Zararlı atıkların ozon ile oksidasyonu
Başlık çevirisi mevcut değil.
- Tez No: 66425
- Danışmanlar: PROF. DR. İLHAN TANILLI
- Tez Türü: Doktora
- Konular: Çevre Mühendisliği, Environmental Engineering
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1997
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Çevre Mühendisliği Ana Bilim Dalı
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 294
Özet
ÖZET Gelişmiş ülkelerde Zararlı Atıklar konusunda yönetmelikler mevcut olup, zararlı atık yönetimi atığın üretiminden nihai uzaklaştırılmasına dek kontrol altında olmasına rağmen, ülkemizde konu ile ilgili yasal bir uygulama bulunmamaktadır. Ayrıca bu alanda çok az bilgi birikimi mevcut olduğundan zararlı atıkların arıtımında da konvansiyonel arıtım yöntemlerinin kullanımına gidilmekte ve bu da arıtma testlerinin işlevlerini gerçekleştirememe problemlerini getirmektedir. Bu çalışmada Zararlı Atıklar kavramından bahsedilerek, Zararlı Atık tanımı, Zararlı Atıkların tespiti için uygulanan yaklaşımlar, Zararlı Atık kaynakları ve Zararlı Atık liste yaklaşımı anlatılmıştır. Zararlı Atıkların yönetim planlaması ortaya konularak, bir Zararlı Atık tanımlama mekanizması önerilmiştir. Yurt dışındaki bazı ülkelerde Zararlı Atik yönetim sistemleri araştırılarak ülkemizdeki durum ortaya konulmuş ve bu çerçevede konu ile ilgili mevcut yönetmelik ayrıntılı bir şekilde değerlendirilerek hatalı veya eksik olduğu düşünülen yönleri belirtilmiştir. Zararlı Atık yönetim sistemi içinde uzaklaştırma teknolojileri belirtilerek, bunlardan Ozonlama yöntemi çeşitli zararlı atıkların arıtımı veya detoksifîkasyonu amacıyla kullanılmıştır. Ozon ile oksidasyon çalışmaları beş farklı zararlı atık/madde üzerinde yürütülmüştür. Bu atık veya maddeler EPA'nın D, F, K, U ve P listelerinde çeşitli Zarar No.ları ile yeralmaktadır. Çalışmada endüstri bazında Metal Son İşlemleri Endüstrisi ve Pestisit Endüstrisi olmak üzere 2 farklı endüstri için ve yine bu endüstrilerin atıksu kompozisyonu ile ilişkili olarak Siyanür, 2,4 D Asit ve 2,4 DCP, Siklohekzanon ve Ksilen'in. sentetik olarak hazırlanan numunelerinde, ozon ile oksidasyon, esas aritmi veya önarıtım olarak incelenmiş ve ayrıca sentetik siyanürün ozonla oksidasyonunda, siyanür giderim hızı üzerinden bir kinetik analiz yapılmış ve siyanür için sanal reaksiyon hız sabitleri tespit edilmiştir. Zararlı atıkların, ozonlama ile detoksifikasyon sağlayarak inhîbisyon etkilerinin giderilmesi amacıyla ozon ile onarttım veya esas arıtım durumlarının değerlendirildiği bu çalışmada gerek endüstriyel bazlı zararlı atıklar gerekse bireysel zararlı maddeler için oldukça yüksek giderim verimleri elde edilmiştir. Bu zararlı atık veya maddelerin ozon ile oksidasyonunda pH ve ozonlama süresinin oldukça etkili faktörler olduğu görülmüştür. Yüksek pH değerlerinde siyanür içeren numunelerde veya siklohekzanon ve ksilen içeren numunelerde ozonlama süresine bağlı olarak %90'nın üzerinde giderim verimi sağlanmış ve yine 2,4 DCP ve 2,4 D Asit içeren numunelerde yüksek pH'larda yüksek giderim verimleri elde etmek mümkün olmuştur. 2,4 D Asit üretimi yapan pestisit endüstrisi atıksuları için en uygun arıtma seçeneği olarak ozon oksidasyonu sonrası biyolojik arıtma olarak saptanırken, Metal Son İşlemleri Endüstrisi kaplama banyoları çözeltilerinde ozonlama ile beraber kimyasal çöktürmenin en uygun arıtma şekli olduğu görülmüştür. İlk yatarım maliyeti dışında yalnızca enerji maliyeti gerektireceğinden özellikle Zararlı Atıkların arıtımında esas arıtım veya önarıtım şeklinde kullanılmasının yararlı olacağı sonucuna varılmıştır. xvii
Özet (Çeviri)
SUMMARY HAZARDOUS WASTE OXIDATION BY OZONE The public, worldwide, has now become acutely aware that its health and the environment is put at risk as the result of past practices of waste dumping. Some of those wastes have proved extremely toxic and hazardous and through uncontrolled dumping have brought about the deaths of livestock and in an increasing number of incidents have caused ill-health in humans. A potentially more serious risk to human health is the contamination of surface and groundwater supply. Countries must indeed the cost of clean-up of old dumps where no check has been kept of the quantities and kinds of wastes deposited, makes it essential for both authorities and the generators to get hazardous wastes under strict control One of the instruments used is through the introduction of legislation. As the effects of hazardous wastes and the significant potential risks they pose to life and life support systems are becoming increasingly recognised, legislation aimed specifically at controlling hazardous wastes are being promulgated by a growing number of countries. To support and enforce these specific measures, the appropriate administrative and organisational structure also needs to be established. Because of the toxic and hazardous nature of the wastes, often highly specialised expertise and sophisticated facilities are needed to ensure their safe disposal Furthermore, monitoring will also be needed to ascertain that the disposal has been effective with no more threat to human health. There is a need for increased education and training of personnel, particularly in the