ENGINEERING CHEMICAL CHEMICAL ENGINEERING TECHNOLOGY IV: UNIT OPERATIONS MODULE C CEM4M3-C CHAPTERS 1-8 3° EDITIONCHEMICAL ENGINEERING TECHNOLOGY IV: UNIT OPERATIONS MODULE C Only Study guide for CEM4M3-C 1/2006- 2008 Compiled by: HGJ Potgieter Moderated by: Dr M Smith CEM4M3-C - Index UNISA Engineering@ 2005 University of South Africa Third Edition All rights reserved Printed and published by the University of South Africa Muckleneuk, Pretoria CEM4M3-C-E/1/2006-2008 In terms of the Copyright Act 98 of 1978 no part of this material may be reproduced, be stored in a retrieval system, be transmitted or used in any form or be published, redistributed or screened by any means (electronic, mechanical, photocopying, recording or otherwise) without the prior written permission of Unisa. However, permission to use in these ways any material in this work that is derived from other sources must be obtained from the original sources. Printed in South Africa by Unisa CEM4M3-C “ie ~ Index UNISA EngineeringCHEMICAL ENGINEERING TECHNOLOGY IV: UNIT OPERATIONS MODULE C STUDY GUIDE OF CEM4M3CE INDEX CONTENTS, 1. DISTILLATION 1 2. | MULTICOMPONENT DISTILLATION 33 3. | RIGOROUS DISTILLATION DESIGN METHOD 69 4, EVAPORATION 84 5. ADSORPTION 118 6. CRYSTALLISATION 147 7. FLUIDISATION 170 8. | MULTICOMPONENT ABSORPTION/STRIPPING 192 REFERENCES 209 SUPPLEMENTARY MATERIAL 210 ‘CEM4M3-C - lie Index UNISA EngineeringCONTENTS 4.1. INTRODUCTION....... 1.4.1 1.1.2 1.1.3 1.1.4 1.1.5 1.2 MULTIPLE FEED AND SIDE STREAMS... 1.2.1 1.3 PONCHON ~ SAVARIT METHOD For TRAY TOWERS”. 1.3.1 CHAPTER 1 DISTILLATION Objectives. McCabe — Thiele Method... Minimum Reflux Ratio, Rim... Number of stages at total reflux ... Batch Distillation.. Objectives Objective... CEMAMS-C UNISA 1 Chapter t Engineering1.14. INTRODUCTION 1.1.1 Objectives Brief revisions of the McCabe — Thiele method and batch distillation are given in this section, Refer to the following sketch “) of a distillation column that operates with a total condenser and a reboiler that vapourises a part of the liquid that leaves the bottom stage. When a partial condenser is used the top product would be a mixture of vapour and liquid. Total condenser Overhead vapor, ( Reflux drum Top stage |_1_ 1 Reflux Distilare Tight ey sole scion » Rectitying D section stager ed | Tight key ! | reed stage mole fraction « F Stripping section stages Bottom | stage Boitup [<2oer Sena reboiler Bontoms Lightkey ‘mole fraction =x Figure 1.1: J.D. Seader and E.J. Henley CEMAM3-C 2 ‘Chapter 1 UNISA EngineeringIn the sketch the more volatile component is referred to as the light key (LK) and the less volatile component as the heavy key (HK). In multi component systems the LK is the most volatile component in the bottom product ( bottoms) and the HK the least volatile component in the top product (distillate). 1.1.2 McCabe — Thiele Method This method is based on the assumption of constant — molar — overflow (equi — molar overflow). The liquid and vapour molar flow rates in the top part of the column (the rectification section ) do not change from stage to stage. This is also the case for the bottom part (the stripping section ) but the flow rates can be different from that in the rectification section. It is assumed that equilibrium is attained in each stage and such a stage is called an equilibrium stage. The vapour that leaves the partial reboiler is also assumed to be in equilibrium with the liquid that leaves it. The reboiler is thus considered to be an equilibrium stage. The vapour leaving the reboiler is called the boilup. The following specifications are required to use this method successfully: The total feed rate, F. The mol fraction of a component (normally the light one ) of the feed, ze. The phase condition of the feed at the column pressure. Vapour — liquid equilibrium data. The mol fraction of the light component of the distillate, xo The mol fraction of the light component of the bottoms, xs, The reflux ratio, R or a factor times Rm ( minimum reflux ratio) The type of condenser (partial or total ) and the type of reboiler (normally partial). The relationship between vapours and liquids at equilibrium is frequently expressed by: y=kx, CEMAN3-C = Chapter 7 UNISA EngineeringWhere y = mol fraction of light component in the vapour x= mol fraction of light component in the liquid Various methods are available for estimating the K — values. The relative volatility, «., indicates the ease or difficulty with which components can be separated. kK, 2 = gh Where 1 refers to light Key and 2 to the heavy key The closer cis to 1 the more difficult the separation. It can be assumed that Raoult's law applies when the components form ideal solutions and the ideal gas law applies in the vapour phase — thus: K, a andK, -@ and a, =—> where P and Pare the vapour pressures It can be shown that: _ 42%, Wa () The amounts of distillate, D and bottoms, B are found by doing a molar balance. The reflux ratio, R = Ly / D determines the liquid flow rate, L, which remains constant in the rectification section. The vapour flow rate is given by L, + D which also remains constant in the rectification section. CEMANB-C + Chapter 7 UNISA EngineeringIt can be shown that the top operating line is given by: Xo Rei @ Tn = Re ghont Equation (2) is a straight line passing through (xo, xo) and (028) iB The bottom operating line is given by: Yon = GX mer Xo (3) Equation (3) is also a straight line passing through ( xs ,X8 ) with a slope of & It is worth remembering that: the compositions of the vapour and liquid leaving a stage is obtained from the equilibrium curve and that the composition of the vapour entering a stage in terms of the liquid leaving stage is given by the operating line. The physical condition of the feed determines the flow rate of the liquid flowing from the feed tray to the stripping section. If the feed is for instance a liquid at its boiling point Lin = LytF. heat tovapourise 1 molof feed The quantity, defined as ar molar latentheat of the feed It can be shown that the equation of the q — line is given by: (4) CEMANB-C = Chapter 1 UNISA EngineeringWhen the feed is (a) acold liquor q> 1 slope is positive (b) liquor at boiling point q = 1 slope is vertical (©) partly vapour0 = ee os =0,425 thus R,, = 0,74. Problems 1, Repeat the above example but with a feed that is 60 % vapour. Answer:9+ theoretical stages; 5 theoretical feed stage. 2. Amixture that contains 40 mass % benzene and 60 mass % ethyl- benzene must be separated into a distillate containing 95 mol % benzene and a bottoms containing 5 mol % benzene. The feed is a liquid at 30°C. The bubble point of the feed is 104°C its latent heat of vapourisation is 36300 kJ / kmol and its specific heat is 160 kJ / kmol K. Determine Rm and the number of actual trays if the efficiency of the trays is 55% and R = 1,5 Rn. a= 6,8 Answer: Rm = 0,318; number of trays = 12 1.1.4 Number of stages at total reflux It is implied in this case that no products are withdrawn and is thus of no practical value. It can, however, be used as a starting point in distillation calculations. The two operating lines merge with the 45° line and stages are stepped off from xp to Xo. CEMAMS-C = ‘Chapter 1 UNISA Engineering1.1.5 Batch Distillation This is an unsteady state distillation process that is frequently used for small scale operations. This type of column consists of a boiler( also called the stil) on top of which a distillation column is installed. A whole batch is charged to the boiler. The vapour is condensed and part of the condensate is returned as reflux. As the distillation process proceeds the composition in the boiler changes continuously. This results in the decrease of the lighter component in the distillate. In order to maintain a constant distillate composition the reflux ratio can be adjusted continuously or the column can be operated initially with a higher concentration of the light component at a given reflux ratio. This ratio is kept constant which will result in a lower concentration of the light component. The distillation is stopped when the required distillate composition is given by the average A batch distillation column is only fitted with a rectification section. The operating line of a rectification section thus applies. Only the constant reflux method will be considered here. Consider the boiler to be initially charged with S; mols of liquid with a mol fraction x, of the light component. The composition of the distillate is xo with Rj the reflux ratio. The distillation is stopped when Sp mols remain with mol fraction x2 . It is necessary to increase the reflux ratio to Re in order to maintain the distillate composition at xo if the number of trays remains the same. A total mol balance gives: S;-S2=D A light component balance gives: S1 Xs1 — Se Xs2 = D Xp From these equations it follows that D = S, [te] (5) CEMAM3-C =10- Chapter 1 UNISA EngineeringThe intercept of the operating line on the Y — axis is Ran Aean)- Fa (6) Equations (5) and (6) allows one to determine the final reflux ratio that is required to obtain a given final concentration in the boiler and the quantity of distillate. dx, Itcan also be shown that: ngs Example 2” A batch distillation column with three theoretical stages (the boiler being the first) is charged with 100 kmol of a mixture of containing 32 mol % n — hexane and the rest n - octane. average Xp = 0,6 and constant R = 1,0. Determine the amount of distillate if the final mol fraction of n — hexane in the boiler is 0,1. o. = 3,7. The equilibrium and 45° line are plotted. A trial — and — error procedure is then required. Assume that the first xo= 0,85 A = 0,425 connect (0,85; 0,85) with this A- value. Step off three stages starting from x.2= 0,32. The third stage ends with (0,85; 0,85). The diagram and the table below illustrate the rest of the procedure. CEMAN3-C Te Chapter 7 UNISA Engineering10 os os 10 Xs x0 A 0,32 0,85 0,425 | 0,16 06 03 07 05 0,25 0,05 03 0,15 4 The plot of xs versus is shown in the following graph. The area is Xo Xs determined between x; = 0,32 and 0,1 and found to be 0,532. CEMAN3-C “2 Chapter 7 UNISA EngineeringO} 0,3 ng 532 thus S, = 587 and D = 413 Dxp =S,x,, —S,X,. = 32-587 thus x, = 063° CEMaNs-C 3 Chapier 1 UNISA Engineering1.2. MULTIPLE FEED AND SIDE STREAMS 1.2.1 Objectives The methods that are required to solve these types of problems are presented here. The McCabe — Thiele method can also be used for multiple feeds and / or side streams. A multiple feed system is shown below. Cooling water D j_______|___, Feed, F; a Side stream L, Feed, F — Feed, Fz t(_)e—Steam Fe gl Condensate B L___, The equation of the operating line in the rectification section of a column with one feed is given by: Ly D Ya=ay Koos *y,% The slope of this equation is & = <|r CEMAM3-C ae Chapter 7 UNISA EngineeringThis remains the slope of the operating line above F, if there are no side streams. The slope of the operating line between F; and F? (no F) is given by L'/V' and it intersects the top operating line at the intersection of the q - line and the top operating line. The operating line of the stripping section is again drawn from (xs; Xs) and the intersection of the second q - line and the second top operating line. Refer to the sketches" below. Saturated vapor assumed Saturated tiavid ‘withdrawn Saturated Tiquie assumed Figure 1.2: Page 389, Seader In the figure on the left F; is a saturated vapour at its dew point while F is a liquid at its bubble point. The third feed stream and side stream are not present. —F; or V = V' + F; as F; is in the vapour phase. L "Fo =L + Fe The figure on the right shows a side stream, Ls that is withdrawn as a saturated liquid between the top of the column and the feed. CEMAM3-C -15- Chapter 1 UNISA EngineeringSide streams may be withdrawn from the rectification and stripping sections as saturated vapours or saturated liquids. u L-L, andV'=V The equations of the operating lines will now be derived and the constructions will be illustrated. Refer to the sketches" below. ‘CEMAM3-C =16- ‘Chapter 1 UNISA EngineeringFigure 1.3: Page 390, Seader Figure 1.4: Page 390, Seader CEMaM3-C = Chapter 7 UNISA EngineeringA material balance over section 1 gives: Vo-1 Yo. L, x, +DXp, (7) ‘A material balance over section 2 gives: (8) (9) By equating the two equations of (9) the intersection of the two operating lines are found to be at x = Xs The intersection of y= x and y= x + x, +Dx, ——2—" occurs at Vv Lyx, +DX_ L,+D (10) Example 3” ‘A mixture of H20 and ethyl alcohol (EtOH) containing 0,16 mol fraction EtOH is continuously distilled in a tray fractionation column to give a product containing 0,77 mol fraction EtOH and a waste containing 0,02 mol fraction EtOH. It is proposed to withdraw 25 % of the EtOH in the feed as a liquid side stream with a mol fraction of 0,5 EtOH. Determine the number of theoretical trays required and the tray from which the side ‘stream should be withdrawn if the feed is a liquid at its bubble point and the reflux ratio is 2. Fe aE | YY TY aT] |] MO 7] Oe | AT | | | RY ED | | er | CEMAMS-C “18° Chapter 1 UNISA EngineeringBasis: 100 kmol feed EtOH in feed = 100 x 0,16 = 16 kmol 25 % of EtOH in side stream = 4 kmol Water in side stream = 4 kmol Thus L, = 8 kmol and xs = 0,5 Top operating line: coordinates: (0,77; 0,77) and (0; 0,77/3) = Overall balance: F=D+L+B=100=D+8+B Thus 92=D+B (1) EtOH Balance: 16 =0,77D+4+0,02B (2) With (1) and (2) itis found that B = 78,45 kmol D = 13,55 kmol L=2D=2x 13,55 = 27,1 kmol V=D+L = 13,55 + 27,1 10,65 kmol = V! L'=L-L,=27,1-8 = 18,1 kmol Second Operating Line: L,x,+Dxp _ 8x0,5+13,55%0,77 absXe — 8%05+13,55%077 _ 9 67 L,+D 8+13,55 be CEMAMS-C =19- ‘Chapter 1 UNISA Engineering y=Second coordinate where x, = 0,5 intersects the top operating line Bottom Operating Line: Coordinates (0,02; 0,02) and where x = zr = 0,16 intersects the second operating line. From the construction below one finds that the number of theoretical trays are 9 and the side stream is withdrawn from the 6" theoretical tray from the top. EXAMPLE 3 oF I 7 OVA 17, 0,77) A Xe =05 os (@; 0,287) CEMAMS-C -20- Chapter 1 UNISA EngineeringProblems 3. Two feed streams containing water and acetic acid are fed to a continuous distillation column. Feed 1 enters as a liquid at its bubble point relatively high up in the column and contains 75 kmol /h water (W) and 25 kmol/h acetic acid (A). The second feed, F. enters lower down, is 50% vapour and contains 50 kmol/h W and 50 kmol/h A. The column is operated at a reflux ratio of 3,0 Rm . The distillate contains 95 mol% W while the bottom product contains 95 mol% A. Determine the number of theoretical trays and the feed trays. x | 0055 | 053 | 125 | 206 | 207 | Si | 649 | 803 | 9594 y | oe) 133 [24 | 338 | 437 [63 [757 | 866 [972 Answer: 16; 9; 13 4. Repeat example 2 by using the relevant equations. That is the equilibrium and operating line equations. Answer: D = 38,3; S2= 61,7; xp = 0,67 5.) Determine the number of theoretical stages and the locations of the feed and side stream when 100 kmol /h of a mixture of A and B is distilled at atmospheric pressure. The mol fraction of A in the feed is 0,26. The distillate contains 95 mol % A and the bottoms 95 mol % B. The side stream is withdrawn as a liquid from the rectification section at a rate of 10 kmol /h that contains 40 mol % A. Relative volatility is 2,23 and reflux ratio is 5. Answer: 14, 6, 9-10 ‘CEMAMB-C “21 ‘Chapter 7 UNISA Engineering4.3. PONCHON - SAVARIT METHOD for TRAY TOWERS”) 1.3.1 Objective This method can be used to design distillation columns for binary, non — ideal systems where equimolar overflow is invalid. ‘The McCabe — Thiele method assumes constant molar overflow which implies that the molar latent heats are constant and that heat of mixing is negligible. For non- ideal systems where the above assumptions are not valid, energy as well as material balances and phase equilibrium relationships have to be utilized to do a proper design. This can be a very tedious process ( except that rigorous computer aided design packages are presently quite freely available ). The Ponchon — Savarit method employs a graphical method for binary non- ideal mixtures that is based on an enthalpy — composition diagram. Consider the following sketch that shows the relationship between the enthalpy of a liquid and a vapour as functions of the liquid and vapour mol fractions: Mass fraction in vapour phase v m B Dew point curve 2 3B zi c 2 ‘A Boiling curve Mass fraction in liquid phase CEMANE-C Be Chapter 7 UNISA EngineeringThe use of this diagram is discussed below. A phase is denoted by mass, composition and enthalpy and is indicated on the above diagram by a point ( for instance A,B or C). In the diagram the mass is, however, not shown. Let the mass of a phase be denoted by m, its composition by x and its enthalpy per unit mass by H. The addition of two phases A and B to give C is governed by the following balances: mat mp = me (14) My Xa + Ma Xe = Me Xo (12) ma Ha + Mp He = Mc He (13) If an amount of heat, Q is added to a mass ma of a phase to increase the enthalpy from Ha to He the following relationship holds. Q Hy +—=He: 14) Mtg He (14) CEMAM3-C 2 Chapter t UNISA EngineeringThese relationships are shown below. Mass fraction in vapour phase Mass fraction in liquid phase The addition of phases A and B is given by point C which lies on the straight line joining A and B. The difference between A and B is found by point C which lies on the extension of line AB. IFA (a liquid) and B (a vapour) are mixed C will be a mixed phase and the following relationship holds: ms _ CB —* = —— (so called lever rule m, CA y The figure” below represents a continuous distillation column. The trays are numbered from the bottom upwards. HY and H' represent the enthalpy of the vapour and liquid respectively while Qc is the heat removed in the condenser (no subcooling ) and Qs is the heat supplied by the reboiler. CEMaM3-C “24 Chapter 1 UNISA Engineering (15)Figure 1.5: Page 461C &R V,=byitD thus V, -L,., =D (16) VaYn Xquq +DXy thus V, Y, —Lay: Xau1 = DXy (7) V,HY =L,,,Hs,,=DH}+Q, thus V,HY-L,,,Ht,, =DH}+Q, (18) Let Hy =Hj+Q,/D Equation (18) thus becomes: VY ~L,,,Hi,, =DHi, (19) CEMAM3-C 25 ‘Chapter 1 UNISA EngineeringSubstitute (16) and (17)] thus. (Lass +D)yn —baesX ner = DX (20) Substitute (16) in (19) (L,.,+D)HY -L,.,H\,,= DH), Thus _L,.,HY -HS,,) = D(Hj -HY) Thus a at : (21) Equate equations (20) and (21) Thus ere - — (22) From the above follows: y, [par (23) Equation (23) is that of the operating line above the feed tray and it is the relationship between the composition of the vapour yq rising from a tray to the composition of the liquid entering a tray. CEMAM3-C -26- Chapter 1 UNISA EngineeringIt is clear from equation (22) that xs and H,are common to all the operating lines above the feed tray. These operating lines pass through a common pole N with coordinates xy and H/,. V,,L,,, and N lie on a straight line It can be shown in a similar manner that all the operating lines in the stripping section pass through a common pole, M with coordinates: Qe xy Hy, where Hi, =Hi, — Ww (24) It can be shown that F, M and N also lie on a straight line. Vpy:bm.sand M lie on another straightline Procedure to determine the number of trays Refer to the sketch” below. Concentration (x ory) Figure 1.6 ‘CEMANB-C “27 Chapter 4 UNISA Engineering11. 