Chapter 1 Basics of Process Engineers | Mole (Unit) | Chemical Compounds

International Oil & Gas Exploration Contracts

Chapter 1 Basics of Process Engineering

Chapter 1 Basics of Process engineering

Page 1 of 23

International Oil & Gas Exploration Contracts

Chapter 1 Basics of Process Engineering

Chapter 1 Contents
1.1 Basic Terminology
1.1.1 Elements and Atoms 1.1.2 Chemical Compounds and Molecules 1.1.3 Physical Compounds 1.1.4 Relative Atomic Mass (Weight) 1.1.5 Relative Molecular Mass (Weight) 1.1.6 The Mole 1.1.7 Valence 1.1.8 Mixture

1.2 Basic Hydrocarbon Nomenclature
1.2.1 Paraffin Series 1.2.2 Olefin or Ethylene Series 1.2.3 Acetylene or Alkyne Series 1.2.4 Diolefins Series 1.2.5 Aromatic (Benzene) Series 1.2.6 Naphthene Series

1.3 Paraffin Hydrocarbon Compounds
1.3.1 Radicals 1.3.2 Alcohols 1.3.3 Mercaptans 1.3.4 Other Carbon-Sulfur Compounds 1.3.5 Organic Nitrogen Compounds – Amines 1.3.6 Glycols

1.4 Acids, Bases and Salts 1.5 Analysis of Mixtures

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These include carbon. 1. oxygen. two atoms of hydrogen combined with one atom of oxygen. A diatomic molecule is formed by the combination of two atoms of the same element.2 Chemical Compounds and Molecules A true compound is a substance composed of more than one atom that satisfies both of the following conditions. sulfur.1.1. 1. Chemical compounds are formed by the union of atoms in the simplest possible numerical proportions. A molecule of water is H2O. Page 3 of 23 .3 Physical Compounds A type of physical compound. nitrogen and helium . Nitrogen (N2) and oxygen (O2) are the most common examples. The atoms have combined chemically. 1. 1. This is reviewed briefly. The compound formed possesses properties different from the atoms of which it is composed. Over 100 materials have been found (or created) which are classed as elements. A gas hydrate is one example of a clathrate. may be formed.1. called a clathrate.International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering Chapter 1 Basic of Process Engineering 1.1 Elements and Atoms All matter in the universe is composed of elements which cannot be broken down or subdivided into smaller entities by ordinary means.all materials occurring in petroleum systems. The atom is the basic unit of each element that can combine with it or the atoms of other elements to form a compound. 2. These compounds are relatively unstable. hydrogen.1 BASIC TERMINOLOGY Throughout this course we will be using some basic chemistry and physics terminology. The molecule is the unit of a compound.

The quantity 0. On this basis. molecules. Water has a relative molecular weight of 18 (H2O =2+16=18).012 kilogram of Carbon-12.International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering 1. Currently. It is convenient to use relative atomic weight. The word "relative" means that the number used is a relative one. A diatomic molecule like oxygen (O2) has a molecular weight of 32. the mol can be defined for engineering usage as that mass in grams equal numerically to the sum of the relative atomic weights of the atoms in the molecule of that substance. Since relative weights represent a fixed number of atoms.1. to express these ratios. One gram of hydrogen and 12 grams of carbon each contain about 6 x 1023 atoms.6 The Mol The term "mol" is the historical abbreviation of the words "gram molecule. These elementary entities must be specified but include atoms.1." The current definition of the mol is: "The mol is the amount of substance of a system which contains as many elementary entities as there are atoms in 0.5 Relative Molecular Mass (Weight) The relative molecular weight of a molecule is the sum of the relative atomic weights of the atoms combining to produce the molecule.4 Relative Atomic Mass (Weight) In forming a compound. ions. etc. Atom Hydrogen Carbon Nitrogen Oxygen Sulfur Symbol H C N O S Relative Atomic Weight 1 12 14 16 32 A relative atomic weight of one element contains about the same number of atoms as a relative atomic weight of any other element. the relative atomic weight of carbon. being assigned the relative atomic weight of 12. 1. Thus. Page 4 of 23 . electrons. the relative mass of the atoms of different elements. Carbon-12 is used as the standard.1. they may be substituted for atoms in calculations.012 kg is 12 g. elements always combine according to fixed mass ratios. 1.". the relative atomic weights of common oil and gas components are shown below (to the nearest whole number).

