CN101514044A - Method for treating low-concentration nitrobenzene waste water by means of three-phase fluidization - Google Patents
Method for treating low-concentration nitrobenzene waste water by means of three-phase fluidization Download PDFInfo
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- CN101514044A CN101514044A CNA2009100260154A CN200910026015A CN101514044A CN 101514044 A CN101514044 A CN 101514044A CN A2009100260154 A CNA2009100260154 A CN A2009100260154A CN 200910026015 A CN200910026015 A CN 200910026015A CN 101514044 A CN101514044 A CN 101514044A
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Abstract
The invention discloses a method for treating low-concentration nitrobenzene waste water by means of three-phase fluidization. The extraction/concentration treatment and the ozone oxidation treatment using organic solvent and ozone are simultaneously carried out on the nitrobenzene waste water with the concentration being lower than 500 mg/L in a three-phase water treatment reactor, wherein, the water treatment reactor using ozone/organic solvent/water adopts a common three-phase water treatment device; and the organic solvent adopts perfluor organic solvent, particularly, the ozone-carrying organic solvent adopts non-toxic inert perfluor linear chain or loop chain perfluoroalkane. The process of the invention for treating the low-concentration nitrobenzene waste water has the advantages of high efficiency and low consumption, the removal rate of nitrobenzene reaches more than 95%, and the effluent quality is stable, therefore, the method deserves popularization and application on a larger scale and is very promising. The invention is applicable to the treatment of waste water containing polycyclic aromatic compounds, organophosphorus or organonitrogen pesticide, antibiotics, estrogens, halogenated aromatic hydrocarbon, phenols and the like.
Description
Technical field
The present invention relates to the method that a kind of processing contains low-concentration nitrobenzene waste water by means, the method for the employing ozone/organic solvent of more specifically saying so/water treating low-concentration nitrobenzene waste water by means of three-phase fluidization.
Background technology
Along with the acceleration of Chinese Urbanization and process of industrialization, the pollution of water bodys such as underground water, surface water and domestic water is more and more serious, and water pollution and control have become the important topic of common concern.People adopt eco-friendly and green methods such as chemical synthesis route from source and fundamentally minimizing pollution on the one hand, on the other hand, at water environment pollution under the new situation, how to set up focus efficient, economic, that novel method that clean, remove up hill and dale water pollutant is also becoming domestic and international concern.Through the joint efforts and the practice of scientists, the treatment technology at pollutents such as the heavy metal in the water, suspended solid (SS), bio-degradable organic pollutant (BOD), nitrogen, phosphorus is gradually improved at present.But for being difficult to biological degradation in the polluted-water, being easy to biomagnification and having the lower concentration toxic organic pollutant that " three cause " acts on, or the processing of some novel organic pollutants, because of its content in water low, be difficult to enrichment and degraded, the directly reuse of restriction treating water, also lack highly effective method and technology at present, so new principle, new technology and the novel method of the more effective specific pollutant control of research and development are extremely urgent problems.
Handle at lower concentration difficult degradation toxic organic pollutant, advanced oxidation water technology (AOTs) is an oxygenant with oxygen or other green hyperoxia voltinism material (as: molecular oxygen, ozone or hydrogen peroxide etc.), it is very ideal toxic organic pollutant control novel method of a class, in control and elimination water body, demonstrate very tempting application prospect aspect the difficult degradation toxic organic compound, be subjected to people's attention in recent years day by day.
In the advanced oxidation Processing Technology Research, research both at home and abroad focuses mostly on based on (light) chemical oxidization method of molecular oxygen, (light) chemical oxidization method of activating hydrogen peroxide, (light) chemical oxidization method that ozone is oxygenant etc.In (light) chemical oxidization method water technology, has the key that high efficiency photocatalyst and technique for fixing thereof become this technology application of restriction based on molecular oxygen.Activating hydrogen peroxide has bigger advantage for (light) chemical oxidization method on basis is primarily aimed at high density, difficult degradation, poisonous and hazardous organic pollutant processing aspect, but reaction can only be carried out (pH＜3) in acidic medium based on Fenton, for the synthetic organic-fuel that extensively exists in the environment, then be difficult to degraded, need research and development can activate H with this method
2O
2Catalyzer.Ozone be oxygenant (light) chemical oxidization method because of its ozone the low solubleness of aqueous phase, unstable, organic matter degradation not thoroughly, high limitation consumes energy, aspect water pollution control, be very restricted, therefore, at the limitation of ozone method in water treatment applications, the water treatment pattern of breaking the normal procedure is researched and developed the focus that heterogeneous ozonization system has become domestic and international concern.
