Asfaltit ve bitümlü şist piroliz ürünlerindeki azotun potansiyometrik yöntemle incelenmesi
The Investigation of nitrogen containing compounds in pyrolysis products of asphaltite and oil shale by nonaoueous potentiometry
- Tez No: 14066
- Danışmanlar: DOÇ.DR. SEZAİ SARAÇ
- Tez Türü: Doktora
- Konular: Kimya, Chemistry
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1988
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 100
Özet
ASFALT İT VE BİTÜMLÜ ŞİST PİROLİZ ÜRÜNLERİNDEKİ AZOTUN POTANSİYCMETRİK YÖNTEMLE İNCELENMESİ ÖZET Petrol ürünlerinin artan fiyatları ve yetersizliği, ülkemizdeki düşük kalor i fik değerli katı yakıtların ve bitümlü şistlerin kullanımı nı ve değerlendirilmesini yeniden gündeme getirmiştir. Bu çalışmada, Silopi ve Şırnak asfaltitleri ile Göynük ve Seyitömer Bitümlü şistleri Heinze retordunda 540 C da piroliz edilmiş, katran verimleri hesaplan mış, piroliz sonucu elde edilen katranın malten kesimi silikajel ko londa alt fraksiyonlarına ayrılarak eluat verimleri hesaplanmış, ali fatik, nötral aromatik ve polar bileşiklerdeki azotun yapısı potansi- yometrik, kromatografik ve spektroskopik yöntemlerle aydınlatılmaya çalışılmıştır. Azot içeren model bileşikler nitrobenzen, klorobenzen gibi çözücülerde, susuz ortamlarda potansiyometrik yöntemlerle titre edil miş, model bileşiklerin sudaki pK değerleriyle susuz çözücülerdeki yarı nötralizasyon potansiyelleri karşılaştırılmış, 4:1 hacım oranında klorobenzen/asetikanhidrit içeren çözücü sisteminin model bileşikler, piroliz ürünleri ve malten kesimleri için potansiyel aralığını geniş lettiği saptanmıştır. Piroliz ürünlerinin malten kesimleri silikajel kolonda parafi- nik, nötral aromatik ve polar fraksiyonlarına ayrılarak, herbir frak siyonun elementer analizleri, sayıca ve ağırlıkça ortalama molekül ağırlıkları hesaplanmıştır. Piroliz ürünlerindeki ve alt fraksiyon eluatlarındaki fonksiyonel gruplar Fourier Transform Infrared Spektros- kopisiyle incelenmiş, heksan eluatlarındaki alifatik bileşenlerin tanınmasında kapiler kolon gaz krcmatografisi kullanılmıştır _ Maltenlerin benzen eluatlarına H n.m.r. yöntemi uygulanarak yapıdaki hidrojen dağılımının miktarı, 13c h.m.r. yöntemi ile de yapıdaki karbon atomlarının dağılımı ve şekli kalitatif olarak ince lenmiştir. _v-
Özet (Çeviri)
THE INVESTIGATION OF NITROGEN CONTAINING COMPOUNDS IN PYROLYSIS PRODUCTS OF ASPHALTITE AND OIL SHALE BY NONAQUEOUS POTENT IOMETRY SUMMARY The increasing costs and shortages of petroleum products have engendered considerable interest in the utilization of low-grade fossil fuels such as oil shale, tar sands etc. Current emphasis on the development of alternate energy sources has stimulated production of synthetic fuels derived from low-grade fossil fuels. The intensive development of research carried out into liquefaction of low-grade fossil fuels observed in recent years has brought the industrial production of liquid fuels from these materials to realization. A number of asphaltic substances are found in South- Eastern Turkey is approximately about 5.2x10 tonnes. The Silopi and Şırnak reserves together comprise the major part of the asphaltite deposits which ranges from asphaltite to asphaltic pyrobitumen according to their degrees of alteration. Oil shale comprise the second largest solid fuel rezerve in Turkey alter lignites, with reserves totalling approximately 5.2x10° tonnes. The geologycal reserve of the Göynük oil shale. deposit is about 2.5x10°, whereas the Seyitömer is only about 1x10° tonnes. The asphaltite bitumens are classified as aromatic- asphaltic oil derived by alteration during migration of aromatic intermediate oils originating from open-water marine sediments laid down in an anoxic environment. The oil shale is composed of kerogen which is insoluble in conventional organic solvents, bitumen which is soluble is organic solvents, and inorganic materials oil shale deposits were formed is ancient lakes and seas by the slow deposition of organic and inorganic compounds remains from the bodies of water. The geology and organic components of oil shale varies with deposit location. All direct coal liquefaction processes produce a coal-derived liquids which contains