III-39H memes ’I’tiIII-IIIIIzsII-I -‘ did {U ,~ '\\~\‘ < 5..- -~ aw. «‘4 - ‘Oct- . . Qt; THERMAL INACTIVATION 0F .POLYALACTURONASE IN A HELICALLY COILED HEAT EXCHANGER Thesis for the Degree of M. S. ‘ MICHIGAN ST ATE UNIVERSITY . PEI ER MINTZIAS ‘ 1977 . Q . - .. I . 0'. r-.—. -. t ‘I -.. ,. .. a ' ' ' 0v " . - . - Univcrsity 6‘ mm.u.:c~A ABSTRACT THEEMAL INACTIVATIG‘I OF RDLYGALACI‘UFONASE IN A HELICALIX (DILED HEAT EXOiANIER By Peter Mintzias The softening of brined cherries was first noticed about 1947. A pectin degrading polygalacturonase has proven to be responsible for this danage. Since spent cherry brine is a strong pollutant, its disposal into rivers and estuaries or into Inmicipal sewage systens my cause serious pollution problems depending upon the size of the systan and the amount of the disposed brine. Recycling of the spent brine seems to be a satisfactory answer to the disposal question. Such a brine must be heated before reusing to prevent softening of the cherries due to polygalacturonase activity. 'Ihe basic objective of this study was to detennine the mount of inactivation of polygalacturonase while it was receiving a certain and carefully controlled heat treatment in a helically coiled heat exchanger. The degree of inactivation was determined by the "cup-plate" procedure as described by Dingle _e_t_a_1_ . (1953) and Athanasopoulos (1976). Predic- tin: of the expected inactivation under pre-establ ished conditions was done by both the general and the analytical methods. Predicted and measured values were found to vary insignificantly, sanetimes less than -1.0%. Peter Mintzias Hot and cold water was used as the heating and the cooling medium, respectively. Side wall friction factors and heat transfer coefficients of a helical tube were found to be higher than those in a straight tube. 'lhe nagnitude of the coil diameter has a significant effect on the pressure drop and heat transfer through the coils. 'Ihe over-all heat transfer coefficient was predicted by an exponential relationship of temperature and time in the helix. 'lhe predicted values and those calculated by taking into account the resistance to heat flow fran one fluid to the other were fomd to vary from -0.9% to +9.0%. Viscosity, density, thermal conductivity, and specific heat of the treated brine were assumed to be identical to those of water. Based on heat transfer informtion and the heat stability of polygalactumnase measured by Athanasopoulos (1976) a tenperature of 80°C throughout the holding coil for 9 sec resulted in 99.985% inact ivat ion . 'I‘HERMAL INACI‘IVAT ION OF FOLYXiAcrURONASE IN A HELICAILY (DILED HEAT EXCHANGER By Peter Mintzias A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF $1M Department of Ibod Science and Human Nutrition 1977 To nw wife, Katherine The author wishes to express his deep sense of gratitude to Professor Alvin L. Rippen, Department of Food Science and Hum Nutrition, for his guidance, support and.patient tutelage throughout the course of this study. Dr. Pericles N. markakis and Dr. Richard.C. Nicholas, Professors of Food Science and Human Nutrition, are also acknowledged for their suggestions. Special appreciation is also due to Lloyd E. Lerew, whose recomnendations were seriously considered during the course of this amukn Finally, the author is particularly indebted.to Dr..Dennis R. Heldman, mailman of the Agricultural Engineering Departnent, for his perceptible assistance and brilliant counsel . iii TABLEOFCINI‘EN’I‘S LIST OF TABLES . LIST OF FIGURES SYLBCIS INI‘WJCI‘ICN LITERATURE REVIEW A. HEATTRANSFERAI‘DPRESSUREDKPINODILS . A—l. Pressure Drop , A—2. Heat transfer in coils B. SHELL-SHE HEAT TRANSFER AND PRESSURE DKP B—l. Pressure drop . B—2. alell—side heat transfer coefficients C. MAME OF HEAT W D. RECYCLING THE CHERRY BRINE. E. THE POLYGALACI‘UKNASE ENZYME E—l. Polygalacturonase in brined cherries E-2. Polygalacturonase kinetics, rate constants and stability F . POLYGALACTUM‘JASE INACI‘IVATIG‘I LEASURFMEN'I‘S AND CALCULATICN , F—l. Enzyme activity measurenents F—2. Process calculation , WWW A. INSIRIWI‘SANDMATERIAIS , B. 'I‘EMPERA’IUREMEASUREMENI‘S iv Page vi vii ix Loewe: 12 13 15 17 19 19 19 22 22 22 26 31 D. E. PRESSURE DRIP AND HEAT TRANSFER DETERMINATION C-l. Pressure drop . . . 0—2. Heat transfer calculations . PERFCRMANCE CALCULATICN . DEGREE OF INACI‘IVATIQ‘I MEASURE/[EMT AND CALCULATION RESULTS AND DISTUSSICN . A. PRESSURE DRIP. B. HEAT TRANSFER. C. PERFORMANCE OF THE EDPERIMENI‘AL HEAT EXCHANGER D. POLYGALACI‘UIDNASE HEAT TREATMENT . . . E. OPERATIONAL (DST OF THE PASI‘EURIZATICN PIDCESS (DNCLUSICNS . BIBLIGERAPHY. APPENDIX A APPENDIX B APPENDIX C .33 .37 -38 «47 ~47 ~52 .59 .63 .73 .76 .78 .85 Table LIST OF TABLES Specifications of the experimental heat exchanger . Calculation of cunnlative lethality. Calculated and neasured total internal pressure drop in the pasteurization unit, at several flow rates . Comparison of calculated and predicted shell-side heat transfer coefficients (W/m2.°C), under different temperature conditions . The over-all heat transfer coefficient (W/m2.°C), calculated under several tenperature conditions Effectivaiess and NTU of the experinental heat exchanger for pasteurizing cherry brine at a flow rate of 1 Kg/min at several process tenperatures Percent inactivation determined by the three nethods and percent deviation of the general and the analytical methods from plating. Polygalacturonase inactivation in each section of the experimental heat exchanger, calculated by the analytical method, using constant tenperature along the holding coil . . . . Rate constants for polygalacturonase at pH=3.0 and for pectinase from P. janthinellum at pH=3.7 Brine couposition for certain cherry varieties in Michigan Vi Page 28 46 52 62 67 72 Figure 10. 11. 