In actual water body, there are many OH inhibitor, as HCO
3 -, CO
3 2-, SO
3 2-Deng, these materials influence the ozonization activity by the formation that suppresses OH, have to use excessive ozone in order to eliminate the influence of these materials in single-phase (water) reaction system.Therefore, how improving solubleness, stability, the service efficiency of ozone in system, reduce production of by-products, is the critical bottleneck of restriction ozone in water pollution control field large-scale application.
, poor stability low at ozone solubleness in water (single-phase), lack selective oxidation, problem such as intermediate product is more and ozone utilization rate is on the low side, research and development two-phase ozone oxidation system may be a kind of more effective water pollution control method, its principle of work as shown in Figure 1, the reaction process of two-phase system mainly is made up of two portions: extract toxic organic compound from liquid phase; In organic phase, carry out the ozone degradation reaction.Consider from using actual angle, except that water, nonaqueous phase (organic phase) must satisfy following the requirement: organic solvent is water insoluble, nontoxic, vapour pressure is lower, density is high, easily separated, can be recycled, the aqueous phase organic pollutant is had high slective extraction, higher ozone solution and stability etc. are arranged.So far, in overwhelming majority's report, all adopt water/organic solvent two-phase oxidizing reaction system, organic solvent uses straight chain perfluoro alkane as organic phase more, and use perfluoro naphthenic hydrocarbon or perfluor mixed solvent as organic phase, and the research of using gas/water/organic solvent three-phase ozone oxidation system that poisonous Persistent organic pollutants are carried out quick oxidative degradation is also rarely reported.
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.Ozone-catalyst (metal) treatment system has the high advantage of ozone oxidation speed, but need to consume a large amount of ozone and expensive catalysts, and catalyst activity is subjected to water quality impact bigger, inactivation easily, regeneration difficulty.Ozone-physical chemistry auxiliary (light, ultrasonic, Fenton, magnetic, energetic ion radiation) though treatment system ozone oxidation speed height, energy consumption height, processing cost height.Particularly to containing the waste water of lower concentration difficult degradation toxic organic compound, its processing cost is higher.
Therefore, lower concentration difficult degradation toxic organic compound water treatment method and technology that cost of development is low, efficient is high, the development trend and the effective way of also current just solution lower concentration difficult degradation poisonous organic wastewater.
Summary of the invention
The technical problem that 1 invention will solve:
In order to address the above problem, the present invention proposes a kind of method for the treatment of low-concentration nitrobenzene waste water by means of three-phase fluidization, can efficient and cost-effective purifying low-concentration nitrobenzene waste water, realize the method for the ozone/organic solvent/water three-phase fluidization treatment of Nitrobenzene waste water of industrial applications.
2 technical schemes:
A kind of method for the treatment of low-concentration nitrobenzene waste water by means of three-phase fluidization in the three-phase water processing reactor, less than the 500mg/L nitrobenzene waste water, with an organic solvent and ozone, is carried out extracting and enriching-ozone Oxidation Treatment for concentration simultaneously.
Above-mentioned three-phase (ozone/organic solvent/water) water processing reactor adopts common three-phase water treating device (three-phase fluidized bed) to get final product.Organic solvent is the perfluor organic solvent, especially adopts nontoxic inertia perfluoro straight chain or loop chain alkane (as: mixture of FC40, perfluorodecalin or FC40 and perfluorodecalin) as carrying the ozone organic solvent.
Water and perfluor volume of organic solvent ratio are 1/3～1/2 scope, can select the kind and the consumption of organic solvent according to toxic organic compound at the concentration of aqueous phase; The perfluor organic solvent is water insoluble, be easy to water sepn and recycle, in reactor, play extraction-inrichment, oil of mirbane 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, under the three-phase fluidization state, in the perfluoro solvent organic phase, high nitrobenzene after ozone with high concentration molecule and the enrichment directly carries out the addition oxidizing reaction, has good selectivity, the speed of reaction height; At aqueous phase, 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, be 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, be good inert organic solvents, in this system, direct addition oxidizing reaction and indirect oxidation reaction are carried out simultaneously.Therefore, in this reaction system, under equal conditions, Oxidation Rate Constants of Antioxidants is bigger more than 1000 times than traditional water/gas two-phase, and the reaction times shortens more than 2/3.
