CN102849875B - System for deep treatment of coking wastewater by means of catalytic ozonation-ceramic membrane filtration - Google Patents
System for deep treatment of coking wastewater by means of catalytic ozonation-ceramic membrane filtration Download PDFInfo
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- CN102849875B CN102849875B CN 201210387521 CN201210387521A CN102849875B CN 102849875 B CN102849875 B CN 102849875B CN 201210387521 CN201210387521 CN 201210387521 CN 201210387521 A CN201210387521 A CN 201210387521A CN 102849875 B CN102849875 B CN 102849875B
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 46
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- 238000005374 membrane filtration Methods 0.000 title abstract 2
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- 238000000926 separation method Methods 0.000 abstract description 3
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- 238000000034 method Methods 0.000 description 18
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Abstract
The invention discloses a system for deep treatment of coking wastewater by means of catalytic ozonation-ceramic membrane filtration, mainly consisting of an ozone generator, an ozone oxidation reactor, a booster pump, a ceramic membrane component, a gas-liquid separator, a tail gas absorbing device, a wastewater reflowing pump, a catalyst reflowing pump, a catalyst adding pump, a catalyst outflowing groove, a catalyst adding groove and corresponding pipe fittings, valves and instruments. According to the system, the application of a powder catalyst in a dynamic reactor can be realized due to the combination of the catalytic ozonation and the ceramic membrane separation; the ozonation and the catalytic ozonation can be guaranteed to be carried out in a single reactor in a segmental way due to the convection current of the reflowing wastewater and the catalyst slurry and the impact of upcurrent; the mass transfer resistance when the ozonation and the catalytic ozonation are independently used can be reduced; the use ratio of hydroxyl free radical and the removal rate of organic matters can be improved; the aims, such as the COD (chemical oxygen demand), the chroma and the turbidity of the deeply-treated coking wastewater, can be achieved; and the problems that the activity is suddenly reduced when the powder catalyst is formed into particulates, the running needs to be suspended when the mass transfer resistance is increased due to the use of the particulate catalyst and the particulate catalyst is changed and the like can be solved.
Description
Technical field
The present invention relates to a kind of new system of advanced treatment on coking wastewater, relate in particular to the system of a kind of O3 catalytic oxidation-ceramic membrane filter advanced treatment on coking wastewater.
Background technology
Coking chemical waste water contains the hazardous and noxious substances of multiple high densitys such as phenol, ammonia nitrogen, cyanogen, benzene, pyridine, indoles and quinoline, and its discharging that exceeds standard has constituted very big harm to mankind, aquatic products, farm crop etc., must pass through processing and can discharge after up to standard.Yet up to the present the improvement of coking chemical waste water remain a global difficult problem.According to statistics, China has tame coal chemical enterprise more than 1300 at present, its Treatment of Coking Effluent is with the main process of multi-form A/O technology as biological treatment mostly, there are certain difficulty in water outlet COD, colourity and the discharging of turbidity stably reaching standard, therefore especially water outlet COD exceeds standard very generally, must adopt effective advanced treatment process.
Ozonation technology is as a kind of high-level oxidation technology, it is the advanced waste treatment method that generally adopts at present, more organism is (as the chain unsaturated compound in can the efficient oxidation coking chemical waste water, phenol, quinoline, pyridine, indoles etc.), yet ozone oxidation is to the long-chain fat hydrocarbon separately, small molecular organic acid, the rate of oxidation of materials such as ester class and alcohols is lower, and these materials also are stored in the water outlet of coking chemical waste water A/O treatment process, pure and mild organic acid is the intermediate product of organism ozone oxidation in many coking chemical waste waters especially, therefore separately during the ozone oxidation advanced treatment on coking wastewater COD clearance not high.
General employing at present adds solid catalyst reinforcement ozone generation hydroxyl radical free radical and improves ozone oxidation efficient, namely adopts catalytic ozonation technology to improve COD or TOC clearance that ozonation technology is handled waste water.In catalytic ozonation technology, the development and application of efficient, economy and stable catalyst is the problem of most critical.The catalyzer of having reported comprises that metal oxide is (as MnO
2, Al
2O
3, Ce
2O
3And Ce
xZr
1-xO2), loaded metal or metal oxide are (as Co/Al
2O
3, Fe/AC, Ru/AC, Cu/Al
2O
3, Fe
2O
3/ Al
2O
3, MnO
x/ ZrO
2And RuO
2/ Al
2O
3) and carbon material (as gac, carbon nanotube).Existing studies have shown that, ozone can cause catalyst deactivation by the carbonoxide material; The oxide compound of metals such as iron, manganese, copper, cobalt is immersed in easy generation metal component stripping in the water and causes catalyst deactivation; CeO
2Metallic cerium oxide compound (Ce with doping Zr
xZr
1-xO
2) in water, have extraordinary stability, in the O3 catalytic oxidation process, also show good activity, and just can obtain the CeO of high reactivity and high stable by simple co-precipitation preparation method
2And Ce
xZr
1-xO
2Fine catalyst.