varying amounts of maltenes, asphaltenes, and preasphaltenes. The thermal decomposition of asphaltic substances and oil shale, pyrolysis or retorting, yield liquid gaseous and solid residue. - VI-The purpose of this study is to investigate the nitrogen, containing compounds in the pyrolysis products of asphaltic substances and oil shales by nonaqueous potehtiometry, column chromatography, size exclusion chromatography, elemental analysis, infrared spectroscopy and İH, ^C n.m.r. spectroscopy. The nitrogen bases in coal and coal-derived liquids, low-grade fossil fuels and derived liquids, even though they are minor components, have not been fully charecterize< The average organic nitrogen content of naturally occuring petroleum from 153 locations is around 0.1 wt % whereas most coals, shale oils and other fossil fuels range from 0.5 to 2.0 wt % nitrogen. Knowledge of the types and quantities of nitrogen compounds in fuels is important because they significantly affect both the refining and stability behaviour of crudes and products. The presence of considerable quantities of nitrogen compounds which is found in low-grade fossil oils would cause a high emission of nitrogen oxides formed during combustion. used di is impo Whether coal-derived liquids are ultimately to be rectly as a utility fuel, or chemical feedstock, it irtant to know as much as possible about the The pyrolysis products of asphaltic substances and oil shales are complex mixtures of alkanes, non polar aromatic compounds, aromatic compounds with functional groups, and heteroaromatic compounds containing significant quantities of nitrogen and sulphur compounds. Because no single technique could give complete information on all possible compound types and because cross-checking qualitative and quantitative data using one or more independent methods is always highly desirable. Because of complex nature of pyrolysis products of asphaltic substances and oil shales, fractionation according to chemical class is required before identification of individual components can be achieved. Traditionally, separation schemes have been developed by using solvent partitioning methods and column chromatography. The chemical charecter ization of such a complex mixture requries prior separation into less complex fractions. Separation procedures have progressed from an elemantary process of separating fuels into oils ( hexan-soluble materials or maltenes) and aspaltenes (benzene-soluble materials) to sophisticated chromatographic techniques. All of the procedures separate coal-derived liquids into fractions that differ according to their chemical - vii-functionality. Silopi and Şırnak asphalite as well as Göynük and Seyitömer oil shale samples were first pyrolysed in a Heinze retort at 540 C and maintained for 30 min. ' The linear heating rates of 5K/min. were used for all pyrolysis experiments. It is noticed that the oil yield is increased at low heating rates. Pyrolysis yields for both asphaltites and oil shales exhibit a common relation between the original aromatic carbon content of the sample and the residual organic carbon after pyrolysis. The Silopi asphaltite and Göynük oil shale gave high >i 1 yields whereas Şırnak asphaltite and Seyitömer oil hale medium and liquar was separated from the pyrolysis.11. Pyrolysis products and maltenes of asphaltites and oil shales were analysed by nonaqueous potentiometry capillary column gas chromatography, fourier transform infrared spectroscopy, ultimate analysis, size exclusion chromatography, *H and *¦*£ nuclear magnetic resonance spectroscopies. This work represents the first study of its kind to use differential, nonaqueous potentiometry for the charecterization of nitrogen-types in pyrolysis products of asphaltite and oil shale in Turkey. The amount of the pyrolysis products titrated ranged from 300 mg to 800 mg. A procedure is described here for classifying nitrogen in the pyrolysis products into three different t types. The basic nitrogen ( pK ^> 2) exists primarily as heteroatomic bases of pyridine, quinoline, piperidine, alkyl-aryl amine types. Weakly basic nitrogen compounds (0
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