Aktif karbon adsorbsiyonu ile kağıt endüstrisi atıksuyundan renk ve kol giderimi
Color and cod removal from pulp and paper ındustry wastewaters using activated carbon adsorbtion
- Tez No: 46262
- Danışmanlar: DOÇ.DR. BİLSEN BELER BAYKAL
- Tez Türü: Yüksek Lisans
- Konular: Çevre Mühendisliği, Environmental Engineering
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1995
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 112
Özet
ÖZET Kağıt Endüstrisi biyolojik arıtma çıkış sulan biyobozunurluğu düşük klorlu organik maddeler içermektedir. Renk ve KOİ'ye sebep olan bu organikler biyolojik yöntemle giderilememekte, üçüncü kademe arıtmayı gerektirmektedirler. Bu parametrelerin giderimi, tesis içinde suyun geri devrettirilerek yeniden kullanımı veya alıcı ortama deşarj durumunda yüzeysel suyun kalitesinin bozulmaması amacıyla önem kazanmaktadır. Bu çalışmada granüler aktif karbon (GAC) adsorbsiyonu ile kağıt endüstrisi atıksuyundan renk ve KOİ giderimi araştırılmış, en uygun aktif karbon sisteminin değişik yüzeysel yükleme, kolon yüksekliği ve debi açısından danecik çapı, sıcaklık ve pH sabit tutularak bulunması amaçlanmıştır. Birinci bölümde çalışmanın tanıtımı yapılmış, amacı ile anlam ve önemi açıklanmıştır. İkinci bölümde adsorbsiyon prosesi hakkında genel bilgi verilmiştir. Üçüncü bölümde renk ve KOİ'nin adsorbsiyonla giderimi anlatılmıştır. Dördüncü bölümde kağıt endüstrisi tanımlanmış, kirlilik bazında değerlendirilmiş ve SEKA- Dalaman fabrikası ile ilgili verilere yer verilmiştir. Beşinci bölümde deneysel çalışmalarda kullanılan malzemeler, deney düzeneği ve izoterm ile kolon çalışmaları açıklanmış, renk ölçümlerinde kullanılan yönteme ait deneysel sonuçlar grafiklerle verilmiştir. Altıncı bölümde izoterm ve kolon çalışmaları sonuçları tablo ve grafiklerle açıklanmıştır. Yedinci bölümde tartışma ve değerlendirmeler sunulmuştur. Sekizinci ve son bölümde ise çalışmanın sonucu açıklanmış ve önerilere yer verilmiştir. vtıı
Özet (Çeviri)
SUMMARY COLOR AND COD REMOVAL FROM PULP AND PAPER INDUSTRY WASTEWATERS USING ACTIVATED CARBON ADSORPTION The objective of this research is to determine the applicability of activated carbon adsorption to the biologically treated pulp and paper industry wastewaters samples taken from the end of aeratod lagoon unit and to investigate the removal of chemical oxygen demand (COD) and color parameters. It is also aimed that finding the best suitable activated carbon system, particularly on granular activated carbon (GAC) and system parameters are evaluated as hydrolic loading, the depth of carbon coloumn bed deth and the operation type, by not changing the carbon partical size, temperature and pH. At the first chapter of the study the description of the work and the importance of the pulp and paper industry concerning environmental impacts are summerized. It is also pointed that as a result of bleaching process nonbiodegredable organics contalbute to the content of wastewater's COD and color. Using the advanced treatment methods is unavoidable because of the decreas in water suplies, and a great intention of wastewater reuse, in all the world, as well. One of the advanced wastewater treatment methods, activated carbon adsorption process is discussed and experimental studies are conducted for removing residual COD an color. Samples taken from SEKA- Dalaman pulp and paper factory contains chlorinated compounds and lignin causing the COD and color parameters. For decreasing the fresh water usage in the factory recsing the wastewater andfor protecting the surface water quality, these parameters in the wastewater must be removed and maximum pollutant elimination is urgently needed. At the second chapter, basic principles of adsorption is summerized. Adsorption is the accumulation of a material at the interfoce between two phases. Most solutes in water accumulate at interfaces and adsorption process take advantage of this phenomenon to remove material from the liquid phose. A number of adsorbents are used in industry, but only one, activated carbon, is both an inexpensive and a nonpolor adsorber. Polor adsorbents attract water and therefore would not be verv useful. A solid surface in contact with a solution tend to accumulate a surface layer of solute molecules because of the unbalance of surface forces. Chemical adsorption results in the formation of a nonomolecular layer of the adsorbate on the surface through forces of residual valance of the surface molecules. Ph ysical adsorption results from molecular condensation in the cappilaries of the solid. In general, substances of the highest molecular weight are most easily adsorbed. axThere is a rapid formation of an equilibrium interfacial concentration, followed by slow diffusion into the carbon particles. The overall rate of adsorption is controlled by the rate of diffusion of