At present, fine catalyst generally is to use in the batch reactor in laboratory, the actual engineering of water treatment overwhelming majority all adopts flow reactor and beaded catalyst, thereby fine catalyst generally will can be applied to actual engineering of water treatment through being shaped to beaded catalyst.O3 catalytic oxidation is handled in the waste water process, current can allow intensity smaller particles catalyzer powder gradually to the shearing force on beaded catalyst surface and flow out reactor with water, thereby cause rapid catalyst deactivation, thereby the beaded catalyst of practical application must possess enough intensity.CeO
2And Ce
xZr
1-xO
2Fine catalyst will be shaped to the beaded catalyst with higher-strength, generally needs through high-temperature roasting.But the high-temperature roasting meeting causes specific surface area of catalyst sharply to diminish, and has reduced the mesoporous and macropore volume that is conducive to the O3 catalytic oxidation reaction especially greatly, and these all can cause catalyst activity sharply to reduce or even lose activity fully.This gives CeO
2And Ce
xZr
1-xO
2The practical application of catalyzer has brought great obstacle.Thereby, for CeO
2And Ce
xZr
1-xO
2Catalyzer preferably can be applied in the actual engineering with the fine catalyst form, and this just needs to improve the apparatus for continous treatment of the normal application beaded catalyst that adopts at present.
Adopt fine catalyst to compare beaded catalyst during the O3 catalytic oxidation advanced treatment on coking wastewater and aspect mass transfer, have more advantage.The O3 catalytic oxidation process has related to processes such as a series of mass transfers, chemical reaction, absorption and desorption, the ozone oxidation of most organism (for example phenol, pyridine, quinoline, indoles etc.) belongs to rapid reaction in the coking chemical waste water, and mass transfer is the rate-limiting step of oxidation operation.In independent ozone oxidation, when gas flow rate was big, resistance to mass transfer was little, and these organism can be removed rapidly.When adopting these organism of beaded catalyst catalytic ozonation degradation, beaded catalyst has increased resistance to mass transfer, reduced ozone contact organism chance, thereby reduced ozone oxidation and removed these organism speed of reaction, though can obtain the COD clearance higher than independent ozone oxidation when this just causes the catalytic ozonation technology advanced treatment on coking wastewater, the clearance of phenol, quinoline and these typical hazardous contaminants of indoles is lower than independent ozone oxidation; Simultaneously, a part of free radical does not have the organism of deoxidation difficult degradation, but consumes in the oxidation of easily biodegradable organics.If adopt micron-sized fine catalyst, then resistance to mass transfer is with ozone oxidation is about the same separately; If more independent ozone oxidation and O3 catalytic oxidation are separated, just can be when guaranteeing that ozone oxidation is removed easy oxidation of organic compounds efficient, the free radical that takes full advantage of the catalysis ozone generation is removed difficult oxidizing substance.
In addition, in the process of the actual coking chemical waste water of O3 catalytic oxidation advanced treatment, because the waste water complicated component is changeable, the easy inactivation of catalyzer must be changed behind the catalyst deactivation.The reactor that adopts beaded catalyst must stopped reaction when catalyst changeout more, each reactor go into operation and when stopping effluent quality relatively poor.And owing to the catalytic ozonation technology search time is shorter relatively, the catalyst stability of exploitation is generally not high at present, and the frequency that catalyzer is changed is higher relatively, and going into operation and stop the phenomenon that causes effluent quality to worsen must be more serious.
Also there is not a kind of apparatus for continous treatment that can use fine catalyst in the prior art.
Summary of the invention
At above problem, the invention provides the system of a kind of O3 catalytic oxidation-ceramic membrane filter advanced treatment on coking wastewater, can be used to the water outlet of Treatment of Wastewater in Coking two stage biological treatment process, water-quality guideline such as the COD of system's water outlet, colourity and turbidity all can stablize reach " integrated wastewater discharge standard " (GB8978-1996) in primary standard, water outlet can also reuse be coke-oven plant's miscellaneous water.
