2

DISTILLATION PROCESSES

2.1

Fundamentals

2.1.1 The nature of crude oil

Crude oil, or petroleum, is a very complex mixture of thousands of different species of chemical components. The most common compounds belong to the paraffins (alkanes), naphthenes (cycloparaffins), aromatics, or combinations such as alkyl substituted aromatics and polycyclic compounds. The number of carbon atoms in the components varies from one to four for gases, while heavy oils and waxes may have fifty or more and asphalts have hundreds. The components have atmospheric boiling ranges from 162C to more than 500C. Distillation has long been used for the separation of multi-component mixtures and still represents the most common separation process in use, even though it is energy-intensive. The same principles that can be applied to the separation of two components that have different boiling points can be applied to the separation of a complex mixture, such as petroleum. Unfortunately, crude oils differ markedly in characteristics, depending on where in the world they are found and on the geologic history of the area. Crude oil from the Far East is generally waxy, black or brown in colour and low in sulphur. Oil from the Middle East is usually black, less waxy and higher in sulphur. Western Australia produces crude oils that can be light, straw-coloured liquids and North-Sea oils are typically waxy and greenish-black in colour. The United States of America produce many different kinds of crude oil because there is a great diversity of geological history in the different regions of the country. Although crude oil consists largely of carbon and hydrogen atoms, other elements are found. Sulphur, in the form of free sulphur, hydrogen sulphide, mercaptans and thiophenes, is common and is an extremely undesirable constituent in any fuel.

Nitrogen also occurs, and is undesirable because it would poison catalysts, which are used in downstream reactors. Other poisons to catalysts that are found in crude oil are arsenic, vanadium and nickel. Oxygen containing components, such as naphthenic acids, are corrosive. Salts, such as sodium chloride as well as sulphates and carbonates of sodium, calcium and magnesium, can cause corrosion or can deposit on the surfaces of equipment, such as heat exchangers, causing fouling and are, therefore, undesirable. The products of the distillation of crude oil are, themselves, complex mixtures unlike in many chemical and specialty chemical processes, where distillation is used to separate pure or high purity products from mixtures. The products from the distillation of crude oil are usually characterized by boiling range and the yields of these products vary significantly, depending on the source of the feedstock. Maples (2000) describes the main refinery products according to atmospheric boiling range and the approximate number of carbon atoms per molecule (Table 1). Refinery distillation columns are usually very large. It is not uncommon for a single crude distillation column to process over 250,000 barrels of crude oil per day (about 12.5 million tons per year). Distillation columns are used for the atmospheric and vacuum distillation of crude oil, fractionation of the gaseous effluent from catalytic and thermal cracking. The equipment consumes large amounts of energy, because of the need to boil and condense the material. Consequently, optimization of design and operation is very important, especially as the configuration of equipment - heat exchangers, furnaces, columns, etc. - can be very complex resulting from the desire to recover as much energy as possible.

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Table 1. Principal refinery products Product Liquefied Petroleum Gases (LPG) Gasoline Kerosene, jet fuel Diesel Atmospheric gas oil Atmospheric residue Vacuum gas oil Vacuum residue Petroleum coke Boiling range (C) 42-0 0-200 190-270 270-340 340-425 425 425-540 540 1,100 430 800 2,500 Average molecular weight 44-58 100-110 160-190 245 320 Carbon atoms per molecule 3-4 4-11 10-15 15-20 20-25 25 25-50 50 200

2.1.2 Petroleum fraction characterization

Gas chromatography, Nuclear Magnetic Resonance (NMR) and other techniques have allowed more precise identification of many individual components in crude oil. However, knowledge of the identity and quantity of each individual component is impossible and quite unnecessary for most analysis and design purposes, because the final products are defined as mixtures with acceptable ranges of boiling points. It is usually satisfactory to characterize petroleum and petroleum fractions by parameters that are derived from normal inspection tests, a laboratory distillation curve and the specific gravity of the mixture. The Technical data book. Petroleum refining (1983) edited by API (American Petroleum Institute) describes five different boiling points and a quantity called the K factor, which is an index of paraffinicity, as useful parameters for the correlation of the thermodynamic and physical properties of petroleum fractions. Based on our knowledge of the properties of defined chemical components, such as ethane, propane, butane, pentane, etc. in the homologous series of normal paraffins, the properties of any unknown fraction can be estimated by comparison of the boiling point and specific gravity (Twu, 1984). The five boiling points are described by the following equations: Volume Average Boiling Point (VABP):
n

[2]

Molar Average Boiling Point (MABP):

n

MAPB
i 1

xiTbi

where xi is the mole fraction of component i and Tbi is the normal boiling point of component i. Weight Average Boiling Point (WABP):
n

[3]

WABP
i 1

xwiTbi

where xwi is the weight fraction of component i and Tbi is the normal boiling point of component i. Cubic Average Boiling Point (CABP):
n

[4]

CABP
i 1

1/3 (xviTbi )3

where xvi is the volume fraction of component i and Tbi is the normal boiling point of component i; in absolute temperature units. Mean Average Boiling Point (MeABP): [5] MeABP MABP CABP 11131121 2

MABP and CABP must be in the same absolute temperature units. Although the volume, mole and weight fractions are not known for undefined mixtures the API technical data book provides empirical correlations for the boiling points based on laboratory distillations. The characterization parameter K, sometimes also described as the KUOP factor, is defined by the equation: [6] (MeABP)1/3 K 1111121211111 specific gravity (60F/60F)

[1]

VABP
i 1

xviTbi

where xvi is the volume fraction of component i and Tbi is the normal boiling point of component i.

where MeABP must be in degrees Rankine. Paraffins have a K value close to 13 (n-hexane 12.81), mono-olefins have a lower K value, with

