CN201347378Y - Batch-type three-phase-fluidization ozone oxidation reactor - Google Patents
Batch-type three-phase-fluidization ozone oxidation reactor Download PDFInfo
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- CN201347378Y CN201347378Y CNU2009200387396U CN200920038739U CN201347378Y CN 201347378 Y CN201347378 Y CN 201347378Y CN U2009200387396 U CNU2009200387396 U CN U2009200387396U CN 200920038739 U CN200920038739 U CN 200920038739U CN 201347378 Y CN201347378 Y CN 201347378Y
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Abstract
The utility model discloses a batch-type three-phase-fluidization ozone oxidation reactor, which belongs to the field of water treatment reactors. The batch-type three-phase-fluidization reactor comprises an airtight container serving as a reactor; the container is filled with inertia perfluoro organic solvent; a gas/water distributing board made of porous quartz ceramics is arranged at the bottom of the container of the reactor; and the reactor forms a part of a circulating fluidization system. The reactor integrates the extractive enrichment with the ozone oxidation to organically solve the problems, such as difficult degradation of toxic organic pollutants, low reaction power and long reaction time of low-concentration ozone in water, and difficult assurance on effluent quality, so that not only the effluent quality is improved, but also the operating cost is greatly reduced. The reactor has compact structure and large effective water treatment volume, and can adjust and control the ozone oxidation reaction time and the operational procedures according to the water handling capacity, the contents of toxic organic pollutants, and the quality of treated water, so that the engineering design is simple, the period for construction and installation is short, and the maintenance is convenient.
Description
Technical field
The utility model relates to a kind of water treatment device of difficult degradation poisonous organic wastewater, a kind of three-phase fluidization ozone oxidation reaction device of saying so more specifically.
Background technology
At present, the bio-refractory poisonous organic wastewater is one of reason that causes China's water pollution aggravation, as some key industry waste water such as printing and dyeing, medicine, chemical industry, papermaking.The general character of this type of waste water is relatively to be difficult to degraded in environment, long-time stable existence, and have biological accumulation, and seriously affect the healthy of the mankind, hindered the Sustainable development of China's economy.Therefore, be difficult point and focus in the current wastewater processing technology at the research of difficult degradation poisonous organic wastewater and application.
Have a variety ofly at the water treatment device of organic waste water, wherein many all is very sophisticated, and has realized industrialization, but also rare at the treatment reaction device of poisonous hardly degraded organic substance.According to the different methods of degradation of organic substances, this type of water treatment device can be divided into materialization water treatment device and biochemical water treatment device two big classes.Typical materialization water treatment device at organic waste water has following a few class: with charcoal absorption, macroporous resin adsorption is the adsorption unit of representative, with reverse osmosis, ultrafiltration is the membrane separation unit of representative, is oxidized to the advanced oxidation device of representative with photochemical catalytic oxidation, overcritical catalyzed oxidation, ultrasonically catalyzing.Biochemical water treatment device pattern kind is more, but can be divided into aerobic and anaerobism two big classes.
Adsorption unit is to utilize the adsorption of different sorbent materials to remove organic pollutant in the water.Absorbent charcoal adsorber can be divided into fixed-bed type, moving bed type, thermopnore type according to the different running method of sorbent material.The shape of activated carbon of sorbent has Powdered and particulate state, and granular active carbon regeneration is easier than powdered active carbon, so the activated adsorption device adopts granular active carbon more.The adsorptive power of gac is very strong, and many organism in the water are all had very strong adsorptive power, can also be used for deodorizing, decolouring and the micro-objectionable impurities of water in addition.The sixties, the macroporous resin adsorption device of development was with the adsorption unit of macroporous resin as sorbent material.Macroporous adsorbent resin can purify many ionic, polarity and nonpolar organism, and its bonding force is smaller, is easy to regeneration, and different with charcoal absorption is that macroporous resin adsorption has very high selectivity, therefore the organism in the recyclable water.
