CN101811769B - Method for treating parachloronitrobenzene waste water through liquid-liquid two-phase fluidization and ozone oxidation - Google Patents
Method for treating parachloronitrobenzene waste water through liquid-liquid two-phase fluidization and ozone oxidation Download PDFInfo
- Publication number
- CN101811769B CN101811769B CN2010101395077A CN201010139507A CN101811769B CN 101811769 B CN101811769 B CN 101811769B CN 2010101395077 A CN2010101395077 A CN 2010101395077A CN 201010139507 A CN201010139507 A CN 201010139507A CN 101811769 B CN101811769 B CN 101811769B
- Authority
- CN
- China
- Prior art keywords
- chloronitrobenzene
- water
- ozone
- organic solvent
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002351 wastewater Substances 0.000 title claims abstract description 42
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims abstract description 25
- 239000007788 liquid Substances 0.000 title claims abstract description 17
- 238000005243 fluidization Methods 0.000 title claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000003960 organic solvent Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 238000000605 extraction Methods 0.000 claims abstract description 6
- 231100000252 nontoxic Toxicity 0.000 claims abstract description 5
- 230000003000 nontoxic effect Effects 0.000 claims abstract description 5
- 229950011087 perflunafene Drugs 0.000 claims description 13
- UWEYRJFJVCLAGH-IJWZVTFUSA-N perfluorodecalin Chemical group FC1(F)C(F)(F)C(F)(F)C(F)(F)[C@@]2(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[C@@]21F UWEYRJFJVCLAGH-IJWZVTFUSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000005273 aeration Methods 0.000 claims 2
- 239000012159 carrier gas Substances 0.000 claims 1
- 231100000331 toxic Toxicity 0.000 abstract description 17
- 230000002588 toxic effect Effects 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000006385 ozonation reaction Methods 0.000 abstract description 5
- 239000005416 organic matter Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 27
- 239000000126 substance Substances 0.000 description 18
- 239000002957 persistent organic pollutant Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- MOSKUAXZYLAGNS-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene hydrate Chemical compound O.C1CCCC2CCCCC21 MOSKUAXZYLAGNS-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种液/液两相流化臭氧氧化处理对氯硝基苯废水的方法，属于有机废水处理领域。在普通的流化反应器中，以载臭氧有机溶剂/和废水形成两相反应体系，对于含低浓度对氯硝基苯废水，使用无毒惰性全氟溶剂作为有机溶剂，在水/有机溶剂两相流化状态下，同时进行萃取富集-臭氧氧化降解水体中对氯硝基苯。本发明全氟有机溶剂易与水分离并循环使用，在同等条件下，与传统水/气两相氧化反应体系相比，臭氧投加量减少1/2以上，反应时间缩短2/3以上，有毒有机物总去除率提高20％以上，且出水水质稳定。本发明具有高效、低耗处理含低浓度对氯硝基苯废水的优点，在实际工程中操作方便，易于控制，很容易实现工业化生产，因而，具有较大的推广应用价值，前景十分广阔。
The invention discloses a liquid/liquid two-phase fluidized ozone oxidation method for treating p-chloronitrobenzene wastewater, which belongs to the field of organic wastewater treatment. In a common fluidized reactor, a two-phase reaction system is formed by carrying an ozone-containing organic solvent/and waste water. For waste water containing low concentrations of p-chloronitrobenzene, a non-toxic and inert perfluorinated solvent is used as an organic solvent. In water/organic solvent Under the condition of two-phase fluidization, simultaneous extraction and enrichment-ozonation oxidation degrades p-chloronitrobenzene in water. The perfluorinated organic solvent of the present invention is easy to be separated from water and recycled. Under the same conditions, compared with the traditional water/gas two-phase oxidation reaction system, the dosage of ozone is reduced by more than 1/2, and the reaction time is shortened by more than 2/3. The total removal rate of toxic organic matter is increased by more than 20%, and the effluent quality is stable. The invention has the advantages of high-efficiency and low-consumption treatment of waste water containing low-concentration p-chloronitrobenzene, and is convenient to operate and control in actual engineering, and is easy to realize industrial production. Therefore, it has great popularization and application value and very broad prospects.
Description
技术领域 technical field
本发明涉及一种处理对氯硝基苯废水的方法，更具体的说是一种两相流化臭氧氧化处理对氯硝基苯废水的方法。The invention relates to a method for treating p-chloronitrobenzene wastewater, more specifically a method for treating p-chloronitrobenzene wastewater by two-phase fluidized ozone oxidation.