A kilomol (kmol) is simply 1000 mol. At a given pressure and temperature equal volumes of different gas contain the same number of molecules.1. to denote this is not a standard mol. 1 kmol = 1000 mol = 2.4 liters. It is particularly useful for gas calculations. If a relative molecular or atomic weight is expressed in pounds mass or kilogram. The question of atomic bonding is a complex subject involving many factors. Natural gas and crude oil are mixtures. 1. The valence number is plus or minus.1. as discussed in standard chemistry references.325 kPa [14.International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering By virtue of the definition.205 lb-mol 1 lb-mol = 454 mol Throughout this course the mol will be used in many cases as a mass term in those processes where no chemical changes occur. whenever the mol is used as a mass quantity without a prefix. The properties of the mixture are a reflection of the properties of the constituents.8 Mixture A mixture is a combination of elements and compounds which may be separated by physical means.7 Valence Valence is a measure of the ability of atoms to form molecules by filling the electron shells of the atoms involved. Page 5 of 23 . respectively. At 0°C [32°F] and 101. a mass in grams is implied. for the number of mols per unit volume is independent of gas composition. The concept is mentioned only to point out that the number of bonds or linkages used in the structural formulas that follow in the next section reflect the valence of the atoms in these compounds. denoting the number of excess or shortage of electrons needed to fill its outer shell. They are analyzed by separating the mixture into its component parts and identifying each by its properties. The mol is thus a useful conversion factor from volume to mass. we will use the terms lb-mol and kmol. 1.7 psia] a mol of any gas contains about 6x10 molecules and occupies a volume of 22.

the ending used for the paraffin series. 1. Most reactions involve the replacement of hydrogen atoms with other atoms. For convenience. these are separated into "families" or homologous series. Long chains containing scores of carbon atoms in series may be formed.International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering 1. a hydrocarbon is any compound composed solely of carbon and hydrogen atoms. all names end in -ane. each of which is given a name. These atoms can combine in a number of ways to satisfy valence requirements.all four carbon bonds are connected either to another carbon atom or a hydrogen atom. The incremental change in relative molecular weight is thus fourteen. the number of hydrogen atoms is two times the number of carbon atoms plus two more for the ends of the chain. The paraffin hydrocarbons are the most stable of the lot because all valence bonds are fully satisfied as indicated by the single line linkage. The carbon atoms can link together to form "chains" or "rings.2." Crude oil and natural gas mixtures consist primarily of "straight chain" hydrocarbon molecules. the only ones normally identified by name contain ten or less carbons. However. In each case. Notice that. the carbon linkage remains stable. with one such atom for each bond. the bulk of which are paraffins.2 BASIC HYDROCARBON NOMENCLATURE By definition.1 Paraffin Series Formula: CnH2n + 2 Hydrocarbons in this series are saturated compounds . Page 6 of 23 . Each successive molecule in the paraffin series is created by adding a carbon and two hydrogens to the previous molecule.

Wt. they are called unsaturated hydrocarbons. the abbreviation C3 for propane. In the structural diagram shown for i-butane we could draw the carbon atom below instead of above the carbon chain. There are only two isomers of butane. this would be just a "mirror image" of the molecule as drawn. Since they are so reactive. They possess different physical and chemical properties. Normal butane (n-butane) Isobutane (I-butane) 1. Compounds which have the same chemical formula but a different atomic structure are called isomers. may be used. 86 100 114 128 142 C2H6 C3H8 C4H10 C5H12 In referring to a given paraffin hydrocarbon. without the replacement of a hydrogen atom. The adjective "normal" is used to designate a molecule wherein all of the carbon atoms are in a straight line. An "isomer" has the same formula but a different arrangement of the carbon atoms. It is the same molecule with the same properties. C4 for butane. 16 30 44 58 72 Name Hexane Heptane Octane Nonane Decane Formula C6H14 C7H16 C8H18 C9H20 C10H22 Mol. In an analysis.2 Olefin or Ethylene Series (Alkenes) Formula: CnH2n The olefin group of compounds is a simple straight chain series in which all the names end in -ene. Hydrocarbons in this series combine easily with other atoms like chlorine and bromine. But. Statements like "propanes plus fraction (C3+)" refer to a mixture composed of propane and larger atoms.International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering Name Methane Ethane Propane Butane Pentane Form ula CH 4 Mol. Ethylene (ethene) C2H4 is the simplest molecule in the series.2. these are often abbreviated as "n" and "i" respectively. etc. Paraffin isomers: When the paraffin series molecule contains four or more carbon atoms there are different ways these can be connected without affecting the formula. Wt. Page 7 of 23 .