developing countries, to deal with this issue of managing and controlling hazardous wastes. The problems posed by the production, transportation, storage and disposal of hazardous wastes are becoming legion, whether one is dealing with the past and its risky practices or making provisions for the future. One problem, for example, in the control and management of hazardous waste concern identification of the waste. Thus there is still no internationally accepted definition of a hazardous waste although technical criteria such as toxicity, flammahility, corrosivity, ignitability and reactivity have been proposed and to some extend used. Another problem concerns ignorance as to the exact location of old hazardous waste dumps and the materials they contain; in fact wastes are often dumped without any real awareness as to their compatibility with one another, and serious harm through the mixing of incompatible wastes has occurred. The problem has been compounded with dumping sites which have been abandoned. XVUlBy identifying these sites and surveying their locations, the impacts on human health and the environment posed by each site, could be assessed. Appropriate mitigating measures could then be formulated and implemented for the specific sites which pose serious threats. Also, control procedures could be set up to ensure that abandoned sites would not be used for activities which would result in environmental and health problem, unless they have been safely decontaminated. One of the most important tasks for hazardous waste management legislation is the designation of responsibility for disposal A number of approaches to regulate this responsibility are used. Basically these involve the authorities either assuming the responsibility or designating it to the generator or a combination of the two. Each approach has its advantages and weaknesses. Regardless of who provides the disposal should take into account choice of appropriate transport and disposal methods for the waste in question and correct declaration and proper labelling according to legal requirements. While the hazardous waste is in transit, the trip-ticket procedure is one of the main methods that is used for control purposes. In addition to containing information on the name of waste, the quantity and certification of accuracy of the information provided, the document should also carry instructions on the procedure to be followed in case of accident A number of methods have been used for disposing hazardous wastes. These include Ian drilling, dumping at sea, incineration and deep-well and underground disposal Similarly, a number of treatment methods based on physical, chemical and biological principles are also used. Each of these disposal and treatment techniques have certain technical and/or economic advantages and disadvantages, which depend upon the quantity and type of hazardous wastes. A careful assessment has to be made before choosing a particular technique so that the most cost-effective results will be obtained. The costs of cleaning up old sites are so punitive that both governments and industry now recognise that the entire chain of processes leading to the production and disposal of hazardous waste must be kept under continual surveillance if there is to be any chance of effective control and management Thus, the policy of waste management must be integrated and comprehensive, starting from the use of raw materials and after the manufacturing process following through transportation, storage, treatment and ultimate disposal of the wastes. From an economic point of view, as well as from pursuing sound environmental practice the aim should be to minimise the amounts of wastes produced. This would involve increased re-use and recycling of residues and promoting the greater use of low and non-waste technologies. Within the institutional framework of a country, incentives could be provided to encourage and promote the implementation of this poEcy. These incentives could include fiscal instruments. Undoubtedly such practice will lead to better use of raw materials and to a smaller volume of wastes to dispose of Nonetheless, certain wastes such as the dioxin by-products of 2,4,5 -T manufacture are very persistent and toxic at extremely low concentrations and have already caused havoc when distributed into the environment The complete life history of such wastes must be followed rigorously in what has been termed a“cradle to grave”policy. XIXWhere estimates of the cost of clean-up exist, they are extremely high. Nevertheless, whatever the ultimate cost an attempt needs to be made to clean up the environment before the damage, including the contamination of land and water supplies, proceeds further. Moreover, when considering costs, the benefits to human health and the ecosystem for present and future generations also have to be taken into account, particularly when the hazardous waste is very persistent. Various surveys have shown that the costs incurred by industry in disposing properly of its hazardous wastes are comparable in different industrialised countries, although in general, countries with the most detailed legislation and regulations