13. LIST OF FIGURES Cross section of a tube in a helix showing secondary flow . . . . . Schematic diagram of the heating and cooling system for pasteurization of cherry brine 'I‘hemocouple locations for the wall, wall surface and fluid stream tenperature neasurement. Standard curve for polygalacturonase activity measurement . . Effect of the Be on the friction factor in straight and coiled tubes for laminar and turbulent flow Effect of curvature ratio on frictional factors in coils Effect of flow rate on the calculated total pressure drop in the coils of the pasteurization unit . . Inside heat transfer coefficients in the coils for different Re and differart curvature ratio Effect of the temperature difference ratio of the two fluids in the heater, on the over-all heat transfer coefficient. Effect of tenperature difference ratio of the two fluids in the cooler on the over-all heat transfer coefficient Tenperature profiles in the heater of the experimental heat exchanger Temperature profiles in the cooler of the experi- mental hat exchanger . . . Effect of temperature on the degree of inactivation . . . . vii Page 27 4O 48 51 53. 57 58 61 Figure 14 . 15. 16. Predicted time-tamerature profiles at several constant tenperatures along the holding coil. Themal resistance curves for pectinase from Aspeiillus niggr at pH 3.0 and for pectinase from Penicillium janthinellum at pH 3.3 . Arrhenius plot for polygalacturonase at pH 3.0 and pectinase from P.janthinellum at pH 3.7. viii .65 7O .71 SYLBOLS A Area, m2 A Proportionality constant in Arrhenius equation, sec41 b Temperature ratio in equation 43 c Specific heat at constant pressure, KJ/Kg—°C di Inside diameter of tube, m Dh Diameter of the helix, m D Decimal reduction time, sec Ea Activation energy, cal / mole f Fanning friction factor g Acceleration of gravity, m/sec2 h Convective heat transfer coefficient, W/m2-°C k Thermal conductivity, W/m— °C k Velocity constant of enzyme activity, sec-1 K Time parameter in equation 43, sec'1 L Length, m m Mass flow rate, Kg/sec P Pressure, N/m2 J Temperature parameter in equation 43, °K Heat transfer rate, KJ/hr R Universal gas constant, cal/g-mol-°K t Time, sec T Temperature, °C or °K U Over-all heat transfer coefficient, W/m2-°C V Velocity, m/sec Design criterion W Mass of brine in contact with the area of the heat exchanger, Kg x Characteristic dimension in the dimensionless groups, m Greek a Thermal diffusivity, mZ/sec B Coefficient of thermal expansion, l/°C 6 Effectiveness 11 Dynamic viscosity, Kg/m—sec v Kinematic viscosity, mZ/sec p Density, Kg/m3 Dimensionless Groups Dn = Re(di/Dh)0'5 Dean number Gr = gB('I\:2- T) x3 Grashof mmber Gz = :1 :p Graetz number Pr = Cpk“ Prantdl number Re = 49—3—1 Reynolds number Nu = 9—1-35 Nusselt number INI‘RGIIZTIQ‘I Spent cherry brine is difficult to handle in conventional waste treatment systems since it contains several thousand ppm 802, color and a considerable amount of solids. The brine has low pH also. Recycling of the brine has been proposed as a solution to the pollution problem and several researchers investigated the feasibility of a reclamation process. Spent brine may be contaminated during brining with polygalacturonase. A possible reuse of this material may result in enzymatic softening of the fruit. Therefore, pasteurization of the recycled brine is necessary. Athanasopoulos and Heldman (1976) examined possible commercializa- tion of a reclamation system based upon the work of other investigators (Soderquist, 1971; Panasiuk 932.1, 1976). Their pasteurization unit consisted of a helically coiled heat exchanger which was connected in line with the brine reclamation system. Pasteurization of polygalacturonase in a continuous process should be examined for a commercial operation to be rapid and controlled. Also such a unit will allow a predictable polygalacturonase inactivation. The objectives of this study were: 1. To determine the amount of inactivation of polygalacturonase present in spent cherry brine after heat treatment in a helically coiled heat exchanger. 2. To review the literature in heat transfer and pressure drop through coils and to modify several equations according to the 1 situation examined. 3. Tb calculate the performance of a helically coiled heat exchanger . LITERATURE REVIEW A. Heat Transfer and Pressure DrOp in Coils Coils have two major advantages over straight tubes, namely: (a) heat transfer coefficients in coils are higher than in straight tubes, (c) coils allow a greater heat transfer area to be packed into a given space more economically and more conveniently than in straight tubes. However, it is much easier to rerove scale from straight tubes than in coils. Friction factors are also higher in coils. The first theoretical analysis of the flow of nonconpressible fluids through helices was done by Dean (1927), who predicted the flow in the helix to be as illustrated in Figure 1, which shows a cross section of the tube in the helix. Figure 1. Cross section of a tube in a helix showing secondary flow. 3 The centrifugal force that exists in a curved pipe creates the secondary flow. This type of flow causes a larger pressure drop and heat transfer rate than that occurring in straight tubes. Dean introduced a dimensionless group which characterizes the dynamic similarity of fluid flow through a helix. This dimensionless group was named Dean's nurber (111) and it is equal to: Dn = Re(di/Dh)°‘5 where Re = Reynolds umber di = inside diameter of the tube (cm) Dh = diameter of the helix (cm) A—l . Pressure drop. Laminar Flow The friction loss in a tube is given by the following equation: AH = 2fLV2/gbdi (1) where AH = Head loss (N/mz) L = Length of the tube (111) di = Inside diameter of the tube (m) gC = Acceleration of gravity (m/secz) f = Fanning friction factors, dimensionless <1 ll Velocity of the fluid (m/sec) In straight tunes f = 16/Re. Therefore, frictional losses are highly dependent on Re. The parameters on the left side in equation (1) are all fixed for a certain process, except f. Thus, determination of f is of great importance in pressure loss calculations. Based on Dean's theoretical analysis, White (1929) proposed the fol lowing equation: f = C( l6/Re) (2) for 11.6 < Dn < 2000 - O . 