Ministry of Higher Education and Scientific Research University Of Diyala College Of Engineering Chemical Engineering Department FOURTH YEAR PETROLEUM REFINERY By Dr. Alyaa M. AwadPetroleum Refining Fourth Year University of Diyala College of Engineering - Chemical Engineering Department Petroleum Refining, Fourth Year - B.S. Syllabus Objectives To impart the basic concepts of petroleum processing and manufacture of Petrochemicals +To develop understanding about refining and post refining operations. Course Description This course presents a comprehensive introduction to petroleum refining technology and calculations. The focus is on transportation fuels refineries is also discussed. The program includes an overview of crude oil supply and petroleum product demand. This is followed with a description of refinery process technology. Major refining technologies are described such as crude oil distillation, heavy oil conversion options, hydrotreating, and catalytic reforming. Learning Outcomes Understanding of oil refining and associated downstream processing technologies: operations and calculations; process safety, oil products — properties and Specifications operations integrity; and methods for oil productions with their calculations. No. | Topics Hours 1 Classification of Crude Oils, Composition of Crude Oils 4 2 Physical and Chemical Properties of Crude oil and Oil Products 10 3 Evaluation of Crude Oil 4 4 Crude Oil Pre-treatment, Fractionation of Crude Oil (Atmospheric and 8 Vacuum Distillation, Light End Fractionation, Process Description) 5 | Thermal Cracking and Coking Processes 6 6 Catalytic Operations (Processes and calculations) - (Fluid Catalytic 14 Cracking, Hydrocracking, Hydrotreating, Catalytic Reforming Isome Alkylation, Catalytic Dewaxing)References 1. Hsu, Ch.s. and Robinson, P.R., Practical Advances in Petroleum Processing+ Springer. 2. Riazi, M. R., Characterization and Properties of Petroleum Fractions, ASTM International. 3. Nelson, W.L., Petroleum Refinery Engineering, McGraw-Hill.Petroleum Refining Fourth Year i: Introduction Petroleum refining plays an important role in our lives. Most transportation vehicles are powered by refined products such as gasoline, diesel, aviation turbine kerosene (ATK) and fuel oil, Petroleum has remained an important aspect of our lives and will do so for the next four or five decades. The fuels that are derived from petroleum supply more than half of the worlds total supply of energy. Gasoline, kerosene, and diesel oil provide fuel for automobiles, tractors, trucks, aircraft, and ships. Fuel oil and natural gas are used to heat homes and commercial buildings, as well as to generate electricity. Petroleum products are the basic materials used for the manufacture of synthetic fibers for clothing and in plastics paints, fertilizers, insecticides, soaps, and synthetic rubber. The uses of petroleum as a source of raw material in manufacturing are central to the functioning of modern industry Composition and Classification of Crude Oils Crude oil is a complex liquid mixture made up of a vast number of hydrocarbon compounds that consist mainly of carbon and hydrogen in differing proportions. In addition, small amounts of organic compounds containing sulfur, oxygen, nitrogen and metals such as vanadium, nickel, iron and copper are also present (See Table below). Element ‘Composition (we%) Carbon 83.0-87.0 Hydrogen 10.0-14.0 Sulphur 0.05-6.0 Nitrogen 0.1-0.2 Oxygen 0.05-2.0 Ni <120 ppm Vv <1200 ppm ‘There are three main classes of hydrocarbons. These are based on the type of carbon-carbon bonds present. These classes are: © Saturated hydrocarbons contain only carbon-carbon single bonds. They are known as, paraffins (or alkanes) if they are acyclic, or naphthenes (or cycloalkanes) if they are cyelic. Unsaturated hydrocarbons contain carbon-carbon multiple bonds (double, triple or both). These are unsaturated because they contain fewer hydrogens per carbon than paraffins. Unsaturated hydrocarbons are known as olefins. Those that contain a carbon-carbon double bond are called alkenes, while those with carbon-carbon triple bond are alkyenes, * Aromatic