12. 13. The feed is a liquid at its boiling point. Point F is thus positioned at x = x on the boiling (bottom) line. Pole N is positioned at ( xs; Hi, ) where: H, = Hi +2 Pole M is located on the extension of NF where the extension cuts the vertical line at xw The vapour leaving the top plate has the same composition as xq and is shown as V; on the dew point (top ) line. The tie line connects V7 with L which gives the equilibrium composition of the liquid on plate 7. The composition of the vapour on plate 6 is found by connecting L; with pole N to obtain Ve. Leis found by using the tie line from Ve to Le, This procedure is carried on until a tie line ( in this case Ts ) gives a liquid composition that is the same as the feed ( or slightly lower) The lower pole (M) must now be used. Lsis connected with the vapour composition that was found by the intersection of the dew point line with the line MEN. V2 is found in this way. This procedure is followed until a liquid composition is found that corresponds with x The condenser duty is given by (Hi, —H} )xD = Q.. The reboiler duty is given by(Ht, Hi, )xW Minimum reflux ratio: The minimum reflux ratio is found by extending a tie line through the feed composition, x; to the point marked Nm on the figure. Because the tie lines have different slopes it can be concluded that each tray will have a different Rm. The tie line that cuts the vertical line at the highest value will be the practical Rn. ‘CEMAM3-C -28- ‘Chapter 4 UNISA EngineeringExample” 1 kg /s of a solution of ammonia in water, containing 30 mass % ammonia is distilled in a tray column to give a top product containing 99,5 mass % ammonia and a bottom product containing 10 mass % ammonia. The reflux ratio is 1,08 Rm. Determine the number of actual trays if the efficiency is 60 %. Determine also the reboiler and condenser duties. A total material and ammonia balance give: D=0,22 kg/s W=0,78 kg/s The enthalpy — composition diagram is shown below. Procedure: 1. Drawa vertical line through xs = 0,995 2. Nmis found by extending the tie line through x; = 0,3 to cut this vertical line 3 a, A lenGthN, A _ 1962-1847 length AL 1547 4. NA= 1,08 Nm A = 1,08 x 405, 5. N has an ordinate of 437 + 1547 = 1984 and abscissa of 0,995. 6. 7. Mis found by extending line NF to cut the vertical line at xy = 0,1 The procedure described above is followed to obtain 5+ theoretical trays and 5/0,6 = 8,33 say 9 actual trays Se = 562 ~(-209)=791 Qa = 791 x 0,78 = 617 KW 9. Q, =length NLxD = (1984-296 )x0,22= 372 kW CEMaM3-C -29- Chapter t UNISA EngineeringEnthalpy (kilkg solution) r _ - a 200 ee | A L 1 Ih-300 oO 0030 O40 8D —0.70 08D FBT 1.00 ‘Mass fraction of ammonia Figure 1.7 Problems 6". 100 kg/h of a methanol — water mixture that contains 50 mass % methanol (MeOH) is fed to continuous tray distillation column at the bubble point of the feed at 1,013 bar (abs). The distillate should contain 98 mass % MeOH and the bottom 96 mass % water. Use the data below to determine: CEM4M3-C ~30- Chapier 1 UNISA Engineering(a) the minimum reflux ratio, Rm (b) _ the number of ideal trays with R = 1,2 Rne (c) _ the reboiler and condenser duty (d) calculate Hy and H, at MeOH mass fractions of 0 ; 0,542 using the steam tables and the specific heat and latent heat of vapourisation of MeOH. Use 0°C as reference temperature ( same as the data in the table ). Answer: Rm = 0,982 ; 9; Q, = 36,7 KW; Qe = 38,8 kW Enthalpy above 0°C kulkg Mass % Saturated vapour Saturated liquid yorx TC Hy TC He 0 100 2672 100 418 0,085 98,9 2547 92,8 380 0,165 97,7 2400 877 336 0,239 96,2 2330 84,4 330 0,308 94,8 2230 81,7 310 0,432 91,6 2050 78 275 0,542 88,2 1900 75,3 250 0,64 84,9 1760 73,4 230 0,73 80,9 1640 71,2 210 0,806 76,6 1530 69,3 200 0,877 72,2 1430 67.6 185 0,941 68,1 1340 66 183 1,0 645 1260 64,5 165 CEMaMS-C 3 Chapter 1 UNISA EngineeringVapour — Liquid Equilibrium Data Mass % MeOH in Liquid 0 3,5 69 10,2 13,4 16,4 23,9 30,8 43,2 54,2 64,0 72,7 87.8 94,1 97,1 100 Vapour 0 21.6 34,7 43,7 50,5 56,1 65,5 71,0 78,4 82,7 86,2 89,3 95,0 97,6 98,8 100 Boiling point, °C 100 96,4 93,5 91,2 89,3 87,7 84,4 817 78 75,3 73,1 71,2 67.6 66,0 65,0 64,5 Heat capacity of MeOH is 2,77 kJ/kg K, its latent heat of vapourization is 1047 kJ/k and its heat of solution is — 95,5 ki/kg, H. = m Cp At + heat of solution x mass of MeOH. CEMaM3-C UNISA Ba Chapter 1 EngineeringCHAPTER 2 MULTICOMPONENT DISTILLATION CONTENTS 2.1 LEARNING OUTCOMES. 21.1 Objectives. 2.1.2 Required Specifications (3). 2.1.3 Multicomponent Flash, Bubble and Dew Points “.. 2.1.4 Isothermal Flash Calculation... 2.1.5 Adiabatic Flash Calculation. 2.1.6 Key components. 2.1.7 Minimum Reflux Ratio 2.1.8 — Colburn’s Method for Minimum Reflux ®.......csseeusee 43 2.1.9 Underwood's Method for Rim... 2.2 SHORT CuT METHODS 7 2.2.1 Number of Trays ( Lewis- Matheson )?®9)... 2.2.2 Feed Tray Location ® 223 Recap. 223 Recap. 224 — Evaluation. CEM4M3-C -33- Chapter 2 UNISA Engineering2.1. LEARNING OUTCOMES After completion of this section the student should be able to do the following. * Be able to determine the dew points and bubble points, at given pressures, of mixtures of vapours and liquids respectively. * Be able to do an isothermal flash calculation * Be able to determine the minimum reflux ratio of multicomponent mixtures * Be able to use the Lewis — Matheson method to determine the number of theoretical trays required to achieve a given separation * Be able to determine the feed tray location for the separation of multicomponent mixtures. 2.1.1 Objectives Approximate methods to solve multicomponent, multistage distillation problems will be discussed. This will be preceded by a discussion of the bubble and dew points of mixtures and a method is given that enables the student to do an isothermal flash calculation. 2.1.2 Required Specifications (3) The following must be established to design a distillation column: 1. Temperature, pressure, composition and flow rate of the feed. 2. Pressure at which the distillation must be carried out. This is frequently determined by the temperature of the cooling medium that will be used in the condenser. 3. The feed should be introduced at the optimum feed tray location 4, Heat losses are assumed to be negligible. CEMAN3-C “34 Chapter 2 UNISA EngineeringIf the above items are established only three of the following can be specified. Total number of trays. Reflux ratio. Ratio of vapour to bottom product produced in the reboiler (reboil rate ). Concentration of one component (maximum two) in one product. Cr Split of a component between the distillate and the bottoms (maximum of two). 6. _ Ratio of distillate to bottoms. In the figure below an algorithm is provided that enables one to determine the operating pressure at which a distillation must be carried out. 49°C is selected as a reference temperature as this is about the maximum temperature at which cooling water should be used. Above this temperature scaling can become excessive. A AP of 0 to 14 k Pa is allowed for the condenser and a column A P of 35 k Pa is selected initially unless more detailed information is available. If the number of trays is known a AP of 0,7 kPa per tray is allowed for operating pressures above atmospheric and 0,35 kPa per tray for vacuum operations. ‘CEMAM3-C 35 Chapter 2 UNISA EngineeringDistitate and bottoms Compositions known oF estimated Calculate bubbie-point | Po-<215 Psia (1.48 Mpa) Pressure (Ps) festa ‘at 120°F (48°) Uso total condenser (eset oto 30 psia Po < 30 psa) Po> 215 sia Po < 365 pala Calculate dew-point Ge2mpa) Estate Calculate bubbie-pont | ettial temperature pressure (Po) of >| Eotoms a| temperature (Ta) of 5 distil a 120°F Uso part ns bottoms at Py condenser Te bottoms Po> 365 psia decomposition or etical temperture Choose a reigerant so nares 25 0 operate paral ee conensar at 415 psia ee) (2.85 Mpa) Figure 2.1 The next figure “” demonstrates the operation of different types of condensers while the following one “) demonstrates reboiler setups. Vapor perer cma distllate Liquid i distilate 0) () Figure 2.2 CEMAM3-C 36- Chapter 2 UNISA EngineeringCondensate }--Steam F Bottoms ondensate [:}-+Condensate (c) Figures 2.3 2.1.3 Multicomponent Flash, Bubble and Dew Points A flash is a single stage equilibrium distillation that is carried out in a simple vessel that allows the vapour and liquid to separate ideally. It is normally assumed that the vapour does not entrain any liquid droplets and that the liquid does not contain any vapour pockets. CEMANS-C “aT ‘Chapter 2 UNISA EngineeringThe following sketch “ shows a liquid feed that is heated under pressure and then allowed to flash adiabatically by lowering the pressure across the valve. Also shown is a vapour feed that is partially condensed before it enters the flash drum. Vy Yi hy Fz, He T Pe ~ Put Lx,H, Vi yuHy PT, Fz, He Te Pe PUT LX,H, Figure 2.4 2.1.4 Isothermal Flash Calculation The following is the Rachford — Rice procedure that can be used for these calculations. 1. TL=Tv 2 PL=Py CEM4M3-C -38- Chapter 2 UNISA Engineering3. Solve f(¥)= ¥ 2(-K) iewk 1) -° where Y=V/F and Kj =Kj (Ty, Py) 4.0 V=FY 8 Q=hyV +h L-heF The procedure is as follows: 1. Specify the temperature and pressure of the liquid and vapour or if possible calculate one if the other one is given. 2. Obtain the Ki's from a source such as the one given at the end of the distillation section 3. Assume a value of that is between 0 and 1,0. A first assumption of 0,5 is normally acceptable. This value is called Y and /(¥) can thus be calculated. 4. The next value of ¥’, called ¥“*, can be calculated by using the following equations: ype) =) CEMAM3-C “39° ‘Chapter 2 UNISA Engineeringwhere 1 )- ae mi ype) yt yar — as close 5. This procedure is repeated until the absolute value of to zero as the designer requires. Example The following stream is flashed isothermally at 3400 kPa (abs) and 38°C. Determine the compositions and flow rates of the vapour and liquid. kmol / h Ki Zi He 909 80 0,435 CH, 909 10 0,435, Benzene 227 0,01 0,109 Toluene = 45 0,004 0,021 Total 2090 1,000 Assume ¥")= 0,5 0,109x0,99 0,021x0,996 4+05x(-099) 1+05x(-0,996) 14+0,5x9 0.435x(-9)* 0109x(099 0,021x(0.996 F gs015 “[r0sxof "[1+05x(-099)F [1+(-0.996)F 5 (18049) _o 5009 33215 CEMaNB-C ~40- Chapter 2 UNISA Engineeringwk)_p _ 08929-0,5 yg 07888 This procedure is now repeated with the new ¥ of ¥* =0,8929 K Aw") FeO) ew yea peo ph a 1 7304933215 [0,5 0,8929__| 0,7858 2 0,2053 [10,5981 —[0,8929 [0.8735 _—| -0,0217 3 0,0261 80768 | 0,8735 | 0,8703 _| -0,00366 4 0,00265[7,7612__|0,8703 | 0,870 =0,00034 L xi vi He 0,00624 0,49907 CH 0,04926 0,4926 Benzene 0,786 0,00786 Toluene 0,1575 0,00063 Total 0,999 1,00016 V = 0,87 x 2090 = 1818,3 k mol /h L = 2090 - 1818,3 = 271,7 k mol/h 2.1.5 Adiabatic Flash Calculation The flash temperature, Ty is guessed. , V,L, x,y are then calculated similarly to the isothermal calculation. A heat balance is then carried out by using the equation Q=hyW +h L—he F. Convergence is attained when Q = 0. Bubble and Dew Points Pure liquids boil at a certain temperature at a given pressure. When a liquid that contains a number of components boils at a given pressure this temperature is referred to as the bubble point. The bubble point is the temperature where the liquid starts to boil at any given pressure. The bubble point is determined by the equation: 5x, K,=10 a CEMAMS-C “a Chapter 2 UNISA EngineeringThe dew point of a vapour that contains more than one component is that temperature where the first droplet of liquid will form if the vapour is cooled at a given pressure. The dew point is determined by the equation: Example Determine the bubble point at 690 kPa (abs) of a liquid with the following composition. Let the first guess be 71°C (160°F). x Ki n-C,4 0,7992 1,0 i-Cs 0,1044 0,51 n-Cs 0,0648 0,38 n-Cs 0,0319 0,14 Dx, K, =0,7992 x10 + 0,104 1x 0,5 + 0,0648 x 0,38 + 0,0319 x0,14 =0,8814 #10 Try T = 170°F (76,7°C) The Kis are 1,13; 0,6; 0,5; and 0,18 respectively. Dx, K, =0,7992 x 113 +0,1041x 0,6 + 0,0648 x0,5 + 0,0319x 0,18 =10037 =10 2.4.6 Key components Lower boiling compounds are called light while higher boiling ones are called heavy. The light key is that component that is present in the bottoms in important amounts. If there are components lighter than the light key in the bottoms it will only be in small CEMAM3-C 42 Chapter 2 UNISA Engineeringamounts. If all components are present in the bottoms in significant amounts then the lowest boiling component is the light key. The heavy key is that component that is present in the distillate in important amounts. If there are components heavier than the heavy key in the distillate it will only be in small amounts. if all components are present in the distillate in significant amounts then the highest boiling component is the heavy key. The relative volatility is always calculated relative to the heavy key. Thus Ky a,=—) Kn 2.1.7. Minimum Reflux Ratio This is the smallest reflux ratio that requires an infinite number of stages to separate the key components. It will be recalled that for a binary system the minimum reflux ratio, Rm is found by drawing a top operating line from (xs, xs) to the co-ordinate where the q — line intersects the equilibrium curve. This constitutes a so called pinch which implies that a separation is impossible in this pinch zone. This also holds for the separation of key components when a multi-component mixture is distilled. In the distillation of multi-component mixtures pinch zones can be found not only at the feed tray but also above or below it in the stripping section. 