Membrane separation unit is to utilize the selection perviousness of film to remove organic pollutant in the water, big I according to membrane pore size is divided into broad varietys such as reverse osmosis and ultrafiltration, can be divided into plate and frame, tubular type, rolling and four kinds of structure formations of tubular fibre formula according to the shape of membrane module.The key distinction of reverse osmosis and ultra-filtration equipment is that its film directly varies in size.The pollutent particle diameter that ultra-filtration membrane is held back is bigger, is about the 2-10000 micron, and it is less that reverse osmosis membrane is held back, be about the 0.4-600 micron, so the corresponding working pressure of ultra-filtration equipment is less, is 101.3-709.3kPa, and reverse osmosis unit is bigger, will exceed an order of magnitude than ultra-filtration equipment.Membrane separation unit is a kind of degree of depth water treatment device, can remove the micro quantity organic pollutant in the water, but the obstruction of film and expensive processing costs are the keys of restriction large-scale application always.
High-level oxidation technology and device starting are later relatively, come down to adopt the catalyzed oxidation technology under the special conditions.The ultimate principle of photocatalytic oxidation device is, rayed is behind semiconductor surfaces such as titanium dioxide, and the hole of generation makes water molecules generate hydroxyl radical free radical, and hydroxyl radical free radical has the strong oxidation capacity of non-selectivity, thereby removes the organic pollutant in the water.The ultimate principle of overcritical catalytic oxidizing equipment is, under the supercritical state of High Temperature High Pressure, organic pollutant molecule, air and aqueous solvent are unlimited to be held mutually, thereby organic pollutant is by exhaustive oxidation almost in the short period of time.
Biological method is to remove the most economical effective means of organism in the waste water, is the Metabolic activity that utilizes in the microbial life process, thereby organism is decomposed into the process that simple inorganics is removed organic pollutant.According in the metabolic process to the conditions of demand of oxygen, microorganism can be divided into aerobic microbiological, anaerobion and marginal aerobic-anaerobic microbe.Be divided into continous way and sequence batch (by water flow mode, be divided into activated sludge process and biomembrance process by the existing way of microorganism.Representative pattern has activated sludge tank, biological filter, biology to connect to separate oxidizing tower, oxidation ditch, blodisc, upflowing sewage sludge reactor, but the processing efficiency at the difficult degradation toxic organic compound is very poor, lower concentration toxic organic compound particularly, as microbiotic, oestrogenic hormon etc. in the water body, its clearance is about 40%.
Above-described various organic waste-water treating apparatus has advantage separately, and shortcoming is separately also arranged simultaneously, can only be suitable for certain scope.The effluent quality of various adsorption units is better, but because a large amount of sorbent material of a large amount of uses, and need regeneration, cause running cost higher.Various embrane method device effluent qualities are also better, but to the having relatively high expectations of film, the cost of manufacture of film is very high, and film is very easily contaminated in the operational process, need comparatively strict pre-treatment.Higher, the easy loss of photocatalyst cost of manufacture in the photocatalysis apparatus, easy inactivation, need comparatively strict pre-treatment, and the light transmitting surface that contacts with water is easy to fouling, oxidising process lacks selectivity, particularly at lower concentration toxic organic compound in the water, the oxidising process motivating force is poor, poor processing effect.Therefore overcritical device needs High Temperature High Pressure, and to the having relatively high expectations of equipment material, fixed cost is higher, and it is difficult to safeguard.Therefore be necessary to develop the novel advanced treatment process of efficient cheapness.
Result of study shows that general water treatment device by ozone oxidation only is applicable to the organic waste water of higher concentration, and the existence that suppressed by the water body free radical influences greatlyyer, generally only is used for water body disinfection and handles.Poisonous organic wastewater for the difficult degradation lower concentration adopts conventional ozone or ozone-biological treatment to be difficult to reach processing requirements, feeds a large amount of ozone usually or prolongs oxidization time, has improved working cost so greatly.Single ozone equipment for treating water, energy consumption is bigger, and can only handle the organism (as: phenol etc.) of easy degraded or disinfect as the follow-up of other treatment processs.For ozone-bioactive carbon treatment system, can be at the degraded of the lower concentration toxic organic compound in the water body, but the activated carbon surface absorption property is subjected to water quality impact bigger, be easy to fouling, activated carbon regeneration difficulty needs special biological degradation flora for difficult degradation toxic organic compound thing, and it is active affected by environment bigger, particularly for containing high-salt wastewater, can't use this treatment system, be the major obstacle of restriction practical engineering application at all.
Summary of the invention
1. invent the problem that will solve
Handle the difficulty of the poisonous organic wastewater existence of difficult degradation lower concentration at single ozone equipment for treating water, the utility model provides the intermittent type three-phase that a kind of cost is low, efficient is high (water/ozone/organic solvent) fluidisation ozone oxidation reaction device, can handle the difficult degradation poisonous organic wastewater.