背景技术 Background technique
随着我国城市化和工业化进程的加速，地下水、地表水以及生活用水等水体的污染越来越严重，水体污染与防治已成为普遍关注的重要课题。人们一方面采用环境友好的和绿色的化学合成路线等方法从源头和根本上减少污染，另一方面，针对新形势下的水环境污染，如何建立高效、经济、清洁、彻底地去除水中污染物的新方法也正在成为国内外关注的热点。经过科学家们的共同努力与实践，目前针对水中的重金属、固体悬浮物(SS)、可生化降解有机污染物(BOD)、氮、磷等污染物的处理技术日趋完善。但对于污染水体中难于生物降解、易于生物富集和具有“三致”作用的低浓度有毒有机污染物，或一些新型有机污染物的处理，因其在水中含量低，难于富集和降解，直接制约处理水的回用，目前还缺乏十分有效的方法和技术，故研究和开发更有效的特殊污染物控制的新原理、新技术和新方法是迫在眉睫的问题。With the acceleration of urbanization and industrialization in my country, the pollution of groundwater, surface water, and domestic water is becoming more and more serious. Water pollution and its prevention and control have become an important topic of widespread concern. On the one hand, people use methods such as environmentally friendly and green chemical synthesis routes to reduce pollution from the source and fundamentally; The new method is also becoming a hot spot at home and abroad. Through the joint efforts and practice of scientists, the treatment technologies for heavy metals, suspended solids (SS), biodegradable organic pollutants (BOD), nitrogen, phosphorus and other pollutants in water are becoming more and more perfect. However, for the treatment of low-concentration toxic organic pollutants that are difficult to biodegrade, easy to bioaccumulate, and have "three-caused" effects in polluted water, or some new organic pollutants, because of their low content in water, it is difficult to enrich and degrade. Directly restricting the reuse of treated water, there is still a lack of very effective methods and technologies. Therefore, research and development of new principles, new technologies and new methods for more effective control of special pollutants is an urgent problem.
针对低浓度难降解有毒有机污染物处理而言，高级氧化水处理技术(AOTs)以氧气或其它绿色高氧化性物质(如：分子氧、臭氧或双氧水等)为氧化剂，是一类非常理想的有毒有机污染物控制新方法，在控制和消除水体中难降解有毒有机物方面显示出十分诱人的应用前景，近年来日益受到人们的关注。For the treatment of low-concentration refractory toxic organic pollutants, advanced oxidation water treatment technology (AOTs) uses oxygen or other green highly oxidizing substances (such as molecular oxygen, ozone or hydrogen peroxide, etc.) as the oxidant, which is a very ideal The new method of controlling toxic organic pollutants has shown very attractive application prospects in the control and elimination of refractory toxic organic substances in water bodies, and has attracted increasing attention in recent years.
在高级氧化处理技术研究中，国内外研究多集中在以分子氧为基础的(光)化学氧化法、活化双氧水为基础的(光)化学氧化法、臭氧为氧化剂的(光)化学氧化法等。在以分子氧为基础的(光)化学氧化法水处理技术中，具有高效率的光催化剂及其固定技术成为制约该技术应用推广的关键。活化双氧水为基础的(光)化学氧化法主要针对高浓度、难降解、有毒有害的有机污染物处理方面有较大的优势，但基于Fenton反应只能在酸性介质中进行(pH＜3)，对于环境中广泛存在的合成有机燃料，则用该方法很难降解，需研究和开发能活化H2O2的催化剂。臭氧为氧化剂的(光)化学氧化法因其臭氧在水相中低的溶解度、不稳定性、有机物降解不彻底、耗能高等局限性，在水污染控制方面受到很大的限制，因此，针对臭氧法在水处理应用的局限性，打破常规水处理模式，研究和开发多相臭氧化反应体系已成为国内外关注的热点。In the research of advanced oxidation treatment technology, domestic and foreign researches mostly focus on (photo)chemical oxidation method based on molecular oxygen, (photo)chemical oxidation method based on activated hydrogen peroxide, (photo)chemical oxidation method based on ozone as oxidant, etc. . In the (photo)chemical oxidation water treatment technology based on molecular oxygen, the high-efficiency photocatalyst and its immobilization technology have become the key to restrict the application and promotion of this technology. The (photo)chemical oxidation method based on activated hydrogen peroxide has great advantages in the treatment of high-concentration, refractory, toxic and harmful organic pollutants, but it can only be carried out in acidic media (pH<3) based on the Fenton reaction. Synthetic organic fuels that widely exist in the environment are difficult to degrade by this method, and it is necessary to research and develop catalysts that can activate H 2 O 2 . The (photo)chemical oxidation method using ozone as an oxidant is greatly restricted in water pollution control due to its low solubility in water phase, instability, incomplete degradation of organic matter, and high energy consumption. Due to the limitation of the application of ozone method in water treatment, breaking the conventional water treatment mode, research and development of multi-phase ozonation reaction system has become a hot spot at home and abroad.
