CN102701496B - Process for treating high-concentration organic wastewater difficult to degrade - Google Patents

Process for treating high-concentration organic wastewater difficult to degrade Download PDF

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CN102701496B
CN102701496B CN 201210210211 CN201210210211A CN102701496B CN 102701496 B CN102701496 B CN 102701496B CN 201210210211 CN201210210211 CN 201210210211 CN 201210210211 A CN201210210211 A CN 201210210211A CN 102701496 B CN102701496 B CN 102701496B
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waste water
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CN102701496A (en
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杨德敏
李大华
夏宏
袁建梅
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重庆地质矿产研究院
重庆华地工程勘察设计院
杨德敏
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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

A kind of technology for the treatment of high concentration hard-degraded organic waste water

One, technical field

The present invention relates to a kind of technology for the treatment of high concentration hard-degraded organic waste water, 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 height, saltiness height, poisonous and harmful hard-degraded substance are many, the pH value changes greatly, biodegradability is poor, part waste water nitrogen and phosphorus content height.According to Chinese environmental situation in 2011, Chinese chemical oxygen demand (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, as heavy metal substances such as polycyclic aromatic hydrocarbons, halohydrocarbon, heterocyclic compound, organic phenolic compound, organophosphorus pesticide, tensio-active agent, organic dye and arsenic, mercury, the very difficult effective processing of this pollutant, easily 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 ripe 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 may 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 handling high concentration hard-degraded organic waste water at present 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.These treatment processs more or less have certain limitation, and are saturated easily as 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 height; The easy inactivation of the catalyzer of catalytic wet air oxidation and stripping bring secondary pollution; Supercritical water oxidation method needs to carry out under the operational condition of High Temperature High Pressure, 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 and pollution feature at high concentrated organic wastewater remove to select proper treatment process, 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 bigger economic benefit, environmental benefit and social benefit obtained.

Coagulant sedimentation be point to add in the waste water certain or certain class can play in and 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 mutually, 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.At present coagulating agent commonly used mainly contains inorganic coagulant (as traditional molysite, aluminum salt, inorganic polymer coagulant), organic coagulating agent (comprise natural and synthetic two kinds) and compound coagulant (mainly being microbial flocculant) three major types.Discover the preferred and composite highly effective coagulation of realizing high concentration hard-degraded organic waste water of coagulating agent.

The pulse electrolysis oxidation style is electrolytic oxidation groove and the pulse power to be connected to form electrolysis system and the electrolytic acid cleaning oxydation process that carries out, it with electronics as reagent, electric field energy is reaction power, generally do not need to 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 the Direct Electrochemistry reaction take place or utilize electrode surface to produce strong active oxide material (as hydroxyl radical free radical, hypochlorite, H at electrode 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, constantly repeat the electrolytic process of " power supply-outage-power supply " owing to pulse electrolysis is one, make that electrolytic efficiency has obtained improving significantly.The conduction time of pulse electrolysis oxidation, the reaction on the electrode was conducive to 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 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, 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.By 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 direct oxidation effect of anode, the indirect oxidation effect of 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 of Chan Shenging, 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 the easy degradation material of small molecules 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 purposes such as flocculating settling effect, and the ozone in the processed waste water easily decomposes, and does not produce secondary pollution.

Three, summary of the invention

The objective of the invention is to propose a kind of technology for the treatment of high concentration hard-degraded organic waste water, 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 be achieved through the following technical solutions:

A kind of technology for the treatment of high concentration hard-degraded organic waste water that the present invention proposes is characterized in that: comprise the following steps:

⑴ regulate homogenizing and handle: 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 sedimentation time is more than 30 minutes;

Wherein, efficient composite coagulant is one or more the mixture in gac and coagulating agent ferrous sulfate, the polymerize aluminum chloride, and the mass ratio of gac and coagulating agent is (0.05~0.15): 1, and total consumption is 3~30g/L; Basifier is a kind of in white lime, the sodium hydroxide; Coagulant aids is polyacrylamide, and consumption is 50~120mg/L;

