Carry out three-diemsnional electrode-Fenton oxide treatment, flocculation sediment processing and ozone Oxidation Treatment more successively, concentration of ozone gas is 85 mg/L, and ozone gas flow is 9 L/h; Reaction pH is 11, and oxidization time is 80 minutes, water outlet COD
CrAll can reach national sewage comprehensive discharge primary standard with colourity; If after the shale gas pressure break returned effluent and carry out spinning and handle; With regard to directly carrying out ozone Oxidation Treatment, be 90 mg/L in concentration of ozone gas, ozone gas flow is that 9 L/h are under 11.5 conditions with reaction pH; Only need oxidization time to be increased to 100 minutes, water outlet COD
CrAlso can reach national sewage comprehensive discharge primary standard with colourity.
Four, description of drawings
Fig. 1 is a kind of process flow sheet that is used for the method and the technology of treatment of high concentration organic wastewater with difficult degradation thereby.
Five, embodiment
A kind of method and technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby that the present invention proposes is characterized in that: comprise the following steps:
⑴ regulate homogenizing and handle: the adjusting and the homogenizing of organic waste water being carried out water quality, the water yield;
⑵ coagulating sedimentation is handled: the waste water after step ⑴ is handled carries out coagulating sedimentation to be handled, and adds efficient composite coagulant, basifier and coagulant aids successively, and reaction pH is 8～10, and the coagulation churning time is 10～20 minutes, and the ST is more than 30 minutes;
⑶ pulse electrolysis oxide treatment: the waste water after the step ⑵ processing is carried out the pulse electrolysis oxide treatment, and current/voltage is 5～20 V, and current density is 30～60 mA/cm
2, pulse-repetition is 5 000～12 000 Hz, and reaction pH is 7～11, and the reaction times is 30～60 minutes;
⑷ spinning is handled: the waste water after step ⑶ is handled carries out spinning to be handled, and use vitriol oil adjusting wastewater pH is 3～5;
⑸ three-diemsnional electrode-Fenton oxide treatment: the waste water after the step ⑷ processing is carried out three-diemsnional electrode-Fenton oxide treatment, and add ferrous sulfate, consumption is 0.5～3.0 mg/L, and current/voltage is 10～20 V, and current density is 30～60 mA/cm
2, oxidizing reaction pH is 3～5, the reaction times is 10～60 minutes;
⑹ flocculation sediment is handled: the waste water after step ⑸ is handled carries out flocculation sediment to be handled, and under agitation condition, adds basifier and flocculation agent successively, and the adjustment wastewater pH is 8～10, and flocculation time is 0.5～2 minute, and the ST is more than 30 minutes;
⑺ ozone Oxidation Treatment: if detect step ⑹ treat effluent COD
CrWhen 150～330 mg/L are above, waste water is carried out ozone Oxidation Treatment; Otherwise step ⑹ treat effluent is directly carried out step ⑻ filtration treatment; Concentration of ozone gas is 70～90 mg/L in the ozone Oxidation Treatment; Ozone gas flow is 6～9 L/h, and using basifier conditioned reaction pH is 11～11.5, and the reaction times is 30～80 minutes;
⑻ filter process: the waste water after step ⑺ handles discharges or reuse after the strainer filtration treatment;
⑼ the mud that system produces is through the pressure filter dehydration, and filtrating entering is regulated balancing reservoir, filter cake mummification brickmaking.
Described efficient composite coagulant is one or more the mixture in rapid precipitation agent flyash or gac or powdery slag and coagulating agent ferrous sulfate, bodied ferric sulfate, the Poly aluminum Chloride (PAC); The mass ratio of rapid precipitation agent and coagulating agent is (0.05～0.15): 1, and total consumption is 3～30 g/L.
Described basifier is a kind of in unslaked lime, white lime, sodium hydroxide, Youxiaolin and the Losantin.
Described coagulant aids is SEPIGEL 305 or active silicic acid or partially hydrolyzed polyacrylamide, and consumption is 50～120 mg/L.
Described pulse electrolysis oxide treatment, adopting iron plate or stainless steel plate is the anodic-cathodic plate, interpole gap is 1.5～3.0 cm.
Described three-diemsnional electrode-Fenton oxide treatment, adopting solubility iron plate is the positive electricity pole plate, and stainless steel plate is the negative electricity pole plate, and interpole gap is 1.5～3.0 cm, and the granule electrode material is a columnar activated carbon, aeration intensity is 600～800 L/h.