2.1.8 Colburn's Method for Minimum Reflux Let A and B the light and heavy key components of a multicomponent mixture. Rim is given by: CEMAM3-C 4 Chapter 2, UNISA Engineering (1)where Xyq and X,, are the top and pinch compositions of the light key Xye and X,, are the top and pinch compositions of the heavy key a9 is the volatility of the light key relative to the heavy key The pinch compositions are only known in the special cases when the pinch and the feed compositions coincide. The following approximation is used. 1 Xqq (approximately)= raynzax (2) q fn on Xj8 (APPTOX. (3) where r, __ is the estimated ratio of the key components on the feed plate. For a liquid feed at its bubble point, r, equals the ratio of the key components in the feed. Otherwise f, is the ratio of the key components in the liquid part of the feed X;,__ is the mol fraction of each component in the liquid portion of the feed heavier than the heavy key «is the volatility of the component relative to the heavy key With this value of Rr, equation (1) can be rearranged to give the mol fractions of all the light components in the upper pinch as: = Xa = a (c-MRa +a (Xp /Xn8) (4-1), as x, is normally very small (4) ‘CEMAM3-C “4a Chapter 2 UNISA EngineeringA similar condition occurs in the stripping section and the concentration of all components heavier than the heavy key is given by: Ona Xw Ong Xw © (Gan 2) Lin /W)+ aKa Xma) Cotas a) Lm /W) (8) x, is normally low and the above equation can be approximated as shown. x,, and x,, are the compositions of a given heavy component in the pinch and in the bottoms. Xna and X,,, are the compositions of the light key component at the pinch and in the bottoms, L,, /W is the molar ratio of the liquid in the stripping section and the bottoms. aaa is the volatility of the light key relative to the heavy key. ais the volatility of the component relative to the heavy key. This method gives an empirical relation between the compositions at the pinches for the condition of minimum reflux. This allows the assumed value of Rm to be checked. This relation is given by: Tm ul —- 6) To (1-2 bya J=25%) where © Tmis the ratio of the light key to the heavy key in the stripping pinch. * tris the ratio of the light key to the heavy key in the rectification pinch. * b,aX,, is the sum of b,, «x, for all the components heavier than the heavy key in the stripping pinch. ‘CEMAMB-C “45 Chapter 2 UNISA Engineering* b,x, is the sum of b,x, for all components lighter than the light key in the rectifying pinch. * bm, by are factors shown in the following diagrams Figure 2.5 2.1.9 Underwood's Method for Rm When the relative volatilities remain constant the following method can be used to determine Rr. he Xe 7) a,-8 G,-0 a,-0 and Oa Xen , Fe Xp , Xe Xe O,-0 Gy-0 a, -0 (8) where Xj4.Xe 1c/Xan Xap sXao @t@ are the mol fractions of components A,B,C etc., in the feed and distillate. A is the light key and B the heavy key q is the ratio of the heat required to vapourise 1 mol of the feed to the molar latent heat of vapourisation of the feed CEMAM3-C -46- Chapter 2, UNISA Engineeringa, Op, ac etc., are the volatilities with respect to the least volatile component. @ is the root of equation (7) which lies between a, and ap. Note: If one component has a relative volatility falling between those of the light and heavy keys, it is necessary to solve for two values of 0. Example ® Use Underwood's method to determine Rm for the following situation. A liquid feed at its bubble point contains 40 kmol hexane, 35 kmol heptane and 25 kmol octane. The distillate contains all the hexane, 34 kmol heptane and 1 kmol octane. xt xa Xw a Hexane_ 0,40 0,534 0 2,70 Heptane 0,35 0,453 0,04 2,22 Octane 0,25 0,013 0,96 1,0 | The light key is heptane and the heavy key is octane and q = 1 Use equation (7). 27x04 | 2,22x0,35 1x0,25 27-0 © 222-0 — 1-0 ° The required value of @ must lie between ag and om thus. 1,0<0< 2,22 Solve the equation by trial and error. With @ = 1,15, the left hand side of the equation is - 0,243. CEMANB-C “47 Chapter 2 UNISA EngineeringWith @ = 1,17, the left hand side of the equation is ~ 0,024. Substitute 6 = 1,17 in equation (8) thus 270534 , 222x0,453 , 1x0,013 270-117 © 222-117 © 1-117 Thus Rm = 0,827 Example ® A mixture of C4 to C7 hydrocarbons must be distilled in a continuous distillation column. The compositions of the streams are shown below. The feed is a liquid at its bubble point of 376 K. The temperature at the top is 343 K and that at the bottom is 416K. Determine Rm using Colbum’s method. Feed,kmol | Feed, | Dist,kmol, [xa Bott, [XW kmol C.K | 40 oF 39 0975 | 1 0,017 Cs, HK | 23 0,23 1 0,025 | 22 0,367 Cs 7 0,47 17 0,283 Cr [20 0,20 20 0,333 Total | 100 1,0 40 T0 60 1.0 Kat 376K @ Ce 1,78 2,25 Cs 0,79 1,0 Cs 0,38 0,48 Cs 0,185 0,23, ‘Assumption: the keys are all in the liquid phase. Thus r= 0,4/ 0,23 = 1,74. CEMANB-C 48 Chapter 2 UNISA Engineering1.74 - - fh = = From equation (2): Xone Sax,) 274x(1=0082+0046) ~ 07 Xop = 0,562 / 1,74 = 0,323 R, 0562 0323, This is the first approximation and can be improved by using equations (4), (5) and (6) and the figures on page 4. The procedure to be followed is : 1. 2. Calculate the liquid and vapour flow rates in the column. Use equation (4) to calculate x, which are the mol fractions of the components lighter than the heavy key. Calculate the bubble point temperature with these x, values such that Yy=DK.x, =10 The bubble point temperature of the upper pinch can be approximated by Ta = Ttop + 0,33 ( Toottoms ~ Top ) Calculate r with these x ,'s Use these x, values to caloulate a bubble point temperature - if the bubble point equation is not satisfied assume another temperature that is used to calculate another set of x, ‘s There are no components in the lower pinch that are lighter than the light key. The simplified form of equation (5) can thus be used to determine Xm. The bubble point temperature of the lower pinch is initially approximated by Tm = Trop + 0,67 (Thotioms ~ Tiop). Use this temperature and the xn's calculated in (6) to determine if the approximated temperature is correct. If not assume another temperature and recalculate the xm ‘s. Redo a bubblepoint calculation to check the correctness of the new Xm 's. Calculate tm, fn and tnt. Compare this ratio with the right hand side of equation (5). If not more or less equal assume another value of Rm and repeat the above calculations until acceptable agreement is found. CEMAM3-C ~49- ‘Chapter 2 UNISA Engineering2.2. Short Cut Methods 2.2.1. Number of Trays ( Lewis- Matheson )?*9) This method assumes constant liquid/vapour ratios in the rectification and stripping section. Operating lines are obtained by striking material balances over the rectification and stripping sections (similar to the McCabe-Thiele method). For multicomponent mixtures operating lines must be constructed for each component. Thus for the rectification section : y, (9) kn V, Equation (9) gives the composition of the vapour rising to a tray in the rectification Zone in terms of the composition of the liquid leaving the tray. The operating line for the stripping section is given by: (10) Equation (10) gives the composition of the vapour rising to a tray in the stripping zone in terms of the composition of the liquid leaving the tray. Equilibrium relationships are also required with equations (9) and (10) in order to carry out these calculations. Let a mixture consist of components A, B, C and D, Let the mol fractions in the liquid phase be denoted by Xa .xs , Xc and xp and in the vapour by ya Ja Vo and yo - Then: Yat Ye+yo+Yo=1 divide by ye Ya Yee yYo 1 an Ye Ye Ys Ye Yo CEMAM3-C -50- Chapter 2 UNISA EngineeringAlso Ya =KaXq and yp =Ky xX, Thus og“ substitute in (11) Xe Xs Xe Xo Xp _1 Ging 28 + dlgg 22 + ogg X2 + ctgg 2 => 12) oF Fan 2 + 68 5° + B00 ge (12) 5 thus E (a0 x,)=72 (13) Thus y, = G9 Xo x And Yes) and Yo" Stores) (14) ne Xn ae Xa It can be shown in a similar manner that: 1 1 Xp= ex, = Matta, = Yelee ote, (15) Ya Ya Ya r-* = = One Ons Ons Example The vapour from the top tray of a distillation column has the composition shown below. The column operates with a reflux ratio of 1,5. It can be assumed that D = 100 kmol/h. CEMAMS-C “51 Chapter 2 UNISA Engineeringmol % « n- Butane, Cy 4 41,2 [n= pentane, Cs (15, 15,9 [n—hexane, Cs 50 62 n- heptane, C7 28 2,47 n= octane, Ce 3 70 Calculate the liquid composition of the two top trays. The liquid leaving the top tray is in equilibrium with the overhead vapour — use equation (15). sia _ 004 015 , 05 , 028 003 Gy 442 159 62 247° 10 =0,2344 Xes = (0,04 / 41,2)/0,2344 = 4,14 x 10° Xes = (0,15 / 15,9)/0,2344 = 0,0402 Xes = (0,5 / 6,2)/0,2344 = 0,344 Xe7 = (0,28 / 2,47)/0,2344 = 0,484 Xea = (0,03 / 1)/0,2344 = 0,128 =x = 1,000834 The top operating line is given by: R Ey So —* thi Ra RS CEMANB-C ~52- Chapter 2 UNISA Engineeringaa) Xe Yo = pg %oe *Zg = 08%nes+O4X, @ The composition of the vapour leaving the second tray is found by using equation (a). Yca = 0,6 x 0,00414 + 0,4 x 0,04 = 0.0185 Yes = 0,6 x 0,0402 + 0,4 x 0,15 = 0,0841 Yes = 0,6 x 0,344 + 0,4 x 0,5 = 0,4064 Yer = 0,6 x 0,484 + 0,4 x 0,28 = 0,4024 Yes = 0,6 x 0,128 + 0,4 x 0,03 = 0,0918 y= 1,0032 0,0185 |, 0,0841 04064 0,4024 _ “a2 159 + 62 + 247 +0,0918=0,32594 Xo4 = 4,49 x 10 */ 0,32594 = 0,00138 xcs = 0,00529/ 0,32594 = 0,0162 Xcs = 0,0655 / 0,32594 = 0,2009 Xe7 = 0,1629 / 0,32594 = 0,4998 Xcs = 0,282 =x = 1,00028 CEMANB-C “53 Chapter 2 UNISA EngineeringExample A mixture consisting of 0,4 mol fraction ethylene, 0,1 ethane and 0,5 propane is fed at its bubble point to a distillation column that is operated with a reflux ratio of 2. The top product contains 0,833 mol fraction ethylene, 0,137 ethane and 0,03 propane. Determine the number of theoretical trays above the feed tray. The relative volatilities can be assumed to remain constant at 4,5 for ethylene, 3 for ethane and 1,0 for propane. Denote ethylene by A, ethane by B and propane by C. As previously: x, = , Yeltse y= Ya z Onc And the operating line: yo = 5° 5X ne + 667 x,,,+0,333%, FE Top tray (1) Yq [ge =0833/4,5=0,1851 Y¥g /t4gc =0,137/3=0,04567 Yc /ctgg =0,03/1=0,03 Lp lg¢ = 0.26077 Xa = 0,1851 / 0,26077 = 0,7098 Xe = 0,04567 / 0,26077 = 0,1751 X oF 0,03 / 0,26077 = 0,115 Total = 0,9999, Tray 2 Yn = 0,667 Xn+ 1 +0,333 xq Ya = 0,667 x 0,7098 + 0,333 x 0,833 = 0,7508 Ya = 0,667 x 0,1751 + 0,333 x 0,137 = 0,1624 CEMAM3-C Chapter 2. UNISA EngineeringYe = 0,667 x 0,115 + 0,333 x 0,03 = 0,0867 Total = 0,9999 ya! ctac = 0,7508 / 4,5 = 0,1668 ye / ogc = 0,1624/3 = 0544 Yc / acc = 0,0867 / 1 = 0,0867 Zyal aac = 0,3082 Xa = 0,1688 / 0,3082 = 0,547 Xe = 0,0541 / 0,3082 = 0,1755 Xc = 0,0867 / 0,3082 = 0,2813 Total = 1,0045 Tray 3 Ina similar manner it is found that: Ya = 0,6427 Ye = 0,1626 Yo = 0,1976 Total = 1,0029 Xa = 0,3619 Xa = 0,1373 Xc = 0,5000 CEMAMS-C “55 UNISA ‘Chapter 2 EngineeringTotal 9992 Tray 4 Ya = 0,5188 Ya = 0,137 Yo = 0,3435 Total 0.9993 Xa = 02285 Xp = 0,0905 Xc = 0,6809 Total = 2999 The liquid compositions of trays 3 and 4 can be compared with the feed composition. It can be concluded that the composition of tray 3 is closest to that of the feed and this tray will thus be selected as the feed tray. 2.2.2 Feed Tray Location © This method also assumes constant liquid/vapour ratios in the rectification and stripping sections. A further assumption is that the optimum feed tray location occurs at the intersection of the operating lines. The operating lines are given by: Ly D La Go Xoo He AND Vn = OX Yo /, V, Vn wm Vy Ww CEMAMS-C -6- Chapter 2 UNISA EngineeringThe first equation can be rearranged as: D Xnet=Yn net a Ls By omitting the tray numbers this equation can be written for each key as follows: v_D v_D a Vex Ep ine 28 Kae = Yin EP Xs Rearrange these equations. Mux yp ¥ie¢ ang = Yan y_p neo XK Xk XK Xan By equating these two equations and rearranging it is found that: x, D D Yin = 2| nc Bone] + Bie (16) HK Ina similar manner can it be shown that for the stripping section: xy w Ww Yu = 8) You += Xen | Xu (17) Xen Vv Vv At the intersection of the operating lines yix, Yu and Xx / Xu« are the same from (16) and (17) and the right hand side of these equations can be equated. INV It then follows that (2) — Wu /V+D Xx na Xs Jeversection Wey /V+D Xyeg /V An overall LK balance gives: FX, 1x =DXix.6+WXixw (19) An overall balance can be struck over the feed plate by referring to the sketch below. ‘CEMANB-C “57 Chapter 2 UNISA EngineeringF4L Vm = V then Also Vm-V =F (q-1) Where q = heat required to vapourise 1 mol feed / latent heat of feed. Manipulation of (19) yields the following: Wri , OXus _ FXucr V V, Vn Vm WV Drea Fug WV DF(Q-1)x, V+F(q-1) VV VV VnV Wve .oxg,[ + — 4 la=1)] _ VPs DECOM Vn V+F(q-1) V,V (V+F(q-1))V The second term on the left of (22) simplifies to: and (22) thus becomes: Wye ,DXxs VEX +DF(A=1) ice ; - hn Vv lV +F(q-1)]V (20) (21) (22) (23) CEMAM3-C “58 UNISA Chapter 2 EngineeringA similar equation can be obtained for the heavy key. Thus: Wr cn OX nea _ VEX rt DE (GAD (24) Vu 7 V+F(@—t]V (24) Combine equations (23) and (24) with (18): Xue _ VE Xu: DF (Q—1)Xix (25) Xi Jetersecton VFXics DF (Q- Xu ButV=L+D andV/D=L/D+1=R +1 substitute in (25) Ce] erate 2) Xie Jyuersecion R* DK: A= DXrs The feed tray location is then given by: fel Celta} ” Xe Jaa Xram Jiter section Xn Example This example is based on one given by Treybal ®). Determine the feed tray for R = 0,8 given that D = 0,38 kmol. The mol fraction of the vapour leaving the top tray is: C; = 0,0789; C 2 = 0,1842; Cs (LK) = 0,3870; C4 = 0,3420; Cs ( HK) = 0,0079. The following temperature profile can be assumed: tray 4 (top ) = 58°C; tray 2= 65; tray 3 = 70; tray 4 = 74; tray 5 = 78; tray 6 = 82; tray 7 = 86°C. The mol fractions of the LK and HK in the feed are 0,15 and 0,3 respectively. a= 067. CEMAM3-C “59- Chapter 2 UNISA EngineeringThe K — values are given in the following graph. Use equation (26). xu = 18x0,15-0,33 x0,387_ Imesecton b8X0,3-0,33x0,0079 = 0,2648 Xu it R x, Top operating lines are: y, ==> Xn. ‘op operating lines are: ¥q=— Xn + BG 4 -0,4444x,,, +0,5555x, CEMAM3-C 7 UNISA Chapter 2 EngineeringThus for C Yq 70,4444 x,,, +0,0438 Ce Yn =0,4444x,.,+0,1023 Cs Yq =0,4444x,,,+0,.2149 Ca Yq =0,4444 x,,, +0,1899 Cs Yq 70,4444 x,,, +0,00439 The equilibrium liquid compositions are determined with equation (15). Top plate (no. 1) T = 58°C K a vi x Cy 19,2 96 0,0789 0,0055 Ce 5,0 25 01842 0,0494 C3 2.2 1 0,387 0.23614 Ca 07 35 0,342 0,66686 Cs 0,2 1,0 0,0079 0,05303 Total 1,000 701 x1 is found as follows by using equation (15): Ya _ 0,0789 01842 0,387 | 0,342 nan “eto 7 35. +0,0079 =0,000822 + 0,00737 + 0,03518 +0,097711+0 = 0,14898 For C; x1 is 0,000822 / 0,14898 = 0,0055 CEMaM3-C “61 Chapter 2 UNISA EngineeringPlate 2; T = 65°C yz is found by using the operating equations: 2 0,4444 x 0,0055 +0,0438 = 0,0462 for Cy K a x yz x Cr 198 76,1 0,0055 0.0462 00024 [C2 5.2 20 0,0494 0,1242 0,0249 Cs 24 92 023614 ——*| 0.3198 0.1395 Ca 0,78 27 0,60686 ‘| 0,4862 07214 Cs 0.26 10 005303 ‘| 0,0279 01178 Total 1,01 71,0043 7,000 Plate 3; T = 70°C K a x2 Ys x Cr 20,2 67,3 0,0024 | 0,0449—_-| 0,00245 C 54 8 00249 —*([0,1784 ‘(0.0287 C 25 8,33 01395 [0.2769 | 0.1227 Cs 0,86 2,87 07214 |0,5105 ‘| 06535 Cs 03 10 01118 | 0,0547 0.1988 Total 09998 | 0,9999 Plate 4; T = 74°C K a x3 ya x Ci 20,6 60.6 0,00245 (0.0449 ~~ 0,0024 Ce 56 165 0,0231 01126 0.0278 Cs 27 79 0.1227 0,2692 0.4092 7 0,92 27 0,6535 ‘| 0,4801 0.5713 Cs 0,34 10 0,1988 —*| 0,0927_——*| 0.2978 Total 0,9999 | 0,9995 70025 CEM4M3-C -62- ‘Chapter 2 UNISA EngineeringPlate 5; T = 78°C K a x ¥s Xs Ci 21,0 56,7 00024 {00,0448 0,028 CG 58 157 00218 [0,112 0.0207 Cs 28 76 0,092 —*|0,2634 | 0,006 Cs [1.0 27 Os7is [04438 [0.4784 Cs [0.37 10 0.2978 | 0.1367 ‘| 0,3978 Total | 1,0025 1,0007 0,9998 Plate 6; T = 82°C. K a Xs Yo Xs Cc 213 51,9 0,0023 0,0448 0,0023 Ce 60 14.6 00207 0.1114 0,02 C3 (29 71 0,1006 0,2596 0,0936 Ce 1,05 26 0,4784 0,4025 0,4073 Cs 0,41 1,0 0,3978 0,1812 0,4767 Total 0,9998 0,9995, 0,9999 Tray 5: xix / xx = 0,1006 / 0,3978 = 0,2529 Tray 6: xix / XHK = 0,0936 / 0,4767 = 0,1963 AS (Xux / Xi )intersecton = 0,2648 which is higher than the value of this ratio on plate 5 the feed tray is plate 5. CEMaN3-C -63- Chapter 2 UNISA Engineering2.2.3 Recap In this section the student has been enabled to determine the dew points and bubble points of multicomponent vapour and liquid mixtures. An algorithm is given that can be used to determine the operating pressures of distillation columns. A method is also presented that can be used to do an isothermal equilibrium flash calculation for multicomponent mixtures. This calculation should preferably done on a spreadsheet by using for instance Excel. ‘Two methods are given that can be used to determine the minimum reflux ratio for the separation of multicomponent mixtures. The Lewis — Matheson method is a short — cut method that can be used to determine the number of theoretical trays required to achieve certain separations of multicomponent mixtures by distillation. A short ~ cut method is presented that can be used to determine the feed tray location of a distillation column that has to separate a multicomponent mixture. 2.2.4 Evaluation Problem 1 ‘An equimolar mixture of ethane, propane, n — butane and n — pentane is flashed isothermally at 65,5°C (150°F) and 14,12 bar (abs) (205 psia). Determine the amounts of vapour and liquid and the compositions. Use Excel to produce a spreadsheet Answer: VIF = 0,19866; yc2 = 0,5567 ; ycs = 0,2792 ; yoa = 0.1161 ; Yes 0,048 ; xc2 = 0,174 ; Xc3 = 0,2428 ; Xc4 = 0,2832 ; CEMANS-C ‘Chapter 2 UNISA EngineeringProblem 2 Determine the dew point at 400 psia (2 760 k Pa ) of the following vapour. k mol/ h ethane 72,5 n-hexane 20 n-heptane 15 Answer: Approximately 350°F (177°C) Problem 3 A mixture of 60,30, and 10 mol % benzene, toluene and xylene respectively is fed at its bubble point to a continuous tray distillation column. The distillate contains 90 mol % benzene, and 1 mol % xylene. The bottom product contains 70 mol % toluene and 2 mol % benzene. Determine: (a) the minimum reflux ratio using Underwood's method (b) the feed tray location with R = 8 Rn (c) _ the vapour and liquid compositions of all the trays down to the feed tray with R=8Rn. The relative volatility of benzene to toluene is 2,4 and that of xylene to toluene is 0,45. It can be assumed that these relative volatilities remain constant throughout the column. Answer: (a) (b) With R = 4 feed tray is number 2 from the top CEMAN3-C “65 Chapter 2 UNISA Engineering(c) Mi x Ye Xe Ys x3 B 0,9 0,7697 0,7958 0,5720 0,6376 0,3424 T 0,09 0,1847 0,1658 0,2808 0,2426 0,3149 x 0,01 0,0456 0,0384 0,1471 0,1197 0,3426 Total 1,00 1,000 1,000 0,9999 0,9999 0,9999 CEMAM3-C Chapter 2 UNISA EngineeringJd equilibria, ~260 to —100°P. [From 8-7. Hadden and H.G, Grayson, nd Petrol. Refer, 40, 207 (Sept. 1961), with permission | Figure 2.6 CEM4M3-C “67- Chapter 2 UNISA EngineeringSSS Figure 2.7 Chapter 2 Engineering “68- CEMANS-C UNISACHAPTER 3 RIGOROUS DISTILLATION DESIGN METHOD: CONTENTS 3.1 LEARNING OUTCOMES. 