在实际水体中，存在许多·OH抑制剂，如HCO3 -、CO3 2-、SO3 2-等，这些物质通过抑制·OH的形成来影响臭氧化反应活性，一个单相(水)反应体系中不得不使用过量的臭氧为了消除这些物质的影响。因此，如何提高臭氧在体系中的溶解度、稳定性、使用效率，减少副产物的产生，是制约臭氧在水污染控制领域大规模应用的关键瓶颈。In actual water bodies, there are many OH inhibitors, such as HCO 3 - , CO 3 2- , SO 3 2- , etc. These substances affect the ozonation reaction activity by inhibiting the formation of OH, a single-phase (water) reaction Excessive amounts of ozone had to be used in the system in order to eliminate the effects of these substances. Therefore, how to improve the solubility, stability, and use efficiency of ozone in the system and reduce the generation of by-products is the key bottleneck restricting the large-scale application of ozone in the field of water pollution control.
截至目前，在绝大多数报道中，均采用水/有机溶剂两相氧化反应体系，且多使用直链全氟代烷烃(如FC40，FC77等)作为有机相，而使用全氟萘烷(C10F18)溶剂作为有机相的研究还少见报道。全氟萘烷(C10F18)是一种全氟代环烷烃，具有化学惰性、热稳定性、密度大、在室温下能大量溶解多种气体、有较宽的沸点范围、无毒甚至作为人造血浆的主要成分，已作为环境友好材料广泛使用，但作为载臭氧有机溶剂并用于水体中低浓度有毒有机污染物的臭氧氧化降解还没见报道。Up to now, in most of the reports, the water/organic solvent two-phase oxidation reaction system is adopted, and linear perfluoroalkanes (such as FC40, FC77, etc.) are mostly used as the organic phase, while perfluorodecalin (C10F18 ) solvent as the organic phase is rarely reported. Perfluorodecalin (C10F18) is a perfluorocycloalkane with chemical inertness, thermal stability, high density, can dissolve a variety of gases at room temperature, has a wide boiling point range, is non-toxic and can even be used as artificial plasma It has been widely used as an environmentally friendly material, but it has not been reported as an ozone-carrying organic solvent and used for the ozone oxidation degradation of low-concentration toxic organic pollutants in water bodies.
研究结果表明一般的臭氧氧化水处理装置只适用于较高浓度的有机废水，且受水体自由基抑制的存在影响较大，一般仅用于水体消毒处理。对于难降解低浓度的有毒有机废水采用常规的臭氧或臭氧-生物处理很难达到处理要求，通常通入大量的臭氧或延长氧化时间，这样大大提高了运行费用。单一臭氧水处理装置，能耗较大，而且只能处理易降解的有机物(如：苯酚等)或作为其他处理方法的后续消毒处理。对于臭氧-生物活性碳处理系统，可针对水体中的低浓度有毒有机物的降解，但活性碳表面吸附性能受水质影响较大，易于结垢，活性碳再生困难，对于难降解有毒有机物物需要特殊的生物降解菌群，而且活性受环境影响较大，特别是对于含有高盐废水，根本无法使用该处理系统，是制约实际工程应用的主要障碍。臭氧-催化剂(金属)处理系统具有臭氧氧化速率高的优点，但需消耗大量的臭氧和昂贵的催化剂，且催化剂活性受水质影响较大，容易失活，再生困难。臭氧-物理化学辅助(光、超声、电Fenton、磁、高能离子辐射)处理系统虽然臭氧氧化速率高，但能耗高、处理成本高。特别是对含低浓度难降解有毒有机物的废水，其处理成本更高。The research results show that the general ozone oxidation water treatment device is only suitable for higher concentration of organic wastewater, and is greatly affected by the existence of free radicals in the water body, and is generally only used for water body disinfection treatment. For refractory low-concentration toxic organic wastewater, it is difficult to meet the treatment requirements by conventional ozone or ozone-biological treatment. Usually, a large amount of ozone is introduced or the oxidation time is prolonged, which greatly increases the operating cost. A single ozone water treatment device consumes a lot of energy, and can only treat easily degradable organic matter (such as: phenol, etc.) or as a follow-up disinfection treatment of other treatment methods. For the ozone-biologically activated carbon treatment system, it can target the degradation of low-concentration toxic organic substances in water, but the surface adsorption performance of activated carbon is greatly affected by water quality, easy to scale, and difficult to regenerate activated carbon. For refractory toxic organic substances need special The biodegradable flora, and the activity is greatly affected by the environment, especially for wastewater containing high salinity, the treatment system cannot be used at all, which is the main obstacle restricting practical engineering applications. The ozone-catalyst (metal) treatment system has the advantage of high ozone oxidation rate, but it needs to consume a large amount of ozone and expensive catalyst, and the catalyst activity is greatly affected by water quality, which is easy to deactivate and difficult to regenerate. Although the ozone-physicochemical auxiliary (light, ultrasonic, electric Fenton, magnetic, high-energy ion radiation) treatment system has a high ozone oxidation rate, it has high energy consumption and high treatment cost. Especially for wastewater containing low concentrations of refractory toxic organic substances, the treatment cost is higher.