hydrocarbons are special class of cyclic compounds related in structure to benzenePetroleum Refining Fourth Year a=: 1- Paraffins General formula: CyH2n2 (1 is a whole number, usually from 1 to 20), straight or branched- chain molecules, can be gasses or liquids at room temperature depending upon the molecule For example, methane, ethane, propane, butane, isobutane, pentane, hexane (CHy—CHy—CH,-CHy (CHy~ CH, CH, CH, ~ CH Butane mPentane % i % CH,—CH —CH, CH,—CH—CH;—CH, — CH; C —CH, Isobutane isopentane ' (2-methyipropane) (2-methyibutane) CH neopentane (2,2-dimethylpropane) 2- Olefins (also known as alkenes) General formula: C,Ho» (n is a whole number, usually from 1 to 20), linear or branched chain molecules containing one carboncarbon double-bond, can be liquid or gas. For example: ethylene, butene, isobutene H,C= CH, CH,~CH=CH, HC=CH Ethylene Propylene Acetylene (ethene) (propene) (ethyne) 3- Naphthenes (cycloalkanes) General formula: C)Hop (1 is a whole number usually from Ito 20), ringed structures with one or more rings, rings contain only single bonds between the carbon atoms, typically liquids at room temperature. For example: cyclohexane, methyl cyclopentane He more | (eee Chet Me Cyciohexane 4- Aromatics General formula: C6HS - ¥ (¥ is a longer, straight molecule that connects to the benzene ring), ringed structures with one or more rings, rings contain six carbon atoms, with alternating double and single bonds between the carbons,typically liquids, For examples benzene, naphthalenePetroleum Refining Fourth Year a=: Benzene Crude oils from various origins contain different types of aromatic compounds in different concentrations. Light petroleum fractions contain mono-aromaties, which have one benzene ring with one or more of the hydrogen atoms substituted by another atom or alkyl groups. Examples of these compounds are toluene and xylene CH, CH= Ch, CHa Toluene Styrene o-xylene (methylbenzene) (1,2-Dimethylbenzene) More complex aromatic compounds consist of a number of benzene rings. These are known as polynuclear aromatic compounds. They are found in the heavy petroleum cuts, and their presence is undesirable because they cause catalyst deactivation and coke deposition during processing, besides causing environmental problems when they are present in diesel and fuel oils. Examples of polynuclear aromatic compounds are shown below ‘Aromatic-cycioalkanes Fiuorenes Binuclear aromatics Phenanthrene Pyrene Chrysene 5- Sulfur Compounds The Sulfur content of crude oils varies from less than 0.05 to more than 10 wt% but generally falls in the range 1-4 wt%. Crude oil with less than 1 wt % sulfur is referred to as low sulfur or sweet. and that with more than 1 wt% sulfur is referred to as high sulfur or sour. Crude oilsPetroleum Refining Fourth Year a=: contain sulfur heteroatoms in the form of elemental sulfur S, dissolved hydrogen sulphide HLS, carbonyl sulphide COS, inorganic forms and most importantly organic forms, in which sulfur atoms are positioned within the organic hydrocarbon molecules. Sulfur compounds lead to environmental pollution, decreases the life of machinery, corrodes of pipes, machines and equipment, affecting the additives used for the purpose of increasing the octane number, reduce the activity of Tetra Ethyl Lead (TEL) added to gasoline. As a result, the engine metal will erode and leads to destruct the metallic parts, Also, their emissions are very dangerous to human safety and environment, In addition, these impurities cause catalyst poisoning and reduce the catalyst activity. Sulfur containing constituents of crude oils vary from simple mereaptans, also known as thiols, to sulphides and polycyclic sulphides (Mercaptans (R-SH), sulphides (R-S-R’), disulphides (R-S-S-R'), Thiophenes) (CHySH s s 8 s hy-0 ( fa) | | methyl mercaptan Cea | (methanethio!) cyclic sulfides ‘Thiophene Benzothiophene _Dbenzothiophene 6-Nitrogen Compounds Crude oils contain very low amounts of nitrogen compounds, less than 1%, The nitrogen compounds in crude oils may be classified as basic or non-basic. Basic nitrogen compounds consist of pyridines. The greater part of the nitrogen in crude oils is the