The dosing method of described ferrous sulfate is continuous dosing method.
Described flocculation agent is SEPIGEL 305 or polymer NSG, and consumption is 30～80 mg/L.
Ozone tail gas in the described ozone Oxidation Treatment gets into the pulse electrolysis oxidation trough, in order to strengthen the treatment effect of pulse electrolysis oxidation to waste water, realizes the comprehensive utilization of ozone tail gas.
Below come further explain the present invention through specific embodiment, but the present invention is not limited to these embodiment.
Embodiment 1:The well-drilling waste water that the PetroChina Company Limited. oil field produces is introduced the adjusting balancing reservoir, carry out the water quality and quantity homogenizing; Under agitation condition, add the mixture (mass ratio is 0.08:1) of efficient composite coagulant gac and Poly aluminum Chloride (PAC) in the waste water after regulating homogenizing, consumption is 15 g/L; Using calcium hydroxide to regulate wastewater pH simultaneously is 9.5, stirred 20 minutes, after add the coagulant aids SEPIGEL 305 again; Consumption is 80 mg/L; Stir fast again, treat to stop after a large amount of alumen ustum form to stir, staticly settle more than 30 minutes; Waste water after the coagulating treatment is carried out the pulse electrolysis oxide treatment, and adopting iron plate is the anode and cathode battery lead plate, and interpole gap is 2.0 cm, and current/voltage is 12 V, and current density is 50 mA/cm
2, pulse-repetition is 8 000 Hz, and reaction pH is 10, and the reaction times is 60 minutes; Waste water after the pulse electrolysis oxide treatment is carried out spinning handle, and use vitriol oil adjusting wastewater pH is 3.6; Waste water after the spinning processing is carried out three-diemsnional electrode-Fenton oxide treatment; Adopting solubility iron plate is the positive electricity pole plate, and stainless steel plate is the negative electricity pole plate, and interpole gap is 2.0 cm; The granule electrode material is a granular carbon; The ferrous sulfate dosage is 2.0 mg/L, and current/voltage is 12 V, and current density is 45 mA/cm
2, aeration intensity is 600 L/h, and reaction pH is 3.6, and the reaction times is 50 minutes; Waste water after three-diemsnional electrode-Fenton oxide treatment is carried out flocculation sediment to be handled; Under agitation condition, add basifier and flocculation agent successively, using sodium hydroxide to regulate wastewater pH is 9, and the consumption of flocculation agent SEPIGEL 305 is 45 mg/L; Flocculation time is 8 minutes, staticly settles more than 30 minutes; Detect flocculation sediment treat effluent COD
CrMore than 150～330 mg/L, therefore the flocculation sediment treat effluent is carried out ozone Oxidation Treatment, concentration of ozone gas is 80 mg/L, and ozone gas flow is 6 L/h, and using calcium hydroxide conditioned reaction pH is 11.5, and reaction is 40 minutes, water outlet COD
Cr＜100 mg/L, colourity is 0 times, has all reached national sewage comprehensive discharge primary standard; Discharge or reuse after the strainer filtration treatment through the waste water after the ozone Oxidation Treatment.Ozone tail gas gets into the pulse electrolysis oxidation trough, in order to strengthen the treatment effect of pulse electrolysis oxidation to waste water.The mud that system produces is through the pressure filter dehydration, and filtrating entering is regulated balancing reservoir, filter cake mummification brickmaking or solidification treatment.
