Ayçiçek yağ endüstrisi yan ürününden piroliz yöntemi ile sentetik yakıt üretiminin incelenmesi
Synthetic fuel production from by product of the sunflower oil industry via pyrolysis
- Tez No: 39208
- Danışmanlar: PROF.DR. H. SEMA TÜLBENTÇİ
- Tez Türü: Doktora
- Konular: Kimya Mühendisliği, Chemical Engineering
- Anahtar Kelimeler: Ayçiçek yağı, Piroliz, Sentetik yakıtlar, Yağ endüstrisi, Sunflower oil, Pyrolysis, Synthetic fuels, Oil industry
- Yıl: 1993
- Dil: Türkçe
- Üniversite: İstanbul Teknik Üniversitesi
- Enstitü: Fen Bilimleri Enstitüsü
- Ana Bilim Dalı: Kimya Ana Bilim Dalı
- Bilim Dalı: Belirtilmemiş.
- Sayfa Sayısı: Belirtilmemiş.
Özet
Dünyada genellikle birincil enerji kaynaklan olan petrol, doğalgaz ve kömürün hızla tükenmesi, buna karşılık insanın ve geliştirdiği endüstrinin artan gereksinimlerine paralel olarak enerji sorunu insanlığın gündeminde kalmakta ve bu nedenle, yeni enerji kaynaklan bulabilmek için araştırmalar büyük bir hızla sürdürülmektedir. Birincil enerji kaynaklan açısından şanslı bir konumda olmayan ülkemizde de alternatif enerji kaynaklan üzerine yapılan çalışmalar sınırlı düzeyde olsa da sürdürülmektedir. Bu araşürmalann en önemlilerinden biri olan biyokütleden sentetik yakıt üretimi bu çalışmanın temelini oluşturmaktadır. Yapılan bu çalışmada, alternatif enerji kaynağı olarak incelenen, ayçiçek yağ endüstrisi yan ürünü pres küspesinin sentetik yakıt üretimi amacıyla değişik koşullarda pirolizi gerçekleştirilmiştir. Piroliz işlemlerinin ilk aşaması normal piroliz ortamında (statik) yapılmış ve piroliz sıcaklığı, ısıtma hızı ve partikül boyutu gibi piroliz değişkenlerinin, piroliz ürün verimlerine etkisi araştınlmıştır. Piroliz çalışmalannın ikinci aşamasında ise, sürükleyici gaz akımı (N2), altında yapılmıştır. Bu grup çalışmada ise, piroliz değişkenleri olarak partikül boyutu ve sürükleyici gaz akım hızlan incelenmiştir. Böylece ayçiçek pres küspesi pirolizinde en uygun koşullar araştınlmıştır. Çalışmada elde edilen sıvı ürünün (katran) İR, !HNMR spekturumlan alınmış, termogravimetrik ve elementel analizleri gerçekleştirilmiş, kalorifik değeri belirlenmiştir. Aynca katran distilasyon ile fraksiyonlanna aynlmış, fraksiyonlann günümüzde yaygın kullanımı olan petrol türevlerinden kerosen ve dizel yakıtla benzetimli distilasyon eğrileri karşılaştınlmıştır. Aynca katran sütun kromatografisinde dört farklı frakiyona aynlmış, fraksiyonlann İR spekturumlan alınmış, elementel analizleri gerçekleştirilerek molar gösterimleri ortaya konmuştur.
Özet (Çeviri)
Devolopping technology and industry requires more energy but as known that the energy resources in the world are very limited. Therefore, the energy nowadays is becoming more and more important. In the next century, primary energy resources, petroleum, natural gas and coal may exhaust so there are some plans on haw to meet energy needs. In this area, scientific investigations are carried out with increasing speed all over the world. Turkey is one of the energy-dependent country. We can not produce satisfactory amount of primary energy resources thus, we have started to import crude petroleum since 1961, coal since 1973 and natural gas since 1987. We should use energy resources in our country in the optimum way and search for new and renewable energy resources such as sun-energy, wind-energy, jeotermal, biomass and hydrolic energy. Bio mass is of more importance in our country. Turkey has a large of agri cultrual and animal biomass resources. Agricultural waste of our country is equal to 9.5 megaton petroleum which is the second biggest amount in OECD countries. The energy obtained from biomass energy resources is equal to 17.2 megaton petroleum in terms of 1984 statistics data. As a result, we should develope new suit able processes to produce biomass energy. The researches in the world are already being carried out to produce new and renewable energy from biomass.Especially, USA is thinking of producing the energy in 1 1-15 % from biomass in teh next century. Liquid and gas fuels have been produced from biomass by using pyrolysis process in the world. Biomass resources are generally agricultural, animal and industrial wastes Liquid product obtained from biomass is equal to petroleum. To obtain liquid product from biomass is more economic compared to its other usages. The lack of the sources of petroleum and the good quality solid fossil fuels in Turkey have prompted us to seek other renewable sources of liquid hydrocarbons. By products and wastes of food industry can be considered as biomass and alternative renewable source for hydrocarbon production. In this work, a method to obtain liquid fuels from sunflower's oil cake as a new and renewable energy source by retording in a Heinze retord at various condition was demonstrated. The liquid products were characterized by several spectroscopic and chromatographic methols and compared with the currently utilized transport fossil fuels. In this study, the investigations of sunflower's oil cake were carried out in two steps. In the first step, humidity, volatile material, total ash, ash undissolved in HCI, crude protein, crude cellulose amounts, elemental analysis and calorific value were of the sample were determined. In the second step, pyrolysis experiments were carried out under normal pyrolysis atmosphere and sweeping gas (nitrogen) atmosphere. The experimental set up used in this study is a Heinze type retort. Retort was inserted in a special furnace. Pyrolysis device was connected to related places. The voltage was adjusted to the required value. It was operated with 30 gr. sample