3.2 ARIGOROuS DESIGN METHOD 71 3.3 TRAY EFFICIENCY 3.4 RECAP... 3.5 EVALUATIO! CEMAM3-C -69- Chapter 3 UNISA Engineering3.1. LEARNING OUTCOMES: After completion of this section the student should be able to: * Do at least a first iteration of a multi-component distilation design using the rigorous method that is discussed here. The calculation should be done by using a spread sheet. Excel is ideally suitable for this calculation. * Calculate the bubble points, based on the calculated compositions, by using the method given earlier. * Calculate the overall efficiency of a tray. CEMAN3-C ~=70- ‘Chapter 3 UNISA Engineering3.2 A Rigorous Design Method The methods that have been discussed, although very useful, cannot be used for final design purposes. They can, however, be used to determine initial values for the rigorous methods. Consider the following sketch" of a general equilibrium stage. Vapor side Liquid from stage above wi Xs byes Tr Pos Head i L Fea =F cu Heat transfer pe—s| stegey Layyy———> F a 5, (+) if from stage Hy (ito stage Ts Vawve Pr v Yuet X: net has my 7 Bet », Liquid side stream |_ baud ste Vp 4 Vapor rom stage Below L Figure 3.1 CEM4M3-C_ 7 ‘Chapter 3 UNISA EngineeringThe following equations are valid for each equilibrium stage. 1. Material balances (M equations): My by Xa t Vier Viner HF) Zp LU, x, — (Ye Wy)y, =0 (1) 2. Phase equilibrium relations (E equations) E,=y,-K,,x,=0 @) 3. Mol fraction summations (S equations) © ,)=dyu- (3) c (8), =L%,)- 10-0 (4) a 4. Energy balance (H equation) Hy=byshy,+Vjahy,, Fhe -t, +U,)h,, -y, +W,)hy, -Q,=0 (6) 5. Total material balance — can be used instead of equations (3) and (4). i Vt (Fn Un Wr )-V, 6) Consider now the general countercurrent cascade of N stages shown below. CEM4M3-C “72 "Chapter 3 UNISA EngineeringF; ———_—> Ve W: ~@——_| es Vs Ws Us Ww, Ua a F, >| Stage) L- AAA —> & Verh u cal neet Une Ws —<——— Lae Fu; ——+-_> | Stage NT} AAA —> Qu Ww Uns Ww <——-4 Lue Fy —____-»+| Stagen | —AAAy—> On ‘, Figure 3.2 The following calculations are carried out to solve a given problem: Aj Xr By XY HE Xia (7) Where: CEMAN3-C 7 Chapter 3. UNISA EngineeringA,=V,+ 51 (Fy Wy Un)“, 25i5N @) [Mt BFW Ua) Wo +(VeW, V6, 536 ® CaViKija ) 1SjsN- (10) -Fz,, 1sjsN (11) In the above equations the subscript i has been deleted from the B, C, and D terms. It must be noted that: x, = 0, Vy.,=0 and Uy =0 The following procedure is followed: For stage 1 equation (7) becomes: B, x,,+C,x,,=D, which can be D,-C,Xi2 solved for the unknown x,» togive x,,= 57“ c, D Let pragt and a= Xs =) — PsXia (12) For stage 2 equation (7) can be combined with equation (12) and solved for x,, to give: CEMANB-C “Ta Chapter 3 UNISA EngineeringLet (13) (14) Xj =O) ~ Pi Xijer (15) Starting with stage 1 the p's and q's are calculated in the order Byes Pa Gz eorseesenee Pot Gr Qn: For stage N equation (15) becomes: x, = Gy (16) Example “ For the distillation column, shown below, do one iteration up to and including the calculation of a new set of T; values. CEMAM3-C_ 1 ” Chapter 3 UNISA EngineeringTotal a condenser. |W” 1 YY Us yo Ve Ys LU; =2.0 Stage 2 (saturated liquid) Vs b F3 = 100 Ibmol/h Stage 3 saturated Tquidat 100 psia } bs Me ce t 1 Gommponent stage 4 Allstages at 3(1) 100 psia NC, (2) 0.30 NCs(3) 0.40 x 1.00 Vs, u Partial Qs reboiler5 [VV Ls = 50 lbmol/h Figure 3.3 Note: Equimolal overflow is normally assumed to initialize the calculation. There are no side streams and only one feed stream — all the W's , U's and alll the F's, except Fs disappear. Overall material balance gives: U; = F3 — Ls = 50 Ib mol/h Li = 2,0 x U; = 100 Ib mol/h Vo = Ly + Uy = 150 Ib mol/h ‘CEMAM3-C “76- Chapter 3 UNISA EngineeringThe T; ‘s are guessed as shown below. Note: The boiling point of pure C3 at 100 psia is 51°F while that of pure Cy is 141°F and that of pure Cs is 219°F. Stage} Vj, Ib mol 7h TF 1 0 65 2 150 90 3 150 115 4 150 140 5 150 _ 165 The K — values are given in the following table. Stage 1 2 3 4 5 C1) x) 763 247 27 333 Cal) 033 05 O71 0.95 125 Cs (3) 0,103 0,766 [0.255 0,36 049 Equation (8) becomes: A, =V, +5: (Fy —U,) with only Fs and Us. Thus: A\=V,+F,-U, CEMANS-C UNISA Chapter 3 EngineeringThus: A, =V, +F, -U, =150+100-50=200 A, =V, +F, -U, =150+100-50=200 A, =V, ~50 =150-50 =100 A, =V; ~50=100 Note: The term 5°(F,-U,,)is only summed to j- 1. Thus Fs does not appear in the value of As and there is no Fz or F; With V; = 0 and the Wm ‘s = 0 equation (9) becomes: 8M EF -U,,)+U,+V, Ky Thus B, =-F,-U,+V.K, «|+-[100-50+150x3,33]--54955 Ibmol/h We tF-Uy+ViKia [150+ 100-50+150x27] —[V, +F,-U, +V, K,3 ]+-[150+100-50+150x2,17]=-525,5, =-[V, -U, +V, K,, }--[150-50+150x163} 3445 —[V, -U, +U, +V,K,, --[150 +0]=-150Ibmol/h From equation (10): C,=V,,.K, he Kaas ‘CEMAM3-C -78- Chapter 3 UNISA EngineeringThus Cy = V2Ki2 = 150 x 1,63 = 244,5 Ib mol/h C25 Vakig = 150 x 2,17 = 325,5 C3 = Vaki4 = 150 x 2,70 = 405 Cy = VsKi1.5 = 150 x 3,33 = 499,5 From equation (11) D,=-F,z,, Thus Dy = D2 = Dg = Ds = 0 and Ds = - 100 x 0,30 = — 30 Ib mol/h 3255, P> = ____1793 =344,5-100x(-163) Ps = 15 _____ 1608 =A,p, —525,5-100x(-1793) 4995 1346 605 —200(-11698) CEM4M3-C -79- Chapter 3 UNISA EngineeringD,-Asq,___ -30-(100x0) jp yee 2 EX) ___ 0.08665 B,-A,p, ~5255-100x(-1793) Ards ___0-200x008665___ 9467 A,P; —605-200x(-11698) Asay 0-200%0,0467 __poa3 mr AsP« 200x(-1346) X,5=ds =0,0333 (Using equation 16) Xy4=Gy Py X;5 = 0,0467 -(—1346) x0,0333=0,0915 X13 =4s —Ps X 4 =0,08665 - (- 11698) x0,0915=0,1937 Xa =z —P2 X13 =0-(-1793)0,1937 =0,3473 X41 =4 -P, X,2=0-(-163)0,3473=0,5660 The above calculations are repeated for nC, and n Cs. It will be found that the mol fractions for any stage will normally not add up to 1. The compositions are then normalized and bubble points are calculated for each stage. With this new set of temperatures and new flow rates that are calculated by doing energy balances the total procedure is repeated until an acceptable convergence is obtained. It is clear that it is a very laborious task, if not impossible, to do these calculations by using a hand calculator. Fortunately computer programs, such as Aspen, Chem Cad and others, are available with which quite complex columns can be designed. CEMANB-C -80- Chapter 3 UNISA Engineering3.3. Tray Efficiency The short — cut and rigorous methods that have been discussed all assume that equilibrium is attained in each stage. Ideality is thus assumed. In practice this is never true and some form of correction must be applied The overall tray efficiency is such a correction. The overall tray efficiency, E, is defined as: number of ideal raysrequired E number of realtraysrequired It is most desirable to have reliable information on E,. In the absence of such information the following figures” can be used to estimate E, . ‘CEMaM3-C “81 Chapter 3 UNISA Engineering7 Zor : S Z iid 2 tihorsan yoarnon somber 3 008 is Bramon Cs inetd Hea ine ton Sym ater © oo e 0.006) cos ; Pew 4 g1OT da eT? ToT TA IO Figure 3.4 Figure 3.5 A reasonable fit of the curve for absorbers is given by ": KM, r 597-0,1991 oo ans }-oa8eo{ SM] PL PL where: K = __K-—value of species being absorbed or stripped. M. = molecular mass of the liquid CEM4M3-C -B2- Chapter 3 Engineering UNISA7 viscosity of liquid, cP pF density of the liquid, Ib / ft 3.4 RECAP * Arigorous distilation design method is given in this section. « All these methods are difficult to accurately design distillation towers by hand. * The student is, however, expected to do a first iteration using a spread sheet. + The concept of overall efficiency is introduced. 3.5 EVALUATION Problem 1 Prepare a spread sheet of the example given in this section Problem 2 Use the spread sheet of the first problem to calculate the liquid compositions of Cs and Cs in all five stages. CEMaN3-C “8 Chapter 3 UNISA EngineeringCHAPTER 4 EVAPORATION CONTENTS 4.1 OUTCOMES..... 4.2. INTRODUCTION 4.2.1. Factors Affecting Evaporation. 36 4.2.2 Single — Effect Evaporators . 88 4.2.3 Effect of Process Variables on the Operation of Evaporators 91 4.2.4 Boiling Point Rise (BPR ) 2 4.3. MULTIPLE - EFFECT EVAPORATORB......... evtssenenneneensesessesees 98 4.3.1 Forward Feed 96 4.3.2. Backward Feed. 96 4.3.3 Parallel Feed. 7 4.3.4. Steam Economy. 99 4.3.5 Vapour Recompression us 4.4 RECAP...... 4.5 EVALUATION . CEMaM3-C “84. Chapter 4 UNISA Engineering44 OUTCOMES The student should be able to solve problems involving single — effect evaporators The student should know the factors that are effecting the evaporation of solvents as well as the process variables that are important in the evaporation process The student must be able to determine the boiling point rise of a solution for a given solute The student must know the types of multiple — effect evaporators The student must understand the concept of steam economy and be able to determine it The student must be able to solve multi — effect evaporator problems The student must understand the vapour recompression process and be able to determine the power requirements of compressors used in this process ‘CEMaM3-C “85 Chapter 4 UNISA Engineering4.2 INTRODUCTION Evaporation is one of the main methods that is used to concentrate aqueous solutions. Inorganic salts are normally not heat sensitive and solutions containing such solutes can be heated to relatively high temperatures. Food products are, however, extremely heat sensitive and care must be taken to prevent overheating. This is usually accomplished by using short residence times and relatively low temperatures. It is advisable that the student should read the section on Evaporation in the study guide of Chemical Engineering Technology Ill ( CEM 321 BE). 4.2.1. Factors Affecting Evaporation 1 Solute Concentration The density and viscosity of the solution increase with the amount of solute that is dissolved until the solution becomes saturated. When the solution becomes too viscous the heat transfer is affected. Crystals form when saturated solutions are heated with the result that the heat exchanger tubes might be blocked, reducing even further the heat transfer rate. Most, but not all, solutes cause the boiling point of the solution to be higher than that of the solvent alone. This is called the boiling point rise (BPR) and it is a function of the concentration of solute. 2. Temperature Sensitivity Inorganic solutes are not really heat sensitive and will not be degraded at the temperatures that are normally used in the evaporation process. Food products, such as milk and fruit juices and pharmaceutical products are, however, extremely heat sensitive. Great care must be exercised not to overheat such products and CEMAM3-C -86- ‘Chapter 4 UNISA Engineeringevaporation is normally carried out under vacuum and the residence time must also be kept to a minimum. 3. Foaming Many organic compounds foam during the evaporation process and some of the liquid in the evaporator can be carried over with the vapour. Compounds that depress the foaming can sometimes be used to limit this carry over. 4. Pressure and Temperature The boiling point of a solvent, and thus also the solution, is a function of the pressure. The higher the pressure the higher is the boiling point. This relationship must be kept in mind when evaporating heat sensitive solutes 5. Scale Formation Solids may be deposited on the heat transfer surfaces in the form of scale. This scale reduces the heat transfer rate significantly and must be removed regularly. 6. Materials of Construction The proper materials must be used to prevent corrosion and in the case of food products discolouration. ‘CEM4M3-C -87- Chapter 4 uUNIsA Engineering4.2.2 Single — Effect Evaporators “ Refer to the following sketch. vapor V Ti, yy,Hy concentrated liquid L Ty, x1, hy Figure 4.1 The following equation is used to determine the capacity of a single — effect evaporator. q=UAAT (1) Where q@ = __ heat transfer rate, W U = _ Overall heat transfer coefficient, W/m? K A = heat transfer surface, m? AT = __ temperature difference between the condensing steam and the boiling liquid, K CEMaNs-C “88 Chapter 4 UNISA EngineeringThe enthalpy of a vapour stream is indicated by H and that of a liquid by h with the reference temperature being 0°C. It is normal practice in these calculations to assume that the steam only loses its latent heat of vapourisation. The condensate thus leaves at the same temperature, Ts as the steam. Thus: =H, hy (2) For steady state FeL+V (3) Asolute balance gives Fx, =Lx, (4) An energy balance based on heat = heat out gives: Heat in feed + heat in steam = heat in liquid product + heat in vapour + heat in condensate, thus: Fh, +SH,=Lh, +VHy+Shs (6) Substitute (2) in (5) Fh, +SA=Lh, +VHy (6) The heat transferred in the heater exchanger is thus: g=S(H, —hs )=S% @ The latent heat of vapourisation of steam at a given pressure is readily available in steam tables, but the enthalpies of the feed and product are frequently not known. Some approximations, indicated below, are normally made. 1. The latent heat of vaporization of the steam is determined at the boiling point of the liquid, Ts, and not at the operating pressure, P; (the equilibrium pressure of pure water). CEM4M3-C -89- Chapter 4 UNISA Engineering2. The heat capacities of the feed Cpr and of the liquid product Cp, are used to calculate the corresponding enthalpies. By doing this the heat of solution is excluded but it is in many cases not known. Example 1 A continuous single - effect evaporator is fed with 9070 kg / h of a solution containing 1, 0 mass % salt at 311 K. The liquid product leaves as a 1,5 % solution. The vapour space in the evaporator is at 101,3 kPa (abs) and saturated steam is supplied at 150,0 kPa (abs). U=1 704 W/m? K. The heat capacity of the feed and liquid product can be taken as that of water, i.e. 4,18 ki / kg K. The following data are taken from the steam tables: At 101,3 kPa T= 100°C hg = 2676 kJ/kg At 150 kPa Ts = 111°C hg = 2694 kJ/kg Overall material balance: 9070 = L + V Solute balance:9070 x 0,01 = 90,7 = L x, = 0,015 L L = 90,7 / 0,015 = 6 047 kg /h Cor (Te ~Toase hy =Coy (T, —Trase = 4,18 x X100=418kd /kg 18 (38-0)=158,8kJ/kg hy= 447 kJlkg hy= 467 kulkg Fh, +SH, =Lh, +VHy +Sh, equation (5) CEMANB-C -90- Chapter 4 UNISA Engineering9070x158,8 +S (2694-467 )=6047 x418+3023x2676 $=4121 kg/h q=UAAT AT =111-100=11 q__4121x(2694-467) UAT 1704x11x3600 =136 m? These calculations can be simplified somewhat by choosing a different base temperature. Choose 100°C (temperature of the vapour product and in this case also the liquid product ) as base. 9070x4,18x(38-100)+2227 S=6047x4,18x(100-100)+3023x2259 S=4122 kg/h 4.2.3 Effect of Process Variables on the Operation of Evaporators 1. Feed temperature The temperature at which the feed enters an evaporator has a significant effect on the steam requirement and thus also the size of the heat exchanger. CEMAM3-C “91 ‘Chapter 4 UNISA Engineering2. Effect of Pressure Lower temperatures in the evaporation chamber can be obtained by operating the evaporator under vacuum. This leads to a large temperature difference and thus a smaller heat exchanger. 3. Effect of Steam Pressure The higher the steam pressure the higher will the temperature difference be resulting in a smaller heat exchanger. The cost of high pressure steam is, however, much higher than low pressure steam and these additional costs should be considered. 