因此，开发成本低、效率高的低浓度难降解有毒有机物水处理方法和工艺，也正是当前解决低浓度难降解有毒有机废水的发展趋势和有效途径。Therefore, the development of low-concentration refractory toxic organic water treatment methods and processes with low cost and high efficiency is also the current development trend and effective way to solve low-concentration refractory toxic organic wastewater.
发明内容 Contents of the invention
1.发明要解决的技术问题1. The technical problem to be solved by the invention
针对臭氧在水相(单相)中溶解度低、稳定性差、缺少选择性氧化、中间产物较多和臭氧利用率偏低等问题，本发明提出一种液/液两相流化臭氧氧化处理对氯硝基苯废水的方法，能有效且经济净化工业有机污染物、实现工业化应用的载臭氧的有机溶剂/水两相(简称液/液两相)流化处理对氯硝基苯废水的方法。Aiming at the problems of low solubility of ozone in the water phase (single phase), poor stability, lack of selective oxidation, many intermediate products and low ozone utilization rate, the present invention proposes a liquid/liquid two-phase fluidized ozone oxidation treatment for The method for chloronitrobenzene wastewater can effectively and economically purify industrial organic pollutants and realize the method for the organic solvent/water two-phase (abbreviation liquid/liquid two-phase) fluidized treatment of p-chloronitrobenzene wastewater for industrial application .
2.本发明的技术方案：2. Technical scheme of the present invention:
原理：两相体系的反应过程主要由两部分组成：从液相中萃取有毒有机物；在有机相中进行臭氧化降解反应。从应用实际角度考虑，除水相外，非水相(有机相)必须满足以下要求：有机溶剂不溶于水、无毒、蒸汽压较低、密度高、易分离、可循环使用、对水相中有机污染物具有高的选择萃取性、有较高的臭氧溶解性和稳定性等。Principle: The reaction process of the two-phase system is mainly composed of two parts: the extraction of toxic organic substances from the liquid phase; and the ozonation degradation reaction in the organic phase. From the perspective of practical application, in addition to the aqueous phase, the non-aqueous phase (organic phase) must meet the following requirements: organic solvents are insoluble in water, non-toxic, low vapor pressure, high density, easy to separate, recyclable, and compatible with the aqueous phase. Medium organic pollutants have high selective extraction, high ozone solubility and stability, etc.
一种液/液两相两相流化处理对氯硝基苯废水的方法，在臭氧的有机溶剂/水两相流化臭氧水处理反应器中，对于浓度小于500mg/L对氯硝基苯废水，使用载臭氧的无毒惰性全氟环烷烃作为有机溶剂，同时进行萃取富集-臭氧氧化处理。A method for liquid/liquid two-phase two-phase fluidized treatment of p-chloronitrobenzene wastewater, in the organic solvent/water two-phase fluidized ozone water treatment reactor of ozone, for concentration less than 500mg/L p-chloronitrobenzene For wastewater, use ozone-carrying non-toxic and inert perfluorocycloalkanes as organic solvents, and simultaneously perform extraction and enrichment-ozone oxidation treatment.