⑶ pulse electrolysis oxide treatment: the waste water after the step ⑵ processing is carried out the pulse electrolysis oxide treatment, and adopting iron plate or stainless steel plate is the anodic-cathodic plate, and interpole gap is 1.5~3.0cm, and current/voltage is 5~20V, and current density is 30~60mA/cm 2, pulse-repetition is 5000~12000Hz, and reaction pH is 7~11, and the reaction times is 30~60 minutes;

⑷ centrifugation is handled: the waste water after step ⑶ is handled carries out centrifugation to be handled, and to regulate wastewater pH with the vitriol oil be 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, adopting solubility iron plate is the positive electricity pole plate, stainless steel plate is the negative electricity pole plate, interpole gap is 1.5~3.0cm, and the granule electrode material is columnar activated carbon, and aeration intensity is 600~800L/h, and add ferrous sulfate, consumption is 0.5~3.0mg/L, and current/voltage is 10~20V, and current density is 30~60mA/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, under agitation condition, add basifier and flocculation agent successively, adjusting wastewater pH is 8~10, flocculation agent is polyacrylamide, consumption is 30~80mg/L, flocculation time is 5~15 minutes, and sedimentation time is more than 30 minutes;

⑺ ozone Oxidation Treatment: handle water outlet COD if detect step ⑹ CrWhen 150~330mg/L is above, waste water is carried out ozone Oxidation Treatment, otherwise step ⑹ handles water outlet directly carries out step ⑻ filtration treatment, concentration of ozone gas is 70~90mg/L in the ozone Oxidation Treatment, ozone gas flow is 6~9L/h, be 11~11.5 with basifier conditioned reaction pH, the reaction times is 30~80 minutes, and the ozone tail gas in the ozone Oxidation Treatment enters the pulse electrolysis oxidation trough, in order to strengthen the pulse electrolysis oxidation to the treatment effect of waste water, realize the comprehensive utilization of ozone tail gas;

⑻ filter process: discharging or reuse after the waste water process filter filtration treatment after step ⑺ handles;

⑼ the mud that system produces dewaters by pressure filter, and filtrate enters the adjusting balancing reservoir, filter cake mummification brickmaking or solidification treatment.

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 technology for the treatment of high concentration hard-degraded organic waste water that the present invention proposes is particularly useful for well-drilling waste water, poly-oil extraction waste water, oil-gas field and the shale gas field pressure break of driving returned high density used water difficult to degradate such as effluent, coking chemical waste water and handled project.

⑶ a kind of technology for the treatment of high concentration hard-degraded organic waste water 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 the actual water quality situation of high concentration hard-degraded organic waste water, expense and time, after coagulating sedimentation is handled, not carrying out pulse electrolysis oxide treatment and centrifugation handles, just directly carry out three-diemsnional electrode-Fenton oxide treatment successively, flocculation sediment is handled and ozone Oxidation Treatment, or do not carry out three-diemsnional electrode-Fenton oxide treatment and flocculation sediment and handle, 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 85mg/L, and ozone gas flow is 9L/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 centrifugation and handle, with regard to directly carrying out ozone Oxidation Treatment, be 90mg/L in concentration of ozone gas, ozone gas flow is that 9L/h and reaction pH are under 11.5 conditions, 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 of the technology for the treatment of high concentration hard-degraded organic waste water.

Five, embodiment

A kind of technology for the treatment of high concentration hard-degraded organic waste water that the present invention proposes is characterized in that: comprise the following steps:

⑴ regulate homogenizing and handle: 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 sedimentation time is more than 30 minutes;

Wherein, efficient composite coagulant is one or more the mixture in gac and coagulating agent ferrous sulfate, the polymerize aluminum chloride, and the mass ratio of gac and coagulating agent is (0.05~0.15): 1, and total consumption is 3~30g/L; Basifier is a kind of in white lime, the sodium hydroxide; Coagulant aids is polyacrylamide, and consumption is 50~120mg/L;

⑶ pulse electrolysis oxide treatment: the waste water after the step ⑵ processing is carried out the pulse electrolysis oxide treatment, and adopting iron plate or stainless steel plate is the anodic-cathodic plate, and interpole gap is 1.5~3.0cm, and current/voltage is 5~20V, and current density is 30~60mA/cm 2, pulse-repetition is 5000~12000Hz, and reaction pH is 7~11, and the reaction times is 30~60 minutes;