non-basic nitrogen compounds, which are generally of pyrrole types. The decomposition of nitrogen compounds in catalytic cracking and hydrocracking processes forms ammonia and cyanides that can SS L 2 Loa N N Ny pyridine quinoline isoquinoline (CoHsN) — (CoHN) (CoH) 7- Oxygen Compounds Less than 1% (found in organic compounds such as carbon dioxide, phenols, ketones, carboxylic acids) occur in crude oils in varying amounts, CH, ~ CH- CH ‘OH CHy-OH 1 is oH ‘methyl alcohol isopropyl alcohol phenyl alcohol (methanol) (2-propanol) (pheno!)Petroleum Refining Fourth Year rd 8- Metals Compounds Metallic compounds exist in all crude oil types in very small amounts. Their concentration must be reduced to avoid operational problems and to prevent them from contaminating the products. Metals affect many upgrading processes. They cause poisoning to the catalysts used for hydroprocessing and cracking. Even minute amounts of metals (iron, nickel and vanadium) in the feedstock to the catalytic cracker affect the activity of the catalyst and result in increased gas and coke formation and reduced gasoline yields. Burning heavy fuel oils in refinery furnaces and boilers can leave deposits of vanadium oxide and nickel oxide in furnace boxes, ducts, and tubes. It is also desirable to remove trace amounts of arsenic, vanadium, and nickel prior to processing as they can poison certain catalysts, 9- Asphaltenes and Resins Compounds Asphaltenes are dark brown friable solids that have no definite melting point and usually leave carbonaceous residue on heating. They are made up of condensed polynuclear aromatic layers linked by saturated links, The presence of high amounts of asphaltenes in crude oil can create tremendous problems in production because they tend to precipitate inside the pores of rock formations, well heads and surface processing equipments. They may also lead to transportation problems because they contribute to gravity and viscosity increases of crude oils. Resins are polar molecules have high molecular weight, which are insoluble in liquid propane but soluble in n-heptane, It is believed that the resins are responsible for dissolving and stabilizing the solid asphaltene molecules in petroleum.Petroleum Refining Fourth Year a=: Products Composition To understand the diversity contained in crude oil, and to understand why refining crude oil is important in our society, look through the following list of produets that come from crude oil: Liquefied Petroleum Gas (LPG) ‘© used for heating, cooking, making plastics ‘* small alkanes (1 to 4 carbon atoms) ‘© commonly known by the names methane, ethane, propane, butane ‘* boiling range < 90 degrees Fahrenheit / < 27 degrees Celsius ‘© often liquified under pressure to create LPG (liquefied petroleum gas) Gasoline © motor fuel © liquid ‘© mix of alkanes and cycloalkanes (5 to 7 carbon atoms) ‘boiling range = 90-220 degrees Fahrenheit / 27-93 degrees Celsius Kerosene ‘© fuel for jet engines and tractors; starting material for making other products © liquid mix of alkanes (10 to 15 carbons) and aromatics boiling range = 315-450 degrees Fahrenheit / 177-293 degrees Celsius % Diesel Fuel ‘* used for diesel fuel and heating oil, starting material for making other products © liquid ‘© alkanes containing 13-18 carbon atoms * boiling range = 450-650 degrees Fahrenheit / 293-315 degrees Celsius ° ting oil * used for motor oil, grease, other lubricants © liquid * long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics ‘© boiling range = 572 to 700 degrees Fahrenheit / 300 to 370 degrees Celsius > Fuel oil ‘© used for industrial fuel; starting material for making other products © liquid ‘¢ long chain (16 to 40 carbon atoms) alkanes, cycloalkanes, aromatics * boiling range = 650-800 degrees Fahrenheit / 315-565 degrees Celsius > Residual oil ‘© coke, asphalt, tar, waxes; starting material for making other products * solid ‘© multiple-ringed compounds with 40 or more carbon atoms ‘© boiling range = greater than 800 degrees Fahrenheit / 565 degrees CelsiusParoleum Refining Fourth Year a= Boling Range °C Number of Carbon Atoms. ‘Asphalt Petroleum 600} --- Cone f---| aod ---| 