根据对氯硝基苯的浓度和废水量，选择有机溶剂在反应器中的用量、进水方式和流化反应时间(或水停留时间)。一般情况下，废水含盐量不受限制，对氯硝基苯浓度在500mg/L以下，水和全氟有机溶剂的体积比为1∶1～1∶3范围。According to the concentration of p-chloronitrobenzene and the amount of waste water, the amount of organic solvent in the reactor, the water inlet mode and the fluidization reaction time (or water residence time) are selected. Generally, the salt content of wastewater is not limited, the concentration of p-chloronitrobenzene is below 500 mg/L, and the volume ratio of water and perfluorinated organic solvent is in the range of 1:1 to 1:3.
可根据有毒有机物在水相中的浓度以及在液/液两相中的分配系数，选择有机溶剂的种类和用量；全氟有机溶剂不溶于水，易于与水分离并循环使用，在反应器中起萃取-富集作用，能够萃取富集大量的水中对氯硝基苯，而且全氟有机溶剂也是良好的载臭氧溶剂，臭氧在有机溶剂中的溶解度是水中的15倍左右。因此，在液/液两相流化状态下，在全氟溶剂有机相中，高浓度的臭氧分子与富集后的高浓度对氯硝基苯直接进行加成氧化反应，具有良好的选择性，反应速率高；在水相中，转移到水中的臭氧分子在分解过程中形成进攻性自由基(如：羟基自由基等)，可进行非选择性进攻有机分子，即间接氧化反应，在整个反应过程中，因C-F键键能很高，全氟有机溶剂不参与臭氧氧化反应，是很好的惰性有机溶剂，在该系统中，直接加成氧化反应与间接氧化反应同时进行，因此，在该反应体系中，在同等条件下，传统水/气两相氧化反应体系相比，臭氧投加量减少1/2以上，，反应时间缩短2/3以上，有毒有机物总去除率提高20％以上，且出水水质稳定。The type and amount of organic solvent can be selected according to the concentration of toxic organic substances in the water phase and the distribution coefficient in the liquid/liquid two-phase; perfluorinated organic solvents are insoluble in water, easy to separate from water and recycled, in the reactor It can extract and enrich a large amount of p-chloronitrobenzene in water, and perfluorinated organic solvents are also good ozone-carrying solvents. The solubility of ozone in organic solvents is about 15 times that of water. Therefore, in the liquid/liquid two-phase fluidized state, in the organic phase of the perfluorinated solvent, the high concentration of ozone molecules and the enriched high concentration of p-chloronitrobenzene directly undergo addition oxidation reaction, which has good selectivity , the reaction rate is high; in the water phase, the ozone molecules transferred to the water form offensive free radicals (such as: hydroxyl radicals, etc.) During the reaction process, because the C-F bond energy is very high, the perfluorinated organic solvent does not participate in the ozone oxidation reaction, and is a good inert organic solvent. In this system, the direct addition oxidation reaction and the indirect oxidation reaction proceed simultaneously. Therefore, in In this reaction system, under the same conditions, compared with the traditional water/gas two-phase oxidation reaction system, the dosage of ozone is reduced by more than 1/2, the reaction time is shortened by more than 2/3, and the total removal rate of toxic organic substances is increased by more than 20%. , and the effluent quality is stable.
3.有益效果3. Beneficial effect
本发明提供一种液/液两相流化臭氧氧化处理对氯硝基苯废水的方法，首次提出了一种全新的臭氧全氟萘烷有机溶剂/水两相流化快速氧化降解对氯硝基苯废水的方法。工艺制作简单，能耗低，处理成本低，实际工程中操作方便，易于控制，很容易实现工业化生产。The invention provides a liquid/liquid two-phase fluidized ozone oxidation method for treating p-chloronitrobenzene wastewater, and proposes a brand-new ozone perfluorodecalin organic solvent/water two-phase fluidized rapid oxidation and degradation of p-chloronitrobenzene for the first time Benzene wastewater method. The process is simple in manufacture, low in energy consumption, low in processing cost, convenient in operation and control in actual engineering, and easy to realize industrial production.
本发明工艺具有高效、低耗处理低浓度对氯硝基苯废水的优点，因而具有较大的推广应用价值，前景十分广阔。本发明也可应用于多苯环芳香族化合物、有机磷或有机氮农药、抗生素、雌激素类、卤代芳烃类、酚类(苯酚、氯酚、对硝基酚)等的臭氧氧化降解，这些化合物广泛存在于国内化工、医药、电子、食品等重点行业废水或城市再生水中。The process of the invention has the advantages of high efficiency and low consumption for treating low-concentration p-chloronitrobenzene wastewater, and thus has great popularization and application value and very broad prospects. The present invention can also be applied to the ozone oxidation degradation of polyphenyl ring aromatic compounds, organophosphorus or organonitrogen pesticides, antibiotics, estrogens, halogenated aromatics, phenols (phenol, chlorophenol, p-nitrophenol), etc. These compounds are widely found in domestic chemical, pharmaceutical, electronics, food and other key industries wastewater or urban reclaimed water.