The present invention is achieved through the following technical solutions:
The system of O3 catalytic oxidation of the present invention-ceramic membrane filter advanced treatment on coking wastewater comprises that ozonizer, ozone oxidation reaction device, topping-up pump, ceramic film component, gas-liquid separator, return of waste water pump, catalyzer reflux pump, catalyzer flow out groove, catalyzer adds groove, catalyzer interpolation pump;
Described ozone oxidation reaction device is vertical tubular structure, its underpart is provided with water-in, inlet mouth, top is provided with water outlet and return of waste water mouth, be provided with the micropore air distribution plate between described water-in and the inlet mouth, ozone oxidation reaction device middle part is provided with backflow waste water shower nozzle, backflow waste water shower nozzle bottom is independent ozone oxidation district, and top, described independent ozone oxidation district is small-bore reaction pipeline section;
The diameter of described small-bore reaction pipeline section is 1/3～1/2 of its elsewhere diameter of ozone oxidation reaction device, and length is 1/3～1/8 of total reactor length, and it is suitable for reading to be connected with 45 °～75 ° inclined-planes with the wall of ozone oxidation reaction device upper and lower respectively with end opening;
Above the described backflow waste water shower nozzle catalyzer mud shower nozzle is set, two shower nozzle spray planes are relative, at a distance of 5cm～20cm, it is the turbulent flow mixing zone between spray plane, backflow waste water shower nozzle area is 2～4 times of catalyzer mud shower nozzle area, and spray speed also is 2～4 times, and catalyzer mud shower nozzle is 1/2～1/4 of ozone oxidation reaction device height to the vertical range at ozone oxidation reaction device top, catalyzer mud shower nozzle top conversion zone is the O3 catalytic oxidation district, and adopting median size is the CeO of 1 μ m～4 μ m
2Or Ce
xZr
1-xO
2Fine catalyst;
Described backflow waste water shower nozzle links to each other with return of waste water pump, return of waste water mouth by the return of waste water pipe, and the return of waste water ratio is 200%～400%;
Described catalyzer mud shower nozzle links to each other with the concentrated solution spout of ceramic film component by catalyzer return line, catalyzer reflux pump;
Described catalyzer return line is provided with two arms, and one pipe coupling catalyzer adds pump and catalyzer interpolation groove, and another pipe coupling catalyst stream goes out groove.
The technical scheme that provides by the invention described above as can be seen, the present invention has following characteristics:
(1) system produces powerful upwards surging force by powerful injection of backflow waste water to catalyzer high return of waste water being set than strengthening organic removal rate simultaneously, suppresses catalyzer because gravity drops into independent ozone oxidation zone; Utilize pipe reactor to dwindle to occupy waste water tunnel with nozzle structure and improve the upwelling flow velocity, the fluid that generation is upwards impacted catalyzer, prevent that catalyzer from sinking, thereby the strictness that realizes independent ozone oxidation unit and O3 catalytic oxidation unit separates, with respect in two reactors, realizing independent ozone oxidation and O3 catalytic oxidation respectively, can save equipment, reduce the ozone solution degree in the time of can also avoiding using pipeline.
According to the characteristics that have the easy degradation material of a large amount of ozone in the coking chemical waste water, in an ozone oxidation reaction device, successively carry out independent ozone oxidation and O3 catalytic oxidation, utilize independent ozone oxidation to remove most readily oxidizable substance in the coking chemical waste water earlier, difficult oxidizing substance in the coking chemical waste water is further removed in the recycling O3 catalytic oxidation.Because most of easily organism of degraded is removed earlier, the strong oxidizing property material (as hydroxyl radical free radical) that produces in the O3 catalytic oxidation process is mainly used to the oxidation hardly degraded organic substance, making does not have optionally the strong oxidizing property material bring into play better effect, can effectively improve coking chemical waste water COD clearance.
Exist large amount of organic and ozone reaction speed very fast in the coking chemical waste water, mass transfer is limiting factor in the reaction process, in a reactor, independent ozone oxidation and O3 catalytic oxidation are separated, solid particulate increases resistance to mass transfer in the time of can avoiding adopting catalyzer, reduces the efficient that independent ozone oxidation is removed readily oxidizable substance.