3 beneficial effects:
The present invention proposes a kind of method of three-phase fluidization fast processing low-concentration nitrobenzene waste water by means.The advantage that technology of the present invention has efficiently, low-concentration nitrobenzene waste water by means is handled in low consumption, the oil of mirbane clearance is more than 95%, and stable effluent quality.Thereby having bigger application value, prospect is very wide.The present invention can be applicable to the ozone oxidation degraded of many phenyl ring aromatics, organophosphorus or organic nitrogen pesticide, microbiotic, estrogens, halogenated aryl hydrocarbon class, phenols (phenol, chlorophenol, p-nitrophenol) etc., and these compounds extensively are present in key industry waste water such as domestic chemical industry, medicine, electronics, food or the city reuse water.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Further specify the utility model by the following examples in conjunction with the accompanying drawings.
The present invention can adopt common three-phase water treating device (three-phase fluidized bed), in certain volumetrical organic solvent is arranged, can determine specification, organic solvent usage quantity and the extracting and enriching-ozone oxidation reaction time of ozonizer according to handling water yield size and toxic organic compound concentration and the partition ratio of oil of mirbane in water and oil phase thereof.If must carry out when SS concentration is higher than 20mg/L in the treating water (as: micro-filtration processing etc.) after the pre-treatment, reach below the 10mg/L, adopt the inventive method to handle again.If processed nitrobenzene-containing waste water saltiness should not adopt method of the present invention greater than 15%, after waste water need carry out desalting treatment in advance, can adopt method of the present invention to handle.Concentration also needs to carry out pre-treatment greater than the 500mg/L nitrobenzene waste water, treats concentration less than 500mg/L, just can adopt the present invention to handle.
Embodiment 1
Processed nitrobenzene waste water enters the three-phase water treating device, and the water yield is lower than 20m
3/ d, concentration is below the 10mg/L, ozonizer is 3.0g/h, and the volume ratio of water and perfluor organic solvent FC40 is 1: 2 in the three-phase water treating device, adopts intermittent loading, then the fluidized reaction time is 3～5min, stop fluidisation, leave standstill, strain water after perfluor organic solvent and the water sepn, and then the water inlet and enter next working cycle, the oil of mirbane clearance can reach more than 95%.
Embodiment 2
Processed nitrobenzene-containing organic waste water enters the three-phase water treating device, and the water yield is greater than 20m
3/ d, concentration is below the 10mg/L, ozonizer is 3.0g/h, the volume ratio of water and perfluor organic solvent perfluorodecalin is 1: 2 in the three-phase water treating device, can adopt continous way water inlet and water outlet, then the fluidized reaction time is 5～10min, and water outlet enters water/organic solvent separate tank, organic solvent after the separation recycles, and the oil of mirbane clearance can reach more than 95%.
Embodiment 3
Processed nitrobenzene-containing organic waste water enters the three-phase water treating device, and the water yield is lower than 20m
3/ d, nitro phenenyl concentration is below the 100mg/L, ozonizer is 5.0g/h, and the volume ratio of the mixture of water and perfluor organic solvent FC40 and perfluorodecalin is 2: 5 in the three-phase water treating device, adopts intermittent loading, then the fluidized reaction time is 15～20min, stop fluidisation, leave standstill, strain water after perfluor organic solvent and the water sepn, and then the water inlet and enter next working cycle, the oil of mirbane clearance can reach more than 95%.
Embodiment 4
The organic waste water of processed nitrobenzene-containing enters the three-phase water treating device, and the water yield is greater than 20m
3/ d, concentration is below the 100mg/L, ozonizer is 8.0g/h, water and perfluor volume of organic solvent ratio are 1: 3 in the three-phase water treating device, the water inlet of employing continous way, then the reaction times is 15～20min, water outlet enters water/organic solvent separate tank, organic solvent after the separation recycles, and the oil of mirbane clearance can reach more than 95%.
Embodiment 5
The main nitrobenzene-containing waste water of processed organic waste water enters the three-phase water treating device, and the water yield is lower than 20m
3/ d, nitro phenenyl concentration is below the 500mg/L, ozonizer is 10g/h, and water and perfluor volume of organic solvent ratio are 1: 3 in the three-phase water treating device, adopts intermittent loading, then the fluidized reaction time is 15～20min, stop fluidisation, leave standstill, strain water after perfluor organic solvent and the water sepn, and then the water inlet and enter next working cycle, the oil of mirbane clearance can reach more than 95%.