附图说明 Description of drawings
图1是本发明处理对氯硝基苯废水工艺流程图。Fig. 1 is the process flow diagram of the present invention for treating p-chloronitrobenzene wastewater.
具体实施方式 Detailed ways
本发明可采用普通具有搅拌或流化系统的反应器，内有一定容积的有机溶剂，可根据处理水量大小、以及有毒有机物浓度及其对氯硝基苯在水相和油相中的分配系数来确定反应器的大小、有机溶剂使用量和萃取富集-臭氧氧化反应时间。若处理水中SS浓度高于20mg/L时须进行预处理后(如：微滤处理等)，达到10mg/L以下，再采用本发明方法进行处理。本方法几乎不受废水中的含盐量影响。The present invention can adopt common reactor with agitation or fluidization system, which has a certain volume of organic solvent, which can be adjusted according to the amount of water to be treated, the concentration of toxic organic matter and the distribution coefficient of p-chloronitrobenzene in the water phase and the oil phase. To determine the size of the reactor, the amount of organic solvent used and the extraction enrichment - ozonation reaction time. If the SS concentration in the treated water is higher than 20mg/L, pretreatment (such as: microfiltration treatment, etc.) must be carried out to reach below 10mg/L, and then the method of the present invention is used for processing. The method is hardly affected by the salt content in the waste water.
实施例1Example 1
使用普通的具有流化系统的反应器，其装置连接臭氧发生器。被处理的有机废水为对氯硝基苯废水，水量低于20m3/d，浓度为10mg/L以下，臭氧发生器为3.0g/h，两相反应器中水和全氟萘烷的体积比为1∶1，在流化反应器中对全氟溶剂预曝气，间歇式进废水，并进行流化，流化反应时间为20～30min，停止流化，静置，全氟萘烷与水分离后滗水，然后再次曝气和进水，进入下一工作循环，对氯硝基苯去除率可达到90％以上。A common reactor with a fluidized system is used, and its device is connected to an ozone generator. The organic wastewater to be treated is p-chloronitrobenzene wastewater, the water volume is less than 20m 3 /d, the concentration is less than 10mg/L, the ozone generator is 3.0g/h, and the volume of water and perfluorodecalin in the two-phase reactor The ratio is 1:1, the perfluorinated solvent is pre-aerated in the fluidized reactor, the wastewater is fed intermittently, and fluidized, the fluidized reaction time is 20-30min, the fluidized is stopped, and the perfluorodecalin is allowed to stand still. After being separated from water, decant the water, then aerate and feed water again, and enter the next working cycle, and the removal rate of p-chloronitrobenzene can reach more than 90%.
实施例2Example 2
使用普通的具有流化系统的反应器，其装置连接臭氧发生器。被处理的有机废水含对氯硝基苯，水量低于20m3/d，对氯硝基苯浓度为100mg/L以下，臭氧发生器为5.0g/h，两相反应器中水和全氟萘烷的体积比为1∶2，在流化反应器中对全氟溶剂预曝气，间歇式进废水，并进行流化，流化反应时间为20～30min，停止流化，静置，全氟萘烷与水分离后滗水，然后再次进水并进入下一工作循环，对氯硝基苯去除率可达到90％以上。A common reactor with a fluidized system is used, and its device is connected to an ozone generator. The treated organic wastewater contains p-chloronitrobenzene, the water volume is less than 20m 3 /d, the concentration of p-chloronitrobenzene is below 100mg/L, the ozone generator is 5.0g/h, the water in the two-phase reactor and perfluorinated The volume ratio of decalin is 1:2, the perfluorinated solvent is pre-aerated in the fluidized reactor, the waste water is intermittently fed, and fluidized, the fluidized reaction time is 20-30min, the fluidized is stopped, and the reactor is left standing. After the perfluorodecalin is separated from the water, decant the water, then enter the water again and enter the next working cycle, and the removal rate of p-chloronitrobenzene can reach more than 90%.
