Göynük bitümlü şistinin demineralizasyonu ve pirolizi
The Demineralization and pyrolysis of Göynük oil shale
- Tez No: 39228
- Danışmanlar: PROF.DR. EKREM EKİNCİ
- Tez Türü: Yüksek Lisans
- Konular: Kimya Mühendisliği, Chemical Engineering
- Anahtar Kelimeler: Belirtilmemiş.
- Yıl: 1993
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Belirtilmemiş.
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: 60
Özet
ÖZET Dünya enerji kaynaklarındaki hızlı tüketim, petrol yerine geçe bilecek sentetik sıvı yakıt üretimini geliştirme çalışmalarına olan ilgiyi artırmıştır. Bitümlü şistlerden elde edilen sıvı yakıt bu probleme bir alternatif teşkil etmektedir. Çalışmanın ilk bölümünde Göynük (A) bitümlü şistleri üzerinde anorganik asitlerle birbirine bağlı üç kademede gerçekleştirilen mineral madde giderme işlemleri gerçekleştirilmiştir. Başlangıçta orjinal şistte bulunan %16.7 oranında bulunan kül miktarı, HC1 ile yapılan birinci kademe sonunda %11.6'ya, HC1 + Zn ile ikinci kademe sonunda %11.2'ye üçüncü kademe sonunda ise HC1 + HF ile %2.3'e indirilebilmiştir. Sonuçta toplam olarak başlangıçtaki külün yaklaşık %86'sımn giderilebildiği gözlenmiştir. îkinci kısımda ise demineralize edilmiş numuneler üzerinde piroliz deneyleri yapılmıştır. Deneyler Heinze retordunda 4°C/dakika ısıtma hızında ve 550°C'a kadar normal atmosfer ortamında gerçekleştirilmiştir. Piroliz sonuçları değerlendirildiğinde katı kalıntının ve kalıntıdaki organik madde içeriğinin giderek azaldığı ve III. aşama sonun da minimuma ulaştığı görülmüştür. Kil minerallerinin ve silikatların yapısında bulunan silisyumun III. kademede önemli ölçüde giderilmesi ile katalitik etkide azalma sağlanmış ve sıvı ürün veriminde sürekli bir artış tespit edilmiştir. iv
Özet (Çeviri)
With the energy climate developing as it is, there is increased interest in the development of synthetic liquid fuels to replace or supplement the dwindling supplies of petroleum. Liquid fuels from oil shales represent an alternative to this problem. Oil shale deposits were formed in ancient lakes and seas by the slow deposition of organic and inorganic remains from the bodies of water. As the waters dried, the deposits compacted and transformed into impermeable rocks. Oil shales contains structures which are complex organic polymers with high molecular weight. Although the geology and the composition of inorganic and or ganic components of oil shales varies with deposit location, general structures are similar. Oil Shales I 1 Anorganic Fraction Organic Fraction I I Bitumen Kerogen Anorganic Fraction: Oil shales generally contain over one-third mi neral matter and this fraction depends on the depositions! environ ment. The anorganic material consists, mainly of clay minerals, cal- cite and dolomite-found in carbonate minerals, pyrite in sulfide mi nerals and silicate minerals principally quartz. Organic Fraction: Bitumen: Bitumen is defined as ttie benzene-soluble organic material formed during the heating period that is nonvolatile and remains in the shale sample. Kerogen: Kerogen is defined as that portion of the organic matter incommon organic solvents. Lt is essentially a“block box”from Wtlicti products evolve upon application of heat. Calorimetric value of the kerogen in oil shale is about 10.000 kcal/kg. Although the kerogen structure varies with deposit location it is referred to as the following ampirical formula: C?qqH200s N5O]]. Carbon to hydrogen weight ratio differs from 7.5 to 10 for kerogens \r\ oil shales. These ratios are 6-7 for petroleum and about 15 for coal. Kerogen can be classified in terms of hydrocarbon generating potential by physical-chemical methods, microscopic and spectroscopic analysis. In other works the potential of an oil shale rock as a liquid fuel input may be evaluated from the kerogen classification. This approach classifies oil shale kerogens into three groups. Type I kerogens originates mainly from marine or lacustrine or ganic material. For that reason this type of kerogen has a higher H/C ratio compared to the type II and type III kerogens. Pyrolysis products are mainly linear or chained hydrocarbon com pounds. Type II kerogen may have a significant component of terres trial as well as marine material. Its H/C ratio is lower than that of type I kerogen and its 0/C ratio is slightly higher. The dominant hydrocarbons are naphthenes and aromatics in the liquid product. Type III kerogen is mainly terrestrial in origin with higher 0/C and lower H/C ratios than other types reflecting the increased proportions of polycyclic aromatics and oxygen containing aromatic groups. The van Krevelen diagram shows the positions for the three types of kero gens on thermal maturation degrees as obtained from vitrinite reflec tance indices, The thermal decomposition of oil shale pyrolysis or retorting, yields liquid, gaseous and solid products. The liquid produced by pyrolysis, is in the form of a vapor and the noncondensable hydrocar bon gases. The remaining organic carbons remains