5 where-é-= l-[l—(ll.6£2%é2il )°°“5]1/M5 Since C is dependent on Re and Dh/di, high velocities and small helix diameters will contribute to high pressure losses. For both isothermal and non-isothermal flow, Seban _e_t__a_tl_. (1963), taking into account the overall pressure drop , deduced the friction factor on the basis of fluid properties at the mean film temperature. They obtained results which were about 8 percent less than those obtained by equation (2). Flow of air within a curved tube was examined experimentally and analytically by Mori gt_a_l_. (1965) . Using an approximation technique for a series solution they derived the following equations for the first and second approximation: (fC/fS)I 0.1080Dn°’5 (3) l-3.253 m0 ' 5 (fa/f5): (fC/fs)1/ (4) where fc Fanning friction factor for coiled tube f 3 Equation (4) gave results similar to those obtained with the following Fanning friction factor for straight tube equation: fC/fs = 21.5 Dn / (1.56 + logm)5°73 (5) Ito (1959) derived the above equation for 13.5 < D1 < 2000 The use of the ratio fc/fs for pressure drop determination has the disadvantage that it cannot be used for Re greater than 2100 because under such conditions, the flow in a straight tube ceases to be in the laminar region while the flow in coiled tubes may be in the laminar region at much higher Re (Srinivasan et a1. 1968). The Critical Reynolds Number The highest Re where the viscous forces still have an effect to the dynamic forces streamline, is called critical feynolds umber. While in straight tubes this value of Re is fixed, at approximately Re 2100, in coiled tubes the curvature ratio determines the magnitude of the critical Re. Ito (1959) related the critical Re and the curvature ratio as follows: (R9) = 20000(di/Dh)°' 32 (6) crit According to Srinivasan et a1. (1968) the critical Re can be calculated as follows: (Re)crit = 2100(1 + 12(di/Dh))°‘5 (7) Turbulent Flow The work on pressure losses in smoth coiled tubes with isothermal turbulent flow was summarized by Ito (1959), who proposed two equations based on the results of several workers, namely fc = 0.0076(Re)-°'25 + 0.00725(di/D)°'5 (8) for 0.034 < Re(di/Dh)2 < 300 and fC/fB = [Re2]°'°5 (9) for R9(di/Dh)2 > 6 where fB is the Blasious value for a straight tube fB = 0.0791/Re Fbr Re in the range of 6000 to 65600, Seban et a1. (1963) obtained friction factors for isothermal and non-isothermal conditions. Their experimental results and those of Ito were found to be in good agreement, although they took the friction factor for a straight tube as fs = 0.046/Re0'2. Rogers and Mayhew (1964) experimentally obtained pressure drop results for isothermal conditions through coils for Re in the range of 3000 to 50000. They used coils with a different curvature ratio and their results agreed within 1.5 percent of those of Ito's equations. For non-isothermal conditions they suggested the following equation: fc = fm, [w]“/3 (10) Where fIto is given by equation (8) or (9), the subscripts b and w refer to the properties estimated at the bulk and wall temperature respectively. Fran the practical point of view, the best equation may be that published by White (1932): fC =0.08 Re-°'25 + 0.012(di/Dh)°‘5 (11) for 1500 < Re < 100000 The simplicity of equation (11) is evident and since it can be applied over a wide range of Re it can be used in various industrial helices where high velocities are encountered. In their investigation of air flowing in curved pipes, Lbri fl. (1967 ) developed a model which gave satisfactory results in comparison to equation (8) and to the experimental work of Seban _e_1_:_a_.]_._. (1963) and Ibgers et a1. (1964). Their model can be simplified as fc = 0.076 39‘0'25 + 0.00725(di/Dh)°°5 (12) A—2. Heat transfer in coils. Generally the heat transfer in tubes depends upon two parameters, namely Reynolds and Prandtl number. In coiled tubes a third parameter is introduced, that is the curvature ratio, di/Dh, which associates the effect of the secondary flow in the mechanism of heat transfer. Laminar Flow For air, water, and Fssolube 30 oil in laminar flow within a coil, Berg and Bonilla (1950) derived the following equation: hidi = [0.00002aa + 0.00063(di/D)] (1a)“29 (13) GP pf f where bi = inside heat transfer coefficient (W/m2.°C) 111. = dynamic viscosity at the film temperature (Kg/m.sec) cp = specific heat of fluid (KJ/Kg.°C) They found higher hi for oil and lower hi for air to the corresponding values of hi in straight tubes, although it is evident that coils have a higher hi. The average hi is specified by Seban ELEL (1963) as - —1/3 h; ‘11 (g) = A [f/8(Re)§]‘/3 <14) for 12 40 This is the region where natural convection predominates. The Nu in this region is given as, Nu =0 [(KGrf)°'5 +Re§]°‘51>r°°25 (25) f where C, and K are constants having different values depending on the geanetry and the tube arrangerent. C. Performance of Heat Exchanger In a conventional direct-type heat exchanger the parameters relating to the heat transfer performance are as follows (Kays and Iondon, 1955): U = The over—all heat transfer coefficient (W/m2.°C) A = The surface area on which U is based (m2) Thi = Inlet temperature of hot fluid (°C) 'IhO = Outlet terperature of hot fluid (°C) TC 0 = Outlet temperature Of the cold fluid (°C) Ch = (mop)h the hot fluid capacity rate (W/°C) Cc = (mcp)c the cold fluid capacity rate (W/°C) 16 Flow arrangement - i.e. counterflow, parallel flow, crossflow, parallel-counterflow or combinations of these basic arrangements. The over-all heat transfer coefficient carbines the convective and conductive mechanisms responsible for heat transfer from the hot to the cold fluid into a relationship similar to (Jim's Law. This relationship can be expressed as: . . 1A. 1 1 A1X A1 1 —‘T' = ‘—.- + + + (25) U1 hl Awkw tho hd AO where Ui = is based on the inside area A1 = Inside area (m2) Aw = Average wall area X = Wall thickness (m) A o = External or outside area kw = Thermal conductivity of the wall (W/m.