实施例3Example 3
使用普通的具有流化系统的反应器，其装置连接臭氧发生器。被处理的有机废水含对氯硝基苯废水，水量大于20m3/d，浓度为100mg/L以下，臭氧发生器为8.0g/h，两相反应器中水和全氟萘烷溶剂的体积比为1∶2，在流化反应器中对全氟溶剂预曝气，间歇式进废水，并进行流化，流化反应时间为20～30min，然后出水，进入水/全氟萘烷分离池，分离后的全氟萘烷循环使用，对氯硝基苯去除率可达到90％以上。A common reactor with a fluidized system is used, and its device is connected to an ozone generator. The treated organic wastewater contains p-chloronitrobenzene wastewater, the water volume is greater than 20m 3 /d, the concentration is below 100mg/L, the ozone generator is 8.0g/h, and the volume of water and perfluorodecalin solvent in the two-phase reactor The ratio is 1:2, the perfluorinated solvent is pre-aerated in the fluidized reactor, and the wastewater is fed intermittently, and fluidized, the fluidized reaction time is 20-30min, and then the water is discharged and enters the water/perfluorodecalin separation pool, the separated perfluorodecalin is recycled, and the removal rate of p-chloronitrobenzene can reach more than 90%.
实施例4Example 4
使用普通的具有流化系统的反应器，其装置连接臭氧发生器。被处理的有机废水为主要含对氯硝基苯废水，水量低于20m3/d，对氯硝基苯浓度为500mg/L以下，臭氧发生器为10g/h，两相反应器中水和全氟萘烷溶剂的体积比为1∶3，在流化反应器中对全氟萘烷预曝气，间歇式进废水，并进行流化，流化反应时间为20～30min，停止流化，静置，全氟萘烷与水分离后滗水，然后再次进水并进入下一工作循环，对氯硝基苯去除率可达到90％以上。A common reactor with a fluidized system is used, and its device is connected to an ozone generator. The organic wastewater to be treated is mainly p-chloronitrobenzene wastewater, the water volume is less than 20m 3 /d, the concentration of p-chloronitrobenzene is below 500mg/L, the ozone generator is 10g/h, the water in the two-phase reactor and The volume ratio of the perfluorodecalin solvent is 1:3, the perfluorodecalin is pre-aerated in the fluidized reactor, the waste water is fed intermittently, and fluidized, the fluidized reaction time is 20-30min, and the fluidized is stopped , stand still, decant water after perfluorodecalin is separated from water, then enter water again and enter the next working cycle, the removal rate of p-chloronitrobenzene can reach more than 90%.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101395077A CN101811769B (en) | 2010-04-02 | 2010-04-02 | Method for treating parachloronitrobenzene waste water through liquid-liquid two-phase fluidization and ozone oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101395077A CN101811769B (en) | 2010-04-02 | 2010-04-02 | Method for treating parachloronitrobenzene waste water through liquid-liquid two-phase fluidization and ozone oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101811769A CN101811769A (en) | 2010-08-25 |
| CN101811769B true CN101811769B (en) | 2012-07-04 |
Family
ID=42619163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101395077A Active CN101811769B (en) | 2010-04-02 | 2010-04-02 | Method for treating parachloronitrobenzene waste water through liquid-liquid two-phase fluidization and ozone oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101811769B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713249A (en) * | 2019-11-01 | 2020-01-21 | 云南大学 | Method for treating hardly biodegradable organic wastewater |
| CN111054306A (en) * | 2019-11-19 | 2020-04-24 | 南京师范大学 | Modified biochar and preparation method and application method thereof |
| CN115594357B (en) * | 2022-11-08 | 2024-04-19 | 煤炭科学技术研究院有限公司 | Fractional treatment method for acylated wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4793931A (en) * | 1987-09-10 | 1988-12-27 | Solarchem Research, A Division Of Brolor Investments Limited | Process for treatment of organic contaminants in solid or liquid phase wastes |
| CN101514044A (en) * | 2009-03-17 | 2009-08-26 | 南京师范大学 | Method for treating low-concentration nitrobenzene waste water by means of three-phase fluidization |
| CN201347378Y (en) * | 2009-01-07 | 2009-11-18 | 南京师范大学 | Batch-type three-phase-fluidization ozone oxidation reactor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7547388B2 (en) * | 2004-07-20 | 2009-06-16 | Think Village-Kerfoot, Llc | Superoxidant poiser for groundwater and soil treatment with in-situ oxidation-reduction and acidity-basicity adjustment |
-
2010
- 2010-04-02 CN CN2010101395077A patent/CN101811769B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4793931A (en) * | 1987-09-10 | 1988-12-27 | Solarchem Research, A Division Of Brolor Investments Limited | Process for treatment of organic contaminants in solid or liquid phase wastes |
| CN201347378Y (en) * | 2009-01-07 | 2009-11-18 | 南京师范大学 | Batch-type three-phase-fluidization ozone oxidation reactor |