Embodiment 2:The well-drilling waste water that the PetroChina Company Limited. oil field produces is introduced the adjusting balancing reservoir, carry out the water quality and quantity homogenizing; Under agitation condition, add the mixture (mass ratio is 0.1:1) of efficient composite coagulant gac and ferrous sulfate in the waste water after regulating homogenizing, consumption is 20 g/L; Using calcium hydroxide to regulate wastewater pH simultaneously is 9.8, stirred 20 minutes, after add the coagulant aids SEPIGEL 305 again; Consumption is 100 mg/L; Stir fast again, treat to stop after a large amount of alumen ustum form to stir, staticly settle more than 30 minutes; Waste water after the coagulating treatment is carried out the pulse electrolysis oxide treatment, and adopting iron plate is the anode and cathode battery lead plate, and interpole gap is 2.0 cm, and current/voltage is 12 V, and current density is 45 mA/cm
2, pulse-repetition is 12 000 Hz, and reaction pH is 9.8, and the reaction times is 50 minutes; Waste water after the pulse electrolysis oxide treatment is carried out spinning handle, and use vitriol oil adjusting wastewater pH is 3.2; Waste water after the spinning processing is carried out three-diemsnional electrode-Fenton oxide treatment; Adopting solubility iron plate is the positive electricity pole plate, and stainless steel plate is the negative electricity pole plate, and interpole gap is 2.0 cm; The granule electrode material is a granular carbon; The ferrous sulfate dosage is 2.0 mg/L, and current/voltage is 15 V, and current density is 55 mA/cm
2, aeration intensity is 800 L/h, and reaction pH is 3.2, and the reaction times is 55 minutes; Waste water after three-diemsnional electrode-Fenton oxide treatment is carried out flocculation sediment to be handled; Under agitation condition, add basifier and flocculation agent successively; Using calcium hydroxide to regulate wastewater pH is 9; The consumption of flocculation agent SEPIGEL 305 is 40 mg/L, and flocculation time is 10 minutes, staticly settles more than 30 minutes; Detect flocculation sediment treat effluent COD
CrBelow 100 mg/L, colourity has all reached national sewage comprehensive discharge primary standard below 50 times, therefore need not carry out ozone Oxidation Treatment to the flocculation sediment treat effluent, and the flocculation sediment treat effluent is directly discharging or reuse after the strainer filtration treatment.The mud that system produces is through the pressure filter dehydration, and filtrating entering is regulated balancing reservoir, filter cake mummification brickmaking or solidification treatment.
Embodiment 3:Gathering of PetroChina Company Limited.'s oil field generation driven oil extraction waste water introduce the adjusting balancing reservoir, carry out the water quality and quantity homogenizing; Under agitation condition, add the mixture (mass ratio is 0.1:1) of efficient composite coagulant gac and Poly aluminum Chloride (PAC) in the waste water after regulating homogenizing, consumption is 25 g/L; Using calcium hydroxide to regulate wastewater pH simultaneously is 10, stirred 20 minutes, after add the coagulant aids SEPIGEL 305 again; Consumption is 100 mg/L; Stir fast again, treat to stop after a large amount of alumen ustum form to stir, staticly settle more than 30 minutes; Waste water after the coagulating treatment is carried out the pulse electrolysis oxide treatment, and adopting iron plate is the anode and cathode battery lead plate, and interpole gap is 2.0 cm, and current/voltage is 15 V, and current density is 60 mA/cm
2, pulse-repetition is 12 000 Hz, and reaction pH is 10, and the reaction times is 60 minutes; Waste water after the pulse electrolysis oxide treatment is carried out spinning handle, and use vitriol oil adjusting wastewater pH is 3.5; Waste water after the spinning processing is carried out three-diemsnional electrode-Fenton oxide treatment; Adopting solubility iron plate is the positive electricity pole plate, and stainless steel plate is the negative electricity pole plate, and interpole gap is 2.0 cm; The granule electrode material is a granular carbon; The ferrous sulfate dosage is 3.0 mg/L, and current/voltage is 12 V, and current density is 50 mA/cm
2, aeration intensity is 800 L/h, and reaction pH is 3.5, and the reaction times is 60 minutes; Waste water after three-diemsnional electrode-Fenton oxide treatment is carried out flocculation sediment to be handled; Under agitation condition, add basifier and flocculation agent successively; Using calcium hydroxide to regulate wastewater pH is 10; The consumption of flocculation agent SEPIGEL 305 is 60 mg/L, and flocculation time is 12 minutes, staticly settles more than 30 minutes; Detect flocculation sediment treat effluent COD
CrMore than 100～330 mg/L, therefore the flocculation sediment treat effluent is carried out ozone Oxidation Treatment, concentration of ozone gas is 90 mg/L, and ozone gas flow is 8 L/h, and using calcium hydroxide conditioned reaction pH is 11.3, and reaction is 40 minutes, water outlet COD
Cr＜100 mg/L, colourity is 0 times, has all reached national sewage comprehensive discharge primary standard; Discharge or reuse after the strainer filtration treatment through the waste water after the ozone Oxidation Treatment.Ozone tail gas gets into the pulse electrolysis oxidation trough, in order to strengthen the treatment effect of pulse electrolysis oxidation to waste water.The mud that system produces is through the pressure filter dehydration, and filtrating entering is regulated balancing reservoir, filter cake mummification brickmaking or solidification treatment.