°C) 1 /hd = Resistance due to scale on the ttbes In situations where the wall is very thin and the resistance due to scale deposit is negligible, equation (25) is reduced to, (26) C:‘.lr--l 51*“ p 5|” 81" Exchange: Heat Transfer Effectiveness According to Holman (1976) actual heat transfer maximum possible heat transfer effectiveness = e = 17 01‘ Cher .- (20‘ T ) 01(1) .__._____= (27) mania); ci : minETh T ) 101 where Cmin is the staller of the Ch and Cc magnitudes. In general it is possible to express 8 = F(NTU, Cmin/Cmax’ flow arrangement) Where NI‘U (Nmber of Heat Transfer Units) is expressed as, mu=—:‘}!=———1 fAUdA (28) NI‘U and e are related asymptotically for a given capacity ratio. Therefore, where NI‘U is small, the effectiveness is low and when NI‘U is large the effectiveness approaches the value of unity asymptotically, or the actual heat transfer approaches the value of the maximum possible heat transfer. D. Recycling the Cherry Brine Sweet cherries to be processed into maraschino, cocktail, or glacé fruit, are placed, directly after harvesting, into barrels that contain a brine solution of sulfur dioxide and various calcium salts. The brining process prevents quality deterioration of the fruit and further bleaches the cherries to a bright light yellow color. The bleached cherries also are stored in brine solution for later distribution in the market. After use, the brine may be discharged to a mimicipal 18 sewage system or it may be stored in tanks, where the solids are reroved by settling and the liquid is sprayed on land. The latter is adopted by a number of plants in Michigan. Spent brine contains a high content of solids, SOz. Ca++ and color pigment. In addition, it is characterized by low pH (Table A-l). Such a material is considered as a very strong pollutant. According to Soderquist (1971) a plant discharging spent brine at a rate of 38m3/day into the sewage system would be exerting a load (in terms of degradable organics) equivalent to 40,000 people or more. Brine recycling and reuse would solve a pollution problem and further lower new brine preparation costs. In 1970 Beavers M. introduced the idea of reclaiming the brine by passing it through activated carbon. Soderquist (1971) and Panasiuk 53131; (1975) examined the feasibility of a brine reclamation system and proved that treatment of brine by passing it through activated carbon does not lower the content of $02, CaH and soluble solids nor does it affect the pH, while cherries stored in reclaimed brine were found to have superior quality to those in a freshly prepared brine. Athanasopoulos and Heldman (1976) developed a large scale brine reclamation system based on the work of previous investigators. The system consisted of the following units: a. sand filter for suspended solids reroval, b. six columns that contained activated carbon for anthocyanin and polyphenol removal , and c. pasteurization unit for the inactivation of PG enzyme. 19 E. The Polygalacturonase Enzyme E—l. Polygalacturonase in brined cherries. Softening of brined cherries was first noticed about 1947 (Wiegand, 1954). In 1954 McCready reported that soft brined cherries seem to be attacked by a pectin degrading enzyme, since the stems fall off and part of the outer skin begins to slough. Fresh cherries infected with "cats claw" type of spoilage were found to contain an excessive amount of POly- galacturonase that causes softening of the fruit when brined (Steele fl. 1960). The polygalacturonase is a pectic enzyme capable of hydrolyzing 1,4—glycositic linkages of pectinic and pectic acids (Kertesz, 1951). Possible sources of polygalacturonase in brined cherries may be from microbial growth, certain cherry diseases, or the fruit itself might synthesize the enzyme during ripening (Steele e311. 1960). The enzyme sometimes retains active in the brine more than a year, and exposure to this brine produces soft fruit (Brekke fl. 1966). Several chemical methods have been proposed for polygalacturonase inactivation but their commercialization is in doubt since the safety of the chemicals involved may still be questioned. Inactivation by heat might be the only approach because no chemicals are needed (Soderquist, 1971 ; Walters et a1. 1961). E—2. Polygalacturonase kinetics, rate constants and stability, The inactivation of an enzyme and the thermal destruction of an organism can be described by first order kinetics, dC/dt = -kC (29) where dC/dt = activity change with time C = activity at any time k = velocity constant of the reaction (sec-1) By integration equation (29) gives, 1n C/Co = ~kt or log C/Co = -kt/2.303 (30) It is obvious that C in this relationship can never reach zero. By introducing the factor D (=2.303/k), which stands for decimal reduction time at a certain temperature, equation (30) gives, C/Oo = 10_t/D (31) Plotting temperature versus D on semi-log paper a straight line is ob- tained, which is called the "thermal-death time" curve of a microorganism or an enzyme. The reciprocal of the slope of the line is termed as the Z value. The straight line can be expressed as, T2 -T1 Z (32) 0T. = no X 10 If the Z value is large the texperature has a sraller effect on the TUI‘ tion if Z is small. Z and D values are fixed for a certain organism or enzyme under specified conditions. Athanasopoulos (1976) emerimeltally and theoretically determined the Z value of polygalacturonase to be 8.4°C and the D value to be 44.76 sec at 70°C. The velocity constant k can be expressed by the Arrhenius equation as follows: 21 k = A exp(—Ea/RT) (33) where Ea = activation energy (cal/mole) R = universal gas constant (cal/g.mole.