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FUNDAMENTALS

cyclo-paraffins lower still, followed by aromatics (1-hexane 12.48; cyclohexane 10.98; benzene 9.72). Many other properties are used to characterize petroleum fractions, such as sulphur content, metal content, salt content, pour point, cloud point, aniline point, freezing point, smoke point, octane number, cetane index, diesel index, refractive index, wax content and carbon content. There are literally tens of such properties, usually classified as refinery inspection properties, which are measured in laboratories and are used to specify the quality of the finished products. Fortunately, these properties are significantly less important than volatility measurements in the design or analysis of a distillation column. ASTM (American Society for Testing of Materials) and TBP (True Boiling Point) analytical distillations are used to define the volatility characteristics of crude oils and petroleum fractions. Both are batch distillations and differ in the degree of fractionation that occurs in the process. Atmospheric pressure ASTM distillations are run in an Engler flask, with no packing and reflux results only from heat losses through the neck of the flask. TBP distillations, on the other hand, are run in multistage columns at high reflux ratio. Although more reliable than ASTM distillations, TBP distillations take a lot longer to run and there is no standardization of the test method. Table 2 summarizes the common methods used for crude oils and heavy fractions. The data from ASTM D86 distillations are plotted as temperature vs. volume percent distilled; D2887 simulated distillations are plotted as temperature vs. weight percent distilled.

When carrying out ASTM distillations there may be residue left in the flask and there well may be losses when the volume of the original charge does not equal the sum of the distillate collected and residue. The loss is assumed to be volatile components that did not condense and is added to the individual measurements of percentage distilled at the reported temperature. Heavier petroleum fractions tend to decompose before they boil a process called cracking. The API technical data book used to recommend the application of a correction to ASTM D86 temperatures above 475F (246C) to adjust for cracking. This adjustment has been dropped in the most recent edition of the technical data book. Table 3 shows a typical ASTM D86 distillation curve for a crude oil that might be obtained from a laboratory. If the pressure at which the distillation is done is not equal to atmospheric (760 mmHg, 101.325 kPa), temperature measurements should be adjusted to equivalent atmospheric pressure by the application of the Sidney Young equation, which for degrees Fahrenheit is: [7] T760 TP 0.00012(760 P)(460 TP)

where T760 is the temperature corrected to 760 mmHg in degrees Fahrenheit, TP is the measured temperature in degrees Fahrenheit and P is the measured pression in mmHg. Although the ASTM test methods are simpler, the TBP distillation provides the best theoretical basis for the characterization of a sample. In the extreme case of a large number of theoretical stages and high reflux, the TBP distillation will tend to separate each component in the sample according to its boiling point. This assumes that the

Table 2. Laboratory assays Test ASTM Method D86 ASTM Method D216 ASTM Method D1160 Applicability Distillation of motor gasolines, aviation gasolines, aviation turbine fuels, naphthas, kerosenes, gas oils, distillate fuel oils and similar products. Distillation is at atmospheric pressure, using exposed thermometer with no stem correction Distillation of natural gasoline at atmospheric pressure For heavy petroleum products which can be vaporized partially or completely at a maximum temperature of 750F (399C) at absolute pressures down to 1 mmHg and condensed as liquids at pressure of test. Pressures range from 1 to 760 mmHg. Temperature is measured with thermocouple Simulated distillation using gas chromatography. Applicable to all petroleum fractions with final boiling point of 1,000F (538C) or less. Boiling range must be greater than 100F (38C) Distillation in column with 15 to 100 theoretical stages at high reflux ratios (5:1 or greater) and at pressures between 10 and 760 mmHg. No standardization of method

ASTM Method D2887 True Boiling Point (TBP)

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Table 3. Typical ASTM D86 laboratory distillation Mid-liquid volume percent 8 25 43 67 75 82 92 Temperature (C at 760 mmHg) 57.2 98.9 187.8 296.1 351.7 426.7 532.2

sample mixture is nearly thermodynamically ideal, which is approximately the case for crude oils and distillate products. A plot of temperature against volume distilled would show a series of stair-steps, with width of each step corresponding to the volume of an individual component and the height of the step being its boiling point. In crude oil there are literally thousands of components, with very close boiling isomers. This causes the stairstep curve to become almost smooth and continuous. Because the degree of fractionation is much greater in the TBP distillation than the D86, the TBP Initial Boiling Point (IBP) is lower than the corresponding D86 IBP and the TBP End Boiling Point (EBP) is higher than the D86 EBP. The curves intersect near the 50% point. There is a further type of laboratory distillation, called Equilibrium Flash Vaporization (EFV). The EFV curve is also a plot of temperature vs. volume percent distilled. A sample is heated in a closed vessel in such a manner that the total vapour produced is kept in contact with the unvaporized liquid until the desired temperature is reached for the pressure at which the experiment is being done. The volume percent vaporized is recorded. Each point on the EFV curve represents a separate vapour-liquid equilibrium experiment and the number of experiments that must be done depends largely on the shape of the curve. At least five experiments are usually required. The component separation achieved in an EFV experiment is less than in the ASTM and TBP distillations. The initial and final boiling points, (the final boiling point being the temperature at which the entire sample is just vaporized), correspond to the bubble and dew points of the mixture being analysed. EFV distillations can be run at several