The structural formula for the olefins uses a double line to indicate the double carbon-carbon linkage.2. Acetylene is the most important member of this series. This satisfies the valence requirements but the carbon linkage is very weak. the most reactive point in the molecule. They may furthermore react at the double bond or be split into two molecules at the double bond to form compounds with different characteristics. Ethylene (Ethene) Propylene (Propene) With four or more carbon atoms.3 Acetylene or Alkyne Series Formula: CnH2n-2 This series is of basic importance only in certain refining and petrochemical applications. It is a necessary but unstable alliance.C C . It has the formula C2H2.H There is a triple bond between the carbon atoms.International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering Unlike the paraffins. Certain crude oils contain them in measurable amounts. Page 8 of 23 . 1. Two adjacent carbon atoms form a "temporary" bond (in the absence of other available atoms) to meet bonding requirements fixed by valence. the maximum bonding capacity of the carbon atom is not fully satisfied by hydrogen or carbon atoms. The structural formula for acetylene is H . The amount of olefins in natural gas usually is fairly small. isomers also may result from the position of the double bond as well as the arrangement of the carbon atoms. 1-Butene 2-Butene These molecules possess many different properties.

2. Ethylene and propylene polymerize to form polyethylene and polypropylene. They normally are named by replacing the -ane for paraffins by -diene. has the structural formula of C6H6.4 Diolefins Formula: CnH2n-2 The diolefins have the same formula as acetylene. Liquid cooking oils (unsaturated) may be hydrogenated to form solid fats. Even small amounts can influence physical behavior and affect design. Page 9 of 23 . They also promote foaming and other operational problems in the production and handling of crude oil and natural gas.the process wherein a very large molecule is built up from the self-addition reaction of small identical molecules (monomers). the basic ingredients in plastic materials. it is almost unstable chemically. a cyclic hydrocarbon. They may be oxidized to form organic acids. Carbon likes the sharing of three valence linkages even less than sharing two. Any analysis of crude oil and natural gas should include aromatics. The members of this series contain two double linkages. Some contain significant amounts. Acetylene polymerizes to form benzene. Since the aromatics are unsaturated. Diolefins are primarily of concern in petrochemical plants. Benzene. They may be hydrogenated. the parent compound of this series. Acetylene not only is unsaturated. These compounds also polymerize . 1. 1. Butadiene is possibly the most interesting and useful since it is a primary ingredient in synthetic rubber compounds.International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering Acetylene is even more reactive than the olefins. a cyclic compound.2. Most petroleum contains only a trace of aromatics. It has the formula: CH2 = CH – CH = CH2 All of these unsaturated compounds are reactive. In the liquid state it is explosive if subjected to a sudden shock. they react readily.5 Aromatic (Benzene) Series Formula: CnH2n-6 Aromatic is the word used to describe an unsaturated hydrocarbon molecule where the carbon atoms form a ring.

and amines in which they are soluble and with which they react to some degree. conditioning. On chromatographic analysis it occurs between n-hexane and n-heptane. They are also conditioned by use of alcohols. This concern includes nitrogen and water and contaminants in the gas. 1. Cyclohexane is a common member of this series. On chromatographic analysis it occurs between n-pentane and n-hexane.3. glycols. Cyclohexane 1. the primary concern is the behavior of the paraffin series hydrocarbons with 10 or less carbon atoms (C1 –C10). This alkyl radical has the formula: Page 10 of 23 . Its structural formula is C6H12. gathering.3 PARAFFIN HYDROCARBON COMPOUNDS In the production. and processing of natural gas and its associated liquids.International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering 1. but it must be remembered that they have been in contact with the chemicals present in the reservoir rock for many millions of years. Being saturated molecules.2. Cyclohexane is similar to benzene except that it is saturated.1 Radicals A radical represents a group of atoms that act as a single unit in the formation of many common compounds.6 Naphthene Series Formula: CnH2n The naphthene series has a ring structure but is saturated. such as sulfur compounds. Naphthenes may be found in most crude oils but are seldom shown in routine analyses. Cyclopentane (C5H10) also occurs. Alkyl Radical: At least the simpler paraffins often react by replacing one hydrogen with some other radical or element. Paraffin hydrocarbons are less reactive with other materials than many hydrocarbons. they are not very reactive.