Embodiment 4:The pressure break that the PetroChina Company Limited. oil field produces is returned effluent introducing adjusting balancing reservoir, carry out the water quality and quantity homogenizing; Under agitation condition, add the mixture (mass ratio is 0.09:1) of efficient composite coagulant gac and ferrous sulfate in the waste water after regulating homogenizing, consumption is 20 g/L; Using calcium hydroxide to regulate wastewater pH simultaneously is 10.5, stirred 20 minutes, after add the coagulant aids SEPIGEL 305 again; Consumption is 70 mg/L; Stir fast again, treat to stop after a large amount of alumen ustum form to stir, staticly settle more than 30 minutes; Waste water after the coagulating treatment is carried out the pulse electrolysis oxide treatment, and adopting iron plate is the anode and cathode battery lead plate, and interpole gap is 2.0 cm, and current/voltage is 15 V, and current density is 45 mA/cm
2, pulse-repetition is 11 000 Hz, and reaction pH is 10.5, and the reaction times is 40 minutes; Waste water after the pulse electrolysis oxide treatment is carried out spinning handle, and use vitriol oil adjusting wastewater pH is 3.0; Waste water after the spinning processing is carried out three-diemsnional electrode-Fenton oxide treatment; Adopting solubility iron plate is the positive electricity pole plate, and stainless steel plate is the negative electricity pole plate, and interpole gap is 2.0 cm; The granule electrode material is a granular carbon; The ferrous sulfate dosage is 2.5 mg/L, and current/voltage is 15 V, and current density is 50 mA/cm
2, aeration intensity is 800 L/h, and reaction pH is 3.0, and the reaction times is 45 minutes; Waste water after three-diemsnional electrode-Fenton oxide treatment is carried out flocculation sediment to be handled; Under agitation condition, add basifier and flocculation agent successively; Using calcium hydroxide to regulate wastewater pH is 9; The consumption of flocculation agent SEPIGEL 305 is 50 mg/L, and flocculation time is 15 minutes, staticly settles more than 30 minutes; Detect flocculation sediment treat effluent COD
CrMore than 100～330 mg/L, therefore the flocculation sediment treat effluent is carried out ozone Oxidation Treatment, concentration of ozone gas is 85 mg/L, and ozone gas flow is 6 L/h, and using calcium hydroxide conditioned reaction pH is 11.5, and reaction is 60 minutes, water outlet COD
Cr＜100 mg/L, colourity is 0 times, has all reached national sewage comprehensive discharge primary standard; Through directly discharging or the reuse after the strainer filtration treatment of the waste water after the ozone Oxidation Treatment.Ozone tail gas gets into the pulse electrolysis oxidation trough, in order to strengthen the treatment effect of pulse electrolysis oxidation to waste water.The mud that system produces is through the pressure filter dehydration, and filtrating entering is regulated balancing reservoir, filter cake mummification brickmaking or solidification treatment.
Embodiment 5:Certain shale gas well water defeated split the effluent of returning that produces in the operation process and introduce to regulate balancing reservoir, carry out the water quality and quantity homogenizing; Under agitation condition, add the mixture (mass ratio is 0.1:1) of efficient composite coagulant gac and ferrous sulfate in the waste water after regulating homogenizing, consumption is 10 g/L; Using calcium hydroxide to regulate wastewater pH simultaneously is 9.0, stirred 20 minutes, after add the coagulant aids SEPIGEL 305 again; Consumption is 50 mg/L; Stir fast again, treat to stop after a large amount of alumen ustum form to stir, staticly settle more than 30 minutes; Waste water after the coagulating treatment is carried out the pulse electrolysis oxide treatment, and adopting iron plate is the anode and cathode battery lead plate, and interpole gap is 2.0 cm, and current/voltage is 15 V, and current density is 45 mA/cm
2, pulse-repetition is 10 000 Hz, and reaction pH is 9.0, and the reaction times is 55 minutes; Waste water after the pulse electrolysis oxide treatment is carried out spinning handle, and use vitriol oil adjusting wastewater pH is 3.5; Waste water after the spinning processing is carried out three-diemsnional electrode-Fenton oxide treatment; Adopting solubility iron plate is the positive electricity pole plate, and stainless steel plate is the negative electricity pole plate, and interpole gap is 2.0 cm; The granule electrode material is a granular carbon; The ferrous sulfate dosage is 2.8 mg/L, and current/voltage is 15 V, and current density is 45 mA/cm