different pressures. There is no standard test procedure for EFV distillations and, because the process is tedious and time consuming to run, EFV distillations are seldom done. Fig. 1 shows the TBP, D86 and EFV curves for a typical kerosene stream. The API technical data book provides a set of procedures that can be used to interconvert one type of distillation curve to any other. The goal, for the purpose of doing any analysis or design work on a crude distillation column is to produce the TBP curve for the crude oil. If the D86 curve is measured, API procedure 3A1.1 provides the means to convert to TBP. If, as is becoming more popular, the D2887 simulated distillation curve is available, API procedure 3A3.1 provides conversion to D86 and procedure 3A1.1 is then used to convert to TBP. EFV curves are seldom produced in the laboratory, but a knowledge of the EFV characteristics of a stream is useful (see Section 2.1.3) for determining the temperature to which a crude oil stream must be heated in order to produce the required distillate products. In fact, the vaporization process in the flash zone of the distillation column is correctly represented by the EFV curves. In the ASTM and TBP distillation the vapours are separated by the liquid immediately after their formation, and this is not the case of the continuous industrial distillation. API Procedure 3B1.1 provides an empirical mechanism for the interconversion of ASTM and EFV curves at atmospheric pressure. Procedure 3B3.1 can be used to interconvert any above atmospheric pressure EFV curve with its corresponding atmospheric pressure curve. An assay of a crude oil always includes, in addition to an ASTM or TBP distillation, an average or whole crude gravity. This is usually
400 350

temperature (C)

TBP D86 EFV

300 250 200 150 100 0 10 20 30 40 50 60 70 80 90 100

percent distilled (liquid volume basis)

Fig. 1. TBP, D86 and EFV curves for a kerosene stream.

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FUNDAMENTALS

Table 4. Measured light-ends analysis Component Ethane Propane Isobutane n-butane Isopentane n-pentane Total Volume percent of crude oil 0.1 0.2 0.3 0.7 0.5 1.2 3.0

Table 5. Laboratory true boiling point (TBP)

distillation, corrected to 760 mmHg

Liquid volume percent 3 5 10 20 30 40 50 60 70 80 100 TBP temperature (C) 36.1 65.0 97.8 165.6 237.2 310.0 365.6 410.0 462.8 526.7 871.1

measured by the ASTM D287 test procedure and reported in degrees API (or API gravity), where: [8] API gravity 141.5 11111111121 131.5 specific gravity (60F/60F)

light-end components and Table 5 for its TBP distillation. Assume, also that the average API gravity is 29.2. The crude oil can be represented by a series of defined components: the light-ends, plus a number of pseudocomponents over the remaining portion of the curve (the curve volume percentages are assumed to include the light-end compositions). Applying a cutting profile for the pseudocomponents, whereby a number of equally spaced intervals of temperature are defined as follows: from 37.8C to 426.7C, 28 cuts (13.9C, or 25F intervals); from 426.7C to 648.9C, 8 cuts (27.8C, or 50F intervals); from 648.9C to 871.1C, 4 cuts (55.6C, or 100F intervals), produces a series of pseudo components depicted by the histogram-like bars in Fig. 2. The profile above is quite arbitrary and is chosen to create a manageable number of pseudocomponents that will capture the shape of the original curve. Too few components, and it will be impossible to reproduce the boiling ranges of the actual material in any of the distillate products. If too many components are chosen, this will add to the computational effort to do any distillation calculations, without yielding any appreciable increase in accuracy. For each pseudocomponent, there is an average boiling point temperature, which is the integrated average of the volume of material boiling between the upper and lower cut-point temperatures. In general this will be close to the arithmetic average of the two temperatures, but curvature within this range can cause minor deviations from this value. Knowing the average boiling point for each pseudocomponents and the K for the whole crude,

Water has an API gravity of 10. Many crude oils have API gravities in the range from 10 to 40. The lighter (less dense) the sample, the higher is the API gravity. With the knowledge of the TBP curve of the crude oil and its K factor, derived from the average gravity and boiling point, the whole crude can be divided into a number of narrow boiling fractions, or pseudocomponents. Each pseudocomponent has an average boiling point and, assuming a constant K, a specific gravity can be derived. For the purposes of illustration, assume a crude oil has the analysis shown in Table 4 for its

1,000 900 800 700 600 500 400 300 200 100 0 100

temperature (C)

input TBP data fitted TBP curve component cuts

10

20

30

40

50

60

70

80

90 100

percent distilled (liquid volume basis)

Fig. 2. Pseudocomponent representation of crude oil.

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which can be assumed to apply to each individual pseudocomponent and in the absence of any other information about the distribution of paraffins, olefins, naphthenes and aromatics, the specific gravity for each pseudocomponent can be calculated. The techniques in the API technical data book can then be applied to generate all the necessary thermo-physical property information required for the simulation of any distillation process. Required properties include molecular weight, critical temperature, critical pressure, acentric factor (w), solubility parameter, ideal gas enthalpy equation coefficients and correlation coefficients for other temperature-dependent thermo-physical properties, such as liquid density, viscosity and thermal conductivity. For example, the methods of Kesler and Lee (Kesler and Lee, 1976) can be used to calculate critical temperature and critical pressure: [9] Tc 341.7 811.0SG (0.4244 (0.4669 3.2623SG) 105 Tb 0.1174SG)Tb

[13]

MW

20.486[exp(1.165 10 4Tb 7.78712SG 1.1582 10 3Tb SG)]Tb1.26007SG 4.98308

where SG is the specific gravity and Tb is the normal boiling point in degrees Rankine. Once all pseudocomponents are characterized and, assuming all property data are available for the defined light-end components, a suitable thermodynamic method can be chosen for use in any computer simulation of the distillation process. In the 1970s, the method of Grayson and Streed (1963), who modified the Chao-Seader (Chao and Seader, 1961) correlation for equilibrium K-values, was often used with good results. In more recent times, equations of state, such as Soave-Redlich-Kwong (Soave, 1972) and Peng-Robinson (Peng and Robinson, 1976) have been increasingly used. The results of any simulation are more sensitive to the choices made when characterizing the pseudocomponent properties than from the choice of thermodynamic method.

