CN103708657B - Deep oxidation treatment method and apparatus for difficultly-degraded organic chemical industry wastewater - Google Patents
Deep oxidation treatment method and apparatus for difficultly-degraded organic chemical industry wastewater Download PDFInfo
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Abstract
A purpose of the present invention is to provide a deep oxidation treatment apparatus for difficultly-degraded organic chemical industry wastewater so as to solve bottleneck problems of low treatment efficiency, poor stability, excessive CODcr in effluent, high equipment investment, large occupation area, high operation cost and the like of the conventional deep treatment method after the organic chemical industry wastewater is subjected to the conventional two-stage biochemistry treatment. The present invention further provides a deep oxidation treatment method for difficultly-degraded organic chemical industry wastewater through combination of acidification bacterial removal, two-stage enhanced electrochemistry (micro-electrolysis) and two-stage heterogeneous catalysis (Fenton-like) oxidation. The apparatus comprises an acidification bacterial removal tank, a first-stage enhanced electrochemistry reactor, a second-stage enhanced electrochemistry reactor, a first-stage heterogeneous catalysis oxidation reactor and a second-stage heterogeneous catalysis oxidation reactor, wherein the acidification bacterial removal tank, the first-stage enhanced electrochemistry reactor, the second-stage enhanced electrochemistry reactor, the first-stage heterogeneous catalysis oxidation reactor and the second-stage heterogeneous catalysis oxidation reactor are sequentially connected through pipelines, the connection pipeline between the acidification bacterial removal tank and the first-stage enhanced electrochemistry reactor is provided with a lift pump, and the second-stage heterogeneous catalysis oxidation reactor is connected with a water outlet pipe.
Description
Technical field
The invention belongs to environmental engineering technical field of waste water processing, particularly a kind of difficult degradation organic chemical waste water deep oxidation treatment process and device.
Background technology
Chemical industry occupies critical role in Chinese national economy, is the mainstay industry of China.Wastewater from chemical industry occupies very large proportion in China's discharged volume of industrial waste water.Along with the expansion with scale that develops rapidly of chemical industry, the harm that environment causes also is being deepened gradually.According to the up-to-date environmental statistic data of State Statistics Bureau, within 2011, China's each department wastewater emission amount is 659.2 hundred million tons, and discharged volume of industrial waste water is 212.9 hundred million tons, wherein chemical industry (comprising chemical feedstocks and chemical preparations manufacture, medicine manufacture and chemical fibre manufacturing) wastewater emission amount is 37.8 hundred million tons, account for 17.8% of national discharged volume of industrial waste water, only than papermaking and paper product industries wastewater discharge 38.2 hundred million tons few 0.4 hundred million tons, and become second largest industry of discharged volume of industrial waste water.Wastewater from chemical industry is bio-refractory wastewater from chemical industry particularly, and be the difficult problem that sewage disposal circle both at home and abroad is at present generally acknowledged, it causes serious pollution to environment.Such waste water has the features such as quantity discharged is large, wide, water quality is complicated, pollutent Stability Analysis of Structures, strong toxicity (as aniline evil, heterocyclic etc.).Because this kind of wastewater treatment difficulty is large, investment and working cost higher, and effective and ripe treatment technology is difficult to seek, a lot of enterprise does not take effective treatment measures, greatly have impact on water ecological environment after making to enter water body environment without the hardly degraded organic substance effectively processed in a large number, threaten HUMAN HEALTH.Given this; Technology Standards Division of national environmental protection portion constantly again works out chemical industry wastewater discharge standard and revises; each province and city step up to work out regulation lifting scheme; emission standard is more and more stricter, and therefore the process of bio-refractory wastewater from chemical industry also becomes a present stage environmental protection technical field difficult problem urgently to be resolved hurrily.
Tradition chemical industry method of wastewater treatment, mainly with " pre-treatment+secondary biochemical treatment ", directly accesses urban wastewater treatment firm after discharge or pre-treatment after standard water discharge and focuses on.At present, although wastewater from chemical industry greatly can improve effluent quality after secondary biochemical treatment, remaining organism is the organism of difficult for biological degradation, the very difficult stably reaching standard discharge had, need to solve long-acting up to standard or be about to face carry mark upgrade problem; Though what have is up to standard, and outlet water organic substance concentration is lower, if carry out reuse, still need further advanced treatment, to reduce the pollutant load in water as far as possible, prevent the accumulation of refractory organic in reuse process.