80 Wax Heavy Fuel ol Parattins Kerosene Aviation Gasoline Evaluation of Crude Oils Base of Crude Oil ‘The crude oil can be classified into, 1) Paraffinic base crude (P) 2) Intermediate bas crude (IN) 3) Naphthenic base crude (N) 1- Composition of Residue parafjin)S%—> P 2~5%paraffin > IN parrafin(2% —> N 2- Sp.gr of two cuts. API fraction 1 API fraction 2 Crude Base = 40 = 30 P 33-40 20-30 IN =33 =20 N 240 20 - 30 PIN (mix) 30-40 = 30 INP (mix)Petroleum Refining Fourth Year 3- Watson Factor (Kw) 3 Ky = 1:37 Where .ean average boiling point (MeABP) K SG = specific gravity at 15.5°C Kw Crude Base 10.5 = 115. P 15-121 IN 12.1 = 12.5 N 12.08 ‘NIN 1.47 PIN 4- Correlation index (CI) c= wee +473.78G ~ 456.8 rs a Crude Base o-15 - 15-50 IN 50-00 N 5- Viscosity Gravity Constant (VGC) 1OSG ~ 1.0752 logiy(Vss ~ 38) NOC asl0=Wegats = 30) SG ~ 0.24 - 0.022 logss(Vop ~ 35.5) Voc = 56=024- 0027 los Where viscosity at 38°C (100F in SUS (Saybolt Universal Seconds) Saylbolt viscosity (SUS) at 99°C (210F) VGC ‘Crude Base <0.82 P 082-09) IN >09 NPetroleum Refining Fourth Year a=: Physical and Chemical Properties of Crude Oil and Oil Products 1. Density, Specific Gravity, and API Gravity Density is defined as mass per unit volume of a fluid. Density is a state function and for a pure compound depends on both temperature and pressure and is shown by p. Liquid densities decrease as temperature increases but the effect of pressure on liquid densities at moderate pressures is usually negligible Liquid density for hydrocarbons is usually reported in terms of specific gravity (SG) or relative density defined as lensity of liquid at temperature T density of water at temperature T Since the standard conditions adopted by the petroleum industry are 60°F (15.5°C) and 1 atm, specific gravities of liquid hydrocarbons are normally reported at these conditions, Water density at 60°F is 0,999 or almost I g/cm’, thus density of liquid at 60°F in gem’ SG (60°F60°F) = (0.999 gem’ ‘The American Petroleum Institute (API) defined the API gravity (degrees API) to quantify the quality of petroleum products and crude oils. The API gravity is defined as mis SG (at 60°F) Crude Oils API = 10 — 50, crude oils can generally be classified according to API as shown API gravity = 1315 Crude Category Gravity Light crudes API > 38 Medium crudes 38 > API > 29 Heavy crudes 29 > APL> 8.5 Very heavy crudes API < 8.5 The definition of specific gravity for gases is somewhat different. The specific gravity of a gas is proportional to the ratio of molecular weight of gas (Mg) to the molecular weight of air (28.97) My SC 3597 2- Viscossity The viscosity of oil is a measure of its resistance to internal flow and an indication of its oiliness in the lubrication of surfaces. There are two types of viscosity: dynamic and kinematics viscosity. Kinematic viscosity (v) = dynamic viscosity (u) / density (p) The unit of dynamic viscosity is poise (0.1 Pa's). It is more commonly expressed, particularly in ASTM standards, as centipoises (cP). While the kinematics viscosity as centiStokes -cSt (10m*-s"). The following equations can be used to calculate the liquid viscosities of petroleum fractions at atmospheric pressure and at temperatures of 37.8 °C(100 °F) and 98.9 °C (210 °F)Petroleum Refining Fourth Year a=: log v219 = —0.463634 — 0.166532(API) + 5.13447 x 10-*(API)? — 8.48995 x 10-K(API) +, 8:0325 x 102K + 1.24899(API) +0 197680(API)? API + 26.786 — 2.6296K log vio = 4.39371 — 1.94733K + 0.127690K? + 3.2629 x 10-4(API)* 1.18246 x 107K (API) 0.17161K? + 10.9943(API) + 9.50663 x 10-2(API)? API + 50.3642 — 4.78231K 0.860218K (API) where vig and y2io are the kinematic viscosities at 100 and 210 °F, in centistokes. The viscosity can be measured by several instruments (U-tube Viscometer, Saybolt Universal Viscosity (SSU), thermo-viscosity, Red wood viscometer and Englar) Thermo. = 15 + 148.5 kinematic Vis. = 46 SSU - 1183 ‘The comparison of viscosity by different instruments is shown in Figure 1> Ex) Calculate the kinematic viscosities for oil which has a MeABP of 320 °C and API gravity of 34 Sol: The boiling point is 593.15 K or 1067.7 R. the specific gravity is 0.855 and the Watson K factor is 11.95 vi0= 5.777 cSt and v219 = 1.906 cStPetroleum Refining Fourth Year a=: nc dn en diy Se eral, ul ar oe Toate tam anand “EOE so sp sane epi aA gia a eae 2000 15900 933 10900 600) 400] 300} 00) 100 80 1 2 abel woe fo a 9 mixtures. 