lnP 8.3634 0.0566 SG (0.24244 c 2.2898 SG 0.11857 SG 2) 10 3Tb (1.4685 3.648 SG 0.47227 SG 2) 10 7Tb2 (0.42019 1.6977 SG 2) 10 10Tb3 where Tc and Tb are the critical and normal boiling temperatures (degrees Rankine), Pc is the critical pressure in psia and SG is the specific gravity (60F/60F). The acentric factor w is estimated from an earlier work by Lee and Kesler (1975): [10] w (lnP b 5.92714 6.09648 TR, b 1.28862 R, lnTR, b 0.169347TR, b6) (15.2518 15.6875 TR, b 13.4721lnTR, b 0.43577TR, b6)

2.1.3 Simulation of crude oil distillation column

Assume we desire to make an initial split of the crude oil described in Tables 4 and 5 into naphtha, kerosene, diesel and Atmospheric Gas Oil (AGO) fractions. A column to achieve this separation might look like the one depicted in Fig. 3. Called an atmospheric tower or topping still, this column takes partially vaporized crude oil, from which most of the water, sediment and salts have been removed, from a furnace and rectifies it at a column pressure usually slightly above atmospheric pressure and less than 2.7 bar absolute. To control the initial boiling points (IBP) of the distillate products, side-streams from the main column are sent to side-stream strippers where steam is injected to remove some of the lighter components, which affect the IBP. Alternatively, these side strippers can be reboiled, but use of steam is more common. Steam is injected into the base of the main column to lower the hydrocarbon partial pressure and to allow vaporization of the hydrocarbons at lower temperatures, thus minimizing thermal decomposition. Reflux to the column is provided, in this example, from four sources. A conventional overhead condenser provides reflux to the top section and three pumparound circuits provide reflux to the lower sections. The presence of

where R and b indicate reduced properties evaluated at the normal boiling point. The ideal gas enthalphy (in Btu/lb-mole) is computed bu integrating the following equation for ideal gas: [11] Cp0 0.33886 0.0368K 2) 10 (CF)[0.26105 10 4T (0.536 0.02827K (0.9291 1.1543K 1.6658 10 7T 2 0.59332w (4.56 9.48w) 0.6828w) 10 7T 2 ]
4T

The factor CF is given by: [12] CF [(12.8 K)(10 K) (10w)]2

where K is KUOP factor, T is the temperature in degrees Ranking and w is the acentric factor. API Procedure 2B2.1 can be applied to estimate the molecular weight of a pseudocomponent, using the following equation:

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ENCYCLOPAEDIA OF HYDROCARBONS

FUNDAMENTALS

naphtha

kerosene stripper crude column steam-2 kerosene diesel stripper steam-3 diesel

crude oil steam-4 steam-1 topped crude

Fig. 3. Typical refinery atmospheric crude distillation column.

gas oil stripper gas oil

these pumparound circuits serves to reduce the reflux requirements on the condenser, while allowing heat to be removed from the column at a higher temperature than at the condenser. Heat is transferred from these pumparound circuits into heat exchangers that preheat the incoming crude oil feed. The pumparound is attractive from the point of view of energy recovery. Pumparound rates and heat exchange are used to control the degree of overflash in the feed zone of the column. The furnace must vaporize sufficient of

the feed to meet the distillate product requirements and provide a small amount of reflux (the overflash) from the trays immediately above the feed entry point to the flash zone. Additional distillates in the 400C to 600C boiling range (light and heavy vacuum gas oils) can be recovered from the topped crude by further rectification in a vacuum distillation column. Such columns are designed to operate at very low overhead pressures, usually in the 100 mmHg range. For the purposes of the example, assume the desired product qualities are described in Table 6. Examining the TBP curve for the crude oil and making some assumptions about the number of theoretical stages in sections of the column, the behaviour of the column can be simulated with the aid of commercial software programs such as PRO/II, from Invensys/SimSci-Esscor and Aspen Plus from Aspen Technology. The pseudocomponents obtained by applying the cutting profile to the TBP curve in Fig. 2 are shown in Table 7. The molecular weights and critical properties are calculated using the equations listed above. From Tables 1 and 6, the TBP mid-points of the desired products can be approximated as 100C, 225C, 305C and 380C for the naphtha, kerosene, diesel and atmospheric gas oil, respectively. These points can be reasonably assumed to lie on the TBP curve of the crude oil. If the chemical components in the crude oil could be separated into fractions where there were no overlapping components (i.e. a clean separation between components with adjacent boiling points) the individual distillate products would have TBP curves that corresponded to the relevant portion of the crude oil TBP curve. For example, the TBP curve of the topped crude, would be the same as the final part of the TBP curve of the crude oil.

Table 6. Example product qualities from atmospheric crude unit ASTM D86 temperatures (C) Volume del Liquid % liquido volume % 0 5 95 100 *TBP Temperature 170 188 Naphtha Kerosene 150 190 270 290 Diesel 230 270 350 370 Gas oil 256 326 475* 510* 375* Topped crude

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Table 7. Selected properties of pseudocomponents derived from assay Component name

Ethane Propane Isobutane n-butane Isopentane n-pentane NBP 44 NBP 59 NBP 73 NBP 86 NBP 100 NBP 114 NBP 128 NBP 142 NBP 155 NBP 169 NBP 183 NBP 197 NBP 211 NBP 225 NBP 239 NBP 253 NBP 267 NBP 280 NBP 294 NBP 308 NBP 322 NBP 336 NBP 350 NBP 364 NBP 378 NBP 391 NBP 405 NBP 419 NBP 440 NBP 468 NBP 495 NBP 523 NBP 551 NBP 579 NBP 607 NBP 634 NBP 675 NBP 729 NBP 784 NBP 842