2. the technical solution of the utility model:
Intermittent type three-phase fluidization ozone oxidation reaction device comprises that an airtight container as reactor, has inertia perfluor organic solvent in container, and its container bottom has the distribute water and air plate of a cellular quartz pottery, and reactor constitutes the part of outer circulation fluidization system.
The utility model will extract-and enrichment/ozone degradation organically combines.For in the water body, the difficult degradation toxic organic compound of lower concentration, nontoxic, inertia perfluor organic solvent plays extraction-inrichment in reactor, described inertia perfluoro solvent is straight chain or ring-type perfluoro alkane solvent or perfluor straight chain and perfluorinated cycloalkanes mixed solvent, as perfluor hexene etc.Have lipophilic molecules state toxic organic compound and very big partition ratio is arranged at the perfluor organic solvent, toxic organic compound in can the extracting and enriching a large amount of water, and the perfluor organic solvent also is good year ozone solvent, the solubleness of ozone in organic solvent is about 12 times in the water, therefore, in reactor, high density toxic organic compound unsaturated link(age) after ozone with high concentration molecule and the enrichment directly carries out the addition oxidizing reaction, has good selectivity, the speed of reaction height, the dissolved ozone molecule forms offensive free radical (as hydroxyl radical free radical etc.) in the water in decomposition course, can carry out non-selective attack organic molecule, it is the indirect oxidation reaction, in entire reaction course, because of C-F key bond energy very high, the perfluor organic solvent does not participate in ozone oxidation reaction, it is good inert organic solvents, in this system, direct addition oxidizing reaction and indirect oxidation reaction are carried out simultaneously, therefore, in this reaction system, Oxidation Rate Constants of Antioxidants is bigger more than 1000 times than traditional water/gas two-phase, and stable effluent quality.
Reactor is squeezed into organic solvent with pump before entering sewage, and feed ozone and carry out after the presaturation stand-by, contain poisonous organic wastewater and squeeze into reactor a certain amount of by water pump from the bottom, organic solvent is 1/2～1 with the ratio of wastewater volume: (lower as if toxic organic compound concentration in the water body about 3, satisfying under the prerequisite of drainage requirement, can extract earlier-the enrichment processing, can carry out extracting and enriching) by the outer outer circulation fluidisation that connects of reactor.Contain ozone gas and blowback stream as continuous fluid power with what ozone reactor produced, in reactor, form ozone/water/perfluor organic solvent three-phase fluidization system, the non-selective ozone oxidation of selectivity ozone oxidation and aqueous phase is carried out simultaneously in extraction-enrichment, the organic phase, therefore, it is less that system is subjected to free radical inhibitors (as hydrocarbonate etc.) influence.The tail gas that contains residual ozone is derived by reactor head.Reaction is carried out stopping to feed ozone after for some time, closes recycle pump, and this moment, water and organic phase were separated in reactor, after separation is finished, is discharged by the water port (controlled by valve) that is higher than about organic phase liquid level 10cm.And then carry out next cyclical operation process.The perfluor organic solvent recycles, and a small amount of organic solvent that runs off can regularly be added to reactor.Whole wastewater treatment process intermittently carries out.
Adopt the utility model, the organic waste water high to suspension content need carry out pre-treatment (or filtration treatment), and the organic solvent number of dropouts is relevant with suspended solids (SS) in the former water body, and it is following optimum that the SS amount should be controlled at 10mg/L in the water body.
If difficult degradation toxic organic compound concentration is lower in the waste water, after guaranteeing under the prerequisite that effluent quality requires, can carrying out organic solvent extraction-enrichment earlier, the back feeds ozone oxidation; If difficult degradation toxic organic compound concentration is higher in the waste water, can extract simultaneously-enrichment-ozonization carries out simultaneously, or with treating water source water diluted).