(2) adopt CeO
2And Ce
xZr
1-xO
2Fine catalyst have that grain diameter is little, specific surface area is big, active high, metal stripping and carbon deposition quantity are little in waste water, catalyst stability is characteristics such as higher height relatively.Simultaneously, the inner mass transfer of fine catalyst almost can be ignored, also can avoid these not fine catalyst active problems that sharply reduces when the roasting moulding of easy-formation, the final powder catalyzer also makes the simple assembly of native system setting can easily carry out the online replacing of catalyzer, is conducive to long-time steady and continuous operation and the full-automatic control of system.
(3) the relative injection structure with catalyzer mud of the backflow waste water of system's setting and upwelling impact structure can improve the gas-liquid-solid three-phase degree of mixing, effectively reduce O3 catalytic oxidation process resistance to mass transfer, improve difficult oxidizing substance clearance.
(4) use ceramic film component can realize the efficient backflow of fine catalyst, turbidity in the waste water almost 100% is removed, utilize in the ceramic film component pressure to rise and further increase dissolved ozone in the water, suppress inorganic pollution and the microbial contamination of ceramic membrane, thereby make the simple washing unit that utilizes native system just can realize the self-stip of ceramic film component.
(5) based on the characteristics of ozone oxidation and the interception capacity of ceramic film component, adopt this system's advanced treatment on coking wastewater, water-quality guideline such as the COD of water outlet, colourity and turbidity all can stablize reach " integrated wastewater discharge standard " (GB8978-1996) in primary standard, water outlet can also be carried out reuse as coke-oven plant's miscellaneous water.
Description of drawings
The structural representation of the system of O3 catalytic oxidation-ceramic membrane filter advanced treatment on coking wastewater of providing for the embodiment of the invention is provided Fig. 1;
Each label is among the figure: 1, ozonizer, 2, the ozone oxidation reaction device, 3, topping-up pump, 4, ceramic film component, 5, gas-liquid separator, 6, the return of waste water pump, 7, the catalyzer reflux pump, 8, catalyzer adds pump, 9, catalyzer flows out groove, 10, catalyzer adds groove, 11, water inlet pipe, 12, inlet pipe, 13, tensimeter, 14, under meter, 15, check valve, 16, inlet mouth, 17, the micro-pore aeration plate, 18, backflow waste water shower nozzle, 19, catalyzer mud shower nozzle, 20, the return of waste water pipe, 21, under meter, 22, the return of waste water valve, 23, the backflow wastewater outlet, 24, the catalyzer return line, 25, check valve, 26, the concentrated solution spout, 27, water outlet, 28, outlet valve, 29, under meter, 30, weather gage, 31, water-in, 32, the permeate flow outlet, 33, weather gage, 34, the gas-liquid separator water intaking valve, 35, the gas-liquid separator water-in, 36, the gas-liquid separator water outlet, 37, the backwashing water outlet, 38, the back flushing water inlet pipe, 39, backwash pump, 40, the back flushing water-in, 41, the back flushing outlet valve, 42, catalyzer adds pipe, 43, catalyzer adds valve, 44, under meter, 45, catalyzer flows out pipe, 46, catalyzer flows out valve, 47, under meter.
Embodiment
For the ease of understanding, the invention will be further described below in conjunction with the drawings and specific embodiments.
The system of O3 catalytic oxidation of the present invention-ceramic membrane filter advanced treatment on coking wastewater, its preferable embodiment is:
Comprise that ozonizer, ozone oxidation reaction device, topping-up pump, ceramic film component, gas-liquid separator, return of waste water pump, catalyzer reflux pump, catalyzer flow out groove, catalyzer adds groove, catalyzer interpolation pump;
Described ozone oxidation reaction device is vertical tubular structure, its underpart is provided with water-in, inlet mouth, top is provided with water outlet and return of waste water mouth, be provided with the micropore air distribution plate between described water-in and the inlet mouth, ozone oxidation reaction device middle part is provided with backflow waste water shower nozzle, backflow waste water shower nozzle bottom is independent ozone oxidation district, and top, described independent ozone oxidation district is small-bore reaction pipeline section;
The diameter of described small-bore reaction pipeline section is 1/3～1/2 of its elsewhere diameter of ozone oxidation reaction device, and length is 1/3～1/8 of total reactor length, and it is suitable for reading to be connected with 45 °～75 ° inclined-planes with the wall of ozone oxidation reaction device upper and lower respectively with end opening;
Above the described backflow waste water shower nozzle catalyzer mud shower nozzle is set, two shower nozzle spray planes are relative, at a distance of 5cm～20cm, it is the turbulent flow mixing zone between spray plane, backflow waste water shower nozzle area is 2～4 times of catalyzer mud shower nozzle area, and spray speed also is 2～4 times, and catalyzer mud shower nozzle is 1/2～1/4 of ozone oxidation reaction device height to the vertical range at ozone oxidation reaction device top, catalyzer mud shower nozzle top conversion zone is the O3 catalytic oxidation district, and adopting median size is the CeO of 1 μ m～4 μ m
2Or Ce
xZr
1-xO
2Fine catalyst;
Described backflow waste water shower nozzle links to each other with return of waste water pump, return of waste water mouth by the return of waste water pipe, and the return of waste water ratio is 200%～400%;
Described catalyzer mud shower nozzle links to each other with the concentrated solution spout of ceramic film component by catalyzer return line, catalyzer reflux pump;
Described catalyzer return line is provided with two arms, and one pipe coupling catalyzer adds pump and catalyzer interpolation groove, and another pipe coupling catalyst stream goes out groove.