and with alkyl radicals to form alcohols. calcium and magnesium to form hydroxides (bases. an acid is formed. It combines with hydrogen to form water . with metallic salts like sodium. ethanol. Both may be written as ROH.sulfite CO3 ." Methanol or methyl alcohol Ethanol or ethyl alcohol Page 11 of 23 . The name of the alcohol ends in "ol.sulfate SO3 . The hydroxyl radical (OH) has a valence of minus one and is sometimes written as (OH)-1. Methyl (C2H5). etc. for ethanol it is C2H5OH. ethyl (C3H7) propyl The parenthesis indicates the radical group. one cannot identify the specific alkyl radical.3. such as methanol. This combination occurs in many common compounds.carbonate HCO3 . It is used only to show general reaction characteristics. The alkyl radical normally has a valence of +1. The scale formed in water systems is caused by precipitation of salts like these. caustics). In many cases the alkyl radical is indicated by the symbol "R.bicarbonate Each of the radicals has a valence found from the valence of its elements. The common names for some common radicals of this type are: SO4 . Mg(OH)2 . Hydroxyl Radical.International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering CnH2n+1 : (CH3). calcium.H (OH) or H2O. (OH). It therefore combines in proportions fixed by this valence: H(OH). If radicals like these combine with hydrogen. (CO3). 1. When "R" is used. When combined with metallic salts like sodium." The formula for methanol is CH3 OH. a salt is formed (which occurs commonly in water systems). and that the sum of plus and minus valences equals zero." or the name of the alkyl radical is followed by the word "alcohol.2 Alcohols The common alcohols are formed from the addition of a single hydroxyl radical to an alkyl radical. NaOH. (SO4).

Amines There are a number of common organic compounds formed by the reaction of organic materials with ammonia (NH3). As the names indicate.ethyl mercaptan 1.3. Its compounds react with carbon steel to form sulfides and oxides of iron. Formulas for typical mercaptans are: CH3SH . There are a large number of amines used in the chemical industry. Some are: Carbonyl sulfide . 1.5 Organic Nitrogen Compounds .3. particularly monoethanolamine and diethanolamine.COS Carbon disulfide – CS2 Thiophene .4 Other Carbon-Sulfur Compounds There are several other carbon-sulfur compounds present in sour petroleum fluids. Many compounds polymerize and form the "sludge" so common in sour petroleum systems. Page 12 of 23 . This sludge is often very corrosive and should be removed by unsaturated compound having the formula: HC = CH – S – HC = CH Sulfur is a very reactive element that combines chemically with many other elements and compounds. 1. the alkanolamines may be considered a combination of an alcohol and ammonia. In this basic reaction one or more hydrogen atoms are replaced by an organic radical. They may be regarded as sulfur alcohols since the formula is the same if you replace the oxygen atom in the (OH) radical by a sulfur atom.methyl mercaptan C2H5SH .International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering Both C2H5OH and CH3OH could be written as ROH in denoting the general reaction of an alcohol.3. The word "amine" is used commonly to denote this type of compound. The alkanolamines are commonly used for treating sour gases and liquids.3 Mercaptans Compounds with the general formula RSH are known as mercaptans.

ethanol minus one hydrogen atom. As with most compounds containing hydroxyl groups. Except for water and hydroxides (compounds containing the OH radical).6 Glycols The glycols are a family of chemicals.3. sometimes called diols. Ethylene Glycol (EG) Diethylene Glycol (DEG) Triethylene Glycol (TEG) 1. the glycols react readily with other compounds and elements. and other such functions of the petroleum industry. 1. They consist of hydrogen combined with an acid radical (anion). Page 13 of 23 . processing. BASES AND SALTS We are always talking about acids and bases in the handling of petroleum-water mixtures. The glycols used for dehydration are based on the ethyl radical. They may be regarded as complex alcohols since they contain alkyl and hydroxyl radicals. In DEG and TEG the oxygen atom also is very reactive.International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering Monoethanolamine Diethanolamine (DEA) Notice that the only difference in the above compounds is how many hydrogen atoms of ammonia are replaced by the radical (C2H4OH). all inorganic compounds of hydrogen are acids.4 ACIDS.