3. beneficial effect
Compare existing sewage-treating reactor, the utlity model has following advantage:
1) will extract-enrichment-ozone oxidation combines, and fundamentally solved little, the long reaction time of conventional ozone oxidation degraded toxic organic compound reaction power, and energy consumption consumption is big, and effluent quality is difficult to guarantee;
2) the utility model directly carries out the addition oxidizing reaction by ozone molecule in organic phase and compound unsaturated chain, has solved problems such as conventional ozone oxidation relies on the more offensive free radical of generation, the objective of the attack compound selective is poor, intermediate product is more;
3) use the utility model to carry out sewage disposal, the ozone oxidation reaction time is very short, and decompose the more offensive free radical of generation with routine by a large amount of ozone in water and compare, the ozone utilization rate height, running cost and operation easier reduce, and effluent quality is reliable;
4) whole apparatus structure system compact, each function part mutual restriction is little, is easy to engineering design, installation, maintenance;
5) can according to different water treatment amounts and concrete water quality can free selecting reactor in consumption of organic solvent, oxidizing reaction schedule of operation;
6) this installs employed nontoxic, inertia perfluor organic solvent, is general common used in industry heat transfer agent, does not have special requirement, and market is easy to buy;
7) be applicable in, the processing of poisonous, the pigmented biological organic wastewater with difficult degradation thereby of lower concentration, be particularly suitable for containing the waste water that lower concentration difficult degradation toxic organic compound influences reclaimed water reuse.
Description of drawings
Fig. 1 is a structural representation of the present utility model;
Fig. 2 is the utility model wastewater treatment process figure.
Embodiment:
Below in conjunction with accompanying drawing the utility model is described further
According to Fig. 1, at first valve-off 8,9,10,11,12,13,14, open inlet valve 1, squeeze into the perfluor organic solvent of certain volume in advance from reactor 2 bottom inlets by intake pump 3, then, to enter from reactor 2 bottom inlets 4 by intake pump 3 through pretreated waste water, open air intake valve 12 simultaneously, containing ozone gas also enters from reactor bottom inlet 4, ozone and waste water is preliminary the mixing before passing through cellular quartz ceramic plate 5, and by after the porous ceramic plate redistribution, gas/water at first enters perfluor organic phase 6, under the disturbance that contains ozone gas and water inlet, system is in the height fluidized state, after liquid level reach a certain height, close inlet valve 1, stop to pump into waste water, and open return valve 13, carry out the container outer circulation and reflux, enter the mouth from reactor bottom enters phegma (by water and organic solvent and contain ozone gas and forms, phegma outlet mounting height is positioned at and leaves standstill 10cm place on the organic phase liquid level).In fluid mapper process, ozone molecule and toxic organic compound shift to the perfluor organic solvent, toxic organic compound extracts in organic phase-enrichment, formation contains the organic solvent of high-concentrated ozone and high density toxic organic compound, simultaneously, organic (oil) mutually in ozone molecule and toxic organic compound carry out selectivity direct addition oxidizing reaction, ozone molecule decomposes in water 7, produce offensive free radical (as oxyradical and hydroxyl radical free radical) and the poisonous organic molecule of attack, carry out indirect ozone oxidation reaction; The gas of residue ozone is handled discharging by subsequent technique.Through (reaching expection and require water quality) after certain reaction times; system is shut down (closing intake pump 3, intake valve 12 and return valve 13); at this moment; because oil, water uncompatibility and density variation; water is separated in reactor with organic (oil); after (10～30 minutes) standing separation, open valve 10 (discharge outlet) through after a while, discharge treating water.Behind the row's for the treatment of treating water, valve-off 10 enters next working cycle.
Poisonous organic wastewater for lower concentration, can be according to its characteristics, do not open earlier ozone intake valve 12, and it is ciculation fluidized to be to use pump 3 to carry out, its objective is in organic phase, to extract-the enrichment processing, do not require or organic solvent extraction when saturated when effluent quality reaches, feed and carry out the three-phase fluidization ozone Oxidation Treatment.
In this utility model, can select the suitable water and the volume ratio of organic phase according to practical situation, as handling low-concentration organic waste water, can suitably increase the organic phase volume, adopt the ozone Oxidation Treatment again of extraction-enrichment earlier, can reduce running cost greatly like this.
Claims (4)
1, a kind of intermittent type three-phase fluidization ozone oxidation reaction device, it comprises an airtight vessel reactor, it is characterized in that placing the inertia perfluoro solvent in reactor, its reactor bottom has the distribute water and air plate of cellular quartz pottery, and reactor constitutes the part of outer circulation fluidization system.