The water-in of described ozone oxidation reaction device is system's water-in, the water outlet of described ozone oxidation reaction device links to each other with the water-in of ceramic film component by topping-up pump, the water outlet of described ceramic film component links to each other with the water-in of described gas-liquid separator, the water outlet of described gas-liquid separator is system's water outlet, and the bottom of described gas-liquid separator links to each other with the back flushing water-in of ceramic film component by back flushing water inlet pipe, backwash pump.
The height of described ozone oxidation reaction device is 10～30 times of base diameter, and waste water residence time in reactor is 30min～90min.
Specific embodiment:
As shown in Figure 1, native system mainly is made up of ozonizer 1, O3 catalytic oxidation reactor 2, topping-up pump 3, ceramic film component 4, gas-liquid separator 5, return of waste water pump 6, catalyzer reflux pump 7, catalyzer interpolation pump 8, catalyzer outflow groove 9, catalyzer interpolation groove 10 and corresponding pipe fitting, valve and instrument.
System of the present invention is work like this: coking chemical waste water is by entering O3 catalytic oxidation reactor 2 by water inlet pipe 11, the ozone and the oxygen mixed gas that come out from ozonizer 1 pass through inlet pipe 12, flow through tensimeter 13, under meter 14, check valve 15 successively, enter ozone oxidation reaction device 2 by inlet mouth 16, behind micro-pore aeration plate 17, form a large amount of micro-bubbles in ozone oxidation reaction device 2, bubble is more little, and resistance to mass transfer is little.Gaseous ozone in the micro-bubble can be dissolved in rapidly in the waste water, organism generation rapid reaction in independent ozone oxidation district and coking chemical waste water.
Exist speed of reaction between a large amount of easily biodegradable organics (as phenol, quinoline, indoles, contain long chain hydrocarbon, aromatic hydrocarbon and the heterogeneous ring compound etc. of two keys and triple bond) and the ozone far above rate of mass transfer in the coking chemical waste water, therefore in the ozone oxidation process, rate of mass transfer is rate-limiting factor.Resistance to mass transfer mainly is resistance between the gas-liquid when adopting independent ozone oxidation, does not adopt catalyzer and resistance to mass transfer between the solid-liquid that brings.Because system has adopted micro-pore aeration, resistance to mass transfer between the gas-liquid is less, speed of reaction is very fast, these readily oxidizable substances can very fast oxidized a large amount of one-tenth molecular weight less organic acid and the alcohol compound of having generated, these compounds are difficult to be risen along reactor with waste water then by the organism of independent ozone oxidation degraded.
In uphill process, the ozone in the gas phase is mass transfer in the liquid phase further, in the make up water because the used up ozone of ozone oxidation separately.Waste water rises and to enter the small-bore reaction pipeline section on top, independent ozone oxidation district, and this section reactor diameter is 1/3～1/2 of its elsewhere diameter of reactor, and length is 1/3～1/8 of total reactor length, is connected with 45 °～75 ° inclined-planes with reactor wall up and down.Because water-carrying section dwindles, thereby the increase of waste water flow velocity, bigger flow velocity can prevent the solid catalyst on top because gravity sinks.Coking chemical waste water continues to rise and arrives backflow waste water shower nozzle 18, and through the space between shower nozzle and the reactor wall, water-carrying section reduces rapidly, and it is big that flow velocity sharply becomes, and current form surging force upwards, further prevent catalyzer because gravity sinks.
