Deri endüstrisi atıksularından protein giderimi
Protein removal from leather industry wastewaters
- Tez No: 66490
- Danışmanlar: PROF. DR. OLCAY TÜNAY
- Tez Türü: Yüksek Lisans
- 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: 122
Özet
ÖZET Bu çalışmada, deri endüstrisi atıksularında önemli bir kirletici olarak ortaya çıkan azot parametresinin kaynaklan olan aminoasit ve proteinlerin yapısı ayrıntılı olarak incelenmiş, proteinin atıksudan çöktürülerek ayrılması konusunda teorik ve deneysel çalışmalar yapılmıştır. Bu amaçla; Deri endüstrisi ve atıksu özellikleri incelenmiş, derinin temel bileşenleri olan protein ve aminoasitlerin yapısal ve kimyasal özellikleri ile deri proteinleri hakkında detaylı bilgi verilmiştir. Protein çöktürülmesi konusunda yapılan teorik araştırmalar ve bu konuda, literatürde yeralan çalışma ve yaklaşımların incelenmesinden sonra üç temel protein giderim yöntemi için aşağıdaki deneysel çalışma planlanmıştır:. İzoelektrik nokta ayarıyla proteinlerin çöktürülmesi. Metal tuzlan ilavesiyle protein çöktürülmesi. Çöktürme yardımcıları ilavesiyle koagülasyondur. Planlanan deneylerle, teorik verilerin güvenilirliğini araştırılmış, seçilen yöntemlerin uygulama esasen laboratuar ölçeğinde saptanmıştır. Seçilen yöntemler, önce, ilerici çalışmalara referans olması bakımından sentetik, daha sonra da sanayiden alman gerçek atıksular üzerinde laboratuar ölçeğinde denenmiş, elde edilen sonuçlar ve deneyler sırasında yapılan gözlemler ışığında yöntemlerin verimlilikleri ve uygulanabilirlikleri belirlenmiştir. Sentetik atıksular üzerinde, çeşitli asitlerle yapılan çöktürme denemeleri çok çözünen aminoasitler için, çözünürlükte pH'a bağlı bir değişim olmadığım ortaya koymuştur. Düşük çözünürlüğe sahip şistinde ise izoelektrik noktasında maksimum çökme gözlenmiştir. Metal tuzlan ile yapılan denemelerde maksimum verim, sistemin CX1SO4 ile çöktürülmesinden elde edilen % 55'lik verimdir. Gerçek atıksularda yapılan pH ayarı ile çöktürme çalışmaları, değişik numunelerde, % 47'den başlayıp % 90'lan bulan organik azot giderimi ile sonuçlanmıştır. Metal tuzları ilavesi ile yapılan denemelerde % 20 ile 30 arası, koagülant ilavesi ile gerçekleştirilenlerde ise çeşitli kompozitler için % 30 civan verim elde edilmiştir. Deney sonuçlan, giderim performansının atıksu yapısına belirgin derecede bağlı olduğunu göstermektedir. Bununla beraber en yüksek verimin, asit ilavesiyle pH ayan olduğu açıktır. Bu aynı zamanda uygulanabilirlik ve ekonomi açısından da optimum yöntemdir. ıx
Özet (Çeviri)
SUMMARY As a result of rapid industrialization, industrial pollution and increasing environmental responsibility and consciousness of public, industrial wastewater treatment has become the subject of detailed scientific researches. Because of the problems envisaged in this field have a very wide range, industrial pollution is the most complex one when compared to other types of pollution. Leather tanning industry, with its very important role in the Turkish economy, has to be considered in detail since its highly complex and unsteady pollutant characteristics. Therefore, researches on leather industry wastewaters need systematic approaches and use of optimization techniques. In these approaches, being organized as industrial states, examining several optimization techniques from separated to combined treatment, process variations, waste minimization, recycling of several wastes, water reuse are some alternatives which could be considered. Beside, several factors should be taken into account as determining the most convenient and economic treatment alternatives and searching and advising for new methods. Wastewaters originating from leather tanning industry contain several important conventional parameters as well as a number of micropollutants. The majority of those pollutants can be removed by conventional processes. However the treatment of wastewaters containing very high nitrogen loads can cause serious problems because of the disadvantages of common used biological treatment technologies such as nitrification - denitrification systems. Protein is the basic source of nitrogen parameter in wastewaters of leather tanning industry. Thus the removal of protein content is meaningful with regard to reduce the organic load entering the wastewater treatment plant. On the other hand, carrying out alternative studies for nitrogen parameter has a great importance because of the value of protein as a raw material.The overall purpose of this study is to define the nitrogenous organic substances in relation with skin structure and the main properties of production processes, determination of appropriate treatment technologies and availability of these technologies in practice. The main concept of this study can be summarized as characterization and treatment of wastewater compounds containing protein and aminoacid, by above mentioned alternative methods which are still quite limited for leather industry wastewaters. In this framework, general properties of leather tanning industry and the wastewater characteristics was investigated. As basic compound of leather, the fundamental features of proteins and aminoacids were reviewed in detail. The current theory and practice of protein removal and recovery was evaluated. Precipitation of proteins has widespread application as a method for protein recovery on both the laboratory and industrial scales. The most common processes are salting out by inorganic salts, such as ammonium sulfate, and the fractionation of plasma proteins by ethanol precipitation. However, neither the effect of concentrated salt nor that of ethanol for promoting aggregation and precipitation is very well understood. Another class of molecules, short fatty acids have long been recognized to be powerful plasma protein precipitants e.g. caprylic acid. Caprylic acid precipitation may provide a valuable alternative to ethanol precipitation. The methods used for protein precipitation appeared in the literature can be summarized as follows:. Precipitation with salt addition. Precipitation with non-ionic polymers. Precipitation with polyelectrolyte addition. Precipitation with metal addition. Precipitation with caprylic acid. Precipitation with ethanol and trichloroacetic acid. Precipitation with pH adjustment XIStudies indicated that among these methods, the protein removal efficiency by pH adjustment method using H2S04 was reported as 80 %. The same method with HC1 in the same conditions gave the efficiency rate of 60 %. By using trichloric acid precipitation the protein removal efficiency reached to a maximum of 85 % while the ammonium sulfate could provide a value