Batman yöresi petrol örneklerinin NMR ile incelenmesi
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Tarih
2019-10-24
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Yayıncı
Batman Üniversitesi Fen Bilimleri Enstitüsü
Erişim Hakkı
info:eu-repo/semantics/openAccess
Attribution-ShareAlike 3.0 United States
Attribution-ShareAlike 3.0 United States
Özet
Çok farklı araştırma alanlarında kullanılan Nükleer Manyetik Rezonans (NMR) petrol araştırmalarında da kullanılmaktadır. Ham petrolün NMR spin-örgü (T1) ve spin-spin (T2) durulma zamanları ile petrolün viskozitesi, difüzyon katsayısı, su ve yağ emülsiyonlarının özellikleri, fraktür karekterizasyonu ve geçirgenlik gibi özellikleri arasındaki ilişkinin incelenmesi düşük alan NMR ile yapılmıştır. Ancak petrol NMR spektrumundaki piklerin T1 ve çizgi yarı genişlikleri yüksek alan NMR ile ölçülmemiştir. NMR durulma oranları (1/T1 and 1/T2) ile çizgi yarı genişliği arasındaki ilişki de ortaya konmamıştır. Bu çalışmanın petrol örnekleri Batman yöresinde bulunan Şelmo 1, Şelmo 2 ve Didan kuyularından alındı. Her bir kuyudan alınan ham petrol ve dötorokloroform (CDCl3) çeşitli oranlarda karıştırılarak, 5 farklı karışımdan ibaret 3 takım hazırlandı. Bu örneklerin spektumları 400MHz 'de çalışan Bruker Avance NMR Spektrometresi ile alındı. T1 ölçümleri inversion recovery (IR) puls adımı [(180-t-90)-PR]- kullanılarak gerçekleştirildi. Tüm örneklerin T1 değerleri, NMR spektrumundaki CH2 ve CH3 piklerinin kimyasal kaymaları ve çizgi yarı genişlikleri ve ayrıca bir örnekten hazırlanan karışımın viskozitesi; karışımın içeriğindeki petrol miktarlarına karşı ölçüldü. Çizgi genişliği verileri kullanılarak, 1/T2 değerleri, teoriden türetildi. NMR ölçümlerinde farklı kimyasal kaymalarda yer alan çok pikli bir spektrum elde edildi. Piklerin kimliklendirilmesi, literature yolu ile sağlandı.Petrol karışımından elde edilen piklerinin 1/T1, piklerinin çizgi yarı genişliği, kimyasal kayma ve çizgi genişliğinden türetilmiş 1/T2 değerlerinin her birinin, karışım içindeki petrol miktarı ile lineer arttığı belirlendi. Viscositenin de karışımdaki petrol oranı ile lineer arttığı gözlendi. Piklerin deneysel 1/T1 ve türetilmiş 1/T2 değerleri ile viskosite değerleri arasındaki ilişkinin lineer olduğu belirlendi. Karışımın hampetrol oranı ile 1/T1 veya 1/T2 değerleri arasındaki çizgisel ilişkin eğimi, birim ham petrol artışına karşı, (1/T1 veya 1/T2) artışını (rölaksivite) ifade etmektedir. İncelenen piklerin rölaksivite değerlerinin kuyudan kuyuya değiştiği ortaya konuldu. Bu değişkenlik, kuyulardaki ham petrolün viskosite farklılıklarına ve paramanyetik iyon muhtevasına atfedildi. Karışımın petrol muhtevası ile piklerin 1/T1, 1/T2, çizgi yarı genişliği ve kimyasal kayma değerlerinin herbiri arasındaki çizgisel ilişki, pik protonları ile solvent arasında hızlı kimyasal değiş-tokuşun durulma mekanizmalarına katkıda bulunduğunu gösterdi. Viskosite ile 1/T1 ve 1/T2 nin herbiri arasındaki lineer ilişki de, dipolar etkileşimin durulmalara katkıda bulunduğunu gösteriyor. Ancak türetilmiş T2 değerlerinin oldukça küçük olması, CDCl3 ün D sinin oluşturduğu elektriksel alan gradienti ile I spinin etkileşimden ileri gelen quadrapol etkileşimin etkisini anlamamızı da önemli kılmaktadır.