⑷ centrifugation is handled: the waste water after step ⑶ is handled carries out centrifugation to be handled, and to regulate wastewater pH with the vitriol oil be 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, adopting solubility iron plate is the positive electricity pole plate, stainless steel plate is the negative electricity pole plate, interpole gap is 1.5~3.0cm, and the granule electrode material is columnar activated carbon, and aeration intensity is 600~800L/h, and add ferrous sulfate, consumption is 0.5~3.0mg/L, and current/voltage is 10~20V, and current density is 30~60mA/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, under agitation condition, add basifier and flocculation agent successively, adjusting wastewater pH is 8~10, flocculation agent is polyacrylamide, consumption is 30~80mg/L, flocculation time is 5~15 minutes, and sedimentation time is more than 30 minutes;

⑺ ozone Oxidation Treatment: handle water outlet COD if detect step ⑹ CrWhen 150~330mg/L is above, waste water is carried out ozone Oxidation Treatment, otherwise step ⑹ handles water outlet directly carries out step ⑻ filtration treatment, concentration of ozone gas is 70~90mg/L in the ozone Oxidation Treatment, ozone gas flow is 6~9L/h, be 11~11.5 with basifier conditioned reaction pH, the reaction times is 30~80 minutes, and the ozone tail gas in the ozone Oxidation Treatment enters the pulse electrolysis oxidation trough, in order to strengthen the pulse electrolysis oxidation to the treatment effect of waste water, realize the comprehensive utilization of ozone tail gas;

⑻ filter process: discharging or reuse after the waste water process filter filtration treatment after step ⑺ handles;

⑼ the mud that system produces dewaters by pressure filter, and filtrate enters the adjusting balancing reservoir, filter cake mummification brickmaking or solidification treatment.

Below further describe the present invention by 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, the mixture (mass ratio is 0.08:1) that adds efficient composite coagulant gac and polymerize aluminum chloride in the waste water of regulating after the homogenizing, consumption is 15g/L, regulating wastewater pH with calcium hydroxide simultaneously is 9.5, stirred 20 minutes, after add the coagulant aids polyacrylamide again, consumption is 80mg/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 2.0cm, and current/voltage is 12V, and current density is 50mA/cm 2, pulse-repetition is 8000Hz, and reaction pH is 10, and the reaction times is 60 minutes; Waste water after the pulse electrolysis oxide treatment is carried out centrifugation handle, and to regulate wastewater pH with the vitriol oil be 3.6; Waste water after the centrifugation processing is carried out three-diemsnional electrode-Fenton oxide treatment, adopting solubility iron plate is the positive electricity pole plate, stainless steel plate is the negative electricity pole plate, interpole gap is 2.0cm, the granule electrode material is granular carbon, the ferrous sulfate dosage is 2.0mg/L, and current/voltage is 12V, and current density is 45mA/cm 2, aeration intensity is 600L/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, add basifier and flocculation agent under agitation condition successively, regulating wastewater pH with sodium hydroxide is 9, and the consumption of flocculation agent polyacrylamide is 45mg/L, flocculation time is 8 minutes, staticly settles more than 30 minutes; Detect flocculation sediment and handle water outlet COD CrMore than 150~330mg/L, therefore flocculation sediment to be handled water outlet and carry out ozone Oxidation Treatment, concentration of ozone gas is 80mg/L, and ozone gas flow is 6L/h, is 11.5 with calcium hydroxide conditioned reaction pH, and reaction is 40 minutes, water outlet COD Cr<100mg/L, colourity is 0 times, has all reached national sewage comprehensive discharge primary standard; Discharging or reuse after the waste water after the ozone Oxidation Treatment is through the filter filtration treatment.Ozone tail gas enters the pulse electrolysis oxidation trough, in order to strengthen the pulse electrolysis oxidation to the treatment effect of waste water.The mud that system produces dewaters by pressure filter, and filtrate enters the adjusting 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, the mixture (mass ratio is 0.1:1) that adds efficient composite coagulant gac and ferrous sulfate in the waste water of regulating after the homogenizing, consumption is 20g/L, regulating wastewater pH with calcium hydroxide simultaneously is 9.8, stirred 20 minutes, after add the coagulant aids polyacrylamide again, consumption is 100mg/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 2.0cm, and current/voltage is 12V, and current density is 45mA/cm 2, pulse-repetition is 12000Hz, and reaction pH is 9.8, and the reaction times is 50 minutes; Waste water after the pulse electrolysis oxide treatment is carried out centrifugation handle, and to regulate wastewater pH with the vitriol oil be 3.2; Waste water after the centrifugation processing is carried out three-diemsnional electrode-Fenton oxide treatment, adopting solubility iron plate is the positive electricity pole plate, stainless steel plate is the negative electricity pole plate, interpole gap is 2.0cm, the granule electrode material is granular carbon, the ferrous sulfate dosage is 2.0mg/L, and current/voltage is 15V, and current density is 55mA/cm 2, aeration intensity is 800L/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, add basifier and flocculation agent under agitation condition successively, regulating wastewater pH with calcium hydroxide is 9, and the consumption of flocculation agent polyacrylamide is 40mg/L, flocculation time is 10 minutes, staticly settles more than 30 minutes; Detect flocculation sediment and handle water outlet COD CrBelow 100mg/L, colourity has all reached national sewage comprehensive discharge primary standard below 50 times, does not need that therefore flocculation sediment is handled water outlet and carries out ozone Oxidation Treatment, and flocculation sediment directly discharges or reuse after handling water outlet process filter filtration treatment.The mud that system produces dewaters by pressure filter, and filtrate enters the adjusting balancing reservoir, filter cake mummification brickmaking or solidification treatment.