NBP (C)
88.63 42.07 11.73 0.50 27.85 36.07 44.34 59.04 72.94 86.74 100.07 114.04 127.99 141.92 155.84 169.75 183.62 197.50 211.38 225.26 239.14 253.05 266.96 280.86 294.78 308.70 322.60 336.49 350.39 364.28 378.10 391.89 405.71 419.64 440.58 468.34 495.20 523.14 551.24 579.16 607.02 634.85 675.10 729.02 784.67 842.10

Specific gravity
0.3564 0.5077 0.5631 0.5844 0.6227 0.6310 0.7073 0.7181 0.7280 0.7375 0.7465 0.7557 0.7647 0.7734 0.7820 0.7903 0.7985 0.8065 0.8144 0.8221 0.8296 0.8371 0.8444 0.8516 0.8586 0.8656 0.8724 0.8791 0.8858 0.8923 0.8987 0.9050 0.9112 0.9174 0.9266 0.9384 0.9496 0.9610 0.9722 0.9830 0.9936 1.0040 1.0186 1.0376 1.0564 1.0752

KUOP
19.43 14.70 13.81 13.50 13.09 13.04 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73 11.73

Molecular weight
30.070 44.097 58.124 58.124 72.151 72.151 75.203 81.525 87.757 94.202 100.674 107.738 115.081 122.720 130.673 138.948 147.550 156.509 165.843 175.569 185.709 196.294 207.329 218.834 230.833 243.355 256.397 269.996 284.184 298.982 314.341 330.332 347.052 364.647 392.558 432.495 474.580 522.309 574.751 631.738 693.896 761.744 871.359 1,042.540 1,253.926 1,516.885

TC (C)
32.30 96.67 134.98 152.00 187.24 196.50 217.54 234.93 250.98 266.58 281.34 296.54 311.45 326.09 340.50 354.69 368.66 382.44 396.06 409.53 422.85 436.06 449.15 462.11 474.96 487.71 500.35 512.88 525.32 537.67 549.89 561.99 574.05 586.14 604.17 627.88 650.60 674.03 697.40 720.46 743.29 765.95 798.50 841.70 885.86 931.06

PC (kPa)
4,883.05 4,248.87 3,647.10 3,799.06 3,380.65 3,368.50 3,890.08 3,691.13 3,515.39 3,351.68 3,203.07 3,056.28 2,918.39 2,788.53 2,665.97 2,550.24 2,440.95 2,337.45 2,239.24 2,145.99 2,057.33 1,972.89 1,892.51 1,815.95 1,742.91 1,673.14 1,606.66 1,543.14 1,482.40 1,424.31 1,369.00 1,316.08 1,265.22 1,216.06 1,145.91 1,059.25 981.72 907.02 837.51 773.45 714.20 659.19 586.44 500.19 422.95 354.12

Acentric factor (w)

0.0986 0.1529 0.1772 0.2013 0.2290 0.2506 0.2344 0.2543 0.2744 0.2954 0.3166 0.3397 0.3636 0.3882 0.4135 0.4395 0.4661 0.4932 0.5209 0.5491 0.5779 0.6072 0.6370 0.6673 0.6980 0.7292 0.7607 0.7926 0.8250 0.8576 0.8905 0.9237 0.9572 0.9914 1.0434 1.1134 1.1822 1.2549 1.3289 1.4034 1.4785 1.5542 1.6644 1.8130 1.9653 2.1186

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1,000 800

EFV curve at 1,406 mmHg TBP curve at 760 mmHg

Table 8. Cut point temperatures between products Cut Cut point temperature (C) 420 340 270 180

temperature (C)

600 400 200 0 10 200 20 30 40 50 60 70 80 90 100

AGO to topped crude Diesel to AGO Kerosene to diesel Naphtha to diesel

percent distilled (liquid volume basis)

Table 9. Approximate percentages of products

based on whole crude

Product Topped crude AGO Volume % of crude oil 39.9 14.9 10.9 12.4 21.9 100.0

Fig. 4. EFV curve for crude oil at furnace outlet pressure and corresponding atmospheric TBP curve.

However, fractionation is imperfect between distillates and there is a considerable overlap of components between adjacent products. This causes the TBP curves for the distillate products to have lower initial and higher end points than the corresponding part of the original crude oil from which they were obtained. The concept of a cut point, relative to the original crude oil TBP curve, is still used and is useful in determining the respective quantities of each distillate product that can be obtained from a given crude oil. It is at this point that knowledge of the Equilibrium Flash Vaporization (EFV) characteristics of the crude is valuable. For the crude oil in this example, assume the maximum temperature to which the crude oil feed can be heated in the furnace is limited to approximately 375C to avoid decomposition of the heavier materials and subsequent coking of the furnace tubes. Fig. 4 shows the EFV curve at the furnace outlet pressure of 1,406 mmHg (188 kPa) overlaid on the TBP curve at 760 mmHg for the crude oil. The EFV temperature of 375C corresponds to a fraction distilled of approximately 60% and an equivalent TBP temperature of 420C. This means that the column and furnace should be able to separate 60%, by volume, of the crude oil into distillate products, leaving 40% as topped crude. The cut point between the heaviest distillate product (the atmospheric gas oil and the topped crude) would be approximately 420C. With this expected cut point between the AGO and the topped crude, the mid-point temperatures of the distillate products can be applied in decreasing order to obtain the cut point temperatures for the other distillates. For example, with the AGO to