3 2 ‘Skefied Castor ‘Mineral ols 2 Alcohol, 40%, 2 1 Zz e 24 4 3 2 Ff ite Grait f [Ti eieenooees 2s theriscosity eho 2 2 att 200 ae 08 mee eave ‘Spear a a Gah Fig.1. Comparison of viscosity by different instruments.(Viscosity must be at the same T.) 3- Pour Point The pour point is defined as the lowest temperature at which the sample will flow and is a rough indicator of the relative paraffinicity and aromaticity of the crude. A lower pour point means that the paraffin content is low and greater content of aromatics, To estimate the pour point of petroleum fractions from viscosity, molecular weight, and specific gravity, the following form is used for this purpose Tp = 130.47[5G27%] x [osins-eensrcn where Tp is the pour point (ASTM D 97) in kelvin, M is the molecular weight, and vss00 is. the kinematic viscosity at 37.8°C (100F) in eSt. This equation was developed with data on pour points of more than 300 petroleum fractions with molecular weights ranging from 140 to 800 and API gravities from 13 to 50Petroleum Refining Fourth Year a=: 4- Carbon Residue, wt% Carbon residue is determined by distillation to a coke residue in the absence of air. The carbon residue is roughly related to the asphalt content of the crude and to the quantity of the lubricating oil fraction that can be recovered, In most cases the lower the carbon residue, the more valuable the crude, This is expressed in terms of the weight percent carbon residue by either the Ramsbottom (RCR) or Conradson (CCR). Crude distilled (%) at 1100°F= 100 - 3*CCR, CCR is the Carbon residue for whole crude oil 5- Salt Content, 1b/1000 bbl If the salt content of the crude, when expressed as NaCl, is greater than 10 1b/1000 bbl, it is generally necessary to desalt the crude before processing. If the salt is not removed, severe corrosion problems may be encountered. If residua are processed catalytically, desalting is desirable at even lower salt contents of he crude. Although it is not possible to have an accurate conversion unit between 1b/1000 bbl and ppm by weight because of the different densities of crude oils, | 1b/1000 bbl! is approximately 3 ppm. 6- Sulfur Content, wt% Sulfur content and API gravity are two properties which have had the greatest influence on the value of crude oil, although nitrogen and metals contents are increasing in importance. The sulfuur content is expressed as percent sulfur by weight and varies from less than 0.1% to greater than 5%. Crudes with greater than 0.5% sulfur generally require more extensive processing than those with lower sulfur content. 7- Flash point Flash point TF, for a hydrocarbon or a fuel is the minimum temperature at which vapor pressure of the hydrocarbon is sufficient to produce the vapor needed for spontaneous ignition of the hydrocarbon with the air with the presence of an external source, ie., spark or flame. From this definition, it is clear that hydrocarbons with higher vapor pressures (lighter compounds) have lower flash points, Generally flash point increases with an increase in boiling point. Flash point is an important parameter for safety considerations, especially during storage and transportation of volatile petroleum products (ie., LPG, light naphtha, gasoline) in a high-temperature environment. The flash point can be estimated using the following equation Tr = 15.48 +0.70704T 0 Where Tio is normal boiling point for petroleum fractions at 10 vol% distillation temperature. Both temperatures (To and flas point (Ts) in Kelvin) Example: A kerosene product with boiling range of 175-260°C from Mexican crude oil has the API gravity of 43.6 and Tyo is 499.9K. Estimate its flash point and compare with the experimental value of 59°C. Solution: By using the last equation, T= 60.4°C, which is in good agreement with the experimental value of 59°C.Petroleum Refining Fourth Year a= 8- Octane number An octane number is a measure of the knocking