Embodiment 3: the poly-oil extraction waste water that drives 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, the mixture (mass ratio is 0.1:1) that adds efficient composite coagulant gac and polymerize aluminum chloride in the waste water of regulating after the homogenizing, consumption is 25g/L, regulating wastewater pH with calcium hydroxide simultaneously is 10, stirred 20 minutes, after add the coagulant aids polyacrylamide again, consumption is 100mg/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 2.0cm, and current/voltage is 15V, and current density is 60mA/cm 2, pulse-repetition is 12000Hz, and reaction pH is 10, and the reaction times is 60 minutes; Waste water after the pulse electrolysis oxide treatment is carried out centrifugation handle, and to regulate wastewater pH with the vitriol oil be 3.5; Waste water after the centrifugation processing is carried out three-diemsnional electrode-Fenton oxide treatment, adopting solubility iron plate is the positive electricity pole plate, stainless steel plate is the negative electricity pole plate, interpole gap is 2.0cm, the granule electrode material is granular carbon, the ferrous sulfate dosage is 3.0mg/L, and current/voltage is 12V, and current density is 50mA/cm 2, aeration intensity is 800L/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, regulating wastewater pH with calcium hydroxide is 10, the consumption of flocculation agent polyacrylamide is 60mg/L, flocculation time is 12 minutes, staticly settles more than 30 minutes; Detect flocculation sediment and handle water outlet COD CrMore than 100~330mg/L, therefore flocculation sediment to be handled water outlet and carry out ozone Oxidation Treatment, concentration of ozone gas is 90mg/L, and ozone gas flow is 8L/h, is 11.3 with calcium hydroxide conditioned reaction pH, and reaction is 40 minutes, water outlet COD Cr<100mg/L, colourity is 0 times, has all reached national sewage comprehensive discharge primary standard; Discharging or reuse after the waste water after the ozone Oxidation Treatment is through the filter filtration treatment.Ozone tail gas enters the pulse electrolysis oxidation trough, in order to strengthen the pulse electrolysis oxidation to the treatment effect of waste water.The mud that system produces dewaters by pressure filter, and filtrate enters the adjusting 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, the mixture (mass ratio is 0.09:1) that adds efficient composite coagulant gac and ferrous sulfate in the waste water of regulating after the homogenizing, consumption is 20g/L, regulating wastewater pH with calcium hydroxide simultaneously is 10.5, stirred 20 minutes, after add the coagulant aids polyacrylamide again, consumption is 70mg/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 2.0cm, and current/voltage is 15V, and current density is 45mA/cm 2, pulse-repetition is 11000Hz, and reaction pH is 10.5, and the reaction times is 40 minutes; Waste water after the pulse electrolysis oxide treatment is carried out centrifugation handle, and to regulate wastewater pH with the vitriol oil be 3.0; Waste water after the centrifugation processing is carried out three-diemsnional electrode-Fenton oxide treatment, adopting solubility iron plate is the positive electricity pole plate, stainless steel plate is the negative electricity pole plate, interpole gap is 2.0cm, the granule electrode material is granular carbon, the ferrous sulfate dosage is 2.5mg/L, and current/voltage is 15V, and current density is 50mA/cm 2, aeration intensity is 800L/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, add basifier and flocculation agent under agitation condition successively, regulating wastewater pH with calcium hydroxide is 9, and the consumption of flocculation agent polyacrylamide is 50mg/L, flocculation time is 15 minutes, staticly settles more than 30 minutes; Detect flocculation sediment and handle water outlet COD CrMore than 100~330mg/L, therefore flocculation sediment to be handled water outlet and carry out ozone Oxidation Treatment, concentration of ozone gas is 85mg/L, and ozone gas flow is 6L/h, is 11.5 with calcium hydroxide conditioned reaction pH, and reaction is 60 minutes, water outlet COD Cr<100mg/L, colourity is 0 times, has all reached national sewage comprehensive discharge primary standard; Directly discharging or reuse after the waste water after the ozone Oxidation Treatment is through the filter filtration treatment.Ozone tail gas enters the pulse electrolysis oxidation trough, in order to strengthen the pulse electrolysis oxidation to the treatment effect of waste water.The mud that system produces dewaters by pressure filter, and filtrate enters the adjusting balancing reservoir, filter cake mummification brickmaking or solidification treatment.