Bio-refractory wastewater from chemical industry advanced treatment is on the basis of traditional secondary biochemical treatment, in order to stably reaching standard discharge or carry mark or before reaching reuse standard to the process that waste water is for further processing.According to the analysis to such waste water industry water quality characteristics and bio-refractory organic pollutant general character, wastewater from chemical industry advanced treatment is badly in need of solving following key issue.
(1) bio-refractory wastewater from chemical industry water quality is complicated, and pollution source is wide, and the method taked must have broad spectrum, and subject range and ability by force, have and destroy pollutent structure, reduction toxicity and remove the multiple efficacies such as COD;
(2) method easy and simple to handle, easily grasp, convenient management;
(3) require low, without the need to High Temperature High Pressure to auxiliary facility or equipment and materials;
(4) investment and running cost relatively low, there is good economy.
Summary of the invention
The present invention aims to provide a kind of difficult degradation organic chemical waste water deep oxidation treatment unit, being intended to solve difficult degradation organic chemical waste water after traditional secondary biochemical treatment, often there is the bottleneck problems such as processing efficiency is low, poor stability, water outlet CODcr exceed standard, facility investment is high, floor space is large, working cost is high in conventional depth treatment process.
The present invention also provides a kind of, two-stage strengthening electrochemistry (light electrolysis), two-stage heterogeneous catalyst (Fenton-like) degerming by acidifying to be oxidized the difficult degradation organic chemical waste water deep oxidation treatment process combined.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of difficult degradation organic chemical waste water deep oxidation treatment unit, comprise the degerming pond of acidifying of pipeline connection successively, primary reinforcement electrochemical reactor, secondary reinforcement electrochemical reactor, one-level multi-phase catalytic oxidation device, secondary multi-phase catalytic oxidation device, connecting pipeline between the degerming pond of acidifying and primary reinforcement electrochemical reactor is provided with lift pump, and secondary multi-phase catalytic oxidation device is connected with rising pipe; In primary reinforcement electrochemical reactor, secondary reinforcement electrochemical reactor, one-level multi-phase catalytic oxidation device, secondary multi-phase catalytic oxidation device, the aerating pipelines be connected with aeration main pipeline is all installed; Primary reinforcement electrochemical reactor and secondary reinforcement electrochemical reactor inside are equipped with micro-electrolysis stuffing layer; Primary reinforcement electrochemical reactor, secondary reinforcement electrochemical reactor, one-level multi-phase catalytic oxidation device, secondary multi-phase catalytic oxidation device inside is provided with effluent weir and the height of each effluent weir successively decreases successively.The present invention is directed to chemical industry bio-refractory wastewater from chemical industry, after traditional secondary biochemical treatment, adopt acidifying degerming+two-stage strengthening electrochemistry (light electrolysis)+two-stage heterogeneous catalyst (Fenton-like) is oxidized coordination technique and device, Persistent organic pollutants are resolved into the inorganic substance such as carbonic acid gas and water, COD and toxicity are reduced greatly, realize the object of wastewater from chemical industry advanced treatment and qualified discharge, a difficult problem for practical solution China's bio-refractory wastewater from chemical industry advanced treatment qualified discharge under the new situation, for the technical support that enterprise provides transformation to provide crucial, promote the coordinated development of chemical industry economic benefit and environmental benefit.
As preferably, in the degerming pond of described acidifying, lower logical dividing plate and aeration tube are set, in the degerming pond of acidifying, the side of lower logical dividing plate arranges sour throwing device, and one end that the opposite side of lower logical dividing plate is adjacent with lift pump is provided with pH controller, and pH controller is used for the sour dosage of interlocked control acid throwing device.
As preferably, primary reinforcement electrochemical reactor is identical with the internal structure of secondary reinforcement electrochemical reactor, and one-level multi-phase catalytic oxidation device is identical with the internal structure of secondary multi-phase catalytic oxidation device.
As preferably, the top of micro-electrolysis stuffing layer is provided with filler and adds post, and filler adds the cylindrical shell that post is upper and lower opening, and the top that filler adds post is positioned at the top of primary reinforcement electrochemical reactor end socket.
As preferably, described aerating pipelines distributes ringwise in each reactor.