tendeney of gasoline fuels in spark ignition engines. The ability of a fuel to resist auto-ignition during compression and prior to the spark ignition gives it a high octane number. Two octane tests ean be performed for gasoline. The motor octane number (MON) indicates engine performance at high way conditions with high speeds (900 rpm). On the other hand, the research octane number is indicative of low-speed city driving (600 rpm). RON of a fuel may be estimated from the pseudocomponent techniques in the following form RON = xxp(RON)xp + 1e(RON)ip + X0(RON)o +an(RON)y +2xa(RON),, a) where x is the volume fraction of different hydrocarbon families ie., n-paraftins (NP). isoparaffins (IP), olefins (O), naphthenes (N), and aromatics (A). RONyp, RONip, RONo, RONy, and RON, are the values of RON of pseudocomponents from n-paraffin, isoparaffins, olefins, naphthenes, and aromatics families whose boiling points are the same as the mid boiling point or the ASTM D86 temperature at 50% point of the fraction and can be determined from Figure 120 100 Research Octane Number $ 40 20 © L-olefins 0 | a malkylcyclopentanes © nealky Ibenzenes 20 100-50 0 50 100-150-200 Boiling Point, °C Figure 2: Research octane number of different families of hydrocarbons, There is another graphical relation for estimation of RON of naphthas in terms of Kw characterization factor or paraffin content (wt%) and mid boiling point as given in Figures belowPetroleum Refining Fourth Year a= Research Octane Number Cd Ns We NS Me NT Ne ng 20 Characterization Factor Figure 3: Research octane number of naphthas — Midboiling point — Soto", puset. 4 00° F L 1 | | 250° F. ae | | 0 | i | | “as0° | 1g 20 ec 90 00 00 00 eer O ees Oe 0g Wt% Paratfin Hydrocarbons Figure 4: Research octane number versus paraffin contentPetroleum Refining Fourth Year a= RON for these various hydrocarbon groups have been correlated to normal boiling point, Tb in the following form: RON =a +bT +cT? +d? +eT* Q) Where RON is the clear research octane number and T = (Tb-273.15)/100 in which Tb is the boiling point in kelvin. Based on the data taken from the API-TDB, the coefficients a - were determined and are given in Table below: Coefficients of eg. 2 for estimation of RON Hydrocarbon family eC RETREATED é a ET »-Paraffins 92.809 =70.97 53 20 +10 isoparaffins 2-Methyl-pentanes 95.927 -157.53 561 600 200 3-Methyl-pentanes 92.069 57.63 65 0 0 2,2-Dimethyl-pentanes 109.38 -38.83 26 0 0 2,3-Dimethyl-pentanes 97.652 8 58 -200 100 Naphthenes ~77.536 418 100 0 ‘Aromatics 145.668 54.336 16.276 0 0 Example: A naphtha sample from an Australian crude oil has the following characteristies: boiling point range 15.5 — 70°C specific gravity 0.6501, n-paraffins 49.33%, isoparaffins 41.45%, naphthenes 9.14%, aromatics 0.08%, clear RON 69.6, and MON 66.2. a) Estimate RON from the pseudocomponent method using experimental composition, b) Estimate RON from Fig.4, and c) Estimate RON from Fig.4, Solution: For this fraction: Tb = (15.5 + 70)/2 = 42.8°C, SG=0.6501, xp = 0.4933, xw = 0.4145 xy = 0.0914, xj =0.008: a) RON can be estimated from Eq.(1) through pseudocomponent method using RON values for pure hydrocarbons calculated from Eq, (2) and Table above with Tb= 315.9K. Results of calculation are (RON): =54.63, (RON)p = (90.94 + 104.83 + 88 + 87.05)/4 = 92.7, (RON)y = $5.57, and (RON), =125.39. In calculation of (RON)w, an average value for RON of 4 families in Table above is calculated, From eq.2, clear RON can be calculated as RON = 0.4933 x 54.63 + 0.4145 x 92.7 + 0.0914 x 55.57 +0.0008 x 125.39 = 70.55. In comparison with the reported value of 69.6 the error is 70.55 - 69.6 = 0.95 b) To use Fig.3 we need Tb = 42.8°C =109F and Kw, which is calculated as Kw = 12.75 Since the Kw is outside the range of values in Fig.3, accurate reading is not possible, but from value of the boiling point it is obvious that the RON from extrapolation of the curves is above 70. ¢) To use Fig. 4 we need total paraffins which is % = 49.33 + 41.45 = 90.78 and Tb = 109F. In this case Tb is outside the range of values on the curves, but with extrapolation a value of about 66 can be read. The error is about = 3.6.