Embodiment 5: certain shale gas well water is 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, the mixture (mass ratio is 0.1:1) that adds efficient composite coagulant gac and ferrous sulfate in the waste water of regulating after the homogenizing, consumption is 10g/L, regulating wastewater pH with calcium hydroxide simultaneously is 9.0, stirred 20 minutes, after add the coagulant aids polyacrylamide again, consumption is 50mg/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 2.0cm, and current/voltage is 15V, and current density is 45mA/cm 2, pulse-repetition is 10000Hz, and reaction pH is 9.0, and the reaction times is 55 minutes; Waste water after the pulse electrolysis oxide treatment is carried out centrifugation handle, and to regulate wastewater pH with the vitriol oil be 3.5; Waste water after the centrifugation processing is carried out three-diemsnional electrode-Fenton oxide treatment, adopting solubility iron plate is the positive electricity pole plate, stainless steel plate is the negative electricity pole plate, interpole gap is 2.0cm, the granule electrode material is granular carbon, the ferrous sulfate dosage is 2.8mg/L, and current/voltage is 15V, and current density is 45mA/cm 2, aeration intensity is 700L/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, regulating wastewater pH with calcium hydroxide is 9.5, the consumption of flocculation agent polyacrylamide is 30mg/L, flocculation time is 10 minutes, staticly settles more than 30 minutes; Detect flocculation sediment and handle water outlet COD CrMore than 100~330mg/L, therefore flocculation sediment to be handled water outlet and carry out ozone Oxidation Treatment, concentration of ozone gas is 85mg/L, and ozone gas flow is 8L/h, is 11.5 with calcium hydroxide conditioned reaction pH, and reaction is 60 minutes, water outlet COD Cr<100mg/L, colourity is 0 times, has all reached national sewage comprehensive discharge primary standard; Discharging or reuse after the waste water after the ozone Oxidation Treatment is through the filter filtration treatment.Ozone tail gas enters the pulse electrolysis oxidation trough, in order to strengthen the pulse electrolysis oxidation to the treatment effect of waste water.The mud that system produces dewaters by pressure filter, and filtrate enters the adjusting balancing reservoir, filter cake mummification brickmaking or solidification treatment.