As preferably, the connecting pipeline between primary reinforcement electrochemical reactor and secondary reinforcement electrochemical reactor is arranged sequentially automatic acid chemicals dosing plant and pH controller; Connecting pipeline between secondary reinforcement electrochemical reactor and one-level multi-phase catalytic oxidation device is arranged sequentially automatic acid chemicals dosing plant, hydrogen peroxide throwing device and pH controller; Connecting pipeline between one-level multi-phase catalytic oxidation device and secondary multi-phase catalytic oxidation device is arranged sequentially automatic acid chemicals dosing plant, hydrogen peroxide throwing device and pH controller.
As preferably, tandem three layers turbulent flow reaction ring is all set in one-level multi-phase catalytic oxidation device, secondary multi-phase catalytic oxidation device from bottom to top---circular turbulent flow reaction ring, one-level taper turbulent flow reaction ring, secondary taper turbulent flow reaction ring.
As preferably, circular turbulent flow reaction ring opening diameter 50mm, radial aperture rate 5%, return port is opened in firsts and seconds taper turbulent flow reaction ring lower end, and orifice diameter is 200mm-500mm; The perforate dislocation of the firsts and seconds taper turbulent flow reaction ring in every grade of multi-phase catalytic oxidation device is split.Circular turbulent flow reaction ring is the circular slab being evenly equipped with multiple hole.One-level taper turbulent flow reaction ring is identical with the structure of secondary taper turbulent flow reaction ring, and entirety is conically, conical opening up.
A kind of difficult degradation organic chemical waste water deep oxidation treatment process, the method adopts foregoing device, the water outlet after secondary biochemical treatment of difficult degradation organic chemical waste water enters in the degerming pond of acidifying and pumps into primary reinforcement electrochemical reactor behind automatical dosing adjust ph to 2.5 ~ 4.0, waste water is from bottom to top by micro-electrolysis stuffing layer, waste water completes one-level light electrolysis and phenyl ring at this, the preliminary open loop chain rupture of the ring-type organic pollutants such as heterocycle, then in the outlet conduit of primary reinforcement electrochemical reactor, acid for adjusting pH value is added to 3.0 ~ 3.5, gravity type boat davit flows into secondary reinforcement electrochemical reactor, waste water continues from bottom to top by micro-electrolysis stuffing layer, complete secondary micro-electrolysis reaction and residue phenyl ring, the thorough open loop chain rupture of the ring-type organic pollutants such as heterocycle, after the outlet conduit of secondary reinforcement electrochemical reactor adds oxygenant, gravity flows into one-level multi-phase catalytic oxidation device, waste water is after one-level multi-phase catalytic oxidation, in waste water, long-chain shape organic pollutant major part is oxidized to short chain organism, after on the outlet conduit of one-level multi-phase catalytic oxidation device, secondary adds oxygenant, gravity flows into secondary multi-phase catalytic oxidation device, secondary multi-phase catalytic oxidation makes the short chain organic pollutant of long-chain organic pollutant and generation be oxidized to carbonic acid gas and water, part forms flco, water outlet carries out mud-water separation with coagulating sedimentation again in follow-up routine.As preferably, described oxygenant is hydrogen peroxide.Added in batches by two-stage multi-phase catalytic oxidation device, the utilization ratio of such oxidant hydrogen peroxide is higher.
Present method is worked in coordination with by many gradients organic contamination concentration, molecular structure and multi-stage oxidizing function, namely utilizes strengthening electrochemistry open loop and catalyzed oxidation chain rupture oxidation; Electrochemistry (light electrolysis) series connection is strengthened, the two-stage of configuration series connection simultaneously heterogeneous catalytic oxidation, the nascent state Fe that the hydrogen peroxide that catalytic section is added and above light electrolysis section produce by two-stage
2+there is the coupling reaction of two Fenton-like catalyzed oxidations, combine and form multi-stage oxidizing Synergistic method technology and device, reach the object of the hardly degraded organic substance remained after the degree of depth effectively removes difficult degradation organic chemical waste water second-stage treatment.
Deep oxidation treatment process is strengthened the multifunction system of electrochemical reactor and two-stage catalyst oxidation reactor organic assembling, and science constructs difficult degradation organic chemical waste water deep oxidation treatment technology system.