Be 19, two relative water distributions of shower nozzle of catalyzer mud shower nozzle above the backflow waste water shower nozzle 18, at a distance of 5cm～20cm, backflow waste water shower nozzle area is 2～4 times of catalyzer mud shower nozzle area, and spray speed also is 2～4 times.Two shower nozzles are at a distance of nearer, the fluid of ejection clashes into mutually, in the middle of two shower nozzles, scatter to reactor limit wall, because the rate of flow of fluid of the backflow waste water shower nozzle of bottom ejection is greater than the rate of flow of fluid of catalyzer mud shower nozzle ejection, therefore the fluid that bumps against forms flow velocity obliquely, channel of reactor along the shower nozzle both sides rises, and is subjected to the waste water impact that reactor bottom rises at a high speed simultaneously, and the reactor area of three strands of current between two shower nozzles forms the turbulent flow mixing zones.In the turbulent flow mixing zone, catalyzer is subjected to the impact of fluid obliquely all the time, is difficult to sink to below the backflow waste water shower nozzle, and this structure of reactor has effectively avoided catalyzer to flow into independent ozone oxidation zone.
Waste water flows through the turbulent flow mixing zone and has just entered the O3 catalytic oxidation district above the catalyzer mud shower nozzle, O3 catalytic oxidation district height is 1/2～1/4 of whole reactor height, because what use is fine catalyst, therefore the catalyzed oxidation district has been full of catalyzer, be difficult in the waste water by the organism of ozone oxidation removal separately under catalyst action, remove by the O3 catalytic oxidation effect, partial organic substances also can be removed by fine catalyst absorption.
The O3 catalytic oxidation process relates to processes such as a series of mass transfers, chemical reaction, absorption and desorption.Wherein, resistance to mass transfer between the gas-liquid and between liquid-solid has significant effects to the O3 catalytic oxidation reaction, turbulent flow between the gas-liquid-solid three-phase mix can farthest reduce between gas phase body phase, the gas-liquid, the liquid phase body mutually and the resistance to mass transfer between the solid-liquid, improve O3 catalytic oxidation efficient; The CeO that adopts
2Or Ce
xZr
1-xO
2The fine catalyst median size is 1 μ m～4 μ m, and specific surface area and catalyst activity are all higher, and catalyst surface almost can be ignored to the resistance to mass transfer in aperture.With respect to the fixed-bed reactor of use beaded catalyst commonly used, these structures make native system have much higher reactor mass-transfer efficiency and O3 catalytic oxidation efficient, thereby the clearance of hardly degraded organic substance is also much higher relatively in the coking chemical waste water.
Backflow waste water shower nozzle 18 links to each other with under meter 21, return of waste water pump 6, return of waste water valve 22, backflow wastewater outlet 23 by return of waste water pipe 20.The return of waste water ratio is 100%～300%, and bigger reflux ratio is conducive to improve organic removal rate, and bigger reflux ratio also can provide flow velocity bigger current for shower nozzle simultaneously.
Catalyzer mud shower nozzle 19 links to each other with the concentrated solution spout 26 of check valve 25, catalyzer reflux pump 7, ceramic film component 4 successively by catalyzer return line 24.
2 water outlets of ozone oxidation reaction device are from water outlet 27, enter topping-up pump 3 through ozone oxidation reaction device outlet valve 28, the ozone amount that dissolves in the waste water after the supercharging increases, under meter 29 is passed through in topping-up pump 3 water outlets successively, weather gage 30, enter ceramic film component 4 by the water-in 31 of ceramic film component 4 and carry out solid-liquid separation, it is 0.1 μ m that the mean molecule of ceramic film component is held back diameter, catalyzer is held back the aperture greater than the ceramic membrane mean molecule and is retained down owing to particle diameter, other particulate matter in the coking chemical waste water also almost all are retained down, and turbidity removal rate almost reaches 100%.The catalyzer of holding back is discharged by concentrated solution relief outlet 26 with concentrated solution, under 7 effects of catalyzer reflux pump, along catalyzer return line 24, via check valve 25, enters ozone oxidation reaction device 2, by 19 ejections of catalyzer mud shower nozzle, realizes the catalyzer reuse again.The water of molecular state then permeation ceramic membrane forms penetrating fluid, penetrating fluid flows out from the permeate flow outlet 32 of ceramic film component 4, pass through weather gage 33 and gas-liquid separator water intaking valve 34 successively, enter gas-liquid separator from gas-liquid separator water-in 35, realize gas-liquid separation here, the tail gas of gas-liquid separator can be delivered to exhaust treatment system and handle.