of 90 %. It is pointed out that the H2S04 use seems to be the most convenient and economic selection in spite of its reduced efficiency as compared to ammonium sulfate. In this study, an experimental research was planned for three following basic protein precipitation methods:. Precipitation by isoelectric point adjustment: The isoelectric point is the point that there is no net migration in the aminoacid solution because of the concentration of anion is the same as the concentration of cation. At isoelectric point, proteins and aminoacids have minimum solubility. In this study, by use of H2S04 and NaOH, pH values of wastewater samples were set to certain pH values which are close to the isoelectric points of the major protein components of the sample.. Precipitation with the addition of metal salts: Another precipitation technique is“salting out”. The solubility of a protein solution is highly dependent on the salt concentration. Addition of high concentration metal salts into protein solution resulted in precipitation of proteins whereas less amounts cause an increase in solubility. Use of metal salts for salting out cause the formation of metal- protein complexes which tend to precipitate. CuS04, ZnS04 and MgS04 were the salts used in this study.. Coagulation by the addition of precipitation agents: Proteins those exist as colloidal form in solution can be removed by flocculation. The removal mechanism is adsorption of colloids on floes and precipitation of proteins in colloidal form with these floes. In this study, A1C13 and FeCl3 were used as precipitation agents. In order to provide some indication about the leather proteins and to have references for the further studies, as a first step, several experiments were carried out with synthetic wastewaters which were prepared with pure aminoacids. These aminoacids were selected according to the natural ratios in the skin, and the solutions were prepared as representative for real leather industry wastewaters. Selected aminoacids were cystin, xncystein, glycine among epidermis proteins and glycine and hydroxyproline among collagen proteins. Then the experiments were done considering the results of the former studies. For the real samples, two different leather production companies were chosen to reflect the differences between calf skin and garment production in regard with processes and wastewater characterization. During the experiments instead of using whole samples, some compositions were prepared. The view point on preparation of this compositions were obtaining minimum flow rate with maximum nitrogen content in order to provide optimum treatment conditions. Experimental studies on synthetic wastewaters indicated that, except cystine, solubilities of all aminoacids higher then their concentration found in the leather industry wastewaters. Moreover pH differences are not effective on the solubility of these aminoacids. In the same manner examined perchloric acid did not change the solubility either. However, studies on cystine in saturation concentration showed that, it has the minimum solubility at its isoelectric point. The experiments above were to check the literature about solubility of related aminoacids, all were confirmed. For the application of heavy metal salts to synthetic wastewaters, hydroxyproline, glycine, and cysteine in high concentrations were used. The results were evaluated as organic nitrogen removal. Amount of metal that added to the solutions were estimated stoichiometricly considering the metal-carboxyl ligand formation. With use of MgS04, for hydroxyproline, precipitation was not observed. However relative efficient removals (%20-30) were obtained by use of the other salts at pH 5,2. In the study released for glycine, it was observed that ZnS04 and CuS04 both succeeded the precipitation but the former one with a removal efficiency of %22 (at pH 8,5) and the latter of %48. For Cysteine removal, an efficiency of %27 with ZnS04 at pH 4,6 and %55 with CuS04 at pH 2 was obtained. And a slight precipitate occurred with MgS04 addition. As a summary, metal precipitation experiments indicated that except glycine, precipitation of other aminoacids occurred at acidic pH values. Due to the fact that those acidic pH values prevent the formation of some insoluble salts, removals should not be considered as the result of adsorption mechanism. Therefore it was clearly understood that the process was formation of metal-protein complex. Otherwise removal by the use of CuS04 for glycine realized only at high pH values but with a very high efficiency more than expected normally obtained only with adsorption mechanism. For the precipitation by adjusting pH to isoelectric point, several compositions of wastewater were used. The results of the experiments indicated that precipitation begins under pH 6 at which the hydrolyses stops. At pH 4 high efficiencies (about % 50-60) were obtained. This application is considered as a successful one for several manners. xmWhile the nitrogen removal is quite high, the hydrolyses is prevented at certain pH level at the same time. Significantly, the most efficient pH value is meaningful being the optimum value determined before with the previous experiments carried out in this study. Suprisingly, addition of some precipitating agents and metal salts in the same sample at the same pH value did not cause any increase in removal efficiency, contrastly because of the changing precipitant character, the results affected negatively. Trials of ZnS04 in increasing concentrations at several pH values did not give high removal efficiencies. Only for the sample at pH 1 1,5 %30 removal obtained. Addition of coagulants in several concentrations, similarly, gave low efficiencies for suspended nitrogen while an unpredictable stability of organic nitrogen had been observed meaning continuous hydrolyses. The results of the whole study indicated that the method of isoelectric point adjustment by use of H2S04 seems as the most convenient one both in economic and applicability manners besides its high precipitation efficiency. To give an overall evaluation it should be emphasized that high nitrogen content in leather industry is a matter of concern for biological treatment systems. Beside that it is a well known fact that proteins included by this wastewater are very valuable raw materials with regard to recycle. In spite of all there has been still a very few studies carried out in this context. Thus the next step should be a little more specific on the researches for the alternative treatment methods for this industry. XIV
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