| CN101514044A (en) * | 2009-03-17 | 2009-08-26 | 南京师范大学 | Method for treating low-concentration nitrobenzene waste water by means of three-phase fluidization |
Non-Patent Citations (1)
| Title |
|---|
| 徐腾娇等.臭氧氧化降解水中对硝基氯苯的效能与机制.《水处理技术》.2007,第33卷(第1期),第27-30页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101811769A (en) | 2010-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Landfill leachate treatment by persulphate related advanced oxidation technologies | |
| Li et al. | Advanced oxidation process based on hydroxyl and sulfate radicals to degrade refractory organic pollutants in landfill leachate | |
| Bello et al. | A review on approaches for addressing the limitations of Fenton oxidation for recalcitrant wastewater treatment | |
| Ince | Ultrasound-assisted advanced oxidation processes for water decontamination | |
| Eryılmaz et al. | Review of treatment technologies for the removal of phenol from wastewaters | |
| CN102173500B (en) | Method for treating water by Fenton oxidization of activated molecular oxygen | |
| Hai et al. | Hybrid treatment systems for dye wastewater | |
| CN102010052B (en) | Method for treating organic sewage by synergy of cavitation effect and sulfuric acid free radicals | |
| CN104003578B (en) | The method of a kind of pair of section ozone-BAF combined treatment trade effluent | |
| Xing et al. | Treatment of antibiotic fermentation‐based pharmaceutical wastewater using anaerobic and aerobic moving bed biofilm reactors combined with ozone/hydrogen peroxide process | |
| Xu et al. | Light-driven breakdown of 1, 4-Dioxane for potable reuse: A review | |
| CN101774673B (en) | Processing method of hardly degraded organic substance | |
| CN108623042B (en) | Method and device for degrading and mineralizing sulfonamide antibiotics by hydroxyl radicals | |
| CN102633410A (en) | Process for recycling and processing hyperhaline reverse osmosis concentrated water | |
| CN101514044A (en) | Method for treating low-concentration nitrobenzene waste water by means of three-phase fluidization | |
| CN110357347A (en) | A kind of persulfate advanced oxidation coupled biological sulfate reduction processing method for waste water | |
| CN107540175A (en) | A kind of method for removing hardly degraded organic substance in Industrial reverse osmosis concentrated water | |
| Qin et al. | Advanced treatment of pharmaceutical wastewater with combined micro-electrolysis, Fenton oxidation, and coagulation sedimentation method | |
| CN101811769B (en) | Method for treating parachloronitrobenzene waste water through liquid-liquid two-phase fluidization and ozone oxidation | |
| CN104355389A (en) | Method and device for removing insoluble organic matters in water | |
| CN101717146B (en) | Method for treating catalytic ozone oxidation water | |
| CN101264969A (en) | Double catalytic oxidation water treatment method | |
| Khadir et al. | Insights of the removal of antibiotics from water and wastewater: a review on physical, chemical, and biological techniques | |
| CN102134133B (en) | Method for treating 2,4-dichlorophenol wastewater by ozone oxidation in organic solvent | |
| Magara et al. | Application of ozone to water treatment and power consumption of ozone generating systems |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHANGSHU NJNU DEVELOPMENT RESEARCH INSTITUTE CO., Free format text: FORMER OWNER: NANJING NORMAL UNIVERSITY Effective date: 20120724 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 210046 NANJING, JIANGSU PROVINCE TO: 215500 SUZHOU, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20120724 Address after: 215500 Changshou City South East Economic Development Zone, Jiangsu, Jin Road, No. 8 Patentee after: Changshu Nanjing Normal University Development Research Academy Institute Co., Ltd. Address before: Ya Dong New District Yuen Road 210046 in Jiangsu province Nanjing City No. 1 Patentee before: Nanjing Normal University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210106 Address after: Building 3, No.88, Xianshi Road, high tech Zone, Changshu City, Suzhou City, Jiangsu Province Patentee after: Changshu Zijin Intellectual Property Service Co.,Ltd. Address before: 215500 8 Jindu Road, Changshou City Southeast Economic Development Zone, Jiangsu Patentee before: CHANGSHU NANJING NORMAL UNIVERSITY DEVELOPMENT RESEARCH INSTITUTE Co.,Ltd. |