for sunflower's oil cake. In all the experimental runs the retort was started at room temperature. The system was left for 30 min. at the pyrolysis temperature and a 7 °C/min, 30 °C/min heating rates were used for experiments. The flow rate of gas being produced and nitrogen flow rate were measured at some intervals during this process. The study conducted under normal pyrolysis atmosphere, was under taken with 0.425- 1.8mm plarticle size at 300,400,450,520,700 and 900 °C pyrolysis temperatures employing low heating rate of 7 °C/min and high heating rate of 30 °C/min in order to investigate the effect of pyrolysis temperature on pyrolysis yields. Of the experiments carried out between 300-900 °C, the one at 400-450 °C pyrolysis temparature and particularly with low heating rate of 7 °C /min showed 38 % tar yield with high heating rate 30 °C/min, tar yield was found 34-35 % at all pyrolysis temperatures However, the gas yield of 16-17 % obtained at low heating rate 7 °C/min increased to the level of 24- 25 %. As aresult, it was shown that the pyrolysis process of sunflower's oil cake was almost complated at 400-450 °C and tar yield was obtained in the highest level with low heating rate. By using these results, in order to establish the effect of raw material particle size on normal atmosphere pyrolysis, four different particle groups of 0.425<Dp, 0.425<Dp<0.850, 0.850<Dp<1.8 and 1.8<Dp mm were chosen and invetigated with low (7 °C/min) and high (30 °C/min) heating rates at 450 °C, set point. As expected at low heating rate the gas yields decreased to 18-20 % and the tar yield increased to 36.8-37 % due to decreasing particle sizes. On the other hand, with high heating rates tar and gas yield reached to 33-34 % and 24-25 %, respectively. In addition, under normal pyrolysis atmosphere, the particle size of 0.425-1.8 mm 7 °C/min heating rate and 450 °C pyrolysis temperature were found to be effective. In investigations carried out under sweeping gas atmosphere, 7 °C/min heating rate and 450 °C pyrolysis temperature were used with four different particle size at 50,100,200,400 and 600 cm^/min sweeping gaz (N2) flow rates. The effect of sweeping gas flow rate and particle size on pyrolysis yields particulary on tar yields were investigated. The nitrogen gas used as a carrier gas in experiments, increased tar yields for each particle size particularly with 100 cm^/min flow rate. The experiments, carried out under sweeping gas showed that to obtain higher tar yields with increasing gas flow rates was not possible due to the reactor geometry in which the sweeping gas was fed under the fixbed. By the measurement of the flow rate of gas leaving the system, it was observed that most of the volatile components went out of the system between 300-350 °C. A bove these tempheratures particularly up to 500 °C it was shown that the tar yield increased. xvIn addition, under sweeping gas atmosphere, the particle size of 0.425-1. 8mm, 7°C/min heating rate and 450 °C pyrolysis temperature were found to be effective. On the other hand, the use of sweeping gas particularly at 100 cm^/min flow rate, seems to be very suitable for increasing the tar yield at the pyrolysis of the sunflower's oil cake. During this study, tar produced under normal atmosphere and the sweeping gas atmosphere was characterized by using spectral and chromotographic methods in order to compare with the other liquid fuels. Humidity, fixcarbon, volatile material, ash and C,H,N,0 elemental analysis of the tar produced under both conditions were determined by using elemental and T.G.A. methods. The elemental analysis and calorific value results of tar produced under normal atmosphere and nitrogen gas atmosphere were found to be very similar.. The H/C ratio of tar is about 1.6, which showed that these is a big similarity with the petroleum and shale oil petroleum whose H/C ratio are 1.5-1.9. IR and ^nmr spectra of the tar were taken to determine the functional groups. Comparing the nitrogen and normal atmospheric pyrolysis products showend that both had nearly the same amount of n-pentane solubles. However, the distribution of the lower fractions had differences. In the latter stages of the study, tars were fractionated into aliphatics, aromatics, and polars by eluding them with n-pentane, toluene, ether and methanol using column chromatography. In some of the studies the products were characterized. To further asses the compatibility of the oil with currently utilized trasport fuels, simulated distilation curves of the pyrolysis oil were obtained. Fractions boilling at 140- 240 °C and 240-350 °C were compared with kerosene and diesel fuel. The simulated distilation curves showed that the whole 140-240 °C fraction was very similar to kerosene and the 240-350 °C fraction was similar to diesel fuel. As a conclusion, an excellent agreement between the fraction of pyrolysis oil and common fuels can easily be seen. In addition, comparision of the H/C ratios of pyrolysis oil with those for conventional fuels indicated that the H/C ratio for the oil obtained from biomass was in between the H/C rations showed that the energy content of the oil is very close to that of petroleum. As the everall conclusion of this study the structure of the resultant oil is very similar to natural crude oil. Therefore, there is a great potential for Turkey to exploit these reserves as possible syntetic petroleum sources. The findings of laboratory scale studies should be applied to pilot and industriel scale as soon as possible.
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