°K) T = absolute temperature (°K) For a given environmelt, the velocity constant, k, for spores of a particular species will be a function of terperature only. Equation (33) can also be expressed as, log k = log A - Ea/2.303RT (34) which is the "Arrhenius Plot" of the reaction. The slope of the line is -Ea/2.303R and the intercept log A. The activation energy of poly- galacturonase is 64668.4 cal/mole (Athanas0poulos, 1976). The inactivation rate constants are highly pH dependent. The pH and decimal reduction time relationship is not linear because of the enzyme being more resistant at pH 2.8 to 3.5 (Athanasopoulos, 1976). Sugar concentration also affects the stability of the enzyme. The decimal reduction time does not change significantly when the soluble solids of the brine are in the range of 9 to 12%. However, when soluble solids exceed 12% they affect the inactivation rate constants since the strergth of the brine varies from one variety to another, influencing the composition (302 content, pH, solids). Windsor brine has a higher conceltration of 302, CaH, and pigrents, and exhibits lower rate constants than Napoleon brine. " 22 F. Polygalacturonase Inactivation Measurements and Calculation F—l. Enzyme activity measurements. The activity of an enzyme can be measured by determining the sub- strate losses or by measuring certain changes in the physical properties such as viscosity. RLmklyadeva and Korchagina (1975) introduced the interferometric method for comrercial pectic enzyme preparation. The method is rapid (less than two hours) and accurate (: 2%). Recently, the solid media technique has been introduced in the quantitative determination of enzyme activity. This procedure, developed for micro- organism cultivation, has been used for detection of enzymes by microorganism (Rankin and Anagnostakis, 1975). The agar "cup-plate" diffusion procedure has been applied to the quantitative determination of polygalacturonase (Dingle $3.1. 1953) . This test has been used by Steele and Yang (1960) and Beavers 323141970) for polygalacturonase activity determination in cherry brine. F—2 . Process calculation . The general method, first described by Bigelow _e_t__al. (1920), was an extension of partial sterilization. Ball _e_t___g.l_. (1957) defined partial sterilization as follows: if the TSP is t; min at T degrees, the: heating which lasts for t; min at T degrees, results in steriliza— tion which is tz/tl complete. Ball proved that sterilities are additive. In 1928 Ball introduced a hypothetical TUI‘ curve passing through 1 min at 250°F. Since lethality of a given process is the time in min of an 23 equivalent process at 250°F, then F in Ball's hypothetical TDI‘ curve is equal to 1, where F is the time required to destroy an organism at 250°F. According to this information equation (32) can be rearranged as follows: 250—T Z (35) log t/F = where t, is the time in min to destroy the organism at T degrees. Since F is 1 min, equation (35) is reduced to: log t = 35%3 (36) or t = 10 2524‘ (37) and l/t = 10 12250 (38) where 1/t is defined as the lethal rate (L) at terperature T. Therefore, for a giver process where Z is fixed and the terperature time relation- ship is known, the total lettality (degree of inactivation) can be calculated since lethalities are additive. Sturbo (1940, 1949, 1953) showed that in the case of conductive heating, a process with F=4 does not have twice the sterilizing capacity of another process with F‘r-Zmin. Deincberfer and Humphrey (1959) introduced the following analytical method: By integration of equation (29) 1n 00/0 = I: kdt = v (39) where V, the design criterion, is a measure of the size of the job to be accomplished or the degree of inactivation. If k varies in accordance with the Arrhenius equation, equation (39) gives 7 = A I: exp (-Ea/RT) dt (40) at constant temperature V = At exp (-Ea/R!1‘) = -kt (41) In continuous sterilization processes, where the medium flows through the heating, cooling, and holding section, V for heating and cooling is calculated from equation (40) and V for holding from equation (41). Therefore: + V + V (42) For a certain process, if the terperature—time profiles are known, them equation (40) results in integrals that can be solved analytically. The disadvantages of the method are: (a) it assumes that the entire population consists of spores of the design species, and (b) it requires heat transfer information for the analytical solution of the integrals. Another method devimd by Stumbo (1949) , Hicks (1951), and Gillespy (1962), bases the process time on the probability survival in the whole container. 25 The following assurption is another approach to the problem: if it is assured that after a process the slowest point is safe, then the rest of the fluid which must have a longer heating time must be safe. Richards (1965) has adopted a graphical solution which provides a ready means for the determination of the normal sterilization cycle. The tixne-terperature profile for a batch sterilization is plotted over the entire cycle. The cumulative values are then determined by stepwise integration over the complete cycle. ME’I‘HIBANDPWJRES A. Instruments and Materials Instruments Figure 2 shows a diagramatic description of the apparatus used in the experiment. The pasteurization unit consisted of three sections, namely, heating, holding, and cooling. The helix in the heater was 5.8 m (19 ft) long, in the cooler 3.97 m (13 ft), and in the holding section 4.88 m (16 ft). The tubes were made of stainless steel. The specifications of the writ are given in Table 1. An open pressure cooker was used to maintain the heating medium at a constant and controlled temperature. The heating medium was recirculated using a centrifugal pmp and the flow rate was measured with a rotameter located in the line downstream from the pump. Tb lessen scale build up on the outside of the brine coil in the heater the heating medium was passed through a cOpper coil immersed in a hot water bath. This enclosed indirect heating system reduced the amount of scale build up essentially to zero. The flow rate of the brine was of great importance. Steady-state condit ions within the pasteurization unit could not have been achieved with a fluctuating flow rate. A varying flow rate would result in a fluctuating and unpredictable degree of enzyme inactivation. The problem was solved by using two pumps and a supply tank positioned four 26 65.5 €020 mo gangs—558 sow Spam mfiaooo o5 gases no same? 0358 .N 0.53m . I assa $240528 $32559 $2; 5: ES E52032 H1... 