Embodiment 6: certain coke-oven plant's coking chemical waste water is introduced regulated balancing reservoir, carry out the water quality and quantity homogenizing; Under agitation condition, the mixture (mass ratio is 0.15:1) that adds efficient composite coagulant gac and polymerize aluminum chloride in the waste water of regulating after the homogenizing, consumption is 12g/L, regulating wastewater pH with calcium oxide simultaneously is 9.0, stirred 20 minutes, after add the coagulant aids polyacrylamide again, consumption is 50mg/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 2.0cm, and current/voltage is 15V, and current density is 60mA/cm 2, pulse-repetition is 12000Hz, and reaction pH is 9.0, and the reaction times is 50 minutes; Waste water after the pulse electrolysis oxide treatment is carried out centrifugation handle, and to regulate wastewater pH with the vitriol oil be 3.0; Waste water after the centrifugation processing is carried out three-diemsnional electrode-Fenton oxide treatment, adopting solubility iron plate is the positive electricity pole plate, stainless steel plate is the negative electricity pole plate, interpole gap is 2.0cm, the granule electrode material is granular carbon, the ferrous sulfate dosage is 3.0mg/L, and current/voltage is 15V, and current density is 50mA/cm 2, aeration intensity is 800L/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, regulating wastewater pH with calcium hydroxide is 10, the consumption of flocculation agent polyacrylamide is 35mg/L, flocculation time is 15 minutes, staticly settles more than 30 minutes; Detect flocculation sediment and handle water outlet COD CrMore than 100~330mg/L, therefore flocculation sediment to be handled water outlet and carry out ozone Oxidation Treatment, concentration of ozone gas is 85mg/L, and ozone gas flow is 9L/h, is 11.5 with calcium hydroxide conditioned reaction pH, and reaction is 45 minutes, water outlet COD Cr<100mg/L, colourity is 0 times, has all reached national sewage comprehensive discharge primary standard; Discharging or reuse after the waste water after the ozone Oxidation Treatment is through the filter filtration treatment.Ozone tail gas enters the pulse electrolysis oxidation trough, in order to strengthen the pulse electrolysis oxidation to the treatment effect of waste water.The mud that system produces dewaters by pressure filter, and filtrate enters the adjusting balancing reservoir, filter cake mummification brickmaking or solidification treatment.

Claims (1)

1. the technology for the treatment of high concentration hard-degraded organic waste water is characterized in that: comprise the following steps:
⑴ regulate homogenizing and handle: 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 sedimentation time is more than 30 minutes;
Wherein, efficient composite coagulant is one or more the mixture in gac and coagulating agent ferrous sulfate, the polymerize aluminum chloride, and the mass ratio of gac and coagulating agent is (0.05~0.15): 1, and total consumption is 3~30 g/L; Basifier is a kind of in white lime, the sodium hydroxide; Coagulant aids is polyacrylamide, and consumption is 50~120 mg/L;
⑶ pulse electrolysis oxide treatment: the waste water after the step ⑵ processing is carried out the pulse electrolysis oxide treatment, and adopting iron plate or stainless steel plate is the anodic-cathodic plate, and interpole gap is 1.5~3.0 cm, 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 centrifugation is handled: the waste water after step ⑶ is handled carries out centrifugation to be handled, and to regulate wastewater pH with the vitriol oil be 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, adopting solubility iron plate is the positive electricity pole plate, stainless steel plate is the negative electricity pole plate, interpole gap is 1.5~3.0 cm, and the granule electrode material is columnar activated carbon, and aeration intensity is 600~800 L/h, 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, under agitation condition, add basifier and flocculation agent successively, adjusting wastewater pH is 8~10, flocculation agent is polyacrylamide, consumption is 30~80 mg/L, flocculation time is 5~15 minutes, and sedimentation time is more than 30 minutes;
⑺ ozone Oxidation Treatment: handle water outlet COD if detect step ⑹ CrWhen 150~330 mg/L are above, waste water is carried out ozone Oxidation Treatment, otherwise step ⑹ handles water outlet directly carries 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, be 11~11.5 with basifier conditioned reaction pH, reaction times is 30~80 minutes, ozone tail gas in the ozone Oxidation Treatment enters the pulse electrolysis oxidation trough, in order to strengthen the pulse electrolysis oxidation to the treatment effect of waste water, realize the comprehensive utilization of ozone tail gas;
⑻ filter process: discharging or reuse after the waste water process filter filtration treatment after step ⑺ handles;
⑼ the mud that system produces dewaters by pressure filter, and filtrate enters the adjusting balancing reservoir, filter cake mummification brickmaking or solidification treatment.
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