Diesel Kerosene Naphtha Total

topped crude cut point as 420C and the AGO mid-point as 380C, the temperature range is (420 380) 40C. Applying this range from the mid-point of the AGO, gives a cut point for the diesel to AGO at (380 40) 340C. For the diesel to kerosene cut point, the temperature range to the mid-point of the diesel is now (340 305) 35C. Applying this from the mid-point of the diesel gives a diesel to kerosene cut point of (305 35) 270C. Repeating the process gives the cut points and the corresponding volume percentages of the original Crude Oil, which can be read from the TBP curve (Tables 8 and 9). The results of simulating this distillation with PRO/II are shown in Fig. 5. The original TBP curve for the crude oil is overlaid with the ASTM D86 curves for the resulting naphtha, kerosene, diesel and atmospheric gas oil. The TBP curve for the topped crude is also shown. The curves for the products show significant tails, indicating that there is a considerable overlap of components between adjacent products. For example, the presence of heavier boiling point components from the diesel cut in the kerosene cause the end point of the kerosene to be higher than the original TBP curve and, similarly, more volatile components from the kerosene cut are present in the diesel, giving it a lower initial boiling point. Clearly, separation could be improved with additional reflux or more stages in the column, but this translates to higher furnace duty (and operating

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Fig. 5. Original crude oil TBP curve with product assay curves overlaid.

1,000 900 800

temperature (C)

700 600 500 400 300 200 100 0 100 10 20 30 40 50 60 70 80 90 100

percent distilled (liquid volume basis) fitted TBP curve naphtha-kerosene cut point kerosene-diesel cut point diesel-gas oil cut point gas oil-topped crude cut point naphtha D86 kerosene D86 diesel D86 gas oil D86 topped crude TBP

cost) and increased capital cost for the column. The additional separation is unnecessary, as long as the distillate products meet their volatility specifications.

2.1.4

Mathematical modelling of distillation columns

Background

For many years computer modelling of crude oil distillation columns was considered very difficult. However, with modern desktop computers and advances in algorithms, numerical analysis of crude towers is a standard

Vj

Lj

Vj

Lj

Fig. 6. Equilibrium stage.

design tool. This section outlines the design equations for modelling crude oil distillation and presents algorithms for solving the equations. The equilibrium model, depicted in Fig. 6, is represented by a set of equations commonly known as the MESH equations. MESH stands for: Material balances, Equilibrium balances, Summation equations, entHalpy balances. Material balances are used to ensure that there is a material balance around each stage; the equilibrium balances ensure vapourliquid equilibrium between the liquid and the vapour; the summation equations ensure that the mole fractions sum to 1; the enthalpy balances ensure that there is an enthalpy balance around the stage. There have been many different solution algorithms proposed for solving the MESH equations. The most popular algorithms are Newton based algorithms and Inside/Out (I/O) algorithms. Newton based algorithms are attractive due to the wide range of systems which can be easily modelled. Design specifications are solved simultaneously with the MESH equations. Newton methods require reasonable starting estimates for the algorithm to converge. The thermodynamic properties of K-values and enthalpies are not usually included in the matrix of

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equations being solved simultaneously, but are solved in external functions. The Inside/Out class of algorithms (Boston and Sullivan, 1974; Russell, 1983) defines a stripping factor (KV/L). For a set of stripping factors and side stream withdrawal factors and a simple K-value model, the component molar flows and tray temperatures can be computed directly. The Inside/Out algorithm is particularly well suited for crude column simulation. In the I/O algorithm each material balance is solved with constant K-values in an inner loop. In the outer loop, the enthalpy balances and design specifications are solved by manipulating the natural log of the stripping factor and the sidestream withdrawal ratios to drive the enthalpy balance errors and design specification errors to zero. The log transformation is used to keep the stripping factors and sidestream withdrawal ratios positive. In the following a distillation column will be considered with all auxiliary equipment (i.e. condenser and reboiler); however, it should be pointed out that the topping column is not equipped with any reboiler, as shown in Fig. 3.
MESH equations and variables

For the purposes of this model it is assumed that each tray operates at a specified fixed pressure. Following are the MESH equations: Material balance equation: [14] mbi, j xi, j 1Lj 1(1 SR L 1) j yi, j
1V 1(1 j

xi, j Lj

nf

yi, j V j i, F zi, k jk

SR V 1) j

k 1

where Fjk is total flowarate of the (k-th) feed to stage j, zi, k is the mole fraction of the (i-ith) component in the (k-th) feed to stage j and nf is the number of feeds to stage j. Vapour/liquid equilibrium equation: [15] eqi, j yi, j K(x,y,T)i, j xi, j
noc

Summation equations: sxj syj

i 1 noc i 1

[16] [17]

xi, j yi, j

1 1

Energy balance equations: ej Lj 1(1 SRL 1)HjL 1(T,x) j Lj H jL (T,x)

nf k 1

[18]

Vj HjV(T,y) V 1HjV 1(T,y) j

F HkF k

The MESH equations can be written using component molar flows or mole fractions as independent variables. The formulation presented here will use mole fractions. When far from the solution, Newton solvers have a tendency to overpredict the corrections to the independent variables. Mole fractions are limited to the range of 0 to 1 because most thermodynamic sub-routines expect this. In particular, cubic equation of states can encounter negative square roots if the mole fractions do not sum to 1. The independent variables are shown in Table 10. In this formulation, there are (2NOC+3) variables for each equilibrium stage, assuming no side draws (NOC is the Number Of Components).

There are a total of (2NOC + 3) equations for each equilibrium stage (excluding side draws).