523 5: v A 3.2,: fl 7 . . has: . . “.285 see. _ _ s - “ ¥z 40 The ratio Gr f/Re2 > 40 indicates that both natural and forced convection coexist, the natural being the predominant. Therefore, equation (24) should be used, where K = 1.7 and C = 0.235. In the cooler, natural convection did not seem to exist since the water was flowing upward while the density was increasing downward. It was assured that, because the velocity of the water was very stall (l m/min), the equations used for the heater would apply. Reynolds nurber calculations were based on the maximum velocity. The maximum velocity was considered to exist in the stallest cross sectional area. As the water flows upward (cooler) or downward (heater) two areas are involved: one between the shell wall and the coil (0.0162 m2) and the other which corresponds to the diameter of the coil (0.0248 m2). Therefore, the Reynolds nurber was based on an area of 0.0162 m2. Assuming no scaling deposit exists on the tubes, equation (26) was used for over-all heat transfer coefficient calculations where kw for stainless steel equals 16.26 W/m.°C. The over-all heat transfer coefficient was also predicted by noting that the wall terperature was found to vary exponentially. If it is assumed that the stream terperature will vary the same way, thei according to Deindoerfer et a1. (1959), T = J (1 + be'Kt) (43) where T = stream terperature at any time t (°K) U = over-all heat transfer coefficient W = mass of flowing medium in contact with the surface area A (Kg) A = surface area across which heat transfer occurs cp= specific heat (KJ/Kg.°C) After time t, the medium will exit the heater at a certain temperature Texit‘ Equation (43) gives T - T . -Kt = 1n (“pf—j—fg—ui) (443) H 0 TH’ Texit’ and TO can be measured, while t could be calculated based on the flow rate and the diameter of the tube. Therefore, K may be predicted relatively easily. A, W, and cp are also known or predictable. Then For the cooling section, b = TO—Tc/Tc, where Tc is the temperature of the cooling medium (°K). After time t' , the medium will exit the cooler at temperature T' exit. Equation (43) then is reduced to T' - T - t' = 1n (‘Tfexitvr C) (44b) 0 C 37 Where K is based on the U, A, W, and CD of the cooler. The over-all heat transfer coefficient may be calculated as given previously. An energy balance in each section of the unit can also give a good approximation of the value of the over-all heat transfer coefficient . Based on the logarithmic mean temperature difference (IMID) the following expression can be used: q=rhcp AT=UAF ATm (440) rate of heat transfer between the fluids (W) where q 8‘ ll mass flow rate (Kg/min) AT = change in bulk tarperature between entrance and exit of the tube ATm IMI‘D (°C) ’11 ll correct ion factor, dimensionless The correction factor for the experimental heat exchanger was assumed to be similar to that of a multiple-pass counterflow heat exchanger. From charts (Holman, 1976) F was found equal to 0.95 and 0.99 for the heater and cooler respectively. D. Performance Calculation The over-all heat transfer coefficient estimation, for the heater and cooler was described in the previous sect ion. Inlet and outlet temperatures of the fluids were recorded on the potentiareter. The fluid capacity rate was calculated by multiplying the flow rate by the specific 38 heat of each fluid. The surface area through which heat transfer occurred was calculated based on the logarithmic mean area of the inner and outer areas of the coils. The effectiveness, 8, of each section was determined by using equation (27), while equation (28) was applied for NTU calculation. E. Degree of Inactivation Measurement and Galculation Purified polygalacturonase was added to the untreated brine at the rate of 1 mg of enzyme per 1 m1 of brine. The pasteurized brine was collected and the degree of inactivation was measured by determining the concentration of the remaining enzyme. The "cup—plate" procedure as used by Athanasopoulos (1976) was applied. Tb the cup of each Petri dish 0.15 ml of enzyme-brine solution was added and incubated for 20 hr at 35°C. The diameter of the clear zone was related to a standard curve and the amount of inactivation recorded. The standard curve was prepared by diluting 100, 80, 60, 40, and 20 mg of enzyme to 100 ml of Napoleon brine. This resrlted in 100, 80, 60, 40, and 20% of enzyme activity. 0.15 ml of each dilution was added to Petri dishes containing the solidified agar. The dishes were placed in the incubator together with those containing the pasteurized brine. The diameter of the clear zone of each dilution was plotted against enzyme concentration on semi-log paper. The straight line obtained was regrded to be the standard curve (Figure 4). The degree of inactivation was calculated by both, the General and the Analytical methods, as illustrated by the following example. 39 Example Problem Napoleon cherry brine containing 1 mg polygalacturonase enzyme per 1 ml of brine was pasteurized in a helically coiled heat exchanger. Determine the amount of inactivation if the following information is available: Heater Cooler Area of coiled tube (m2): 0.129 0.088 Length of coil (m): 5.8 3.96 Brine flow rate (Kg/min): 1 U (W/mz. °C): 1085 1011 Mount of brine in contact with coil (Kg): 0.180 0.124 Time of heat exposure (sec): 10.83 7.45 Specific heat of brine: 4186.9 J/Kg.°C Constant in Arrhenius equation, A (sec ‘1): 7.5 x 1039 Velocity constant of polygalacturonase at 76.66°C: 0.3057 sec"1 Activation energy of polygalacturonase: 64668 cal/mole A value of polygalacturonase 8.4°C Temperature—time profile in coils: exponential A. Analytical Method. According to equation (40), for both heating and cooling, 7 = A I: em(-Ea/Rl‘)dt 100 ‘7» ACTIVITY ZONE DIAMETER, mm Figure 4. Standard curve for polygalacturonase activity measurement. 