PH value needed for primary reinforcement electrochemical reaction, control ph is convenient in the acid neutralization reaction zone arranged by acidifying degerming pond leading portion, the degerming pond of acidifying all adopts air aeration to stir, acidifying degerming pond useful volume is not less than the 2.0h residence time, realize dual-use function, one is meet pH value requirement, two is make tiny microorganism residual in second-stage treatment (biochemistry) water outlet above and zoogloea dehydration death by acidifying aeration, prevent the hole of the jelly blocking micro-electrolysis stuffing in waste water, improve light electrolysis efficiency.
Present method front end adopts the two-stage strengthening electrochemical reactor of high and low concentration section, and rear end adopts two-stage heterogeneous catalyst (Fenton-like) oxidation; Two-stage strengthening electrochemical reactor arranges end socket by device top, arranges in the middle of it to add stock column and carry out adding and the micro-electrolysis stuffing that consumes in postreaction process.All aerated conduit is set and air flowmeter is installed bottom two-stage strengthening electrochemistry and two-stage Fenton-like catalyst oxidation reactor, control oxidation reaction zones at different levels aeration intensity respectively.
Chemical industry development rapidly, the wastewater from chemical industry complicated of meanwhile discharging in production process, organic content is high, saltiness is high, colourity and toxicity large, environmental pollution also increasingly sharpens; Process this type of waste water technically or all there is larger difficulty economically, conventional depth disposal methods often invest high, floor space is large, working cost is high, waste water resource, user is difficult to bear.Along with the requirement of energy-saving and emission-reduction is more and more higher, discharge standard is increasingly strict, the 13 class industries such as chemical industry, pharmacy, plating, synthetic leather and leatheroid improve pollution discharge standard, and to special sensitizing range as Taihu Lake basin etc. sets the special emission standard of country.In the face of new emission standard and reduction of discharging requirement, how toxicity difficult degradation organic chemical waste water is carried out advanced treatment and make it stably reaching standard discharge or be better than effluent standard or reuse, alleviate environmental pollution, development of new energy-conserving and emission-cutting technology is the most important thing.The present invention less energy-consumption is strengthened electrochemistry (light electrolysis) method and heterogeneous catalyst (Fenton-like) method for oxidation carries out collaborative and integrated, formation broad spectrum is strong, reliable, easy to operate, economical and effective deep treatment method Technology and equipment, solving difficult for biological degradation wastewater from chemical industry secondary biochemical effluent can not stably reaching standard, and advanced treatment carries the technical barrier such as mark and reuse difficulty, will play key effect to the advanced treatment of the industry toxicity difficult degradation wastewater from chemical industry such as China's medication chemistry.
Accompanying drawing explanation
Fig. 1 is the structural representation of apparatus of the present invention;
Fig. 2 is the structural representation of the present invention's circular turbulent flow reaction ring;
Fig. 3 is the side-looking structural representation of taper of the present invention turbulent flow reaction ring;
In figure:
Logical dividing plate, the degerming pond of 5-acidifying, 6-pH controller, 7-lift pump under 1-workshop water shoot, 2-acid throwing device, 3-aeration tube, 4-,
8-primary reinforcement electrochemical reactor, 8.1-rich shape perforate water distributor, 8.2-filler supporting plate, 8.3-micro-electrolysis stuffing layer, 8.4-effluent weir, 8.5-end socket, 8.6-primary reinforcement electrochemical reactor filler feed intake post, 8.7-access opening, 8.8-gas sampling pipe, 8.9-automatic acid chemicals dosing plant, 8.10-pH controller, 8.11-blow-down pipe, 8.12 water outlets
9-aeration main pipeline, 9.1-aerating pipelines,
10-secondary reinforcement electrochemical reactor, 10.1-hydrogen peroxide throwing device,
11-one-level multi-phase catalytic oxidation device, 11.1-effluent weir, 11.2-end socket, 11.3-gas sampling pipe, 11.5-rich shape perforate water distributor, 11.7-circular turbulent flow reaction ring, 11.8-one-level taper turbulent flow reaction ring, 11.9-react ring bracing frame, the reaction of 11.10-secondary taper turbulent flow ring, 11.11-blow-down pipe
12-secondary multi-phase catalytic oxidation device,
13-rising pipe.
Embodiment
Below by specific embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention and/or change all will fall into scope.
Embodiment:
A kind of difficult degradation organic chemical waste water deep oxidation treatment unit as shown in Figure 1, comprise the degerming pond 5 of the acidifying connected by pipeline successively, primary reinforcement electrochemical reactor 8, secondary reinforcement electrochemical reactor 10, one-level multi-phase catalytic oxidation device 11, secondary multi-phase catalytic oxidation device 12, secondary multi-phase catalytic oxidation device 12 is connected with rising pipe 13, and the water outlet through rising pipe 13 enters in follow-up routine and coagulating sedimentation finally completes mud-water separation.