4.2.4 Be ing Point Rise ( BPR ) This aspect is covered in the study guide of CEN321BE but will be very briefly discussed here. Strong solutions of dissolved solutes can cause significant BPR’s and this cannot be ignored in the design of evaporators in which such solutions are concentrated Duhring’s rule can be used to determine the BPR of solutions containing certain solutes. Example 2 A 30% NaOH solution is boiled at 25 kPa (abs). Determine the boiling temperature of the solution and the BPR by using the Duhring plot below. From the steam tables is found that the boiling point of water at 25 kPa (abs ) is 65°C (149°F). From the plot — boiling point of the solution is 175°F = 79,4°C. BPR = 79,4 - 65 = 14,4°C CEMaM3-C “92- Chapter 4 UNISA Engineering300) wt Noll ff 0 iow enone tI so| Boiling point of sodium hydroxide solution (°F) Boiling point of sodium hydroxide solution (°C) ro Lusi ae 80500 Boiling point of water (°F) Dithring lines for aqueous solutions of sodium hydroxide. Figure 4.2 A very useful plot to determine the BPR's of a number of solutes is given below. CEMANS-C “8 Chapter 4 UNISA Engineeringhoot sau Soiceat ‘ONsNO ‘ONHalySOy akicbs cathog), 22093 Mose oct aay scien ; 50,0 0 a0 $ : 220 180 160 Exompie far 27°F 9 22% CaCly solution hose ber of STF Note Ponte. shown 9 dosed mosy on Simoephene eating So 40 120 Boling point ise of aqueous solutions, Crt F-32) doo Figure 4.3 Example 3“ 4.500 kg/h of a 20% solution of NaOH in water is fed to a single effect evaporator at 60°C. The liquid product contains 50% NaOH. Saturated steam at 175 kPa (abs) is fed to the heat exchanger. The vapour space of the evaporator is operated at 15 kPa (abs). The overall heat transfer coefficient is 1 560 Wim’K. The specific heat of the feed is 3,57 kJ/kg°C and that of the liquid product is 5,64 kJ/kg°C. Calculate the steam usage, the heat transfer surface and the steam economy. From the steam tables: at 175 kPa T= 116 °C; hg = 2701 kJ/kg; hig = 487and hy= 2214 CEMAMS-C “94- Chapter 4 UNISA EngineeringAt 15 kPa: T = 54°C Overall balance: 4500 =L+V NaOH balance: 4500x0,2=0,5L thus L =1800 and V=2700 At 54°C (129°F) and 50% NaOH the boiling point of the 50% solution is found from the Duhring plot to be 204°F = 95,5°C ( BPR = 41,5°C). At 95,5°C Hy = 2668 kJ/kg AL 116°C 2 = 2214 kikg Fh, + SH, =Lh, +VHy +Sh, Fh, +S2=Lh, +VHy 4500%3,57 xx60+2214 S = 1800x5,64x95,5+2700x2668 $=3256kg/h q=2S=2214x3256=7,208« 10° kJ/h AT=116-95,5=205 7,208x10° 100x156 x20,5 ‘Steam economy=2700/3256 = 0,829 kg steam fed / kg water evaporated 32,6m? CEMAM3-C -95- Chapter 4 UNISA Engineering4.3 MULTIPLE - EFFECT EVAPORATORS In multiple effect evaporators use is made of the steam that is generated in the vapour space of an evaporator by feeding it to the heat exchanger (called calandria) of the next evaporator. The vapour that is generated in the second evaporator is then fed to the calandria of the third evaporator. The steam economy ( total steam generated/steam fed to the first calandria) is significantly increased in comparison with a single — effect. Three types of operation can be used, i.e. forward feed, backward feed and parallel feed. 4.3.1 Forward Feed In this type of operation the feed and steam flow in the same direction as shown in the following sketch Water Condenser Dy + t Om | Barometric leg Ty {WL} “ fiwi-D,-D,) L Trap Trap Steam condensate Condensate Condensate Product W-D)-D,-Ds Forward feed arrangement for triple effect evaporator Figure 4.4 4.3.2. Backward Feed CEMANB-C -96- ‘Chapter 4 UNISA EngineeringIn this type of operation the feed and fresh steam flows in opposite directions as shown in the next sketch. The steam that is generated still flows in the same direction as is the case with the forward feed set - up. = : : grdvecuum oO @ @ a sem EL, lly a rap rap rep Probus Condensate Condenste—=—=—Candanste Figure 4.5: Backward-feed arrangement for a triple-effect evaporator 4.3.3 Parallel Feed This type of operation is shown in the next sketch. In this case the feed is fed to all three evaporators simultaneously. c To condenser c or le Regenesis Steom—— I 1, ‘“—k Feed: Trap Trap Trap Condensate Condensate Condensate CEM4M3-C “o7- Chapter 4 UNISA EngineeringFigure 4.6: Parallel-feed arrangement for a triple-effect evaporator CEMAM3-C “98- Chapter 4 UNISA Engineering4.3.4 Steam Economy In the next sketch the steam economy of the three types is compared. It can be seen that the backward feed set — up is better than the other two at the lower feed temperatures. At the higher feed temperatures the reverse is true with the forward feed being the best. The parallel feed type is often used where the deposition of salt crystals from salt solutions makes it difficult to use the standard forward feed set — up. Initial feed temperature (°F) 150 200 250 | 100 | i i | | 50 4.00 3.50 3.00 Economy 2.50 2.00 sol__1 J 280 300 320 340 360 380 400 Initial feed temperature (K) Figure 4.7: Economy of triple effect evaporators Temperature Drops and Capacity of Multiple — Effect Evaporators cEMaNES a Chapter 4 uNISA Engineering1. The amount of heat transferred in the first effect of a forward feed set — up is : 4: =U, A, AT, (8) Where AT is the difference between the condensing steam and the boiling point of the liquid, AT=T,-T, For the second and third effects equations similar to equation (8) are valid, thus: q,=U, A, AT, andq, =U; A, AT, It is normally assumed the sensible heat that is required to heat the feed to the boiling point of the liquid can be neglected. It is also assumed that there is no BPR. Under these circumstances the latent heat of the condensing steam appears as latent heat in the vapour of the first effect. When this vapour condenses in the second calandria approximately the same amount of heat will be given off. The same reasoning holds for the third effect. Thus: Gs =42=45 Thus: U,A, AT, =U; A, AT, =U; A; AT; The heat transfer surfaces of the calandrias are normally equal, thus: rer AT, =U, AT, =U, AT, The total temperature difference is given by: DAT=AT, +AT, +AT, =Ts -Ty, Use equation (11) to obtain the following: (9) (10) (1) (12) CEMANB-C “100 UNISA Chapter 4 Engineeringq q q AT,= AT, = AT, = AU, \ Substitute these AT’s in equation (12). Thus: Ear-gf i ara from which follows that: AT, eae (13) a U, U, U; 1 U, Similarly: AT, => AT! att and AT, =, AT] ~—> (14) U, U2 2. A rough estimate of the capacity of a three — effect evaporator compared to a single effect can be obtained by adding the q's of each calandria. Thus: =, +4, +45 =U, A, AT, +U, A,AT, +U; As AT, (15) With the assumption that: U, = =U. equation (15) becomes: g=UA(AT, +AT, +AT, ) =UA AT (16) A single — effect evaporator .with the same A ,U, and AT would have the same capacity as the three — effect but the steam economy of the three — effect is considerably higher. CEMAMS-C ~107- Chapter 4 UNISA EngineeringStep — by — step Method for Triple — effect Evaporators A trial and error procedure is used to solve these problems. The given or known values that are normally known are: (a) _ the steam pressure to the first effect. (b) _ the pressure in the vapour space of the last effect. (6) the feed conditions and its flow rate. (4) __ the concentration of the liquid leaving the last effect. (e) _ enthalpies or heat capacities of liquids and vapours. (f) the overall heat transfer coefficients. (9) __ the areas of the calandrias are normally assumed to be equal. 1 Determine the boiling point in the last effect by using the outlet concentration and the pressure in this effect. Use the Duhring plot or the plot from Perry if there's a BPR. 2. Determine the total amount of water evaporated by an overall material balance. For the first trial it is assumed that V; = V2 = Vs. Lr ,Lo and Ls can now be determined. Determine the concentration of solids in each effect by doing a salt balance. 3. Use equations (13) and (14) to estimate the temperature drops AT; , ATz and AT3. Any effect that has an extra heat load, such as when the first one is fed with a cold feed, requires a proportionately larger AT. The boiling points can now be calculated for each effect. Note: If there is a significant BPR the pressures in effects 1 and 2 must be estimated. These pressures enable one to determine the boiling points of pure water in these two effects. Use these boiling points and the concentrations to determine the BPR's. CEM4M3-C =102- Chapter 4 UNISA EngineeringTheZAT that is available is found by subtracting the sum of all the BPR’s from the overall AT of T; - Ts. The new boiling points can now be calculated. Only a crude estimate of the pressures is required as the BPR is almost independent of pressure. 4. Use heat and material balances in each effect to calculate the amount vaporised and the liquid flows. If the amounts vaporised differ appreciably from those calculated in step 2, then steps 2,3, and 4 can be repeated by using the amounts of evaporation just calculated 5. Calculate the value of gin each effect by using the equation q=UAAT Calculate A,,A,,andA,. Determine the average heat transfer surface as A\+A,+As follows: A,, . If these areas are reasonably close to each other the calculation is terminated. If not, a second trial must be performed as follows. 6. Use the values of L,,L,,L;,V;,V,,and V, ,calculated in step 4 by doing the heat balances, to calculate the new solids concentrations in each effect by doing a solids balance. 7. Obtain new values of AT,,AT,, and AT, by using the following equations: ATA AT, A, AT; A, AT=— aT, = 2? aT, = 2 An TR By > (AT, +AT, +AT,) must be equal to the original "AT. If this is not the case readjust all the AT values proportionately so that the above requirement is met. The boiling points in each effect are now determined CEMAMS-C “103° Chapter 4 UNISA Engineering (17)8. Use the new AT values from step 7 to repeat the calculations starting with step 4. Two trials are usually sufficient to obtain reasonably close values of the areas. Note: If there are significant BPR’s use the new concentrations from step 6 to determine these BPR's. A new value of AT is now available by subtracting the sum all the three BPR's from the overall AT. Use equation (17) to calculate AT,,AT,,and AT,. The sum of these AT's must be readjusted to this new value of SAT. Next the boiling point in each effect is calculated. Step 7 is a repeat of step 3 except that equation (17) is used to obtain better values of AT. Example “ ‘A forward feed triple — effect evaporator is used to concentrate a 10% sugar solution to 50%. The BPR's can be estimated from the following equation: BPR (°C) = 1,78 x +6,22 x* where x is the mass fraction of sugar. Saturated steam is available at 205 kPa (abs). The pressure in the vapour space of the third effect is 13 kPa (abs). The feed rate is, 22680 kg/h at 27°C. The heat capacity of the solution is given by Cp = 4,19 - 2,35 x (kJ/kg K). The heat of solution is negligible. The overall heat transfer coefficients are estimated as U; = 3,123 ; Uz = 1,987 and Us = 1,136 kW/ m? K. The heat transfer surfaces are the same in all three effects. Calculate the area of the calandrias, the amount of steam used and the steam economy. Step 1 At 13 kPa Ts = 51°C ( from the steam tables) The BPR in the third effect is BPRs = 1,78 (0,5)+6,22 (0,5) = 2,4°C CEM4M3-C =104- ‘Chapter 4 UNISA EngineeringTa = 51 42,4 = 53,4°C Step 2 Overall balance F = 22680 = L3 +(V: #V2 + Vs) Sugarbalance 22680 x 0,1 = 2268 = 0,5La Lg = 4536 kg/h And Vi + V2 + Va = 18 144 kg/h Assume that equal amounts are vapourised in the three effects, thus: V1 = V2 = V3 = 6048 kg/h Do material balances on each effect, thus: (1) F=22680=V; +L; = 6048 +L, ; Li = 16 632 kg/h (2) Ly = 16 632 =V2 + Lp = 6048 +L2 , Le = 10 584 kg/h (3) Le = 10 584 = V3 + Ls = 6048 + Ls ; Ls = 4536 kg/h Do a solids balance to determine the sugar concentrations in each effect. (1) 22.680 x 0,1 = 2268 = Ly x1 = 16 632 x1; x1 = 0,1364 (2) 16 632 x 0,1364 = Lz x 2= 10 584 x2 ; X2= 0,2143 (3) 10584 x 0,2143 = La xg = 4536 x3 ; CEMAM3-C “105- Chapter 4 UNISA EngineeringStep 3 Calculate the BPR's in each effect: 1 BPR; = 1,78 x; + 6,22 x1? = 1,78 x 0,1364 + 6,22 x 0,1364? = 0,36°C 2. BPR, = 1,78 x 0,2143 + 6,22 x 0,2143? = 0,66°C. 3. BPR3 = 1,78 x 0,5 + 6,22 x 0,5" = 2,44°C The temperature of the steam at 205 kPa = 121°C = Ts ¥AT (available) =T, -T, (saturation)—(BPR, +BPR, +BPR, ) YAT (available) =121-53,4—(0,36 +0,66+2,44)=641° C Use equation (13) to determine the temperature differences. 1 1 3123 Pear = 3B Fr 20°c tei 3123 1987 1136 AT,=189°C AT, =332°C As the feed enters as a cold stream the first effect requires more heat. AT, must be increased and AT, and AT, must be decreased proportionately. Adjust the temperature differences as follows: CEMAM3-C_ ~106- Chapter 4 UNISA EngineeringAT,=16 AT, =179 AT, =302 Calculate the boiling point in each effect, thus: (1) T,=T.,-AT,=121-16=105 °C T,,=121°C = temperature of steam fed to first effect (2) T)=T,-BPR, ~ AT, =105-036-179=8674°C Ts =T, -BPR, =104,76 °C= temperature of steam fed to second effect (3) 1, =T,-BPR, -AT, T;, =T, -BPR, =86,74—0,66 =86,08 °C = temperature of steam fed to third effect 6,74 -0,66 —30,2=55,88 °C (4) Ts,=T, -BPR, =55,88-2,44=53,44 °C = temperature of steam leaving the third effect and then enters the condenser. The temperatures in the three effects are as follows: Effect Effect 2 Effect 3 Condenser To =121 [> T,, =104,76 Lf Te» =86,08 re T,=105 T, =86,74 T, =55.88 Step 4 The heat capacities are calculated by using the given equation. F: Cp = 4,19 ~ 2,35 x 0,1 = 3,955 kJ/kg K CEMAMS-C “107- Chapter 4 UNISA EngineeringLy :Cp = 4,19 — 2,35 x 0,1364 = 3,869 Le: Cp=4,19 — 2,35 x 0,2143 = 3,686 Ls: Cp = 4,19 - 2,35 x 0,5 = 3,015 The enthalpy values of the various vapour streams are now obtained from the steam tables Effect 1 T= 105°C Ts2 = 104,76 BPR = 0,36 Ts =121 H, =Hg, (saturation enthalpy at Ts, )+2,055(0,36 °C superheat ) = 2683,4+1884x0,36=2684 kJ /kg ‘ug, = Hg, (vapour saturation enthalpy )—hs, (liquid enthalpy at T;,) =2200 kJ/kg =h,, at 120°C, Note: The BPR's are low in this case and could have been ignored. The method shows, however, how to provide for high BPR's. The BPR's will be ignored in the following calculations. Effect 2 674 =Ts5 H, =2680kJ/kg ego =2291kJ/kg CEMAM3-C “108° Chapter 4 UNISA EngineeringEffect 3 T, =5588=Ts, ig =2368,5kJ/kg Heat balances are now made on each effect. V,=22680-L, V,=L,-L, V,=L, 4536 L, =4536 (1) Fp(T, -0)+S2g, =L, Cp(T, -0)+V,H, 22680x3,955 x27 +Sxx2280=L, x3,869x105+(22680-L, )x2684 2,422x10 ° +2280S=406,245L, +(22680-L, )2684 L, Cp(T, -0)+V, 2g =L, Cp(T, -0)+V, H, Lx 3869x105 +(22680-L, )x2291=L, x3,686x86,74+(L,—L, «2680 406,245L, +5196x10 ° -2291L, =319,724L, +2680L, -2680L, L,=11383+0517L, (2) L, Cp(T, -0)+V3 Ass =Ls Cp(T, -0)+V3 Hy (3) L,x3,686x86,74 +(L, -L, )2368,5=4536x3,015 x55,88+(L, -4536)x23086 L, =11400 this is found by substituting the value of the above value of L, L,=16897 L, =4536 S = 8755 \V, =22680 -16897 =5783 V, =L, -L, =5497 V, =L, -4536=6864 The calculated values of V,,V, and V, are relatively close to the assumed values. More accurate values can be calculated by repeating steps 2, 3, and 4 and using the calculated vapour streams as the starting point. CEMAN3-C =109- Chapter 4 UNISA EngineeringStep 5 q,=She: (28 ).2280-ssaskw 3600 2=Vyhsa= (3 oes 201 3680kW 5497 3600 554) U, AT, ar “Hats 3680 ow }eate 3615kW =111m? =103,5m? Step 6 The areas are quite close to the average but a new solids balance will be done to illustrate the calculation procedure. The BPR’s will, however, be ignored. Solids in = 22680 x 0,1 = 2268 kg/h (1) x; =2268/16897 = 0,134 (2) X2 = 2268/11400 = 0,199 (3) x9 = 2268/4536 = 0,5 Step 7 CEMAM3-C “110- Chapter 4 UNISA EngineeringAT,A,_ 16x111 A, 1067 AT, Aa _17,9xx1035 A, 1067 AT, As _30,2%1055 Ay 106,7 AT, 16,6°C =17,4°C AT, = 99°C YAT=166 +17,4+-29.9=63,9(should be 64,1) Readjust these AT's such that)’ AT=64,1 AT,=174 — AT,=30 The heat capacities are now: F: Cp=419-2,35 x0,1=3,955 kJ/kgK L, Cp=4,19-2,35x0134=3,875 L, Cp=419-2,35x0,199=3,722 L, Cp=419-2,35x0,5=3,015 The new temperatures are: T,=121-167=1043 T,=104,3-17,4=86,9 T, =869-30=569 At T, H,=26838 and 2,=22456 T, H,=2654 and 2,=2291 T, H,=2604 and 2, =2366 Writing the heat balances for each effect again. CEMAM3-C i ~~ Chapter 4 UNISA Engineering(1) 22680 x 3,955 x 27 +2280 S = L; x 3,875 x 104,3 +(22680 —L; )2684 2280 S = 58,451 x 10°- 2279,8 Li (2) Lyx 3,875 x 104,3 + (22680 — Ly) x 2246 = Le x 3,722 x 86,9 + (Li = La) x 2654 Ly = 11330 +0,518 Lo (3) Lex 3,722 x 86,9 + (Ly — La) x 2291 = 4536 x 3,015 x 56,9 + (L-— 4536) x 2604 Le = 0,501 Li + 2413,6 Thus 12=10918 Ly = 16895 Ls = 4536 S = 8653 V2= 6067 V1 = 5695 Vs = 6302 CEMAMS-C az Chapter 4 UNISA Engineering6067%2291_ js =V2 hp 3600 a $480 U,at, 3423x167 10O'™ a 3552 Ao AT, dare 174 Oe” -3860__ 1435 1136x30 Ag AOHle027199 67 V#V, +Vy_ 5695 +6067 +6302 Steam econom tf s 8653 =2,09 Summary of the Above Procedure The pressure in the last effect is normally given. Use the steam tables to determine Ts. Adjust this temperature if there is a significant BPR. 2. Use the final concentration to determine L; 2 V is now known. ‘Assume Vi = V2 = Vs - 3. Determine Li, La, and Ls. Determine the concentration of solids in each effect. 5. Calculate the BPR's. Use these figures to adjust the temperatures of the vapours leaving each effect. Ignore the BPR's if they are small. 6. Calculate EAT that is available. 7. Determine the individual T's. 8. Adjust the AT's if the feed is at a temperature that is much lower than Ty. 9. Calculate the boiling points in each effect. 10. Caloulate the heat capacities of the liquids. CEM4M3-C -113- — Chapter 4 UNISA Engineering11. Obtain the total heat content and the latent heat of vapourisation of the vapours leaving each effect. 12. Do heat balances on each effect. New L's and V's are obtained. 13, Determine the heat loads. 14. Determine the areas of the calandrias and the mean area. If there are significant differences between the individual areas and the mean repeat the calculation using corrected AT's. Repeat the previous calculations. 