41 Since the terperature—time profiles are exponential, carbination of equation (40) and (43) results in integrals which are first order exponential integrals that can be numerically evaluated for the various values of their lower limits or argtments. Thus for exponential temerature—time profiles in the heating and cooling sections we have: A a a v=— E1(-—-—)-E1( ) (45) K 1+b lib-kt A -3. '- E E1( _a)-E1(——§ka-a) l+b 1+be co e-x By definition E1(z) = fz 7 dx (46) z = lower limit or argument E1= first order exponential integral function For positive arguments up to 15, the first order exponential integral function can be taken from tables (Deindoerfer et a1. 1959). Above this argument, the following approximation yields a satisfactory value: .2 . E (z) = g— (47) To solve the problem equation (45) and (47) should be used. Heat ing Sect ion 93.9 + 77.5 2 = 84.7°C or 358.9°K J = heat source temperature = 64668 a = 1.987 x 358.9 = 90'68 J T: K = U A = 1085 WLm2.°C x 0.1294 m2 x 1JjW.sec cp 0.180 Kg x 4186.9 J/Kg.6C _—_ 0 To 295.4 K, T - T b = 0 H = -0.1769 e‘Kt — 0.147 TH a a fig - 110.16 , 1+be-Kt = 93.10 a a ——-a=18.48, ——_——_a=2.42 1H) 1+be Kt .- e—llO-lo _ -50 E.(110.10)— W - 1.3 x 10 E1(93-10) = 3.% X 10-73, E1(18.48) = 5 X 10-10 E1(2.42) = 3.67 x 10‘2 A no Ae”a K = 4.03 X 10 K = 16.73 Equation (45) becomes, 4.03 x 10"0 [1.30 x 10'50 — 3.96 x 10"“) = 0.186 sec"1 — 16.73 [5 x 10‘” — 3.67 x 10' ] = -0.01595 + 0.61399 vheat. = 0.59804 Cooling - _ 13 + 22 c cool1ng medium temerature - ---2—— = 17.5°C = 290.7°K 43 64668 a = 1.9877 290.7 = ”1'95 _ 1011 x 0.0885 x 1 = -1 K - 0.124 X 4196.9 0.1723 sec To = 349.86°K , b = 0.2035 , e‘Kt = 0.277 a a __-_.. = 93.02 , -— = 105.97 1+5 1+be-Kt a a ———a=-18.93, -——-:—-—a=5.98 1+b 1+be Kt Ae‘a - A/K=4.35X10"° , '12—": 1.17x10 ° E1(93.02) = 4.29 x 10‘” , E1(105.97) =-- 8.96 x 10'” E1(—18.93) = -8791114.3 , E1(-5.98) = -66.12 Equation ( 45) becomes, 4.35 x 10"0 [4.298 x 10‘“3 - 8.96 x 10‘”] —1.17 x 10"° [—8791114.3 + 66.12] = 0.01869 + 0.10285 V = 0.12154 cool. .. _._ ‘1 = Vhold.‘ kt 0.3057 sec X9.02 sec 2.7574 (the brine is exposed in the holding coil for 9.02 sec) Vtota1'_'vheat. + vcool. + vhold. = 0.59804 + 0.12154 + 2.7574 = 3.47698 44 V total = 1n NO/N , (assume N0 = 100) then, lOO/N = 32.36 and N = 3.09% or 100 - 3.09 = 96.91% inactivation B. General Method A basic requirement in process calculation by the general method is measurement of the terperature of the sterilized medium during heat treatment. In the preselt study the temperature of the treated brine was measured at several points. The temperature between these points was predicted by using equation (43). Therefore, the following method may be considered as a modification of the general method. For the heating section equation (43) becales, T = 358.9 (l-0.769 e'°'“”5’c ) t varies from O to 10.83 sec For the cooling section equation (43) gim, T = 290.7 (1 + 0.2035 e‘°'1mt t varies from 0 to 7.47 sec By giving t several values, the cormpcnding temperatures can be obtained. A plot of temperatureversus tine results in the temperature -time profile (Figure 14). The first colum of the following table represeits the midpoint time for time intervals 1 sec. The second colum is the temperature that 45 corresponds at each time, and is taken from Figure 14. From equation (38) T-250 Z (F=1min) In the problem the process terperature is 170 F(76.66°C) 76 250°F, therefore, Fun + 1 min. Thus the above equation will become T — 76.66 Z Since the time intervals = 1 sec, the third colum, which represents the time interval lethality T - 76.66 =LXAt=1X10 Z sec Table 2. Calculation of cumulative lethality. T - 76.66 Midpoint Time Midpoint Temp. 10 Z sec °C 0.5 27.5 1 x 10"’_ 1.5 37.8 2.3 x 10 5 2.5 46.0 0.00022 3.5 52.5 0.00132 4.5 58.0 0.0060 5.5 62.5 0.020619 6.5 66.4 0.06005 7.5 69.5 0.14048 8.5 72.5 0.31971 9.5 75.0 0.63442 10.5 76.5 0.95708 11.5 76.66 1.0 12.5 76.66 1.0 13.5 76.66 1.0 14.5 76.66 1.0 15.5 76.66 1.0 16.5 76.66 1.0 17.5 76.66 1.0 18.5 76.66 1.0 19.5 76.66 1.0 20.5 70.0 0.16117 21.5 61.6 0.01611 22.5 54.5 0.00230 23.5 48.7 0.00046 24.5 43.6 0.00011 25.5 36.2 0.00001 26.5 35.5 - Tbtal = 11.3200 sec Cumulative lethality = 11.3200 The cumlative lethality represents the equivalent process time at temperature 76.66°C. Since k = 0.3057 sec'1 , equation (30) becures, 1n C/Co = - kt -0.3057 sec-1 X 11,3200 sec If 00 = 100, then C = 3.14% Thus, the process resulted in 100 - 3.14 = 96.86% inactivation. REalLT‘S AND DISCUSSKN A. Pressure Drop The frictional losses in a pipe are higily dependent on the fluid films that exist on the metal walls. Since the fluid flow pattern (laminar or turbulent) effects these boundary layers, the degree of turbuleice determines the amount of pressure drop through a pipe. Figure 5 illustrates the effect of Reynolds nmber on the friction factors in laminar and turbulent flow, for straight and coiled pipes. The friction factors are affected to a greater extent by the Re in the laminar flow conditions than in turbulent flow. This holds for both straight and coiled pipes. The fact that, in the laminar flow the friction factor is inversely proportional to Re (equation 2) while in the turbulent region it is inversely proportional to Re°°2 (fs = 0.046/me°'2), which explains the previously mentioned effect on the friction factors. There- fore, with an increasing Re, the friction factors fall more gradually in the turbulent flow than in the laminar flow region. The centrifugal force which exists in a curved pipe produces a pressure gradient in a cross section. This pressure gradient yields a pair of secondary flows which cause a larger anomt of pressure drop in coiled pipes than in straigit 1313368. The curvature ratio (di/Dh) may be ceisidered as an expression of the magnitude of the centrifugal force. The coil diameter is the factor that determines the value of this force 47 48 Iamfinar Turbulent 0.01- 0.001 . ill, . .4, l L l_ll, . 