on the retorted shale, the mineral matter, as a cokelike deposit. Fischer Assay method is commonly used to define the shale oil potential. In brief, the Fischer Assay consists of heating a 100 g sample of minus B mesh oil stiale to 500°C at l2°C/min and maintaining this temperature for 40 minutes. The Fischer Assay is a specification test and does not provide any information about the quantity or quality of the organic matter (kerogen) in the shale. It is essentially a black box from which oil and gas products evolve from the application of heat. The importance of kerogen structure on the conversion behavior viof oil shales becomes more apparent when the conversion behaviour of oil shales from different deposits, geologic ages, and depositions! environments are compared. During the last decade, because of the development of solid-state nuclear magnetic resonance techniques, that the aliphatic/aromatic carbon distribution in oil shale kerogens can be measurede. The combined use of both methods makes it possible to determine the effects of kerogen structure on the conversion behavior of oil shales. The inorganic part consists of essentially nonspherical particles, smaller than 44, which have considerable surface area. An estimate made from surface-area suggests that only a small amount of the organic is either directly or chemically bonded to the mineral, constituents. That is to say, the organic matter is between the inorganic particles. Mineral matters posses difficulties during combustion and utili sation techniques.. It is observed that demineralisation process applied to Seyitbmer oil shales has increased the calorific value of the products. The study of the organic matter in oil shale often requires its isolation. Several approaches can be taken. For removing the mineral matters from the oil shale, besides some techniques such as ultrasonic, electrostatic, magnetic seperation, physical processes (santrifuges etc) can also be applied. Whereas these methods are effective for dissol ving small amounts of mineral fraction. Therefore chemical methods in demineralisation are the most common approach. Carbonate and sulphate minerals can be removed by extracting the oil shale samples with hydrochloric asid. In this process carbonates dissolve according to the following reaction. CO32 + 2HC1 > C02 + H2Q + CI" Sulphates remain in the solution. To remove silica minerals -hydrofluoric asid and hydrochloric asid are used. 4HF + SiQ2 FeCl2 + ZnClz + H2S In this study a consecutive three stage mineral acid deminera- lisation is investigated. The 16.6% mineral matter content of origi nal oil shale was reduced to 11.6% by HC1 extraction of the first stage, to 11.2% by Zn+HCl extraction (the second stage) and to 2.3% after the last stage by HC1 + HF extraction. At the end of the demi- neralization 86.2% of the original mineral matter content of the oil shale was removed. Pyrolysis experiments were carried out in a Heinze retort. The temperature was controlled using a thermocouple inside the retort. The tar and aqueous liquer was collected in liquid trap cooled by ice 20 g samples from each demineralization stages was fed to the retort for each experiment. The system was held 30 minutes at the maximum temperature 550°C and a 4°C/min heating rate was used for all experi ments. The retort exit pipe and liquid trap was washed with toluene. However during this some light components having lower boiling points than that of toluene may be lost. For this reason two parallel expe riments.were carried out. At first experiment, the liquid; trap andt the retort exit pipe were washed with toluene and the amount of water was obtained by Dean- Stark method. At second experiment, retort exit pipe and the liquid trap were cleaned up by lower boiling point dichlorpmettiane. After that tar was dissolved in n-hexane to determine the oil yield. Then the produced shale oil was characterized using silicc\ gel column chromatography. The oil are fractionect'into aliphatics, aromatics and polars. Same of the experimental results obtained for this studies are summerized in the following table. vmTable 1: The experimental results of the demineralized oil shales and the original sample. According to the table while pyrolysis tar increased at the end of the third stage, solid residue decreased as a result of deminera- lisation processes. In other words in the tar yields was related to a decrease in semi coke yields. Demineralisation processes may be effective for that. By pre venting the mass adsorbtion of liquid products, the loss of pyrolysis tar may be elimaneted. The asphaltene contents of tar was observed to increase for the third extraction of oil shale sample, where oil yield showed a de crease. Aliphatic and aromatic fraction of oil showed a decreasing trend. However an increase was observed in the polar fractions. Mo lecules which consist of polar groups may become volatile and joins the pyrolysis tar. IX
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