4.3.5. Vapour Recompression A single — effect vapour recompression evaporator, fitted with a compressor is shown in the sketch “ below. makeup steam vapor compressor drive 4 ‘condensate cate concentrated (for desuperheating) product feed heater 7 eee Figure 4.8: Simplified process flow for mechanical vapour recompression evaporator. In this mechanical vapour recompression evaporator the cold feed is preheated with the condensate. The vapour that is formed flows to a centrifugal or positive displacement compressor, driven by an electric motor. The compressed steam has a higher temperature than the steam leaving the evaporator. A temperature difference is thus created that ensures that the required evaporation rate is achieved. The latent heat of the vapour formed is thus used to vapourise more water instead of discarding it as condensate. CEMANS-C “Tia Chapter 4 UNISA EngineeringProvision is made, as can be seen in the sketch, to supply make — up steam and/or condensate to the system if required. The injected condensate is used to remove any superheat that might develop during the compression stage. These types of units operate optimally with temperature differences varying between 5 and 10°C. Itis claimed that the steam economy of these units is equivalent to a multiple — effect evaporator with about 10 units. ‘An alternative to mechanical compression of the vapour is to use a steam ejector that is supplied with high pressure steam. This allows the entrainment of some of the vapour formed in the vapour space of the evaporator. This type is shown in the sketch below. 1kgH.P. steam, at 928 kN/m? 0.75kg__1kg Vapour Condenser Feed 1.75 kg i a LP. steam at 170kN/m? Trap Product Condensate 1.75kg Figure 4.9: Vapour compression evaporator with high pressure steam-jet compression 44 RECAP CEMANB-C 7 i5- Chapter 4 UNISA EngineeringThe student should read the Evaporation section in the study guide of Chemical Engineering Technology ( CEM321BE). Factors affecting evaporation are discussed. These are solids concentration ( boiling point rise ), the temperature sensitivity of especially food products, foaming, pressure / temperature relationship, scale formation and materials of construction. The formulae that are required to solve problems involving single — effect evaporators are given and examples are provided. Process variables, affecting the operation of evaporators are discussed (BPR) boiling point rise is discussed (refer also to CEM321BE ) and two plots are given that can be used to determine the BPR's of various solutes. The types of multiple — effect evaporators, i.e., forward feed, backward feed and parallel feed are discussed The steam economy of the three types is discussed. An iteration method to solve multi — effect evaporator problems is provided. ‘Assummary of this iteration method is given. Vapour recompression that is used with a single — effect is discussed. ‘CEMaNB-C “16 Chapter 4 UNISA Engineering4.5 EVALUATION Problem 1 A solution with a negligible BPR is being evaporated in a triple — effect evaporator using saturated steam at 121,1°C. The pressure in the vapour space of the last effect is 25,6 kPa (abs). The overall heat transfer coefficients are U; = 2,84 , Uz = 1,988 and Us = 1,42 kWim?K. The heat transfer areas are equal. Estimate the boiling points in all three effects. Answer: 1;=108,6°C = T, = 90,7°C. Ts = 65,6°C Problem 2 A triple — effect forward feed evaporator concentrates a sugar solution from 5 mass % to 25%. Any BPR can be neglected. The feed enters at 22 680 kg/h at 300 K and the pressure in the vapour space of the third effect is 13,65 kPa (abs). The fresh saturated steam is available at 205 kPa (abs). The liquid heat capacity is given by: Cp = 4,19 — 2,35 x where x is the mass fraction of sugar. The heat transfer coefficients are U; = 3,123 , Uz = 1,987 and Us = 1,136 kWim’K. Calculate the heat transfer surface of each effect if all areas are equal, the steam rate and the steam economy. Do only one iteration. Answer: 100 m?; S = 8976 kg/h _ Steam economy = 2,02 Problem 3 An aqueous solution containing 2 mass % organic solids is fed at 38 °C to a double — effect backward feed evaporator. The BPR's can be ignored and the product contains 25% solids. Each effect has a heat transfer area of 93 m? and the heat CEMAM3-C 7 Chapter 4 UNISA Engineeringtransfer coefficients are U; = 2,837 and Uz = 3,972 kW/m? K. The feed enters effect no. 2 and saturated steam is fed to number 1 at 690 kPa (abs). The pressure in the vapour space of number 2 is 21 kPa (abs). The heat capacities of all the liquids = 4,19 kJ/kg K. Calculate the feed rate and the product rate. Use as basis a feed rate of 1000 kg //h to calculate the area. Use the given areas to prorate the feed and Ly. Do only one iteration. Answer: F = .55 000 kg/h and L; = 4 300 kg/h (these values are obtained if the AT's are not adjusted — with adjusted AT's F will be closer to 60 000 and L; closer to 4800 kg/h) Problem 4 2 kg/s of an aqueous solution containing 10 mass % solids is fed to a triple - effect backward feed evaporator at 21°C. The solution that is withdrawn from the first effect contains 50 % solids. The third effect is operated at 13 kPa (abs) while the dry saturated steam fed to the first effect is at 205 kPa (abs). The specific heat of all liquids can be assumed to be 4,18 kJ/kg K. It can also be assumed that there is no BPR. Estimate the heat transfer areas assuming that they are equal in size, the temperatures in each effect and the steam consumption. The overall heat transfer coefficients are Us = 2,5 ; Uz = 2,0 and Us = 1,6 kWim? K Do only one iteration. Answer: An = 27m’; S = 0,6 kg/s; T; = 103°C; T= 80°C; T; = 51°C CEMaM3-C “118- "Chapter 4 UNISA EngineeringCHAPTER 5 ADSORPTION CONTENTS 5.1. LEARNING OUTCOMES. 5.2 INTRODUCTION. 5.2.1. Physical Properties of Adsorbents. 5.2.2. The Adsorption Process 5.2.3 Equilibrium Relations... 5.2.4 Batch Adsorption... 5.3. DESIGN OF FIXED BED COLUMNS (A).. 5.3.1 Breakthrough Concentration Curve ......... 5.3.2 Capacity of Column and Scale — up Design Method 5.4 DESIGN OF COUNTERCURRENT FLOW OF SOLIDS 5.4.1 Design Method for Countercurrent Fiow.. 5.5 RECAP 143 5.6 EVALUATION. 145 CEMaNs-C “19 Chapter 5 UNISA Engineering5.1 LEARNING OUTCOMES * The student should be able to identify practical applications of adsorption * The student should understand the similarities between adsorption and absorption processes. * The student must be able to use some equilibrium equations and be able to determine the break — through times for batch and fixed bed operations as well the bed heights. * The student must be able to determine the number and height of the transfer units and the bed heights of countercurrent adsorption processes. CEMANB-C =120- Chapter 5 UNISA Engineering5.2 INTRODUCTION In adsorption processes one or more components are removed from a gas or liquid stream by contact with a solid phase. The adsorbent is usually in the form of small particles with a high surface area. The intemal surface area of a particle is usually significantly larger than its external surface area. To obtain a very large surface area per unit volume of solid requires that the solid is very porous. The pores must have small diameters and be interconnected. The adsorbed solute is referred to as the adsorbate while the solid is referred to as the adsorbent. In an adsorption process the molecules diffuse into the pores of the solid where they bond with the solid surface by physical or chemical forces. The latter process is referred to as chemisorption. In commercial processes, the solid particles are charged to a fixed bed. The fluid, from which a component must be removed, passes through the bed. When the bed is nearly saturated the process is stopped and normally it is thermally regenerated In the regeneration step desorption of the adsorbate occurs. The adsorvate is recovered and the adsorbent is then ready for another cycle. Liquid phase adsorption is used for the removal of organic compounds from water and organic solutions, the removal of sulphur compounds from organic solutions and the decolourisation of solutions. Gas phase adsorption includes the removal of organics and sulphur compounds from vent streams, solvents and odours from air, CO2 from natural gas and NO, from No. 5.2.1 Physical Properties of Adsorbents CEMAMS-C “ai Chapter 5 UNISA EngineeringAdsorbents are normally small beads, pellets or granules ranging in size from 2 A to 150 A. Some typical adorbents and their physical properties are given in the following table. Table 5.1 pasopent — | Nate Pore Diameter | Patice | paride ——_—| surface wea | Capasiy fr HO Fi Porsiys, | densiyen | Saami | Vaporat 2°and 46 ced ten? remit. Wt (Dry | Bass) aeons P1075 35 1 ro 7 | suina | anerpous | | See gor — op 1 | sma pore | nyeroptoti, | 22:28 oar 1.09 rosso | at | aoe poe | amopneus | 100380 | o74 ose 300350 aeated | Frere carer Amorphous | sat pore 1025 oaos — fosoe | ato-tz00 1 Large pore >a - esos zooso | - | coor — rracenan — 2-70 5 33 0 > | | stove carton Wasa —] Pa 30 oes} S70 we | steve zeottes. | nycropnitc exystatne Pana —= cy THORS 700 i | ansobens The following relationships can be used to calculate some other properties. =>. where V, is the specific pore volume Pp where &, is the bed porosity Ps is the bulk density CEMANE-C ae Chapters UNISA Engineeringwhere p, is the true solid density 5.2.2. The Adsorption Process Physical adsorption “) occurs when the intermolecular attractive forces between the gas molecules and the solid molecules are greater than those between the gas molecules. This is an exothermic process. The magnitude of the heat of adsorption can be less or greater than the heat of vapourisation. Physical adsorption occurs rapidly and can be monomolecular or multimolecular in nature. In physical adsorption the process begins as a monolayer that can become multilayered, and if the pores are close to the size of the molecules, condensation may follow. The pores then are filled with adsorbate. The maximum capacity of a porous adsorbent can thus be closely related to the pore volume rather than to its surface area. For gases above their critical temperatures, only monolayers are formed, Chemisorption involves the formation of chemical bonds between the adsorbate and adsorbent in a monolayer. The heat release is frequently much greater than the heat of vapourisation. Gas phase chemisorption normally only occurs appreciably above 200°C. 5.2.3. Equilibrium Relations The equilibrium relationship between the concentration of an adsorbate in the fluid and its concentration on the adsorbent resembles the equilibrium solubility of a gas ina liquid. Some typical isothermal relationships “ are shown below. CEMAM3-C “123- Chapter 5 UNISA EngineeringFreundlich, favorable Langmuir, strongly a favorable kg adsorbate/ kg adsorbent c, kg adsorbate/m? fluid Figure 5.1 The linear relationship is not common but it can be used in the dilute region to approximate the data of many systems. This relationship is similar to Henry's law and can be expressed by: q=Ke a) where K has the dimension of m* / kg adsorbent. The Freundlich empirical equation apparently often approximates the data for many syslems and is very useful for liquids. This equation is given by: q=Ker (2) where K and n are constants that must be determined experimentally. The Langmuir equation is given by: ac 6. 3 Kee 8) CEMAM3-C “24- Chapter 5) UNISA Engineeringwhere q, is a constant with kg adsorbate/kg adsorbent as unit K is a constant, kg/m?, Equation (3) can be rearranged to: AKee KO 9 4S GC (4) This is the equation of a straight line and when ~ is plotted vs. ~ the slope is given q c by: a and the intercept by: oe Example 1“ In batch experiments solutions of phenol in water were contacted with granular activated carbon. The following results were obtained at room temperature. ‘CEMAM3-C “25- Chapter 5 UNISA Engineeringc, kg phenol/m® solution q, kg phenol/kg carbon 0,322 0,15 0.117 0,122 0,039 0,094 0,0061 0,059 0,0071 0,045 Assume that the Freundlich isotherm can be used to model this system. Determine the constants. ‘A log — log plot shows that the data are on a straight line. a a pn lS. load, _ -08239-(~13468) _9 54 loge, loge, —0,4921-(-2,9586) CEMAN3-C ~126- Chapter 5 UNISA Engineeringlogk =logq, -0,212loge, =~ 0,8239-0,212(-0,4921)=-0,7196 k=0191 q=01910°7" 5.2.4 Batch Adsorption Batch operations can be considered when small quantities of contaminated solutions must be treated. Let: M=kg adsorbent cr = __ initial concentration of adsosorbate in solution (kg/m*) c SI final equilibrium concentration of adsorbate in solution (kg/m*) =m’ of solution ae = ___ initial mass of adsorbate per unit mass of adsorbent a = _ final mass of adsorbate per unit mass of adsorbent An adsorbate balance then yields: ox StqxM=oxS+qxM (6) When q is plotted against c a straight line with a negative slope is obtained. If this line is plotted on the same graph as the equilibrium data the intersection will give the final equilibrium values of q and c. The final values of q and c can be found by equating the equilibrium equation and equation (5). A trial — and — error procedure is, however, required to solve these equations. It is thus easier to use the graphical procedure. CEMAM3-C “127 Chapter 5 UNISA EngineeringExample 2 Use the equilibrium data of Example ‘to solve the following problem. 1 m? of an aqueous solution containing 0,21 kg phenol/m? of solution is mixed with 1,4 kg of fresh granular activated carbon. The mixture is allowed to reach equilibrium. Determine the final equilibrium values and the percentage phenol that is removed S=1m*; cr =0,21 kg phenolm®, = M=1,4 kg; ge =0 q=0,15-0,714¢ The above equation and the equilibrium data are plotted on the following graph. From the graph: q=0,104 c= 0,064 % recovery = (0,21 — 0,064) x 100/0,21 = 69,5% ‘CEM4M3-C -128- Chapter 5 UNISA EngineeringExample 2 5.3. DESIGN OF FIXED BED COLUMNS (4) Mass transfer resistances are important here and the process is not in steady state. The equilibrium conditions are still important but the overall dynamics of the process determine its efficiency. The fluid to be treated is usually passed down the bed of granules. The concentrations in the fluid and of the adsorbent change with time. ‘CEMAM3-C ~129- Chapter 5 UNISA EngineeringIt is assumed that the adsorbent contains no adsorbate at the inlet when the process is started. Most of the mass transfer and adsorption occur as the fluid first contacts the inlet of the bed. The concentration in the fluid drops very rapidly with distance in the bed and reaches zero before the end of the bed is reached. After a short time the solid at the entrance to the bed becomes nearly saturated and adsorption now occurs slightly further away from the entrance. As the process continues, the point where the bulk of the adsorption occurs moves further and further away from the entrance. The concentration profiles at various times, as functions of bed height, are shown as part (a) on the next sketch. c, is the feed concentration and c the fluid concentration at a point in the bed. Consider the graph at time t; At the entrance the adsorbent is nearly saturated while at height H; practically no adsorption has occurred. The dashed line at ts shows the concentration in the fluid that is in equilibrium with the solid. The difference in concentration is the driving force for mass transfer. 