Primary reinforcement electrochemical reactor 8, secondary reinforcement electrochemical reactor 10, one-level multi-phase catalytic oxidation device 11, secondary multi-phase catalytic oxidation device 12 inside are all provided with the aerating pipelines be connected with aeration main pipeline 9, and aerating pipelines distributes ringwise in each reactor.Connecting pipeline between the degerming pond 5 of acidifying and primary reinforcement electrochemical reactor 8 is provided with lift pump 7.Primary reinforcement electrochemical reactor, secondary reinforcement electrochemical reactor, one-level multi-phase catalytic oxidation device, secondary multi-phase catalytic oxidation device inside is provided with effluent weir and the height of each effluent weir successively decreases successively.
Workshop water shoot 1 accesses the degerming pond 5 of acidifying, in the middle of acidifying degerming pond 5, lower logical dividing plate 4 is set, the front end of lower logical dividing plate 4 as acid neutralization reaction zone, be equipped with sour throwing device 2, aeration tube 3 and pH controller 6, pH controller be used for the sour dosage of interlocked control acid throwing device.Acid throwing device 2 is positioned at lower logical dividing plate 4 side adjacent with workshop water shoot 1, and pH controller 6 is positioned at the opposite side of lower logical dividing plate 4.
Primary reinforcement electrochemical reactor 8 is the tube structure with end socket 8.5, this inner barrel sets gradually rich shape perforate water distributor 8.1, aerating pipelines 9.1 from bottom to top, filler supporting plate 8.2, micro-electrolysis stuffing layer 8.3, the bottom of primary reinforcement electrochemical reactor 8 is connected with blow-down pipe 8.11, end socket sealing is reserved at top, prevent that waste gas is excessive causes atmospheric pollution, gas sampling pipe 8.8 is offered in end socket side, and double as foam gathering system interface, the blow-down pipe 8.11 of this Guan Keyu reactor bottom is communicated with, and docks with defoaming system.The top of primary reinforcement electrochemical reactor 8 sets out mill weir 8.4 and collects the even water outlet of reactor surrounding, and set out the mouth of a river 8.12 in outlet area correspondence, the connecting pipeline between primary reinforcement electrochemical reactor 8 and secondary reinforcement electrochemical reactor 10 is arranged sequentially automatic acid chemicals dosing plant 8.9 and pH controller 8.10.This section of connecting pipeline one end connects water outlet, and the other end is connected with the rich shape perforate water distributor in secondary reinforcement electrochemical reactor 10.Effluent weir 8.4 and the automatic acid chemicals dosing plant 8.9 be equipped with and pH controller 8.10, with meeting tier 2 strengthening electrochemical reactor to the requirement of pH value.The top of primary reinforcement electrochemical reactor 8 arranges the filler be communicated with micro-electrolysis stuffing layer 8.3 and adds post 8.6, the top of micro-electrolysis stuffing layer is provided with filler and adds post, filler adds the cylindrical shell that post is upper and lower opening, and the top that filler adds post is positioned at the top of primary reinforcement electrochemical reactor end socket.The reactor cylinder body sidewall of micro-electrolysis stuffing layer 8.3 correspondence position is equipped with access opening 8.7.
The structure of secondary reinforcement electrochemical reactor 10 is with primary reinforcement electrochemical reactor 8, both differences are only that the height of the effluent weir that secondary reinforcement electrochemical reactor 10 inside is arranged is lower than the effluent weir of primary reinforcement electrochemical reactor 8, the connecting pipeline between secondary reinforcement electrochemical reactor 10 and one-level multi-phase catalytic oxidation device 11 is arranged sequentially automatic acid chemicals dosing plant 8.9, hydrogen peroxide throwing device 10.1 and pH controller 8.10.