1 is an example of a chromatogram (chart) from a chromatographic analysis. The attenuation factor is used to convert the peak height shown to analysis. Acids have a pH less than 7. Notice that only paraffin hydrocarbons are shown. It runs between 0 and 14. The instrument is calibrated using standard samples of known analysis so that peak area can be converted to the amount present. a solution possessing a pH of 5. Since the valence of the sulfate radical is -2. Since pH is a logarithmic function.0 is 100 times more acidic than one with a pH of 7. The printed output from this technique is a series of "peaks" rising from a base line. The combination of a metal cation such as sodium with the hydroxyl anion (OH) produces a base. When the ordinary peak height is so low it is difficult to measure. The area under the peak for any component is proportional to the amount present. 1. The acidity or alkalinity of a material is measured on a scale similar to that of a thermometer. This is the rule to be followed in all compound formation.International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering Acid Radical (anion) Chloride Carbonate Sulfate Nitrate Phosphate Symbol Cl-1 CO3-2 SO4-2 NO3-1 PO4-3 Acid Hydrochloric Carbonic Sulfuric Nitric Phosphoric Formula HCl H2CO3 H2SO4 HNO3 H3PO4 Notice that hydrogen (valence of +1) combines with the acid radical in a proportion such that the net valence of the compound formed is zero. This is not entirely correct. Notice also that all molecules heptane and larger are lumped together as a heptanes plus fraction. Sodium hydroxide (NaOH) is commonly called caustic. The hydrocarbon portion of an analysis like this usually is obtained from a chromatograph. pH. Page 14 of 23 . bases (alkaline solutions) have a pH greater than 7. Figure 1. This pH scale is the logarithm of the reciprocal of the hydrogen ion concentration. A pH of 7 is neutral. it is attenuated (multiplied). it takes two hydrogens.1. although the paraffins may be the predominant series present.0.5 ANALYSIS OF MIXTURES A routine analysis of a hydrocarbon mixture is shown in Table 1.

The nonparaffins combine with a single peak which is reported (erroneously) as being a paraffin material. Adequately characterize the heaviest fraction Page 15 of 23 .1 Fluid Analysis The chromatograph used to obtain Figure 1. are unable to detect all of these components. Notice that all of these occur in the hexane-heptane range of molecules.International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering Table 1. Many system operating problems are the direct or indirect result of inadequate analysis. Analyze for CO2 and sulfur compounds 2. Many chromatographs. This may result from failure to: 1. Identify the presence of aromatics and other nonparaffin hydrocarbons 3.1 was capable of showing hydrocarbons other than paraffins. particularly those used for routine gas analyses.

however. Always analyze for CO2 and H2S. some general guidelines. characterizing the heaviest fraction through C7+ may be adequate. Some crude oil may contain up to 10-12% aromatics. if it is wellbore gas it may not be adequate. Crude oil may need to be characterized through C20+ to achieve reliable equilibrium predictions.International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering Figure 1. 1. Page 16 of 23 . The prompt and proper analysis of representative samples is a critical factor. If the sulfur content (reported as H2S) is higher than this. Failure to be aware of this affects mechanical design problems and reduces validity of equilibrium calculations. If the gas is from a separator. Any calculation is an exercise in futility unless the analyses used are reliable. Inadequate sampling and analysis is a major cause of problem systems. Sulfur contents as low as 3-10 parts per million may prove troublesome. 3. A sampling program should be planned carefully.1 Chromatogram of Condensed Liquid There are. a special analysis for carbonyl sulfide (COS). 2. carbon disulfide (CS2) and mercaptans is intelligent.

International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering Appendices Nomenclature of Hydrocarbons Page 17 of 23 .

International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering A-1 Some Paraffinic Hydrocarbons Page 18 of 23 .

International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering A-2 Some Naphthenic Hydrocarbons Page 19 of 23 .

International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering A-3 Some Olefinic Hydrocarbons Page 20 of 23 .

International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering A-4 Some Diolefinic Hydrocarbons Petroleum Processing A-5 Some Acetylenic Hydrocarbons Page 21 of 23 .

International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering A-6 Some Aromatic Hydrocarbons Page 22 of 23 .

International Oil & Gas Exploration Contracts Chapter 1 Basics of Process Engineering A-6 Some Aromatic Hydrocarbons (Continued) Page 23 of 23 .

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