10 & 0s- 0 0 H, Hy Hy Hy Height of adsorption bed, @) 10 a mass-transfer | zone & 05+ break point 0 0 4 nos bo Time, (b) Figure 5.2 CEMAM3-C ~130- Chapter 5 UNISA Engineering5.3.1. Breakthrough Concentration Curve “ The (b) part of the above curve shows the concentration profile as a function of time. At time ts the outlet concentration is still approximately zero. This remains the case until time t; is reached when the outlet concentration starts to rise. At time ts the outlet concentration has risen to cp, that is called the break point. After ts the concentration rises rapidly up to cy. This is the end of the breakthrough curve and the bed is now ineffective. The ratio cy/ce is about 0,01 to 0,05 while cco is approximately one. CEMAM3-C “181 Ghapier’S UNISA Engineering5.3.2. Capacity of Column and Scale — up Design Method “ ‘Some theoretical methods predict the mass transfer zone and concentration profiles in the bed, These predicted results may be inaccurate and laboratory experiments are necessary in order to scale up more accurately. If the entire bed comes to equilibrium with the feed the total capacity of the bed is proportional to the area between the curve and the line at cle = 1,0. Refer to the following sketch. Figure 5.3 The total shaded area represents the total capacity of the bed. It can be shown that: (6) where t, is the time equivalent to the total capacity. CEMAN3-C ~132- Chapter 5 UNISA EngineeringThe usable capacity of the bed up to the break point, 1, is the crosshatched area, thus: @”) where t, is the time equivalent to the usable capacity or the time at which the effluent reaches its maximum permissible capacity. The ratio t, /t, is the fraction of the total bed capacity or length that is utilised up to the break point. For a total bed length H,, H, is the length of bed that is used up to the break point. Thus: (8) The length of unused bed Hyyg is the unused fraction times the total length. tu Huns -(-)h, (9) tt Hye represents the mass transfer section of the bed. It depends on the fluid velocity and is essentially independent of the total bed length. Hye is normally determined in a small diameter laboratory column with the desired adsorbent and at the design velocity. For the final design H, is calculated using the relationship H, «ct, - CEM4M3-C =133- Chapter 5 UNISA EngineeringHuy is then added to H, to obtain H,. Example 3“ A stream of alcohol vapour in air was adsorbed by activated carbon in a packed bed with a diameter of 4 cm and length of 14 cm. The bed contained 79,2 g carbon. The inlet gas stream had a concentration, co of 600 ppm and a density of 0,00115 g/cm’. The inlet gas entered at 754 cm*/s. The data below give the concentrations of the breakthrough curve. The break-point concentration, cy is set at c/co = 0,01. (a) _ Determine the break — point time, the fraction of total capacity used up to the break — point, the length of unused bed and the saturation loading capacity of the carbon. (b) If the break — point time required for a new column is 6 hours, determine the height of the required column Breakthrough Concentration [Time h cles Time, h_ ele, fo 0 55 0,658 3 0 6,0 0,903, | 3,5 0,002 6,2 0,933, | \4 0,03 65 0,975 [45 | 0.155 68 0,993 | _ 5 0,396 (a) The data are plotted in the graph below. ‘CEMAM3-C ~134- Chapter 5 UNISA EngineeringExample 3 Az3,55 Ag = 1,55 ty=3,6h th CEMAN3-C 35 UNISA Chapter 5 EngineeringFraction of total capacity to breakpoint, $2 = 355 =0,696 8A oH, = 696x14=9,74 om. From equation (8) the length of the used bed is H, The unused bed is given by equation (9) thus: Huns (: =) IH, =(1-0,696)14=4,26em The saturation capacity is determined as follows: Air flow rate = 754 x 3600 x 0,00115 = 3122g/h. Total alcohol adsorbed (= 10° Jar22.61-9559 Saturation capacity = 9,55/79,2 = 0,12 g aleohol/g carbon 60 (b) For new t,=60h Hy==5>x974=165 cm H, =16,5+4,26=20,76 cm Note In the scale — up from laboratory scale to production scale it may be necessary not only to change the height but also the diameter of the column. The mass velocity per unit cross — section must be the same for both columns and this results in an increased column diameter for the plant scale. Bed heights of 0,3 m to 1,5 m are typically used with downflow of the gas while superficial velocities are between 0,15 and 0,5 m/s. The pressure drops across the CEMaM3-C ~136- Chapter S UNISA Engineeringbeds are low and of the order of a few cm water. The adsorption time varies between 0,5 and 8 h. For liquids the superficial velocity of the liquid varies between 0,03 and 0,07 m/s. 5.4 DESIGN OF COUNTERCURRENT FLOW OF SOLIDS Better utilisation of adsorbent ® is achieved when the adsorbent is removed to be regenerated as soon as it becomes saturated. This can be achieved if the adsorbent moves slowly downwards in the column while the feed gas moves upwards through the bed. This type of operation is achieved in the so called hypersorber of which a sketch is given below. Cooler am i Top Sorption section —. TRC Feed Rectitying i Side cut section steam {Bottom oe Stripper Feeder Lift blower Figure 5.4 The Higgins contactor®), shown below, is operated intermittently but continuous adsorption is also approached in this contactor. CEMAM3-C “137- Chapter 5) UNISA EngineeringPiston stationary Piston Piston Liquid to be treated Treated liquid [7 Regenerating liquic Y YY The temporarily stationary upper bed of adsorbent is contacted with liquid that flows downward so that the solid is not fluidised as shown in figure (a). In the lower bed the adsorbent is regenerated by an eluting liquid. Figure 5.5 After a relatively short time the liquid flow is stopped and the valves are turned as shown in figure (b). The liquid filled reciprocating pump is started for a few seconds. During this short time some solids are moved hydraulically in a clockwise direction. The valves are then moved to the original positions, the movement of adsorbent is completed and the liquid flows are started again. CEMAN3-C ~138- Chapter 5 UNISA Engineering5.4.1 Design Method for Countercurrent Flow The adsorption of only one component from a fluid stream will be discussed here. The process can be considered to be analogous to gas absorption with the adsorbent replacing the liquid phase. Refer to the following sketch. AosonBEnT ar i aA T t ia | Cereus curararert citemcntore a) ‘component Figure 5.6 G, and S, are the solute ~ free fluid and solid mass velocities respectively expressed as mass/(cross-sectional area of column x time). Solute concentrations are expressed as mass of solute/mass solute — free substance. The following derivation is for a gas stream but it also holds for a liquid stream if G. is replaced by Ls. CEMAMS-C 139- Chapter 5 UNISA EngineeringAn adsorbate balance over the whole column yields: Gg (¥,-Y2)=Ss (XX) (10) An adsorbate balance over the top part of the column yiels: Gs (Y¥~Y2)=Ss(X-Xo) (11) Equation (10) is the operating line with slope end it passes through the s coordinates (X1 ; Ys) and (X2 ; Y2). The equilibrium curve, at the given temperature and pressure, is again plotted on the ‘same graph as the operating line. For adsorption the equilibrium curve will be below the operating line and above it for desorption. The minimum adsorbentfluid ratio is again given by the operating line with a maximum slope which touches the equilibrium curve anywhere. The above derivation is only valid for isothermal conditions. This implies that only dilute mixtures are considered. Like in absorption a balance is struck for the transfer of adsorbate over the differential height of the adsorber dZ, thus: S,dX=G, dY=K, a, (Y-Y")dZ (12) where CEMAMS-C “140- Chapter UNISA EngineeringY’ is the equilibrium composition in the gas corresponding to the adsorbate concentration. The driving force Y-Y" is represented by the vertical distance between the operating line and the equilibrium curve. Similar to absorption can it be shown that: (13) where G. Ka, Nios = the number of transfer units and Hog = (14) Hyog is again the height of a transfer unit. The height, Z is determined by solving the first integral of equation (13) graphically and a knowledge of the height of a transfer unit, Hio- The mass transfer within the pores of the adsorbent can be characterised by an individual mass — transfer coefficient k, a, or height of transfer unit. H,s thus: (15) where m=dY" /dX the slope of the equilibrium curve. CEMANS-C “at Chapter 5 UNISA EngineeringH,, and kya, can be estimated for moving beds by using the correlations that are available for fixed beds. Example 4° For the adsorption of water from air by silica gel the following relations have been determined by using fixed bed/semicontinuous technique. ky a, =316G'° kgwater/m?sAY k, a, =0,965kg water /m? sAX where G' is the mass velocity of the gas, kg/m’s. The apparent bed density is 671,2 kg/m? and the average particle size is 1,727 mm. The external surface of the particles is 2,167 m’/kg. Determine the height of a continuous countercurrent isothermal adsorber operating at 26,7°C and 1,013 bar (abs) that has to decrease the water content of air from 0,005 kg water/kg dry air to 0,0001 kg water/kg dry air. The entering gel will be dry. The flow rate of the gel is 0,68 kg/m? s and that of the air is 1,36 kg/m’s. The equilibrium relationship is given by Y° =0,0185X Y;=0,005 ; Y2=0,0001; Ss=0,68 ;Gs=1,36 ;X2=0 X; is determined from equation (10), thus. x, (0,005 -0,0001)+0=0,0098 Gsiy _ S, (Y,-Yo )+Xo When the equilibrium curve and the operating line are both straight the logarithmic average of Y- Y at the inlet and outlet is used to calculate Niog = —t=~2 — (Y-Y") sogmean CEMANE-C “ae Chapier 5 UNIsA EngineeringY, Yj =0,005 -0,01850,0098=0,00482 Y, -¥; =0,0001 . (0,00482-0,0001) (OY aren = 9100482 0,0001 =0,001218 (¥%,=Ye)___ 0,005-0,0001 Nes (YY Jinan 00T218 “0? G s, From equation (15) Hyg =-"S~ and Hy, =" kya, 8 kea, 136 ho gugeqagss700963M and His = From equation (15) Hoo Hie MOE, 20185198 0 7047 -00624 Ss 06 Z=Nyog Hios = 4,020,0624=0,25m Note Treybal calculates a relative average velocity of air and the solid that amounts to G = 1,352 kg/m’s. The resultant H; oc = 0,0365 m instead of the 0,0363 m calculated above. 5.5 RECAP + Some physical properties of commercial adsorbents are given. ‘* Equilibrium relations are discussed and it is shown how to determine which one fits the experimental data best. CEMaM3-C “143 Chapter 5 UNISA Engineering* Methods are given to solve batch adsorption, fixed bed and countercurrent flow problems. CEMAM3-C 14a Chapter 5 UNISA Engineering5.6 EVALUATION Problem 1% Equilibrium isothermal data for the adsorption of glucose from an aqueous solution by activated alumina are as follows: ¢, kgim™ | 0,004 [9.0087 [0019 [0,027 [0,094 —*0,73 akg 0026 [0,053 | 0,075 [0,082 0,123 [0,120 solute/kg alumina Determine the isotherm that fits the data and give the constants of the equation. Answer: Langmuir isotherm, q = 0,143 o/(0,0179 +c) Problem 2 A waste water solution with a volume of 2,5 m® contains 0,25 kg phenol/m® of solution. This solution is mixed thoroughly in a batch process with 3,0 kg of granular activated carbon until equilibrium is reached. Use the isotherm of Problem1 to calculate the final equilibrium values and the percentage phenol removed. Answer: c = 0,064 kg/m?; q = 0,115 kg phenol/kg alumina; 68 % Problem 3 Using the break — point time and other results from Example 3 do the following: (a) The break — point time for a new column is to be 8,5 h. Calculate the new total length of the column required, column diameter, and the fraction of total capacity used up to the break point. The flow rate is to remain constant at 754 cm'/s. CEMAMB-C “145- Chapter 5 usa Engineering(b) Use the same conditions as part (a) but the flow rate is to be increased to 2.000 om/s. Answer: (a) Hr = 27,15 cm; 0,849 fraction; same column diameter of 4 om (b) D=6,51.m Problem 4“? Water is removed from nitrogen by passing it through a packed bed that is filled with molecular sieves. The bed is operated at 28,3°C. The bed height is 0,268 m with the bulk density of the solids being 712,8 kg/m The mass velocity of the nitragen is 4.052 kg/m*h. The inlet water concentration c. = 926 x 10® kg water/kg nitrogen. The breakthrough data are given below. [hr 0 8 [92 |96|10 |i04 [ekgH2 O/kg Nox 10" [<06/06 [26 [27 [ot | 235 [tr 70.8 | 11,25] 41,5 | 12 [125/128 [@ Rg HOTKG Nex 10" 418 [630__| 717 [855 | 906 | 926 | A value of c/cy = 0,02 is required at the break point. Do the following. (a) Determine the break — point time, the fraction of total capacity used up to the break point, the length of the unused bed and the saturation capacity of the solid. (b) For a proposed column length Hr = 0,40 m calculate the break — point time and fraction of total capacity used. Answer: (a) _ ty = 9,6h, fraction used = 0,89; ,189 kgwaterlkg mol sieve saturation capacity = CEMAN3-C “146 Chapter 5 UNISA Engineering(b) break point time = 14,9 h; 0,927 Problem 5“) A dilute mixture of NOz in air is fed to a continuous countercurrent adsorber that contains silica gel. The gas enters the adsorber at a rate of 0,126 kg/s and contains 1,5 % NOz by volume. 90% of the NOz must be recovered. The process is operated isothermally at 25°C and 1,013 bar (abs). The equilibrium adsorption isotherm at 25°C is given below. Partial pressure NO2,mmHg |0/2 |4 |6 9,4] 11,2 [12 kg NO2/100kg gel 0/0,4 | 0,9 | 1,65 | 2,6 | 3,65 | 4,85 (a) Calculate the minimum of gel required per hour (b) Calculate the number of transfer units required for 2 x minimum gel rate. (c) A superficial air rate of 0,407 kgim/s is to be used. Assume that the characteristics of the gel are the same as that in Example 4, Assume also that the mass transfer coefficients, used in the example, can be used as such in this problem. Estimate the value of Hog and calculate the corresponding height of the adsorber. Answer: Nios = 4,29; Hiroe = 0,09 m ; Z = 0,4m CEMANS-C “147- Chapter 5 UNISA EngineeringCHAPTER 6 CRYSTALLISATION CONTENTS 6.1 LEARNING OUTCOMES... 6.2 INTRODUCTION... 6.2.1 Effect of Temperature on the Solubility of Solutes.. 6.2.2 Fractional Crystallisation ... Yield of Crystals Vacuum Operation Some Types of Crystallisers.. 63 RECAP. 6.4 EVALUATION.. CEMAM3-C -148- UNISA Chapter 6 Engineering6.1 LEARNING OUTCOMES After completion of this section a student should know how some common types of crystallisers look and how they function. * Be able to do solute and solvent balances * Be able to determine the energy requirements of crystallisers. * Be able to use equilibrium diagrams 6.2 INTRODUCTION Crystallisation is an operation which allows a solute to be recovered as solid crystals from a solution. It can be used to purify mixtures or to produce crystals with the desired size range. The production of sugar from sugar cane or beetroot is an example of a large scale crystallisation process. Crystallisation is effected by either lowering the temperature of a solution or by evaporating some of the solvent. The energy that is required during a cooling process includes the sensible heat of the solution and the heat of crystallisation. In the evaporative process the major energy requirement is the latent heat of vapourisation of the solvent. Benzene's heat of crystallization is 126 kJ/kg while its latent heat of vapourisation is 394 kJ/kg. It is thus clear that, from an energy point of view, cooling is the preferred process. The crystallization process consists essentially of two stages which proceed simultaneously. The first is the formation of nuclei, which must exist in the solution before crystallization will commence. This is followed by the growth of the crystals. Normally a degree of super - cooling is required before crystallization will commence. A metastable condition thus exists at temperatures that are slightly below the temperature where nucleation should start. CEMAN3-C -149- Chapter 6 UNISA Engineering6.2.1 Effect of Temperature on the Solubility of Solutes In crystallisation equilibrium is attained when the solution ( also called mother liquor ) is saturated. This is represented by a solubility curve. Solubility is mainly dependent on temperature and pressure has a negligible effect. In solubility plots the solubility data are normally given as parts by mass of anhydrous material per 100 parts by mass of solvent The solubility of some solutes in water'?) are shown in the following sketch. Liquor temperature ( °C) {kg salv'100 kg water) 3 8 300 350 400 Liquor temperature (K) Figure 6.1 CEMANE-C “150- Chapter 6 Engineering UNISAThe solubility of a solute normally increases with increasing temperature and this increase is called a positive temperature coefficient. When the solubility decreases the temperature coefficient is negative. In some cases the coefficient can be zero. Refer to the curves of sodium phosphate and ferrous sulphate. It can be seen that the curves are discontinuous when the crystal forms change as the temperature is altered. The temperature coefficients change from positive to negative as the temperature is increased. Anhydrous salts tend to have negative coefficients. KCIO; has a large positive coefficient and can be readily crystallized by cooling a saturated solution. NaCI has a small positive coefficient and it is thus not possible to crystallize this salt effectively by cooling. The curves of sodium hydrogen phosphate and ferrous sulphate show discontinuities when a crystal form changes to another. Crystallisation of a saturated ferrous sulphate solution below about 320 K results in the formation of FeSO,.7H.0. Between about 320K and 330K FeSO,.4H,0 will crystallize, and above 330K FeSO,. 6.2.2 Fractional Crystallisation Consider the phase diagram of ortho-, meta- and para- mononitrotoluene. CEMaM3-C ~151- Chapter 6 UNISA EngineeringPara 324.7 K (51.5°C) 100% — Temperature (°C) Eutectic 270.4 28°C) Eutectic 256.9K (-16.3°C) Ortho 269K (-4°C) Meta 289 K (16°C) Phase equilibrium diagram for ortho-, meta-, para-mononitrotoluenes Figure 6.2 Point P represents a mixture containing 3% ortho, 8,5% meta and 88,5% para isomer. If this molten mixture is at a temperature that is above 46°C no crystals are formed and only at this temperature will crystals start to form. On further cooling the composition of the remaining liquor is shown by the line PQRS for various temperatures indicated by the horizontal lines. On cooling only the para isomer crystallizes and the ratio of ortho to meta remains constant. This situation prevails until point S is reached when further cooling along line SE results in the crystallization of the meta isomer. Further cooling to point E results in the formation of a ternary solid eutectic mixture. It is thus undesirable to cool below point E. When the mixture represented by point P is cooled to 0°C, the recovery of the para isomer is about 85%. Cooling to ~ 18°C gives a recovery of about 95%. This ‘CEMAM3-C ~152- ‘Chapter 6 UNISA Engineeringincreased recovery is, however, only possible by using a refrigerant that significantly increases the recovery costs. Note: An eutectic mixture is defined as one in which the constituents are in such proportions as to solidify at one temperature. 