2, aeration intensity is 700 L/h, and reaction pH is 3.5, and the reaction times is 45 minutes; Waste water after three-diemsnional electrode-Fenton oxide treatment is carried out flocculation sediment to be handled; Under agitation condition, add basifier and flocculation agent successively; Using calcium hydroxide to regulate wastewater pH is 9.5; The consumption of flocculation agent SEPIGEL 305 is 30 mg/L, and flocculation time is 10 minutes, staticly settles more than 30 minutes; Detect flocculation sediment treat effluent COD
CrMore than 100～330 mg/L, therefore the flocculation sediment treat effluent is carried out ozone Oxidation Treatment, concentration of ozone gas is 85 mg/L, and ozone gas flow is 8 L/h, and using calcium hydroxide conditioned reaction pH is 11.5, and reaction is 60 minutes, water outlet COD
Cr＜100 mg/L, colourity is 0 times, has all reached national sewage comprehensive discharge primary standard; Discharge or reuse after the strainer filtration treatment through the waste water after the ozone Oxidation Treatment.Ozone tail gas gets into the pulse electrolysis oxidation trough, in order to strengthen the treatment effect of pulse electrolysis oxidation to waste water.The mud that system produces is through the pressure filter dehydration, and filtrating entering is regulated balancing reservoir, filter cake mummification brickmaking or solidification treatment.
Embodiment 6:Certain coke-oven plant's coking chemical waste water is introduced the adjusting balancing reservoir, carry out the water quality and quantity homogenizing; Under agitation condition, add the mixture (mass ratio is 0.15:1) of efficient composite coagulant gac and Poly aluminum Chloride (PAC) in the waste water after regulating homogenizing, consumption is 12 g/L; Using quicklime to regulate wastewater pH simultaneously is 9.0, stirred 20 minutes, after add the coagulant aids SEPIGEL 305 again; Consumption is 50 mg/L; Stir fast again, treat to stop after a large amount of alumen ustum form to stir, staticly settle more than 30 minutes; Waste water after the coagulating treatment is carried out the pulse electrolysis oxide treatment, and adopting iron plate is the anode and cathode battery lead plate, and interpole gap is 2.0 cm, and current/voltage is 15 V, and current density is 60 mA/cm
2, pulse-repetition is 12 000 Hz, and reaction pH is 9.0, and the reaction times is 50 minutes; Waste water after the pulse electrolysis oxide treatment is carried out spinning handle, and use vitriol oil adjusting wastewater pH is 3.0; Waste water after the spinning processing is carried out three-diemsnional electrode-Fenton oxide treatment; Adopting solubility iron plate is the positive electricity pole plate, and stainless steel plate is the negative electricity pole plate, and interpole gap is 2.0 cm; The granule electrode material is a granular carbon; The ferrous sulfate dosage is 3.0 mg/L, and current/voltage is 15 V, and current density is 50 mA/cm
2, aeration intensity is 800 L/h, and reaction pH is 3.0, and the reaction times is 50 minutes; Waste water after three-diemsnional electrode-Fenton oxide treatment is carried out flocculation sediment to be handled; Under agitation condition, add basifier and flocculation agent successively; Using calcium hydroxide to regulate wastewater pH is 10; The consumption of flocculation agent SEPIGEL 305 is 35 mg/L, and flocculation time is 15 minutes, staticly settles more than 30 minutes; Detect flocculation sediment treat effluent COD
CrMore than 100～330 mg/L, therefore the flocculation sediment treat effluent is carried out ozone Oxidation Treatment, concentration of ozone gas is 85 mg/L, and ozone gas flow is 9 L/h, and using calcium hydroxide conditioned reaction pH is 11.5, and reaction is 45 minutes, water outlet COD
Cr＜100 mg/L, colourity is 0 times, has all reached national sewage comprehensive discharge primary standard; Discharge or reuse after the strainer filtration treatment through the waste water after the ozone Oxidation Treatment.Ozone tail gas gets into the pulse electrolysis oxidation trough, in order to strengthen the treatment effect of pulse electrolysis oxidation to waste water.The mud that system produces is through the pressure filter dehydration, and filtrating entering is regulated balancing reservoir, filter cake mummification brickmaking or solidification treatment.
