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Petroleum and petroleum products. Basic properties and laboratory analysis

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The standard methods of technical analysis of petroleum and petroleum products are considered. Brief information on the need to determine the main operational indicators of petroleum, distillate fuels, oils and heavy residues is provided. Classical and modem methods of analysis are given. The tutorial is intended for students studying Bachelor programs in the fields of 18.03.01 "Chemical Engineering" and 21.03.01 "Petroleum Engineering": for students studying Master programs in the fields of 18.04.01 "Chemical Engineering". It can be also useful for students studying Bachelor and Master programs of Petroleum and Petrochemistry Faculty. The tutorial is prepared by Chemical Technology of Petroleum and Gas Processing Department.
Емельянычева, Е. А. Emelyanycheva, Е. Petroleum and petroleum products. Basic properties and laboratory analysis : tutorial / Е. Emelyanycheva, B. Vagapov ; The Ministry of Science and Higher Education of the Russian Federation, Kazan National Research Technological University. - Kazan : KNRTU Press, 2020. - 100 p. - ISBN 978-5-7882-2808-2. - Текст : электронный. - URL: https://znanium.com/catalog/product/1899125 (дата обращения: 13.07.2024). – Режим доступа: по подписке.
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The Ministry of Science and Higher Education of the Russian Federation Kazan National Research Technological University


E. Emelyanycheva, B. Vagapov

PETROLEUM AND PETROLEUM PRODUCTS.
BASIC PROPERTIES AND LABORATORY
ANALYSIS

Tutorial






Kazan
KNRTU Press
2020

       UDC 665.6(075)
       LBC 35.51Чя7



Published by the decision of the Editorial Review Board of the Kazan National Research Technological University

Reviewers:
Ph. D. R. Kashapov
Ph. D. I. Galimullin



       Emelyanycheva Е.
       Petroleum and petroleum products. Basic properties and laboratory analysis : tutorial / Е. Emelyanycheva, B. Vagapov; The Ministry of Science and Higher Education of the Russian Federation, Kazan National Research Technological University. - Kazan : KNRTU Press, 2020. - 100 p.

       ISBN 978-5-7882-2808-2

     The standard methods of technical analysis of petroleum and petroleum products are considered. Brief information on the need to determine the main operational indicators of petroleum, distillate fuels, oils and heavy residues is provided. Classical and modern methods of analysis are given.
     The tutorial is intended for students studying Bachelor programs in the fields of 18.03.01 “Chemical Engineering” and 21.03.01 “Petroleum Engineering”; for students studying Master programs in the fields of 18.04.01 “Chemical Engineering”. It can be also useful for students studying Bachelor and Master programs of Petroleum and Petrochemistry Faculty.
     The tutorial is prepared by Chemical Technology of Petroleum and Gas Processing Department.

UDC 665.6(075)
LBC 35.51Чя7

ISBN 978-5-7882-2808-2   © Emelyanycheva Е., Vagapov B., 2020
                         © Kazan National Research Technological University, 2020

            TABLE OF CONTENT



INTRODUCTION ...................................................5
1. LABORATORY ANALYSIS OF OIL .................................12
1.1. Determination of residual water in oil....................12
1.2. The density of oil........................................14
1.3. Viscosity of oil .........................................19
1.4. Oil pour point ...........................................22
1.5. Determination of resin-asphaltene substances in oil ......23
1.6. Sulfur and sulfur compounds of oil .......................27
2. ATMOSPHERIC AND VACUUM DISTILLATION OF OIL .................32
2.1. Atmospheric and vacuum laboratory distillation of oil .....32
2.2. Atmospheric and vacuum distillation on oil refineries......42
3. LABORATORY ANALYSIS OF GASOLINE FRACTIONS....................46
3.1. Knock resistance of gasoline fractions ...................47
3.2. The fractional composition of gasoline fractions .........48
3.3. The saturated vapor pressure of gasoline fractions .......51
3.4. Corrosion activity of gasoline fractions .................52
3.5. The actual resin oils content in gasoline fractions.......53
3.6. Determination of the total amount of sulfur in light oil products, including gasoline fractions, by the lamp method................55
3.7. Determination of the group composition of gasoline ........57
4. LABORATORY ANALYSIS OF DIESEL FUELS.........................66
4.1. Ignition properties of diesel fuel........................67
4.2. Distillation properties of diesel fuels...................69
4.3. Flash point of diesel fuels...............................73
4.4. Kinematic viscosity of diesel fuels.......................76
4.5. Low-temperature flow properties of diesel fuels............79
4.6. The determination of water-soluble acids and alkalis .....81
4.7. Some other properties of diesel fuels ....................82

