PHAN TICH DAU THO VA SAN PHAM

KỸ THUẬT PHÂN TÍCH DẦU THÔ VÀ CÁC SẢN PHẨM DẦU MỎ Analytical techniques for crude oil and petroleum fractions NỘI DUNG I Thành phần dầu thô sản phẩm dầu mỏ II Tách phân tích dầu thô phân đoạn dầu mỏ III.Xác định tính chất đặc trưng dầu thô sản phẩm dầu mỏ từ phân tích cấu trúc IV Xác định tính chất đặc trưng phân đoạn dầu mỏ kỹ thuật sắc ký Content I Composition of crude oil and petroleum products II Fractionation and Elemental analysis of crude oils and petroleum cuts III.Characterization of crude oils and petroleum fractions based on structural analysis IV Characterization of Petroleum fractions by chromatographic techniques Chương 1: Thành phần dầu thô sản phẩm dầu mỏ Các cấu tử nguyên chất a Các hydrocarbon b Các hợp chất khác Các hợp chất hóa học phức tạp a Asphaltène b Nhựa Chapter 1: Composition of crude oil and petroleum products Pure components a Hydrocarbons b Non-Hydrocarbons compounds Compounds whose chemistry incompletely defined a Asphaltenes b Resins is Composition of Crude Oils and petroleum products Principal petroleum product, their boiling range temperatures and their number of carbon atom Composition and chemical structures Hydrocarbons Carbon - Carbon molecule Linked by Single bond C C Multiple bonds C C -ene C C -yne Saturated aliphatic hydrocarbons Saturated cyclic hydrocarbons cycloparaffins naphtenes Aromatic hydrocarbons Unsaturated aliphatic hydrocarbons olefins alkenes Composition and chemical structures Non Hydrocarbon compounds Molecules contain atoms other that carbon and hydrogen Sulfide Hetero-organic compounds C S C Disulfide C Sulfur compounds Thiols CH2 S S S C Thiophene S H OH Furane Phenol Oxygen compounds O Carboxylic acid R COOH R Ether COO R Amines Nitrogen compounds Amides C Organometallic compounds N O Complex with metals Ni, V R R R NH2 NH R' N R' R" Composition and chemical structures Complement for Nitrogen compounds Neutral compounds Basic nitrogen Composition and chemical structures Complement for Organometallic compounds ELEMENTAL ANALYSIS Oxygen analysis Oxygen is present only in small quantities in petroleum Principle Material is pyrolized in inert gas at 1100°C in the presence of carbon or catalyst such as Platonized or nickelized carbon or a mixture of carbon, platinum and nickel The detection is by infrared spectroscopy or gas phase chromatography Difficulties The presence of sulfur, nitrogen, halogen, etc… can interfere with the test After pyrolysis it is necessary to eliminate the following components : acid gases by absorption in soda lime sulfur compounds, either by cold separation with liquid nitrogen or by fixation on reduced copper at 900°C Concentration method : This method can measure concentrations on the order to 5000 ppm for value less than 100 ppm The most successful method and the most costly is neutron activation ELEMENTAL ANALYSIS Oxygen analysis Oxygen is present only in small quantities in petroleum NEUTRON ACTIVATION • Neutron bombardment in accelerator • 16O is converted to 16N having a half-life of seven seconds • Accompanied by emission of β and γ rays • Oxygen concentration as low as 10 ppm detected Fractionation and elemental analysis of crude oils ELEMENTAL ANALYSIS Sulfur analysis Knowledge of sulfur content in petroleum products is imperative The analytical methods are numerous and depend on both : the concentration being measured the material being analyzed ELEMENTAL ANALYSIS sulfur analysis by X ray fluorescence This method is widely use in the petroleum industry for studying the whole range of products and for analyzing catalysts as well Concept of analysis by X-ray fluorescence FIGURE 2-6 page 33 Sulfur is analyzed on the Kα emission at 5.573  This method can attain (depending on the sample) concentrations on the order of 10 ppm or, with an error on the order at 20 % Fractionation and elemental analysis of crude oils ELEMENTAL ANALYSIS Analysis of metals in petroleum cuts The petroleum industry faces the need to analyze numerous