One-level multi-phase catalytic oxidation device 11 is also the tube structure with end socket 11.2, this inner barrel sets gradually rich shape perforate water distributor 11.5 from bottom to top, aerating pipelines 9.1, circular turbulent flow reaction ring 11.7, one-level taper turbulent flow reaction ring 11.8, secondary taper turbulent flow reaction ring 11.10, the bottom of primary reinforcement electrochemical reactor 8 is connected with blow-down pipe 11.11, end socket sealing is reserved at top, prevent that waste gas is excessive causes atmospheric pollution, gas sampling pipe 11.3 is offered in end socket side, and double as foam gathering system interface, the blow-down pipe 11.11 of this Guan Keyu reactor bottom is communicated with, dock with defoaming system.As shown in Figure 2, it is the circular web plate being evenly equipped with multiple hole to the structure of circular turbulent flow reaction ring 11.7.The structure of one-level taper turbulent flow reaction ring 11.8 and secondary taper turbulent flow reaction ring 11.10 is shown in Fig. 3, entirety conically, conical opening up, one-level taper turbulent flow reaction ring 11.8 and secondary taper turbulent flow react ring 11.10 and are fixed on one-level multi-phase catalytic oxidation device by reaction ring bracing frame 11.9 inner.The height of the effluent weir that one-level multi-phase catalytic oxidation device inside is arranged, lower than the effluent weir of secondary reinforcement electrochemical reactor, the connecting pipeline between one-level multi-phase catalytic oxidation device and secondary multi-phase catalytic oxidation device is arranged sequentially automatic acid chemicals dosing plant 8.9, hydrogen peroxide throwing device 10.1 and pH controller 8.10.
Circle turbulent flow reaction ring 11.7 in the present embodiment, and one-level taper turbulent flow reacts ring 11.8 and secondary taper turbulent flow reaction ring 11.10 all can be replaced by the screen net structure of applicable perforate size.
The structure of secondary multi-phase catalytic oxidation device 12 is identical with one-level multi-phase catalytic oxidation device 11, and difference is only that the effluent weir position arranged is relatively low.
Tandem three layers turbulent flow reaction ring is all set in two-stage multi-phase catalytic oxidation device---circular turbulent flow reaction ring 11.7, one-level taper turbulent flow reaction ring 11.8, secondary taper turbulent flow reaction ring 11.10, can when not increasing power by the configuration of thtee-stage shiplock turbulent flow reaction ring, make useless Organic substance in water and oxygenant, catalyzer etc. form heterogeneous turbulent flow to react, realization increase oxygenant and catalyzer are at intrasystem catalytic oxidation time and raising oxygenant---the dual-use function of the utilising efficiency of hydrogen peroxide.In the present embodiment, circular turbulent flow reaction ring opening diameter 50mm, radial aperture rate 5%, return port is opened in firsts and seconds taper turbulent flow reaction ring lower end, and orifice diameter controls within the scope of 200mm-500mm; The perforate dislocation of the firsts and seconds taper turbulent flow reaction ring in every grade of multi-phase catalytic oxidation device is split, and forms stronger turbulent reaction effect.
Table 1, table 2 are respectively and adopt treatment process of the present invention and device to carry out the detection water quality after continuous advanced treatment and direct coagulating sedimentation effluent quality to the water outlet of certain difficult degradation organic chemical waste water secondary biochemical precipitation.
In this wastewater treatment test: test former water pH value about 6.5, the two-stage light electrolysis time is 60min, and the two-stage catalyzed oxidation time is 60min; The volume percent of hydrogen peroxide dosage and waste water is 3 ‰, two-stage each 1.5 ‰.
Table 1: difficult degradation organic chemical waste water advanced treatment catalog data
Table 2: difficult degradation organic chemical waste water secondary biochemical effluent direct flocculation sediment processing data table look-up
Note: often organize data in table and be 5 sampling determination mean values.
From table 1 data analysis, to certain difficult degradation organic chemical waste water, water outlet water outlet after deep oxidation process provided by the invention after routine biochemistry second-stage treatment, average COD is degraded to 116.8mg/L by the 278.9mg/L of intaking, and clearance is 58.2%; After directly carrying out coagulating sedimentation, water outlet average COD is degraded to 257.9mg/L by the 278.9mg/L of intaking, and COD clearance is 7.8%; The two difference 50.4%, after adopting deep oxidation method of the present invention, the processing efficiency of COD is improved significantly, and stable water outlet is enhanced, and water outlet COD, all lower than 150mg/L, reaches the secondary standard in national sewage comprehensive emission standard.
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.