tend to incur higher costs than countries with a more generalised approach to waste disposal There is a significant amount of trade in hazardous wastes between some highly industrialised countries in Europe, for example exporting to countries that have established appropriate facilities for treating/disposing particular types of hazardous wastes. There is concern that this practice could be extended to the developing countries, which do not have such facilities nor the qualified manpower to closely supervise and monitor proper disposal of the wastes which is exported to them. Strong support should be given to the integrated“cradle to grave”policy for managing hazardous waste, which will have to include the necessary institutional frameworks not only strictly to enforce the regulations promulgated but also provide different encouragement's and incentives to industry to use processes which produce lower quantities of hazardous wastes. Oxidation of hazardous wastes by ozone is one of the major treatment methods based on chemical principles. Ozone, O3 is a strong oxidant that can be generated on-site by an electrical discharge through dry air or oxygen. Ozone is employed as an oxidant gas at levels of 1-2 wt% in air and 2-5 wt% in oxygen. It has been used to treat a large variety of oxidizable contaminants, effluents, and wastes in the following categories:. Municipal drinking water Disinfection; color, taste and odor removal at more than 1000 installations globally.. Wastewater Disinfects and removes oxidizable chemical contaminants from municipal and industrial wastewater. Oxidizes organic compounds, including unsaturated alcohols, phenols, aldehydes; inorganic species, including H2S, nitrite (to less toxic nitrate), cyanide and Fe+2 (to insoluble FeQDI)).. Sludges containing oxidizable constituents. Gas streams containing toxic gases and odor-causing organic compounds. XXA safety advantages with ozone is its generation on site so that oxidant does not have to be stored and shipped. Its toxicity and status as an air pollutant are disadvantages, and scrupulous measures must be employed to prevent its release. In this study, individual hazardous materials such as cyanide (EPA hazard number PQ21, P029, P030, P098, P104, P106, P121), 2,4 DicMorophenoxyaseticacid (EPA hazard number; D016) and 2,4 Dichlorophenol (EPA hazard number; U081), cyclohexanon (EPA hazard number; U057) and xylene (EPA hazard number; U239) and hazardous wastes such as spent cyanide plating bath solutions from electroplating operations (EPA hazard number; F007), plating baths from electroplating operations where cyanides are used in the process (EPA hazard number; F008) and pesticide industry's wastewater (EPA hazard number; K043, K099) which is produced 2,4 D Acid were oxidized by ozone. The planning of study are shown as the following; r I Ozonization Cyanide Spent Plating Solutions of Metal Finishing Industry £ Pesticide industry Chemical Precipitation Electroplating Bath Residues T Sludge Disposal Toxicity 2,4 DCP and 2,4 D Acid Cyclohexanon and xylene Biological Treatability Figure 1. Experimental planning Cyanide, as sodium cyanide (NaCN) or hydrogencyanic acid (HCN) is a widely used industrial material. A major source of waste cyanide is the electroplating industry. Electroplaters use concentrated cyanide baths to hold metallic ions. Dragout of the plating solution, containing cyanide ions and metal-cyanide complexes, contaminates rinsewaters. Several methods of treating cyanide wastes are in current use. Some of these are ozonization, alkaline chlorination, electrolytic decomposition, reverse osmosis, ion exchange, catalytic and thermal oxidation, Inco process, Kastone process. Some of advantages of ozonation are that no dissolved solids are added in the treatment step and to effectively oxidize cyanate to end products. In this study xxicyanide oxidation to cyanate were investigated at different pH values such as (pH 7, 9.5, 11), different cyanide concentrations (100 mg/1 total cyanide and 200 mg/1 total cyanide) and different ozonization times (15, 30, 60, 120 minutes). Kinetic studies were performed for different total cyanide concentrations and different pH values. For a batch system the general rate expression for the reaction of ozone with cyanide can be expressed as -d[03]/dt = k[CNTr[03f (1.1) in literature where k is the reaction rate constant. Hence, the cyanide removal by ozone can be expressed as -d[CNT]/dt = k[CNT]n[03r (1.2) Using this equation, the pseudo first order rate constant of cyanide at pH 1 1. 8, 9. 