6.2.3 Yield of Crystals The yield of crystals can be calculated by doing solvent and solute balances. The initial and final concentrations of the solute must be known. When the solvent is water hydrated salts can form at certain temperatures, and this aspect must be taken account of. The initial solvent present is then equal to the sum of the final solvent in the mother liquor, the crystal water in the hydrated salts and any water that has evaporated. ‘A water balance is then: w,=w, +(y aa )+w,E (1) where: w,,w, are the initial and final masses of solvent (water) y __ isthe yield of crystals R__ is the ratio of the molecular mass of the hydrate / molecular mass of anhydrous salt E ratio of mass of solvent evaporated / mass of solvent initially present A solute balance gives: w,c,=w, 6, +% 2) where c,,c, are the initial and final concentrations of the anhydrous salt expressed as mass of anhydrous salt/unit mass of solvent. From equation (1) CEMAM3-C “153- Chapter 6 UNISA Engineering(1-£) LED 8) it can be shown that by substituting (3) in (2) that: (4) Note: mother liquor is a term frequently used instead of solution. Example1” A solution of 500 kg Naz SO, in 2500 kg of water is cooled from 333 K to 283 K in an agitated mild steel crystalliser. At 283 K the stable crystalline form is Naz SOx.10 H20. During cooling 2 mass % of water is lost by evaporation. Estimate the yield of crystals. At 283 K the solubility of Naz SO, is 8,9 kg/100 kg water. R= 322/142 = 2,27 = 500/2500 = 0,2 kg/kg water 2 = 8,9/100 = 0,089 = 2.500 kg water E = 0,02 kg/kg water Equation (4) then gives: CEMAM3-C -154- Chapter 6 UNISA EngineeringExample 2 Determine the heat that must be removed for the above example given the following: mass of mild steel crystalliser = 750 kg specific heat of mild steel = O5kd/kgk heat of solution of NazSO;.10H20 = — -78,5MJ/kmol specific heat of solution = 36k /kgK latent heat of vapourisation = 2400 kd/kg Heat of crystallization is the opposite of the heat of solution = + 78,5 Md/kmol = 78500/322 = 243,8 kJ/kg Thus heat of crystallization = 243,8 x 723 = 176 267 kJ Heat removed to cool crystalliser = 750 x 0,5 (333 - 283) = 18750 kJ Heat removed by cooling the solution = (500 + 2500) x 3,6 x 50 = 540000 kJ Heat lost by vapourisation of 2% water = 2500 x 0,02 x 2400 = 120000 kJ Heat to be removed = 176267 + 18750 + 540000 ~ 120000 = 615017 kJ 6.2.4 Vacuum Operation Crystallisers are frequently operated under a vacuum. The amount of evaporation can be calculated by using the following formula that is based on a heat balance. Heat balance: Solvent evaporated x latent heat = drop in sensible heat +heat of crystallisation ‘CEMANB-C -185- ‘Chapter 6 UNISA EngineeringThus: Ew,2=C, (T,-T,)w, (1+¢,)+4.¥ (6) where: 2. is the latent heat per unit mass a is the heat of crystallisation Cc, is the mean heat capacity of the solution T,andT, are the initial and final temperature of the solution w, is the initial mass of solvent in the liquor °, is the initial concentration of the solution (mass of anhydrous salt per unit mass of solvent) ‘Substituting equation (4) in (5) yields: 9 R(C,-C2)+C, (T, ~Ts (146, [1-2 (R-1)] . n=, (R—1)]-a, Rez (6) Example 3?) Determine the yield of CH3COONa.3H20 when an aqueous solution containing 40% CH COONa is crystallized in a vacuum crystalliser that operates at 1,33 k Pa. The solution is fed to the crystalliser at 0,63 kg/s at 355 K. The solution has a boiling point rise of 11 K. The heat of crystallization is 144 kJ/kg while the mean heat capacity of the solution is 3,5 kJ/kg K. At 1,33 kPa water boils at 284,5 K and its latent heat of vaporisation is 2 477 kJ/kg. Solubility data: | Temperature, K [273 283 293 303 313 Solubility, 36,3 | 408 465 545 65,5 kgi/kg water CEMaMS-C “186- Chapier 6 UNISA EngineeringThe solubility data is plotted in the following graph. Temperature | 273 283 | 293 303 313 K ‘Solubility 36,3 40.8 465 545 655 Kg/kg water 8 7 60 g a) g 2 ” » 0m 290 300 310 = 1K Solubility graph ‘Temperature of the liquor = boiling point of water + boiling point rise = 284,5 + 11 = 295,5K At 295,5 K the solubility of CH; COONa is found from the graph to be 49 kg/100 kg water. Thus C2 = 0,49 kg/kg water. cr = 0,4/0,6 = 0,667 R= 136 / 82 = 1,66 CEM4M3-C —tB7- UNISA Chapter 6 EngineeringSubstitution of these numerical values in equation (6) yields: ge _ (144166 x( 0,667 -0,49)) +35 355 ~205:5)(1+0,667)[1-0.49(166~1)] ~ 2477[1-0,49(166-1)]-144x166x0,49 = 0,373kg/kg water Feed rate of water = 0,6 x 0,63 = 0,378 kg/s Substitution of these values in equation (4) yields: 4466x0,378 {0,667 -0,49(1-0,373)] [1-0,49(166-1)] roan 6.2.5 Some Types of Crystallisers Swenson — Walker Crystalliser This type, shown below, consists of a relatively long, horizontal open trough that is fitted with some scraping mechanism. It is divided in a number of sections each with a cooling jacket. It is thus possible to control the cooling rate quite effectively. The scraper keeps the cooling surfaces free of crystals. Spontaneous nucleation is effected in the first section by suitable adjustment of the temperature. Cooling water or refrigerated brine can be used in the jacket. CEMAMS-C 158- Chapter 6 UNISA Engineering‘Swenson Walker crystalliser Figure 6.3 Wulff — Bock Crystalliser ? This crystalliser, shown below, is similar to the Svenson — Walker crystalliser but air cooling is used and it is claimed to give uniformly sized crystals. This crystalliser is fitted with a rocking mechanism that causes a slow side to side rocking. It is also fitted with side baffles that are alternately fitted to opposite sides. CEMAM3-C -159- Chapter 6 UNISA EngineeringWulff-Bock crystalliser Figure 6.4 Double Pipe ( Votator ) 7 This a linear type cooler crystalliser. The cooling medium flows through the annular jacket while the process fluid passes through the inner pipe that is fitted with a scraper. Very high heat transfer coefficients are obtained due to the turbulence that is created by the scraper. It is very suitable for viscous or heat sensitive liquids. A sketch of a votator is shown below. CEMaMS-C ~160- Chapter 6 UNISA Engineeringrout inte Product inlet Heat transfer medium inlet === ]— Inlet temperature gauge _ j (era Outlet temperature gauge Heat transfer mecwmouter | | Extrusion valve product outlet The Votator apparatus Figure 6.5 Oslo Crystalliser This type of crystalliser is shown in the following sketches. A supersaturated solution is passed upwards through a bed of crystals that is kept in a fluidised state. Uniform temperatures are relatively easily obtained in fluidised beds and this is also the situation here. The smaller crystals segregate at the top of the bed with the larger ones at the bottom. Refer to the sketch of the cooler crystalliser. Mother liquor is withdrawn near the feed point E by a circulating pump that passes this stream through a cooler where the solution becomes supersaturated. It is then fed to the bottom of the crystalliser through pipe B. 6 UNISA Engineering CEMAMS-C ~161- ChapterThe final product is removed entirely through valve M at the bottom of the vessel. A uniform product is obtained because the crystals are only discharged once they have grown to the required size. In the evaporative crystalliser an evaporator is installed on top of the crystalliser. This type can be used for compounds with small temperature coefficients. The solution first passes through a heater and then to the flash evaporator before being returned to the crystalliser. i Motor and pimp} ah J | a —— slo cooler erystaliser (Oslo evaporative crystaliser Figures 6.6 CEMANB-C “162° Chapter 6 UNISA EngineeringExample 4 @ A solution containing 23 mass % NasPO, is cooled from 313 K to 298 K in a Swenson — Walker crystalliser to form crystals of Nas PO, . 12 HzO. The solubility of NasPO, at 298 K is 15,5 kg/100 kg water. The required flow of crystals is 0,063 kg/s. The mean Cp of the solution is 3,2 kJ/kg K and the heat of crystallization is 146,5 kJ/kg. The cooling water enters at 288 K and leaves at 293 K. The overall coefficient U is 0,14 kWim? K. The heat transfer area that is available is 1. m’/m length. Determine the length of the crystalliser. Assume that the evaporation is negligible. Let the basis be 1 kg of feed MM (molecular mass) of hydrate = 3 x 23 +31 + 64 + 12 x 18 = 164 + 216 = 380 MM of anhydrous salt = 164 R = 380/164 = 2,32 1 = 23/77 = 0,299 62 = 0,155 w; = 0,77 _Rw,[e,-c,(1-E)] _ 232x0,77[0,299-0,155(1-0)] = 0:323kg [1-c,(R-1)] [1-0,155(2,32-1) Required feed rate = 0,063/0,323 = 0,195 kg/s Heat duty Sensible cooling heat = 0,195 = 3,2 x 15 = 9,36 kW Heat of crystallization = 0,063 x 146,5 = 9,23 kW Total duty = 18,59 kW ‘Assume counter flow CEMANS-C 6a Ghapier 6 UNISA Engineering313 298 293 288 a 13 — 293 = 20 98 — 288 = 10 (20 — 10V/In 20/10 = 14,4 K A0m A= 18,59/(0,14 x 14,4) = 9,22 m? L=9,22m Example 5 Solve the following problem by doing material balances and compare the answers with that obtained by using the formulae given above. 10 000 kg of a salt solution that contains 30 mass % Naz COs is cooled to 293 K. The salt crystyllises as the decahydrate. What will be the yield of Naz CO3 . 10 H2 O if the solubility at this temperature is 21,5 kg Naz COs per 100 kg water.(a) assume no water is lost by evaporation (b) assume that that 3 % of the total mass of the solution fed is lost by evaporation during the cooling process. CEMAM3-C ~164- Chapter 6 UNISA EngineeringWkg He O S kg solution 10 000kg soln. fs 21,5 kg Naz COs / 100 kg He O crystalliser 30 % Nap COs C kg crystals, Naz COs . 10 H 20 > (a) W=0 MM of hydrate = 2 x 23 + 12 + 48 + 10 x 18 = 106 + 180 = 286 Water balance: 0,7 x 10 000 = 100S/(100 + 21,5) + (180/286) C +0 Naz COs balance: 0,3 x 10000 = 21,5S/(100 + 21,5) + (106/286)C From these two equations C = 6357 kg _S = 3643 kg Use the formulae R = 286/106 = 2,7 c; = 0,3/0,7 = 0,4286 C2 = 0,215/1 = 0,215 wi = 7000 kg 2,7x7000[0,4286-0,215] 277000104286 02191 6363 k [1-0,215x17] o (b) Water lost by evaporation = 0,03 x 10000 = 300 kg Water balance: 7000 = 0,823 S + 0,629 C + 300 Salt balance: 3000 = 0,176 S + 0,371C These two equations yield: C = 6627 kg and S = 3073 kg The formula yields: y = 6637 kg with E = 300/7000 = 0,0428 CEMAM3-C =165- Chapter 6 UNISA EngineeringExample 6” A feed solution of 2268 kg at 328 K that contains 48,2 kg MgSO4/100 kg water is cooled to 293K where MgSO, . 7 Hz O crystals are removed. The solubility of the salt at 293 K is 35,5 kg MgSO,/100 kg water. The average heat capacity of the feed solution is 2,93 kJ/kg K while the heat of solution at 293 K is — 13,31 x 10° ki/k mol hydrate. Calculate the yield of crystals and the heat absorbed assuming no water is vapourised. MM MgSOg . 7 He O = 24 +32 + 64+ 7 x 18 = 120 + 126 = 246 He O balance: (100/(100 + 48,2) x 2268 = 1531 = 0,738 S + 0,512C Salt balance: (48,2/(100 + 48,2) x 2268 = 737 = (36,5/(35,5 + 100)) x S + (120/246) These two equations yield C = 632 kg and S = 1636 kg Sensible heat of cooling = 2268 x 2,93 x ( 328 - 293 ) = 232583 kJ Heat of crystallization = + 13,31 x 10° x 632/246 = 34195 kJ Use the formulae: R =246/120 = 2,05 wy = 2268 x (100/(100 + 48,2)) = 1531 kg cy = 0,482 62 = 0,325 15x1531% {0,482 [1-0355x 105] 55) = 635 kg andS= 268-635-1633 kg Sensible heat of cooling = 2268 x 2,93 x (328 - 293) = 232583 kJ Heat of crystallization = + 13,31 x 10° x 632/246 = 34194 kJ CEMAM3-C ~166- Chapter 6 UNISA EngineeringHeat to be removed = 232583 +34194 = 266777 say 266800 kJ 6.3 RECAP * Crystallisation is introduced to the student * Some typical equilibrium diagrams are discussed ‘© The fractional crystallisation of an isomer from a mixture of isomers is discussed * Equations are derived that can be used to do material balances of the solvent and the solute + Itis shown how energy balances can be made for crystallisers + Some types of crystallisers and their operation are discussed CEMAMS-C “167- Chapter 6 UNISA Engineering6.4 EVALUATION Problem 1 1 000 kg of KC! is dissolved in sufficient water to make a saturated solution at 363 K. At this temperature the solubility of KCI is 35 mass %. The solution is cooled to 293 K at which temperature the solubility is 25,4 mass %. Determine: (a) the mass of water required to obtain the required solution and the mass of KCI crystals formed after the solution has been cooled to 293 K and what is. the amount of crystals obtained if no water evaporates? (2) What is the mass of crystals obtained if 5% of the original water evaporates on cooling? Answer: (a) 1857 kg water, 368 kg crystals (b) 399 kg crystals Problem 2 A feed solution Of 4500 kg at 54°C containing 47 kg FeSO,/100 kg water is cooled to 27°C where FeSO, . 7 H2 O crystals are removed. At 27°C the solubility is 30,5 kg FeSO,/100 kg water. The average heat capacity of the feed solution is 2,92 kJ/kg K. The heat of solution is -18400 kJ/k mol FeSO4.7H20. Calculate the yield of crystals and determine the amount of heat that must be removed. Assume that no water is vapourised. Answer: 1233 kg FeSOx.7H,0; heat to be removed = 436 400 kJ. CEMAMS-C -168- ‘Chapter 6 UNISA EngineeringProblem 3 A hot aqueous solution of Ba (NO; )2 contains 30,6 kg Ba(NOs )2/100 kg water. This stream is fed to a crystalliser where the solution is cooled and Ba (NOs). crystallises. On cooling 10% of the original water present evaporates. For a feed solution of 100 kg calculate: (a) the yield of crystals if the solution is cooled to 290 K where the solubility is 8,6 kg Ba (NO3)2/100 kg water (b) the yield if the solution is cooled to 283 K where the solubility is 7,0 kg Ba (NOs)o/100 kg water. Answer: (a) _17,51 kg Ba (NOs), crystals, (b) 18,6 kg Ba (NO;),crystals Problem 4? Naz SO,.10 H-0 is to be produced in a Swenson — Walker crystalliser by cooling an aqueous solution of NaSO, to 290 K which saturates at 300 K. Cooling water enters and leaves the unit at 280 K and 290 K respectively. How many sections of crystalliser, each 3 m long, will be required to process 0,25 kg/s of the product? The solubilities of anhydrous Naz SO, in water are 40 and 14 kg/100 kg water at 300 K and 290 K respectively. The mean heat capacity of the liquor is 3,8 kJ/kg K and the heat of crystallisation is 230 kJ/kg. For this crystalliser the available heat transfer area is 3 m’/m length. The overall heat transfer coefficient is 0,15 kWim*K. The molecular masses are: NazSOx.10 H2O = 322 kg/kmol and NazSO, = 142 kg/k mol. Assume no evaporation. Answer: about 9 CEMAM3-C =169- Chapter 6 UNISA EngineeringProblem 5” What is the evaporation rate and yield of CH;COONa.3H,0 from a continuous evaporative crystalliser operating at 1 kPa when it is fed with 1 kg/s of a 50 mass % aqueous solution of CH;COONa at 350 K? The boiling point rise of the solution is 10 K and the heat of crystallisation is 150 kJ/kg. The mean heat capacity of the solution is 3,5 kJ/kg K and 1 kPa water boils at 280 K at which temperature the latent heat of vapourisation is 2 482 kJ/kg. Over the temperature range 270 to 305 K the solubility of CH3COONa in water s at T (K) is given by s = 0,61 T — 132,4; kg/100 kg water. MM of CH;COONa.3 HO = 136 kg/k mol and that of CH;COONa = 82 kg/k mol. ‘Answer: Evaporation rate, E = 0,265 kg/kg water (0,132 kg/s); y = 0,79 kg/s CEMAM3-C “170- Chapter 6 UNISA EngineeringCONTENTS 7.4 OUTCOMES. 7.2. INTRODUCTION™....... 7.24 7.2.2 7.2.3 7.24 7.25 7.2.6 7.27 7.2.8 7.2.9 7.2.10 MASS TRANSFER BETWEEN FLUID AND PARTICLE..... 7.2.11 Fluidised Bed Applications ... 7.3. RECAP..... 7.4 EVALUATION... CHAPTER 7 FLUIDISATION ; . 172 Effect of Fluid Velocity and Pressure Gradient... 174 Pressure Drop @) 176 Minimum Fluidising Velocity . 177 Minimum Fluidising Velocity for Non — ore Particles “o, sooo 180 Relation Between Bed Height and Porosity. 183 Effective Mean Diameter of Particles With Different Sizes .. 184 Expansion of Fluidised Beds" . 185 189 191 191 191 2194 192 Heat Transfer From or To a Surface ... Heat Transfer Between Fluid and Particles .. ‘CEM4M3-C_ UNISA aT Chapter 7 Engineering7.1. OUTCOMES + The student should have a good understanding of this process that is gaining importance in a range of industrial applications. + The student should be able to caloulate the pressure drop at calculated fluid velocity through the bed + The student should be able to determine the minimum fluidising velocity * The student should be able to calculate the bed height at given fuidising velocities. * The student should be able to distinguish the two types of fluidisation. 7.2. INTRODUCTION ® When a fluid passes downwards through a bed of solids particles, called a packed bed, there is no movement of the particles relative to each other. This is not necessarily the case when the flow is upwards. At low linear velocities there will still be no movement of the particles and the pressure drop will be same for both cases. As the flow is increased the frictional drag on the particles becomes equal to their weight less buoyancy and they become rearranged. They then offer less resistance to the flow of the fluid and the bed starts to expand. This process continues as the linear velocity of the fluid is increased until the bed has assumed the loosest stable form of packing. If the velocity of the fluid is further increased the individual particles are separated and the bed has reached the fluidized state. At even higher fluid velocities the particles will separate even further but the pressure difference across the bed will remain constant. The fluidized bed now behaves like a liquid or a gas. CEMAMB-C “72 Chapter 7 UNISA Engineering