2, intermittent type three-phase fluidization ozone oxidation reaction device as claimed in claim 1 is characterized in that waste water and contains ozone gas entering from the container bottom inlet, handles the back discharge outlet and is arranged on the organic solvent interface; Water and oil phase are after same reaction gas is separated, and treating water discharges through discharge outlet; The tail gas of residue ozone is derived from reactor head in the oxidation reaction process.
3, intermittent type three-phase fluidization ozone oxidation reaction device as claimed in claim 2 is characterized in that the inertia perfluoro solvent is straight chain or ring-type perfluoro alkane solvent or perfluor straight chain and perfluorinated cycloalkanes mixed solvent.
4, intermittent type three-phase fluidization ozone oxidation reaction device as claimed in claim 2, the outer circulation fluidization system is made up of reactor, intake pump and external pipeline.
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| Application Number | Priority Date | Filing Date | Title |
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| CNU2009200387396U CN201347378Y (en) | 2009-01-07 | 2009-01-07 | Batch-type three-phase-fluidization ozone oxidation reactor |
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| CNU2009200387396U CN201347378Y (en) | 2009-01-07 | 2009-01-07 | Batch-type three-phase-fluidization ozone oxidation reactor |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811769A (en) * | 2010-04-02 | 2010-08-25 | 南京师范大学 | Method for treating parachloronitrobenzene waste water through liquid-liquid two-phase fluidization and ozone oxidation |
| CN103861532A (en) * | 2014-03-03 | 2014-06-18 | 北京旭荣工程设计有限公司 | Homogeneous three-phase reactor for jet aeration |
| CN104478067A (en) * | 2014-12-15 | 2015-04-01 | 浙江中凯瑞普环境工程股份有限公司 | Ozone catalytic oxidation reactor for treatment of inner circulation sewage and sewage treatment method using reactor |
| CN104478066A (en) * | 2014-12-15 | 2015-04-01 | 浙江中凯瑞普环境工程股份有限公司 | Catalytic ozonation reactor for treatment of external circulating wastewater and wastewater treatment method |
| CN104478065A (en) * | 2014-12-15 | 2015-04-01 | 浙江中凯瑞普环境工程股份有限公司 | Catalytic ozonation reactor for expanded bed and sewage treatment method of catalytic ozonation reactor |
| CN104609500A (en) * | 2015-01-19 | 2015-05-13 | 中国科学院过程工程研究所 | Ozone-photocatalysis reactor and water treatment method |
| CN110713249A (en) * | 2019-11-01 | 2020-01-21 | 云南大学 | Method for treating hardly biodegradable organic wastewater |
-
2009
- 2009-01-07 CN CNU2009200387396U patent/CN201347378Y/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811769A (en) * | 2010-04-02 | 2010-08-25 | 南京师范大学 | Method for treating parachloronitrobenzene waste water through liquid-liquid two-phase fluidization and ozone oxidation |
| CN101811769B (en) * | 2010-04-02 | 2012-07-04 | 南京师范大学 | Method for treating parachloronitrobenzene waste water through liquid-liquid two-phase fluidization and ozone oxidation |
| CN103861532A (en) * | 2014-03-03 | 2014-06-18 | 北京旭荣工程设计有限公司 | Homogeneous three-phase reactor for jet aeration |
| CN103861532B (en) * | 2014-03-03 | 2015-11-18 | 北京华石联合能源科技发展有限公司 | A kind of jet-flow aeration three-phase homogeneous reactor |
| CN104478067A (en) * | 2014-12-15 | 2015-04-01 | 浙江中凯瑞普环境工程股份有限公司 | Ozone catalytic oxidation reactor for treatment of inner circulation sewage and sewage treatment method using reactor |
| CN104478066A (en) * | 2014-12-15 | 2015-04-01 | 浙江中凯瑞普环境工程股份有限公司 | Catalytic ozonation reactor for treatment of external circulating wastewater and wastewater treatment method |
| CN104478065A (en) * | 2014-12-15 | 2015-04-01 | 浙江中凯瑞普环境工程股份有限公司 | Catalytic ozonation reactor for expanded bed and sewage treatment method of catalytic ozonation reactor |
| CN104609500A (en) * | 2015-01-19 | 2015-05-13 | 中国科学院过程工程研究所 | Ozone-photocatalysis reactor and water treatment method |
| CN110713249A (en) * | 2019-11-01 | 2020-01-21 | 云南大学 | Method for treating hardly biodegradable organic wastewater |
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| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091118 Termination date: 20110107 |