the solute molecules within the capillary pores of the carbon particles. The rate varies reciprocally with the square of the particle diometer, increases with increasing concentration of solute, increases with increasing temperature and decreases with increasing molecular weight of the solute. The adsorptive capacity of a carbon for a solute will likewise be dependent on both the carbon and the solute. Because of the many complex interactions that exist between the adsorbent and adsorbate, the adsorption process is often conceptualized as a three- step process involving macrotransport, microtransport and sorption. Macro-transport (bulk transport) involves the movement of the contaminant with the water, microtransport is used to describe the diffusion of the contaminant in the quiescent liquid layer next to the soil. The nonspesifw term sorption is used to describe the attachment of the contaminant to the surface of the soil and its subsequent movement within the soil structure. Adsorption models used in the study of removal of contaminants from solution are based on equilibrium conditions, even though equilibrium is rarely achieved in practice. Because these models are used to describe relationships, at constant temperature, they are known as adsorption isotherms. To describe the adsorption of constituents from solution the models proposed by Freundlich and Langmuir are commonly used. Description between adsorption models is made by fitting the data to the expressions. Adsorption systems can be classified as batch and continuous systems. Continuous systems are completely mixed reactors (system used powdered activated carbon) and coloumn systems. Coloums systems are classified as fixed bed, fluidized bed and expanded bed systems. Fixed bed systems are used for experimental studies. Breakthrough curves are obtained for GAC adsorption, that describes adsorption efficiancy and indicates the applicability of activated carbon treatment for the given industry. At the third chapter, removal of color and COD using adsorption process is given by studies conducted in the removal of color mainly four types of approach can be discussed. These are chemical ocsidation, chemical precipitation, reverse osmoz and adsorption. Color accurance is based mostly by organic materials in wastewater, by extended aeration systems it is not possible to obtain desired color level General measurement methods used for color measurement in pulp and paper industry are comparator type, the filter fotometer and spectrophotometer. Of several factors affecting color measurement, the choice of wavelength must be considered. To eliminate inaccuries and make color specification independent of particular observers, spectrofotometric curves must be examined to discover those areas of the visible spectrum that indentify an exact match of sample and standard. Modern theories agree that the chemical structure of a compound determines its final color and that this color is caused by the displacement of oscillating electrons which asborb aspecific part of impinging white light. Several studies experimentaly conducted for removing color and COD from wastewaters and these studies show s that %90 removal of both COD and color can be achieved. In the literature based studies, the relationship between color and COD removal is explained. Applications show that activated carbon adsorption is effective in color and COD removal but it highly depends on the design and operation conditions. At the fourth chapter, pulp and paper industry and its specification based on pollution is evaluated and SEKA-Dalaman industry is discussed by process and environmental aspects. Paper is comosed primarily of cellulose. The purpose of the pulping process is to separate out from the raw materials the nonsellulose components, leaving behind almost pure cellulose, to which other substances can be added to develop special qualities is so desired. Any fibrous material is suitable as a raw material. In practice, wood provided about 70%, waste parer 20%, and rags and other plant materials the remaining 10% of the raw stocks. The papermaking process consist of four basic steps: 1. Breaking down the raw materials to fine particles by mechanical mean. 2. Dissolving the lignin and other noncellulose compounds chemically so as to form pulp. 3. Forming a layer of pulp slurry, which is then dried on a paper machine, yielding a mat of cellulose fibers, a paper sheet. 4. Possible addition, at some point in the process, of dyes, coating materials or preservatives, depending upon the end use of peper. The environmental pollution problems associated with paper production are three fold. 1. Air pollution problems arise in the conversion of wood to paper pulp. 2. The pulping process releases much BOD. (This is the most serious of the pollution problems.) 