Claims (4)
1. a difficult degradation organic chemical waste water deep oxidation treatment unit, it is characterized in that: comprise the degerming pond of acidifying of pipeline connection successively, primary reinforcement electrochemical reactor, secondary reinforcement electrochemical reactor, one-level multi-phase catalytic oxidation device, secondary multi-phase catalytic oxidation device
Connecting pipeline between the degerming pond of acidifying and primary reinforcement electrochemical reactor is provided with lift pump, in the degerming pond of described acidifying, lower logical dividing plate and aeration tube are set, in the degerming pond of acidifying, the side of lower logical dividing plate arranges sour throwing device, and one end that the opposite side of lower logical dividing plate is adjacent with lift pump is provided with pH controller;
Secondary multi-phase catalytic oxidation device is connected with rising pipe; In primary reinforcement electrochemical reactor, secondary reinforcement electrochemical reactor, one-level multi-phase catalytic oxidation device, secondary multi-phase catalytic oxidation device, the aerating pipelines be connected with aeration main pipeline is all installed;
Primary reinforcement electrochemical reactor and secondary reinforcement electrochemical reactor inside are equipped with micro-electrolysis stuffing layer, the top of micro-electrolysis stuffing layer is provided with filler and adds post, filler adds the cylindrical shell that post is upper and lower opening, and the top that filler adds post is positioned at the top of primary reinforcement electrochemical reactor end socket; Primary reinforcement electrochemical reactor, secondary reinforcement electrochemical reactor, one-level multi-phase catalytic oxidation device, secondary multi-phase catalytic oxidation device inside is provided with effluent weir and the height of each effluent weir successively decreases successively;
Connecting pipeline between primary reinforcement electrochemical reactor and secondary reinforcement electrochemical reactor is arranged sequentially automatic acid chemicals dosing plant and pH controller; Connecting pipeline between secondary reinforcement electrochemical reactor and one-level multi-phase catalytic oxidation device is arranged sequentially automatic acid chemicals dosing plant, hydrogen peroxide throwing device and pH controller; Connecting pipeline between one-level multi-phase catalytic oxidation device and secondary multi-phase catalytic oxidation device is arranged sequentially automatic acid chemicals dosing plant, hydrogen peroxide throwing device and pH controller;
Tandem three layers turbulent flow reaction ring is all set in one-level multi-phase catalytic oxidation device, secondary multi-phase catalytic oxidation device from bottom to top---circular turbulent flow reaction ring, one-level taper turbulent flow reaction ring, secondary taper turbulent flow reaction ring, circular turbulent flow reaction ring opening diameter 50mm, radial aperture rate 5%, return port is opened in firsts and seconds taper turbulent flow reaction ring lower end, and orifice diameter is 200mm-500mm; The perforate dislocation of the firsts and seconds taper turbulent flow reaction ring in every grade of multi-phase catalytic oxidation device is split.
2. difficult degradation organic chemical waste water deep oxidation treatment unit according to claim 1, it is characterized in that: primary reinforcement electrochemical reactor is identical with the internal structure of secondary reinforcement electrochemical reactor, one-level multi-phase catalytic oxidation device is identical with the internal structure of secondary multi-phase catalytic oxidation device.
3. a difficult degradation organic chemical waste water deep oxidation treatment process, it is characterized in that: this technique adopts device as claimed in claim 1, the water outlet after secondary biochemical treatment of difficult degradation organic chemical waste water enters in the degerming pond of acidifying and pumps into primary reinforcement electrochemical reactor behind automatical dosing adjust ph to 2.5 ~ 4.0, waste water is from bottom to top by micro-electrolysis stuffing layer, then in the outlet conduit of primary reinforcement electrochemical reactor, acid for adjusting pH value is added to 3.0 ~ 3.5, gravity type boat davit flows into secondary reinforcement electrochemical reactor, waste water continues from bottom to top by micro-electrolysis stuffing layer, after the outlet conduit of secondary reinforcement electrochemical reactor adds oxygenant, gravity flows into one-level multi-phase catalytic oxidation device, waste water after after one-level multi-phase catalytic oxidation, on the outlet conduit of one-level multi-phase catalytic oxidation device, secondary adds oxygenant gravity flow into secondary multi-phase catalytic oxidation device, carry out secondary multi-phase catalytic oxidation, water outlet carries out mud-water separation with coagulating sedimentation again in follow-up routine.
4. difficult degradation organic chemical waste water deep oxidation treatment process according to claim 3, is characterized in that: described oxygenant is hydrogen peroxide.
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