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5. LABORATORY ANALYSIS OF PETROLEUM LUBRICATING OILS ..........................................................85
5.1. Viscosity-temperature properties of lubricating oils .....85
5.2. Flash point of lubricating oils...........................89
5.3. The color of lubricating oils.............................91
5.4. Some other properties of lubricating oils.................93
6. LABORATORY ANALYSIS OF PETROLEUM RESIDUES....................95
6.1. General testing indicators for petroleum residues ........95
6.2. Laboratory analysis of petroleum bitumen..................95
    6.2.1. Bitumen ductility test .............................97
    6.2.2. Bitumen penetration test ...........................98
    6.2.3. Bitumen softening point test .......................99
BIBLIOGRAPHY ..................................................100

                INTRODUCTION





      The task of technical analysis of oil and oil products is the production and technical assessment of oil in order to determine the option of its processing.
      Oil is a natural and complex mixture of a large number of hydrocarbons of various classes and non-hydrocarbon components: sulfur, oxygen and nitrogen-containing compounds, resinous and asphaltene substances.
      The types of hydrocarbons occurring in the crude oil depend on the origin of crude oil. The main types of them are:
      Straight-chain paraffins or alkanes:
      -  normal paraffins or linear alkanes:




CH-CH-CH-CH-CH, CH -(CH,)-CH,
3    2   2   2  3    3   2'n 3



where n is the number of carbon atoms, = 3-50;
      -  branched alkanes or isoparaffins, for example,

CH₃-CH-CH₂-CH₃

-CH₂-(CH₂)„-CH₂-CH-

CH₃

—(CH₂)„ —



where (n + m) < 60.
      C1-C4 straight-chain paraffins are in the gaseous state at a temperature of 20 °C and atmospheric pressure. C5-C16 paraffins are in the liquid state, and they occur in the lighter fractions of the crude oil (naphtha, kerosene, gasoil). C17 and heavier hydrocarbons under normal conditions (20 °C, 1 bar) are in the solid state, and they occur dissolved in the higher boiling point fractions (gasoils and base oils).

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Cycloparaffins:

where R is an alkyl group.
      Cycloparaffins (or naphthenes) with five- or six-membered ring and their lighter alkyl derivates (C6-C8) occur in naphthas, while other nonaromatic cyclic compounds with higher boiling points occur in kerosene, gasoil and base oil fractions.
      Aromatic hydrocarbons:
      -  monoaromatics:

- polyaromatics:

      Benzene and its homologues with their alkyl sides are in the lighter fraction. Polyring and partially saturated polyring aromatics and their alkyl and dialkyl derivates occur in the heavier fractions (gasoil, base oil).
      Olefins (alkenes) are open-chain unsaturated hydrocarbons rarely (usually < 0.1 %) occur in crude oil. These compounds are produced in refinery conversion technologies.

6

      Sulfur compounds:
      -  H2S (hydrogen-sulfide);
      -        mercaptanes: R-SH, where R hydrocarbons with a carbon number of 3-30;
      -  mono- and disulfides: R-S-R’, where R, R‘ are alkyl groups:

CH-S-CH₃, dimethyl-sulfide CH-S-S-CH₃, dimethyl-disulfide

C₂H-S-CH₃, ethyl-methyl-sulfide C₂H-S-S-C₂H₅, diethyl-disulfide

- thiophenes:

Thiophene Alkyl-thiophenes Benzothiophenes

Dibenzothiophenes


      Nitrogen-containing compounds:

      - amines:

where R = 3-30;
       -  nitriles: R-CN, where R = 3-30;
       -  pyridine derivates (pyridine, quinoline, acridine):

       -  pyrrole derivates (pyrrole, indole, carbazole):

7

Oxygen-containing compounds:
-  aliphatic carboxylic acids: R-COOH;
-  naphthenic (carboxylic) acids:

- furan derivates:

- phenols:

Resinic and asphaltenic compounds:
-  asphalthenes (M > 3000 g/mol, C/H = 0.79):

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       - resins (M = 800 g/mol, C/H = 0.72):


      - polyaromatic compounds (M = 400-600 g/mol, C/H = 0.54):


      Metal-containing compounds (especially Ni: Nickel and V: vanadium containing compounds):


       Oil lies in porous rocks: sands and sandstones, limestones and clayey rocks. Usually oil is accompanied by hydrocarbon gases and water with salts dissolved in it.