Nuclear Magnetic Resonance (NMR), which is used in many different fields of research, is also being used in petroleum research. The relationship between NMR spin-lattice (T1) and spin-spin (T2) settling times and crude oil properties such as viscosity, diffusion coefficient, water and oil emulsion features, fracture characterization and permeability were investigated with low field NMR.However, the T1 and half line widths of the peaks in the petroleum NMR spectrum were not measured with the high NMR field. The relationship between NMR relaxation rates (1/T1 and 1/T2) and line half width was also not demonstrated. Crude fluid samples of this study were taken from Şelmo 1, Şelmo 2 and Didan wells in Batman region Dechlorochloroform (CDCl3) and crude oil from each well were mixed in various proportions to prepare three sets of 5 different mixtures.Spectrum of these samples were taken with Bruker Avance NMR Spectrometer operating at 400MHz.T1 measurements were performed inversion using recovery (IR) pulse step [(180-t-90) -PR] -. T1 values of all mixtures, chemical shifts and half line widths of the CH2 and CH3 peaks in the NMR spectrum, as well as the viscosity of the mixture prepared from a sample were measured against fluid content in the mixture.Using half line width data, 1/ T2 values were derived from theory. A multi-peak spectrum of different chemical shifts was obtained in NMR measurements. Identification of peaks was achieved through literature. It was determined that the 1/T1, line half with and chemical shift and the derived 1/T2 values of the peaks obtained from the mixture increase linearly with the amount of crude fluid in the mixture. It was also observed that viscosity increases linearly with the fkuid content in the mixture. The relationship between experimental 1 / T1 and derived 1 / T2 values and viscosity values of the peaks was found to be linear. The slope of the linear relation between the fluid content and the 1 / T1 or 1 / T2 values represents the incremental increase 1 / T1 or 1 / T2 versus unit concentration of the fluid (relaxivity). It was revealed that the relaxivity values of the examined peaks varied from well to well. This variability was attributed to the viscosity differences and paramagnetic ion content of crude oil in the wells. The linear relationship between the fluid content and each of 1 / T1, 1 / T2, line half-width and chemical shift values of the peaks indicates that a rapid chemical exchange between the peak protons and the solvent contributes to the relaxation mechanismsThe linear relationship between viscosity and each of the 1 / T1 and 1 / T2 also shows that dipolar interaction contributes to the relaxations. However, the fact that the derived T2 values are quite small makes it important for us to understand the effect of the quadrapol interaction resulting from the interaction of the electrical field gradient created by D of CDC3 and I spin.
Nuclear Magnetic Resonance (NMR), which is used in many different fields of research, is also being used in petroleum research. The relationship between NMR spin-lattice (T1) and spin-spin (T2) settling times and crude oil properties such as viscosity, diffusion coefficient, water and oil emulsion features, fracture characterization and permeability were investigated with low field NMR.However, the T1 and half line widths of the peaks in the petroleum NMR spectrum were not measured with the high NMR field. The relationship between NMR relaxation rates (1/T1 and 1/T2) and line half width was also not demonstrated. Crude fluid samples of this study were taken from Şelmo 1, Şelmo 2 and Didan wells in Batman region Dechlorochloroform (CDCl3) and crude oil from each well were mixed in various proportions to prepare three sets of 5 different mixtures.Spectrum of these samples were taken with Bruker Avance NMR Spectrometer operating at 400MHz.T1 measurements were performed inversion using recovery (IR) pulse step [(180-t-90) -PR] -. T1 values of all mixtures, chemical shifts and half line widths of the CH2 and CH3 peaks in the NMR spectrum, as well as the viscosity of the mixture prepared from a sample were measured against fluid content in the mixture.Using half line width data, 1/ T2 values were derived from theory. A multi-peak spectrum of different chemical shifts was obtained in NMR measurements. Identification of peaks was achieved through literature. It was determined that the 1/T1, line half with and chemical shift and the derived 1/T2 values of the peaks obtained from the mixture increase linearly with the amount of crude fluid in the mixture. It was also observed that viscosity increases linearly with the fkuid content in the mixture. The relationship between experimental 1 / T1 and derived 1 / T2 values and viscosity values of the peaks was found to be linear. The slope of the linear relation between the fluid content and the 1 / T1 or 1 / T2 values represents the incremental increase 1 / T1 or 1 / T2 versus unit concentration of the fluid (relaxivity). It was revealed that the relaxivity values of the examined peaks varied from well to well. This variability was attributed to the viscosity differences and paramagnetic ion content of crude oil in the wells. The linear relationship between the fluid content and each of 1 / T1, 1 / T2, line half-width and chemical shift values of the peaks indicates that a rapid chemical exchange between the peak protons and the solvent contributes to the relaxation mechanismsThe linear relationship between viscosity and each of the 1 / T1 and 1 / T2 also shows that dipolar interaction contributes to the relaxations. However, the fact that the derived T2 values are quite small makes it important for us to understand the effect of the quadrapol interaction resulting from the interaction of the electrical field gradient created by D of CDC3 and I spin.
Açıklama
Anahtar Kelimeler
Batman Yöresi, Dötorokloroform (CDCl3), Ham Petrol, Nükleer Manyetik Rezonans (NMR), 1 / T1 Spin-Örgü Rölaksasyon Oranı, 1 / T2 Spin-Spin Rölaksasyon Oranı, Batman Region, Crude Oil, Dechlorochloroform (CDCl3), Nuclear Magnetic Resonance (NMR), 1 / T1 Spin-Örgü Relaxation Ratio, 1 / T2 Spin-Spin Relaxation Ratio
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Künye
Kal, D. (2019). Batman yöresi petrol örneklerinin NMR ile incelenmesi. (Yayınlanmamış Doktora Tezi). Batman Üniversitesi Fen Bilimleri Enstitüsü, Batman.