Claims (9)
1. method and a technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby is characterized in that: comprise the following steps:
⑴ regulate homogenizing and handle: the adjusting and the homogenizing of organic waste water being carried out water quality, the water yield;
⑵ coagulating sedimentation is handled: the waste water after step ⑴ is handled carries out coagulating sedimentation to be handled, and adds efficient composite coagulant, basifier and coagulant aids successively, and reaction pH is 8～10, and the coagulation churning time is 10～20 minutes, and the ST is more than 30 minutes;
⑶ pulse electrolysis oxide treatment: the waste water after the step ⑵ processing is carried out the pulse electrolysis oxide treatment, and current/voltage is 5～20 V, and current density is 30～60 mA/cm
2, pulse-repetition is 5 000～12 000 Hz, and reaction pH is 7～11, and the reaction times is 30～60 minutes;
⑷ spinning is handled: the waste water after step ⑶ is handled carries out spinning to be handled, and use vitriol oil adjusting wastewater pH is 3～5;
⑸ three-diemsnional electrode-Fenton oxide treatment: the waste water after the step ⑷ processing is carried out three-diemsnional electrode-Fenton oxide treatment, and add ferrous sulfate, consumption is 0.5～3.0 mg/L, and current/voltage is 10～20 V, and current density is 30～60 mA/cm
2, oxidizing reaction pH is 3～5, the reaction times is 10～60 minutes;
⑹ flocculation sediment is handled: the waste water after step ⑸ is handled carries out flocculation sediment to be handled, and under agitation condition, adds basifier and flocculation agent successively, and the adjustment wastewater pH is 8～10, and flocculation time is 5～15 minutes, and the ST is more than 30 minutes;
⑺ ozone Oxidation Treatment: if detect step ⑹ treat effluent COD
CrWhen 150～330 mg/L are above, waste water is carried out ozone Oxidation Treatment; Otherwise step ⑹ treat effluent is directly carried out step ⑻ filtration treatment; Concentration of ozone gas is 70～90 mg/L in the ozone Oxidation Treatment; Ozone gas flow is 6～9 L/h, and using basifier conditioned reaction pH is 11～11.5, and the reaction times is 30～80 minutes;
⑻ filter process: the waste water after step ⑺ handles discharges or reuse after the strainer filtration treatment;
⑼ the mud that system produces is through the pressure filter dehydration, and filtrating entering is regulated balancing reservoir, filter cake mummification brickmaking or solidification treatment.
2. a kind of method and technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby according to claim 1 and 2; It is characterized in that: described efficient composite coagulant is one or more the mixture in rapid precipitation agent flyash or gac or powdery slag and coagulating agent ferrous sulfate, bodied ferric sulfate, the Poly aluminum Chloride (PAC); The mass ratio of rapid precipitation agent and coagulating agent is (0.05～0.15): 1, and total consumption is 3～30 g/L.
3. a kind of method and technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby according to claim 1 and 2 is characterized in that: described basifier is a kind of in unslaked lime, white lime, sodium hydroxide, Youxiaolin and the Losantin.
4. a kind of method and technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby according to claim 1 and 2 is characterized in that: described coagulant aids is SEPIGEL 305 or active silicic acid or partially hydrolyzed polyacrylamide, and consumption is 50～120 mg/L.
5. a kind of method and technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby according to claim 1 and 2 is characterized in that: described pulse electrolysis oxide treatment, and adopting iron plate or stainless steel plate is the anodic-cathodic plate, interpole gap is 1.5～3.0 cm.
6. a kind of method and technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby according to claim 1 and 2; It is characterized in that: described three-diemsnional electrode-Fenton oxide treatment; Adopting solubility iron plate is the positive electricity pole plate, and stainless steel plate is the negative electricity pole plate, and interpole gap is 1.5～3.0 cm; The granule electrode material is a columnar activated carbon, and aeration intensity is 600～800 L/h.
7. a kind of method and technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby according to claim 1 and 2, it is characterized in that: the dosing method of described ferrous sulfate is continuous dosing method.
8. a kind of method and technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby according to claim 1 and 2 is characterized in that: described flocculation agent is SEPIGEL 305 or polymer NSG, and consumption is 30～80 mg/L.
9. a kind of method and technology that is used for the treatment of high concentration organic wastewater with difficult degradation thereby according to claim 1 and 2; It is characterized in that: the ozone tail gas in the described ozone Oxidation Treatment gets into the pulse electrolysis oxidation trough; In order to strengthen the treatment effect of pulse electrolysis oxidation, realize the comprehensive utilization of ozone tail gas to waste water.
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