8 and 7.4 were determined 48 sec“1, 35 sec”1 and 30 sec“1 for total concentration of 100 mg/1 and at pH 11, 9.5 and 7 were determined 24 sec”1, 22 sec“1 and 16 sec”1 for 200 mg/1, respectively. According to these pseudo first order reaction constants, cyanide is at a much slower rate as compared ozone self-decomposition rate which is determined in literature, hence it can be said that the reaction order with respect to cyanide has not been first order which is consistent with the literature. In ozone treatment of cyanide oxidation to cyanate is very rapid at pH >11. In the absence of any metals, cyanide was completely oxidized in nearly 5-15 minutes. After that cyanate started to react with ozone at a much slower rate. In the presence of heavy metals such as spent plating solutions (F007) and plating bath residues (F008), cyanide oxidation to cyanate and to final end product is at a much slower rate as compared with the synthetic results. The concentration of cyanide in spent plating solutions were measured as 3100 mg/L After pre and second ozonizations, cyanide concentration were decreased 1000 mg/1 and 169 mg/L, respectively. Under the same conditions, It was observed that high removal efficiencies were performed for heavy metals. The concentration of cyanide (14 000 mg/1) in plating bath residues were measured as 11 000 mg/1 and 560 mg/1 after chemical precipitation and ozonization, respectively. Whether spent plating solutions or bath residues, high removal efficiencies were obtained after ozonization for cyanide and heavy metals. In Table 1, Table 2, Table 3 and Table 4 are summarized the removal efficiencies of heavy metal, COD and cyanide for plating solutions and plating bath residues. XXllTable 2. Cyanide and COD Removals For Plating Solutions Parameter Raw Water Preozonation (120min.) Chemical Precipitation Second Ozonation (120 min.) Cyanide (mg/I) COD (mg/I) 3100 8210 1000 4925 980 3589 169 2240 Table 4. Cyanide and COD Removals For Plating Bath Residues Parameter Raw Water Chemical Precipitation Ozonization (120 min.) Cyanide, mg/I COD, mg/I 14 000 10 460 11000 4 030 560 450 Pesticide industry wastewater which produces 2,4 D Acid was ozonated under neutral pH and 120 minutes ozonization time. COD measurement have been controlled by total organic carbon (TOC) measurement and outcoming results indicated that there is an inconsistency between COD and TOC values. Therefore, it has been considered that some compounds in the wastewater cause an interference and standart COD test. Fish bioassays have been performed with the ozonated xxmwastewater to control the toxicity of the intermediate products. Increasing Tlm values have been determined due to residual ozone and intermediate products. Since precipitation of organics is more easier after ozonation, Jar-test has been run for the ozonated samples using optimum 800 mg/1 FeCk and 1 mg/1 polyelectrolytes. At the end of this test COD removal performance has been obtained as 60%. 2,4 DCP and 2,4 D Acid, cyclohexanon and xylene are present the mostly pesticide industry. 2,4 DCP and 2,4 D Acid were studied different pH, ozonization times and different 2,4 DCP initial concentrations. At high pH values such as 11.6, 2,4 DCP removal is quite highly and total 2,4 DCP removal efficiency is nearly 97%. Cyclohexanon and xylene were also studied under different pH values and ozonization times. According to experimental results, it is possible to reach very effective removal efficiencies such as 88% at high pH values (pH>l 1.5). On the other hand, ozonization was evaluated as a preozonation before biological treatability of cyclohexanon and xylene samples and preozonation was being very important process preparing samples to biological treatability. In literature results indicate that preozonation could either promote or retard the biodegradability, depending primarily on whether or not the sludge used in the subsequent biological system had been acclimated before hand. Some of compounds have been reported to be exteremely resistant to biodegradation, either in nature or in the treatment systems receiving the waste streams. One of the purpose of this study is to evaluate ozone oxidation process as preozonation before biological treatability of cyclohexanon and xylene compounds. For the understanding of with or without ozone pretreatment, this study were performed in two activated reactors. On the other hand activated sludge reactors were controlled with the blank reactors which does not include biomass and hence the volatilization of the cyclohexanon and xylene were determined. The results of experimental study are given in Table 5. According to results, it is observed cyclohexanon and xylene were converted to intermediate products which have low volatility. Ozonization system were investigated with several individual hazardous materials and hazardous wastes for the purposes of treatability, preozonation and detoxification. As a result, it can be said that it is possible to achieve high performance for treatability, preozonation and detoxification for hazardous materials or hazardous wastes. Except the capital cost, ozonization system does not require high operational costs when compared other treatment systems. It is recommended to use ozone oxidation with chemical precipitation for electroplating bath solutions and bath residues which are listed as F007 and F008 EPA Hazard Code Numbers, because of high removal efficiencies of cyanide and heavy metal concentrations and with biological treatment for pesticide industry which are listed K043 and K099. XXIV1.a e > o C «o (2 §.a * e 15 1) IS S O H O t-. o 1.s s S o o es VO O Ov 3?“8 « ”§. İR §8 o o oo Ov f> t 1 ı i* S Q e o a o il Mı "a -2 s s 1 | o NO 00 VO 2 s I I (b tt. I? ?s -1
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