2.1.5 Solving the MESH equations

The first step solving the equations refers to a distillation column without any auxiliary equipment (conventionally called absorber). Solving the MESH equations is generally done with Newtons method (also known as the Newton-Raphson algorithm) or some modification of Newtons method. Newtons method considers only the first derivative and uses this to compute corrections so that all of the equations are solved using one linear correction term to each

Table 10. Independent variables in mathematical model xi,j yi,j Lj Vj Tj SRL j SRV j Liquid phase mole fraction of component i on stage j Vapor phase mole fraction of component i on stage j Total liquid phase molar flowrate leaving stage j Total vapor phase molar flowrate leaving stage j Temperature of liquid and vapor phases on stage j Liquid side stream withdrawal ratio on stage j, 0 no draw, 1 total draw Vapor side stream withdrawal ratio on stage j, 0 no draw, 1 total draw

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B A

C B A C B A C B A C B A C B

flexible enough to handle the addition of pumparounds and design specifications. One of the problems with using Newtons method is that the corrections returned from the Newton update formula may result in one or more of the independent variables going outside of physically meaningful bounds. For example, it is possible that one or more mole fractions could become greater than one or less than zero if the full Newton step is applied. To avoid this, a damping factor is typically applied [20] xik
1

xik aDxik

Fig. 7. Block tri-diagonal matrix structure.

independent variable. In matrix form Newtons method is expressed as: [19] Dx J

1f (x)

where J is the (n n) Jacobian matrix of first derivatives and f (x) is the vector of equation residuals from the MESH equations. For an absorber the Jacobian matrix J has the block tri-diagonal structure illustrated in Fig. 7. This was first reported by Naphtali and Sandholm (1971). In Fig. 7, the A sub-matrix represents the Jacobian coefficient contributions from the liquid entering from the stage above, the B sub-matrix is the contributions from the liquid and vapour leaving the stage and the C sub-matrix is the contributions from the vapour below. Each of these sub-matrix blocks will contain their own sparsity pattern. Outside of these blocks the remaining entries in the Jacobian are all zeros. The structure shown in Fig. 7 can be solved using a block tri-diagonal form of the Thomas algorithm for solving tri-diagonal systems. However, in practice this approach is not used because it is not
overhead vapour distillate product

where x is any variable and a is a scalar between 0 and 1. The scalar a is determined so that variables do not exceed upper and lower bounds and so that the variable does not change beyond some reasonable value. When solving wide boiling systems and in particular crude oil distillation problems, it is particularly important that if a given mole fraction is below some tolerance, it is not included in the decision to determine the limiting value of a. Often during solution a trace component on a stage may get a correction large enough to influence a. Typically some component with a mole fraction less than 1.0 10 6 may have a negative correction larger than the value of the mole fraction. Suppose some mole fraction of 1.0 10 10 has a correction of 1.0 10 8: this would result in an a value of 0.01 and if used would impede the convergence. For this reason some tolerance must be set to determine if a variable and its correction are to be used in determining a. When a trace component mole fraction has a negative correction from the Newton step, some action must be taken to prevent the mole fraction from becoming negative. One heuristic that works well is to move the variable from the current value half way to the lower bound. Alternatively the value of a can be used in the update expression to facilitate line searching for the minimum in the search direction. For these special trace components the following update formula can be used for negative corrections: [21] xik
1

xik

a(xik

x LO)0.5

vapour feed from top of tray section energy stream reflux return to top of tray section
Fig. 8. Equilibrium condenser.

where the constant 0.5 indicates that for a full step the value of x moves half way to the lower bound. This sort of heuristic is very important for successful solution of crude oil distillation problems using Newtons method.

overhead liquid distillate product

2.1.6 Condensers and reboilers

Adding condensers and reboilers is straightforward using Newtons method. Fig. 8

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Table 11. Additional variables associated with condenser Qc Qr SRL 1 Condenser duty Reboiler duty Side stream withdrawal ratio for liquid distillate product at condenser

represents the specified vapour flowrate, the design specification equation is: [26] sp1 V1 V1SP

The liquid distillate rate specification must be cast in a form that uses the liquid side stream withdrawal ratio. As above, let represent the specified liquid distillate flowrate. The design specification is: [27]
SP L sp2 L1SR1 L1

shows the schematic diagram of a condenser with both a liquid and vapour distillate product as well as the reflux stream returning to the top of the tray section. Because the formulation chosen here uses total liquid and vapour rates as independent variables, the mass balance at the condenser is quite straightforward: [22] mbi, j xi,1L1 yi,1V i,1 yi, j
1V 1(1 j
nf

SRjV 1)
nf

k 1

F zi, k k

where L1 is the total liquid leaving the condenser and L SR1 is the fraction of the total liquid removed as a side draw product. For this definition of the reflux ratio the vapour distillate will be ignored. Taking the reflux ratio as the ratio of the reflux flowrate to the liquid distillate product and RRSP as the specified reflux ratio given results in the design specification of: [28] sp3
L L1(1 SR1 ) 112121 RRSP L L1SR1

The enthalpy balance becomes: [23]

L V V e1 L1H1 V H1 V H2 1 2

k 1

F HkF Q1 k

This reduces to: [29] sp3

L SR1

where L and V represent the total liquid and vapour leaving the stage. The mole balance for stage 2 is given as follows: [24] mbi,2
L xi,1L1(1 SR1 )

1 1121 RRSP 1

xi,2 L2
V SR2 1)

nf

yi, j V i,2

yi,2

1V 1(1 2

k 1

F zi, k k

2.1.8 Solving the MESH equations for the fully equipped distillation column
Adding in design specifications changes the structure of the Jacobian matrix. Often design

There is no change to the material balance at the reboiler but the enthalpy balance becomes: [25] er Lr
L 1Hr 1

Lr HrL V r
V V2H2

nf

k 1

F F Hk Qr k

Adding the condenser and reboiler has introduced three new independent variables, shown in Table 11. These three new variables introduce three degrees of freedom into the problem. This requires three design specifications to be made to fully specify the system.

B A

C B A C B A C B A C B A design specifications (equations) C B

2.1.7 Design specifications

One of the strengths of Newtons method is the wide range of design specifications that are possible. For this example, the following design specifications will be added: vapour distillate rate, liquid distillate rate, reflux ratio. The vapour distillate rate specification is easy to implement because the total vapour leaving each equilibrium stage is an independent variable. If V1SP

Fig. 9. Block tri-diagonal block bordered matrix structure.