Embodiment 6
Processed organic waste water is main nitrobenzene-containing waste water, and the water yield is greater than 50m
3/ d, concentration is less than more than the 50mg/L, ozonizer is 10.0g/h, water and perfluor volume of organic solvent ratio are 1: 2, the water inlet of employing continous way, water enters water/organic solvent separate tank, and the organic solvent after the separation recycles, then mixing liquid fluidisation (stop) time is 5～10min, and the oil of mirbane clearance can reach more than 95%.
Claims (4)
1. the method for a treating low-concentration nitrobenzene waste water by means of three-phase fluidization is characterized in that in the three-phase water processing reactor, less than the 500mg/L nitrobenzene waste water, with an organic solvent and ozone, carries out extracting and enriching-ozone Oxidation Treatment simultaneously for concentration.
2. the method for the treatment of low-concentration nitrobenzene waste water by means of three-phase fluidization according to claim 1 is characterized in that organic solvent is the perfluor organic solvent.
3. the method for the treatment of low-concentration nitrobenzene waste water by means of three-phase fluidization according to claim 2 is characterized in that the perfluor organic solvent is for carrying the nontoxic inertia perfluoro alkane of ozone.
4. according to the method for each described treating low-concentration nitrobenzene waste water by means of three-phase fluidization in claim 2 or 3, it is characterized in that the carrier gas ozone concn at 3-10g/h, water and perfluor volume of organic solvent ratio are 1: 2～1: 3, and the reaction times is 5～20min.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2009100260154A CN101514044A (en) | 2009-03-17 | 2009-03-17 | Method for treating low-concentration nitrobenzene waste water by means of three-phase fluidization |
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| CNA2009100260154A CN101514044A (en) | 2009-03-17 | 2009-03-17 | Method for treating low-concentration nitrobenzene waste water by means of three-phase fluidization |
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Cited By (6)
| 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 |
| CN102557179A (en) * | 2011-11-17 | 2012-07-11 | 南京理工大学 | Method for removing nitrotoluene in high-concentration waste acid |
| CN102781843A (en) * | 2009-12-16 | 2012-11-14 | 巴斯夫欧洲公司 | Method for recycling exhaust gases comprising NOx from wastewater streams from nitrating plants |
| CN103080012A (en) * | 2010-08-12 | 2013-05-01 | 巴斯夫欧洲公司 | Method for treating wastewaters from the reprocessing of crude aromatic nitro compounds |
| EP2586519A1 (en) | 2011-10-24 | 2013-05-01 | cobos Fluid Service GmbH | Processing of contaminated waste water from the production of plant protection agents |
| CN104355455A (en) * | 2014-11-20 | 2015-02-18 | 郑州航空工业管理学院 | Ortho-aminophenol wastewater treatment method |
-
2009
- 2009-03-17 CN CNA2009100260154A patent/CN101514044A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102781843A (en) * | 2009-12-16 | 2012-11-14 | 巴斯夫欧洲公司 | Method for recycling exhaust gases comprising NOx from wastewater streams from nitrating plants |
| CN102781843B (en) * | 2009-12-16 | 2014-06-18 | 巴斯夫欧洲公司 | Method for recycling exhaust gases comprising NOx from wastewater streams from nitrating plants |
| 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 |
| CN103080012A (en) * | 2010-08-12 | 2013-05-01 | 巴斯夫欧洲公司 | Method for treating wastewaters from the reprocessing of crude aromatic nitro compounds |
| EP2586519A1 (en) | 2011-10-24 | 2013-05-01 | cobos Fluid Service GmbH | Processing of contaminated waste water from the production of plant protection agents |
| CN102557179A (en) * | 2011-11-17 | 2012-07-11 | 南京理工大学 | Method for removing nitrotoluene in high-concentration waste acid |
| CN104355455A (en) * | 2014-11-20 | 2015-02-18 | 郑州航空工业管理学院 | Ortho-aminophenol wastewater treatment method |
| CN104355455B (en) * | 2014-11-20 | 2016-04-13 | 郑州航空工业管理学院 | A kind of Ortho-Aminophenol method of wastewater treatment |
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Open date: 20090826 |