Gas-liquid separator water outlet 36 is the water outlet of total system.The backwashing water outlet 37 of gas-liquid separator bottom links to each other by the back flushing water-in 40 of back flushing water inlet pipe 38 with backwash pump 39, ceramic film component 4, open back flushing outlet valve 41, backwash pump 39, catalyzer reflux pump 7, check valve 25, just can clean ceramic film component.After waste water was discharged ozone oxidation reaction device 2, remaining solvability ozone still in the water have germicidal action, thereby microorganism was difficult to growth in the ceramic membrane, and it mainly is inorganic pollution that ceramic membrane pollutes, and only depends on simple washing just can realize the self-stip of ceramic membrane.
When ozone oxidation reaction device height is 10～30 times of base diameter, waste water residence time in reactor, coking wastewater deep treatment can obtain optimum effect when being 30min～90min.Because O3 catalytic oxidation has very strong oxidation of organic compounds ability, thereby to the colourity (mainly being that organic chromophoric group produces) of coking chemical waste water two stage biological water outlet and the clearance height of COD; Also near 100%, solvability ozone residual in the waste water has disinfecting power to ceramic film component to the clearance of particulate matter.When the COD of coking chemical waste water two stage biological technology water outlet is 200～400mg/L, water-quality guideline such as the COD of system's water outlet, colourity and turbidity all can stablize reach " integrated wastewater discharge standard " (GB8978-1996) in primary standard, water outlet can also be carried out reuse as coke-oven plant's miscellaneous water, 1～2 yuan/ton of the running cost of total system.
When catalyst reactor need be changed, can add at catalyzer and prepare the mud that contains catalyzer in the groove 10, catalyst concn is consistent with concentration in the catalyzer return line in the mud, open catalyzer then and add catalyzer interpolation valve 43 and the catalyzer interpolation pump 8 of managing on 42, close the check valve 25 on the catalyzer return line 24, add under pump 8 effects at catalyzer, the catalyzer mud for preparing adds pipe 42 along catalyzer, enter catalyzer return line 24 through under meter 44, finally enter ozone oxidation reaction device 2.
Open and to open the catalyzer that catalyzer flows out on the pipe 45 when catalyzer adds valve 43 and flow out valve 46, the catalyzer mud that flows out in the catalyzer reflux pump 7 just can flow out pipe 45 along catalyzer, flow out valve 46 and under meter 47 through catalyzer successively, enter catalyzer and flow out groove 9.Catalyzer in service adds speed and catalyzer outflow speed is consistent, after treating to be full of catalyzer mud in the catalyzer outflow groove 9, close catalyzer successively and add valve 43, catalyzer interpolation pump 8, catalyzer outflow valve 47, open the check valve 44 on the catalyzer return line 24, system becomes can get back to normal operation.
It is simple that whole catalyzer is changed process, can adopt automated installation control entire operation process, and the catalyzer after the replacing can be transported to functional body outward and carry out catalyst regeneration.
The above; only for the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (3)
1. the system of O3 catalytic oxidation-ceramic membrane filter advanced treatment on coking wastewater, it is characterized in that, comprise that ozonizer, ozone oxidation reaction device, topping-up pump, ceramic film component, gas-liquid separator, return of waste water pump, catalyzer reflux pump, catalyzer flow out groove, catalyzer adds groove, catalyzer interpolation pump;
Described ozone oxidation reaction device is vertical tubular structure, its underpart is provided with water-in, inlet mouth, top is provided with water outlet and return of waste water mouth, be provided with the micropore air distribution plate between described water-in and the inlet mouth, ozone oxidation reaction device middle part is provided with backflow waste water shower nozzle, backflow waste water shower nozzle bottom is independent ozone oxidation district, and top, described independent ozone oxidation district is small-bore reaction pipeline section;
The diameter of described small-bore reaction pipeline section is 1/3～1/2 of its elsewhere diameter of ozone oxidation reaction device, and length is 1/3～1/8 of total reactor length, and it is suitable for reading to be connected with 45 °～75 ° inclined-planes with the wall of ozone oxidation reaction device upper and lower respectively with end opening;
Above the described backflow waste water shower nozzle catalyzer mud shower nozzle is set, two shower nozzle spray planes are relative, at a distance of 5cm～20cm, it is the turbulent flow mixing zone between spray plane, backflow waste water shower nozzle area is 2～4 times of catalyzer mud shower nozzle area, and spray speed also is 2～4 times, and catalyzer mud shower nozzle is 1/2～1/4 of ozone oxidation reaction device height to the vertical range at ozone oxidation reaction device top, catalyzer mud shower nozzle top conversion zone is the O3 catalytic oxidation district, and adopting median size is the CeO of 1 μ m～4 μ m
2Or Ce
xZr
1-xO
2Fine catalyst;
Described backflow waste water shower nozzle links to each other with return of waste water pump, return of waste water mouth by the return of waste water pipe, and the return of waste water ratio is 200%～400%;
Described catalyzer mud shower nozzle links to each other with the concentrated solution spout of ceramic film component by catalyzer return line, catalyzer reflux pump;
Described catalyzer return line is provided with two arms, and one pipe coupling catalyzer adds pump and catalyzer interpolation groove, and another pipe coupling catalyst stream goes out groove.