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specifications are placed on the bottom rows of the matrix and the additional variables are added to the right hand side of the matrix. This is done to keep each B sub-matrix square. Strictly speaking this is not necessary because the rank of the Jacobian is not a function of the location of the design specification equations, but it typically makes programming easier. Fig. 9 shows the structure of the resulting block tri-diagonal block bordered matrix that emerges from summing the design specifications and addition variables to the Jacobian matrix.

2.1.9 Pumparounds
Pumparounds are used as a heat transfer mechanism in crude oil distillation columns. Due to the wide boiling nature of the crude mixture and the large temperature change across the crude distillation tower, pumparounds are used to remove heat and hence create a more even distribution of liquid reflux. Fig. 10 shows the schematic diagram of a pumparound. Pumparounds introduce additional terms into the heat and material balances as follows: Material balance: [30] mbi, j xi, j Lj xi, j 1Lj 1(1 SRjL 1) yi, j V j yi, j 1Vj 1(1 SR jV 1) i,
nf nf k 1 nf

Fig. 10. Pumparound schematic diagram.

F zk, i k

k 1

L Lk SRk xi, k

where the term

k 1

L Lk SRk xi, k represent the contribution

specified in standard liquid volume units, reflecting standard design practice. The other degree of freedom can be a constant duty specification or a temperature drop across the pumparound heat exchanger. These rating specifications are used to determine the separation for a fixed amount of heat transfer. Design specifications are sometimes made for only one pumparound quantity, allowing the other degree of freedom to be used for a performance specification: for example, the D86 cut point may be specified. This allows the engineer to ask the question how much cooling needs to be provided in

from pumparounds on other stages entering stage j. Energy balance: [31] ej Lj 1(1 SRjL 1)HjL 1(T,x) L (T, x) V H V(T,y) V H V (T,y) Lj Hj j j j 1 j 1
nf nf k 1 nf

B A

C B A C B A C B A C B A design specifications (equations) C B D

F F Hk k

k 1

L L Lk SRk Hk

L L where the term Lk SRk Hk represents the enthalpy k 1 contribution for each pumparound entering stage j.

Design specifications for pumparounds

Pumparounds add variables for the side stream withdrawal ratio used to determine the flowrate of the pumparound and the energy added or removed in the pumparound. Therefore each pumparound introduces two additional degrees of freedom to the equation set. Pumparound rate specifications are often included in the design equations. Usually the rate is

Fig. 11. Jacobian structure with pumparound.

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2.1.10 Side-strippers
The final component needed for modelling a crude distillation tower is a side-stripper. Side-strippers are used to perform stripping on distillation products. Usually stripping steam is fed to the bottom of the side-stripper, although some sidestrippers are reboiled. Side-strippers provide an additional degree of operational control to determine product initial and end points of distillation curves. Fig. 12 shows the schematic diagram of a stem fed side-stripper.

References
API (American Petroleum Institute) (1983) Technical data book. Petroleum refining, Washington (D.C.), API, 2v.; v. I. Boston J.F., Sullivan S.L. Jr. (1974) A new class of solution methods for multicomponent, multistage separation processes, Canadian Journal of Chemical Engineering, 52, 52-63. Chao K.C., Seader J.D. (1961) A general correlation of vapor-liquid equilibria in hydrocarbon mixtures, American Institute of Chemical Engineering Journal, 7, 598-605. Grayson H.G., Streed C.W. (1963) Vapor-liquid equilibria for high temperature, high pressure hydrocarbonhydrocarbon systems, in: Proceedings of the 6th World petroleum congress, Frankfurt am Main, 19-26 June. Kesler M.G., Lee B.I. (1976) Improved prediction of enthalpy of fractions, Hydrocarbon Processing, 55, 153-158. Lee B.I., Kesler, M.G. (1975) A generalized thermodynamic correlation based on three-parameter corresponding states, American Institute of Chemical Engineers Journal, 21, 510-527. Maples R.E. (2000) Petroleum refinery process economics, Tulsa (OK), PenWell. Naphtali L.M., Sandholm D.P. (1971) Multicomponent separation calculations by linearization, American Institute of Chemical Engineers Journal, 17, 148-153. Peng D.Y., Robinson D.B. (1976) A new two-constant equation of state, Industrial and Engineering Chemistry Fundamentals, 15, 59-64. Russell R.A. (1983) A flexible and reliable method solves single-tower and crude-distillation-column problems, Chemical Engineering, 90, 53-59. Soave G. (1972) Equilibrium constants from a modified Redlich-Kwong equation of state, Chemical Engineering Science, 27, 1197-1203. Twu C.H. (1984) An internally consistent correlation for predicting the critical properties and molecular weights of petroleum and coal-tar liquids, Fluid Phase Equilibria, 16, 137-150.

steam feed
Fig. 12. Side-stripper schematic diagram.

side product

order to achieve this distillation cut point specification. Crude distillation towers may typically contain three pumparounds. In this situation, while there are interactions between the pumparounds and the side products from the crude tower, a given pumparound will have the strongest effect on the draw tray closest to the pumparound moving down the tower. This is because the pumparound causes an increased flow of reflux which moves down the tower and provides additional rectification for product draws below the pumparound.
Jacobian matrix with pumparounds

Adding pumparounds to a distillation column results in off-diagonal blocks containing non-zero components. This occurs because the pumparound links stages that are not adjacent. Fig. 11 shows the resulting Jacobian matrix structure. Sub-matrix block D is the result of the pumparound contribution.

David Bluck
Invensys SimSci Esscor Lake Forest, California, USA

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