9

       Oils of various fields differ significantly in chemical composition. Therefore, to select the most appropriate option for processing a particular oil, it is necessary to know its composition and properties as a whole and for individual fractions. To facilitate the study of oil, it is divided into narrow fractions that differ within the boiling point. During the laboratory workshop students get acquainted with the state-standard methods for the analysis of oil and oil products.
       Distillation material balance and true boiling point curve (TBP) are formed on the basis of the results of oil distillation. True boiling point curve gives an idea of the quantitative content of any fractions and residues in oil. The analysis of the selected fractions characterizes their operational properties. Comparing the results of the analysis of petroleum products with the requirements of Russian Federation Standards (specifications) for a particular petroleum product, a conclusion is made about its quality.
       Based on the analysis of oil and oil products, it is necessary to draw a conclusion about the use of the studied oil, i. e. about a possible way of its processing.
       Before embarking on a study, it is necessary to study the appropriate literature and methods of work. These guidelines briefly describe the procedures for performing analysis of petroleum products in accordance with Standards (specifications). For a detailed review, use the relevant Standards (GOST). Table shows the scheme of laboratory analysis of oil and oil products.


Scheme of laboratory analysis of oil and oil products


The stages

Basic operations or methods of analysis

     of analysis


1. Physicochemical characteristics of oil

2. Atmospheric and vacuum distillation of oil

1. Determination of residual water content (GOST 2477-65)
2. Density determination (GOST 3900-85)
3. Determination of relative viscosity (GOST 6258-85)
4. Determination of pour point (GOST 20287-91)


1.  Atmospheric laboratory distillation of oil
2.  Vacuum laboratory distillation of atmospheric residue


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3. Analysis of     1. Density determination (GOST 3900-85)                  
gasoline           2. Determination of fractional composition (GOST 2177-99)
fractions          3. Copper plate test (GOST 6321-92)                      
                   4. Determination of actual resins (GOST 8489-85)         
                   5. Determination of saturated vapor pressure             
                   (GOST 1756-2000)                                         
4. Analysis of     1. Density determination (GOST 3900-85)                  
diesel fractions   2. Determination of fractional composition (GOST 2177-99)
                   3. Determination of kinematic viscosity at 200 °C        
                   (GOST 33-82)                                             
                   4. Determination of flash point in a closed crucible     
                   (GOST 6356-75)                                           
5. Analysis of oil 1. Determination of kinematic viscosity at 50 and 100 °C 
fractions          (GOST 33-82)                                             
                   2. Determination of flash point in a closed crucible     
                   (GOST 6356-75)                                           
                   3. Determination of flash point in an open crucible      
                   (ST.SEV 5469-86)                                         
6. Analysis of pe- 1. Softening pointtest (GOST 33142-2014)                 
troleum residues   2. Penetration test (GOST 33136-2014)                    
(tars)             3. Ductility test (GOST 33138-2014)                      

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                1. LABORATORY ANALYSIS OF OIL





      The purpose of the work is to get acquainted with the methods of analysis of dehydrated oil.
      Before doing work, you need to study the following issues:
      1.       The possible water content in oil, the source of its appearance, the determination of residual water in oil.
      2.       The concept of absolute and relative density of oil. Dependence of density on temperature. The relationship of density with the chemical nature of oil. Methods for determining the density of oil.
      3.       Viscosity as a qualitative characteristic of oil and oil products. Dynamic viscosity, kinematic, conditional. Angler viscometer for determining the conditional viscosity, its device and analysis technique, water number of the viscometer.
      4.       The reasons for the loss of mobility of oil. Method for determining the pour point.


            1.1.    Determination of residual water in oil


      During oil production, it is accompanied by formation water with salts dissolved in it (chlorides, sulfates, carbonates). The content of water and salts in oil varies widely depending on the conditions of occurrence, development methods and methods of oil production. Mineralized water is present in oil as emulsified globules, which form, mainly, an oil emulsion of the inverse type—water in oil. The oil emulsion is stabilized by strong adsorption films at the oil-water interface, which are a physical barrier to contact between dispersed water globules, prevent their coalescence (coalescence) and deposition (sedimentation). This barrier is created by natural stabilizers (emulsifiers)—various high molecular weight oil components and impurities. These are polar substances such as resins, asphaltenes, salts of naphthenic acids, as well as solid, refractory paraffins and various mechanical impurities (clay, silt, silica sand, water-insoluble salts, iron oxides (II, III), iron sulfide, etc.).
      Pumping and processing of watered oils causes a number of difficulties and complications in the operation of technological equipment.



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