3. The conversion of pulp to paper sheet requires large amount of energy whose production generates air pollution. Additional BOD and some specific chemicals are also released in this process. Pulp bleaching effluent constitute the most problematic part of the whole pulp and paper industry. As a result of bleaching with chlorine, chlorine dioxide, hypochlorite etc. the bleaching effluents contain large amounts of halogenated organics which have low biodegredability. Thus by biological treatment only a part of the COD and color can be removed. Pollutant parameters in pulp and paer industry wastewaters are BOD, TSS (total suspended solids), pH, oil and gress as convantional pollutants and COD, color,. NH3 as non conventional pollutants according to the classification mrtde by LPA. By using the activated carbon adsorbtion process, 2mg/l BOD level can be achieved in wastewater XISEKA-Dalaman pulp and paper factory is one of the largest industrial water users in Turkey and hence produces considerable effluent volumes. These effluents are a major source of pollution as they have high color and COD. The reason of color and COD is chlorinated compounds and the compounds are toxic and mutagenic. They also import a color to the effluent which is aesthetically undesirable. In SEKA- Dalaman factory, 4500 m3/hour wastewater is dischargedwith 600 mg/1 TSS, 200 mg/1 BOD5, 550 mg/1 COD and 8-9 pH. The wastewater treatment plant is composed of grid, neutralization, precipitation, aerated lagoons, stabilization ponds and lqst aeration ponds. At the fifth chapter, used materials in isotherm and coloumn studies are given. As an adsorbent 2514 Merc granu lar activated carbon which has 1,5 cm particle diameter and 1.55 uniformity coifficient is used. Uniformity coifficient is carried out by sieve analysis and granulometric eurve is planed. For determining of the treatment stages in coloumn studies and for controlling the reduction of color and COD values whether the objected level is reached or not, spectrofotometre is used, as a measurement device. Wastewater is analyised for time to time and results tabulated. Experimental system is described by means of changed parameters during all the coloumn studies. This parameters are tabulated In coloumn studies, adsorbtion systems used in experimental studies is brietly described and surface loading that must be in the interval of 0.08-0.4 m3/hour is evaluated. In this chapter isotherm studies conducted in this study is given all the details. Spectronic 80 D Spectrofotometre is used in 350 nm wavelength to measure the effectiveness of batch and continuous systems. 350 nm is the highest point which adsorption is occi,rpd and this wavelengh is obtained by measuring the color by an interval of 5nm. Wavelenght. COD removal efficiency is measured by using micro COD tests. Data for plotting isotherms are obtained by treating fixed volumes of the liquid to be tested with a series of known concentrations of wastewaters and a series of known activated carbon dosages. The carbon liquid mixture is agitated for a fixed time at constant temperature. After the carbon has been removed by filtration, the residual organic content of the solution is determined. From these data, all of the values necessary to plot an isotherm is calculated. A contact time sufficiently long to insure a reasonable equilibrium should be chosen from these data for the isotherms. At the sixth chapter experimental results arc submitted by means of isotherms and breakthrough curves. Wastewater is diluted to 95-90-80-50-30-10-5-1 % and input and out put COD and color values are measured, j sotherms are plotted and linearized according to the Langmuir and Freundlich equations. All the batch studies are conducted at constant temperature (23°C) and 250 ml erlenmayer is used each of the sample. Experimental results are also obtained by using different carbon mass by using the some material and method. Isotherms briefly discussed by regression analysis and constants. Slope is found from the linearized isotherms and equation of line is obtained. Breakthrough curves for each flowrate and bed depth and their combinations are plotted and why their shape seems like those is briefly discussed. xnAt the seventh chapter of this study, all the data evaluated and compered each other by the general point of view. As a conclusion, granular activated carbon is found highly effective in color and COD removal applied on to the biologically treated pulp and paper industry wastewater, but design parameters and operation conditions effects the removal efficiancy. The best flowrate is found 15 ml/min and 0.05 m3/m2 minute for 2.5 cm diameter colounm. At the eight chapter as a final part of this study, results are summerized and proposals are given. xw
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