2. the system of O3 catalytic oxidation according to claim 1-ceramic membrane filter advanced treatment on coking wastewater, it is characterized in that, the water-in of described ozone oxidation reaction device is system's water-in, the water outlet of described ozone oxidation reaction device links to each other with the water-in of ceramic film component by topping-up pump, the water outlet of described ceramic film component links to each other with the water-in of described gas-liquid separator, the water outlet of described gas-liquid separator is system's water outlet, and the bottom of described gas-liquid separator is by the back flushing water inlet pipe, backwash pump links to each other with the back flushing water-in of ceramic film component.
3. the system of O3 catalytic oxidation according to claim 1 and 2-ceramic membrane filter advanced treatment on coking wastewater, it is characterized in that, the height of described ozone oxidation reaction device is 10～30 times of base diameter, and waste water residence time in reactor is 30min～90min.
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| CN103145266A (en) * | 2013-03-20 | 2013-06-12 | 上海大学 | Method for treating coking wastewater by using ozone under catalysis of activated carbon |
| CN103570120B (en) * | 2013-03-27 | 2015-09-23 | 北京林业大学 | A kind of preparation of cerium oxide changed red mud catalyzer and the application in water technology thereof |
| CN104529001B (en) * | 2014-12-24 | 2016-09-21 | 北京桑德环境工程有限公司 | Efficiently remove COD in waste watercro3 catalytic oxidation fluidized-bed reactor |
| CN106045005B (en) * | 2016-08-08 | 2023-10-20 | 苏州希克曼物联技术有限公司 | Device and method for synergistic oxygenation of organic matters by heterogeneous catalytic ozonation |
| CN106630110A (en) * | 2017-03-01 | 2017-05-10 | 南京大学 | Integrated fluidized bed device for gradient ozone catalyzing and application of integrated fluidized bed device |
| CN109516589B (en) * | 2017-09-20 | 2020-11-17 | 清华大学 | Process for treating coking wastewater by membrane method |
| CN112678985B (en) * | 2019-10-18 | 2023-04-18 | 中国石油化工股份有限公司 | Method and device for pretreating negative-hardness water containing scale inhibitor |
| CN111484118A (en) * | 2020-04-28 | 2020-08-04 | 光大水务科技发展（南京）有限公司 | Powder catalyst ozone catalytic oxidation effluent disposal system |
| CN111792751A (en) * | 2020-06-18 | 2020-10-20 | 神马实业股份有限公司 | Treatment method of caprolactam production wastewater |
| CN112007591B (en) * | 2020-09-15 | 2022-06-10 | 江苏诺盟化工有限公司 | Method for treating phenolic wastewater by adopting loop reactor |
| CN114426352A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Coking wastewater treatment device and method |
| CN115520953A (en) * | 2022-06-28 | 2022-12-27 | 胡长龙 | Coal chemical industry advanced wastewater treatment CoSD reaction tower |
| CN115739066A (en) * | 2022-10-31 | 2023-03-07 | 西安建筑科技大学 | Biochar catalyst, preparation method thereof, and landfill leachate treatment system and method |
| CN115849595A (en) * | 2022-11-15 | 2023-03-28 | 上海交通大学重庆研究院 | Micro-nano O catalyzed by percolate concentrated solution 3 -membrane electrochemical treatment apparatus and method |
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| US7214350B2 (en) * | 2002-03-13 | 2007-05-08 | Capital Technology, S.A. | Device for the continuous burning of carbon particles |
| CN102001767B (en) * | 2010-10-26 | 2012-12-05 | 中国矿业大学(北京) | Advanced treatment system of coking wastewater |
| CN202465455U (en) * | 2012-01-05 | 2012-10-03 | 大连善水德水务工程有限责任公司 | Novel membrane concentrated water treatment device |
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