elements which are either naturally present in crude oil as is particularly the case for Nickel and Vanadium or those elements that are added to petroleum products during refining Three methods are used : X-ray fluorescence Atomic absorption Argon plasma emission ELEMENTAL ANALYSIS Analysis of metals in petroleum cuts USING X-RAYS FLUORESCENCE FOR ANALYSIS OF METALS The metals most frequently analyzed are the following: Nickel (Nr), Vanadium (V), Iron (Fe), Lead (Pb) as well as metalloids, phosphorous (P), Sulfur (S) and Chlorine (Cl) in petroleum products Copper (Cu), Magnesium (Mg) and Zinc (Zn) in lubrication oil additives The detectable limits for a dispersion apparatus are a few µg/g and vary according to the environment around from a few µg/g for heavy elements in light matrices to a few mg/g for light elements Analysis of metals in petroleum cuts USING ATOMIC ABSORPTION FOR ANALYSIS OF METALS PRINCIPLE   The sample to be analyzed can be dissolved in organic solvent The sample is generally mineralize in H 2SO4, evaporate and the test is conducted in an aqueous environment (matrix effect)  The solution is nebulized, then atomized : (either in air) acetylene flame (most often) or in nitrogen protoxide acetylene flame, or in graphite furnace for analysis of trace quantities  In both case the aerosol is subjected to temperature exceeding 2300°C  At these T, the molecules or salts are dissociated into their elemental atomic components The atoms have the capacity to absorb energy carried by the photons provided they have a well defined frequency Analysis of metals in petroleum cuts These techniques are mono elemental methods and require a high calibration per element and a different source for each one * The detectable limits are given for samples such as they are introduced into the apparatus; They should be previously diluted in order to be nebulized It thereby is useful to apply a dilution coefficient, usually at least 10 The dilution depends on the sample viscosity **After mineralisation Atomic absorption is extremely sensitive It is particularly suited to the analysis of lead in gasoline for sodium in fuels oils and for mercury in gas condensate Chương 3: Xác định tính chất đặc trưng dầu thô phân đoạn dầu thô từ phân tích cấu trúc Phân tích họ hydrocarbon Xác định tính chất đặc trưng phân đoạn dầu mỏ phân bố nguyên tử carbon Chapter 3: Characterization of crude oils and petroleum fractions based on structural analysis Analysis by Hydrocarbon Family a Using Mass Spectrometry for determining distribution by chemical families b Use of Ultra-Violet Spectrometry to obtain Distribution Hydrocarbon Family Characterization of a petroleum fraction by Carbon Atom Distribution a Using Infrared Spectrometry to Characterize petroleum fraction according to the nature of the Carbon Atom b Determining the parameters of a petroleum fraction by nuclear magnetic resonance   Khi nhiệt độ sôi  → phân đoạn trở nên phức tạp → phương tiện phân tích phải phù hợp với phức tạp Fig 3.4 3.5 → phương pháp tách phân tích sản phẩm dầu mỏ thường áp dụng The cuts become more and more complex and the analytical means must be adapted to the degree of complexity We describe below the most widely used petroleum product separation scheme and the analyses that are most generally applied Table 3.5 Separations and analysis of a vacuum residue Saturate, Aromatic, Resin, and Asphaltene (SARA) ... 400°C ASTM D-86 This method applied to gasoline, kerosene, heating oils and similar petroleum products Heavy fractions ASTM D-1160 Applied for petroleum can be partially or completely vaporized... Precipitation Subtractive methods for a chemical family Liquid chromatography PREPARATION AND ANALYTICAL FRACTIONATIONS Preparatory laboratory distillation ASTM D-2892 test method Corresponded to a... atom Composition and chemical structures Hydrocarbons Carbon - Carbon molecule Linked by Single bond C C Multiple bonds C C -ene C C -yne Saturated aliphatic hydrocarbons Saturated cyclic hydrocarbons