1 2 3 4 5 6 7 8 9 10 XI103 Re Figure 5. Effect of Reynolds number on friction factor in straight and.coiled tubes for laminar and.turbulent flow. 49 for a certain inside tube diameter. Snall coil diameters contribute to a larger centrifugal force and larger pressure gradient. Figure 6 shows the variation in the friction factors among coils with different diameters. Under a constant Re, smaller coil diameters result in friction factors of higher values. Probably the most important factor that influences the pressure drop in a tits is the flow rate. The relationship between frictional pressure losses and flow rate is shown in Figure 7. The pressure losses increase gradually with small flow rates (low fluid velocity), whereas the pressure drop increases rapidly at high flow rates (high fluid velocities). Such a relationship may be expected since, according to equation (1), the pressure drop is directly proportional to the square of the fluid velocity. Table 3 and Figure 7 give a canparison between the calculated and the measured pressure drop. The calculated values were found to deviate from -l.3 to 49.2% from the measured ones. Actually, equation (9) was developed for isothermal conditions. The use of mean film tenperature may give a good approximation. The shell-side pressure drop was measured. Seven trials gave values from 689 N/mz (0.1 psi) to 1034 N/mz (0.15 psi). The enall velocities that were encountered in the shell-side in both sections contributed to the lower pressure drop . Therefore, it may be concluded that under the conditions carried out in the experiment the shell-side pressure drop is of no significance. 2 x 10" - 10" L P p Re: - o di/D = 0.043 . 0 Straight tube a di/D = 0.033 I di/D - 0.058 .007 .0075 .008 .0085 .009 .0095 Figure 6. Effect of curvature ratio on frictional factors in coils. 5x10“ PRESSURE DROP, Wm2 51 X Measuredpressuredrop p ‘H ‘ - O 0.5 1 1.5 2 FLOW RATE, Kglmin Figure 7. Effect of flow rate on calculated total pressure drop in the coils of the pasteurization unit . 52 Table 3. Calculated and measured total internal pressure drop in the pasteurization unit, at several flow rates. Flow rate Calculated Measured Difference (Kg/min) AWN/m2) ANN/m”) % l .0 12769 13858 -7 . 85 l . 2 16915 17161 -1 . 43 l . 5 24483 22414 +9 . 23 2 . 0 42196 42754 -1 . 30 B. mat Transfer The influence of the curvature ratio on the inside heat transfer coefficient is similar to that of the pressure drop described previously. The straight lines in Figure 8 are derived from equation (17) using different (ii/DI1 values. The centrifugal force promotes mixing in the coiled pipe and this results in higher heat transfer coefficients in coils than in straight tubes. Figure 8 also shows how high Re contributes to high heat transfer coefficients as a result of increasing turbulence with increasing Re. Coils with the same tlbe diameter but different coil diameter will give different heat transfer coefficients urnder the same conditions. Those with a smaller diameter give the higher values. When the influence of the coil diameter on the centrifugal force and the effect of coil diameter on the heat transfer coefficients are considered, the values given in Figure 8 are valid and reasonable. Also illustrated in Figure 8 the higher Nu of coils when canpared with th0se in straignt tubes. o di/D = 0.058 . di/D = 0.043 g di/D = 0.033 I Straight tube -0.4 Nu1,Prf 5‘2 o 01 5" 01 63b 6.5 7 Figure 8. Inside heat transfer coefficients in coils for different Re and different curvature ratio. 7.5 x 103 8 95998989 9035 hows; u a. 0.358969 “03:0 05.5 a one H3 5.55.2333 soda noes: u . 9 1092.893 soda .9qu u Be as- 22 82 «.2 a: 4.8 m8 9:- 82 «8.2 4.8 ado. 98 «.«« «2+ 82 22 o.«« o2 can 2.2 o.«. 22 82 out. ozmo s2 «.«« 92 ea: 82 m2 o2 «.«m at. on- 22 22 was 2.8 o.«s «.«« «8+ 82 3.2 o.o« an m2 :8 «.2 82 82 «.«s 25 cos m.m« I- senescence 85.898 one is one Es on. Co 85423, .528 51.2sz seam BE .6 as: . maoH peonoo garage H8833 noon: .80 {:55 3822358 nonhuman some 86288 386vo can 83958 no 339.8 .4 23 55 The Grashof and the lbynolds nurber of the shell-side varied from 5 x 106 to 1.2 x 107 and 50 to 70 respectively. This indicates that natural convection was the precbminant force in the heat transfer mechanism in the stell—side. Outside heat transfer coefficients were calculated by equation (24). They were also predicted through equations (44a) and (44b) for heating and cooling respectively. In Table 4 the difference between the predicted and calculated values is illustrated. They were found to vary from -3.0 to +ll.6%. Actually, in the cooler, natural convection did not seen to exist because the water was flowing upward while the density was increasing downward. The assurption that natural convection equations can be applied to the shell—side of the cooler due to the low velocities of the water (lm/min), seems to be correct as illustrated in Table 4. The outside heat transfer coefficients were found to be smaller than those in the inside. The lower inlet to outlet velocities in the shell—side than those inside the coils may have contributed to the lower heat transfer coefficients. The most important heat transfer parameter in designing a heat exchanger is the over—all heat transfer coefficient. Equations (25), (44c), and (44a) or (4411) for heating and cooling respectively, were used to calculate the over-all heat transfer coefficient. In Table 5 the results of the three approaches are presented. The three methods were found to be in satisfactory agreenent. Figure 9 and 10 illustrate the relationship between over-all heat transfer coefficients and the logarithmic temperature difference ratio. The straight line in Figure 9 is the solution of equation (44a) and in Figure 10 the solution of equation (44b). Both figures indicate that for constant heating or cooling medium temperatures the difference between inlet and outlet g 85.2098”? #0350 .0983 u m. H3 gage p038 05.5 n one 8858.888 822 can u Be 0.858893 822 scene 1 e 82 22 82 «.2 T: 4.8 m8 22 82 8: 4.2. 8.8. 98 «.«« 2o :2 «82 o.«« o2 o8 H2 ««2 82 so: miss 8.8 e2. «.«« men 48 to o2 o2 «.«m at man «o2 82 is 2.8 o.«e «.«« «8 Re 88 o2 a: new 58 o2. .82 mSH «.«e 28 0.2 m.m« 888m 8.82 $8 8888 348 .8 88$ :2 85cm 9se 8e one Be 0 O EHUHPHHU a: g alas a; .6 gm. . mace p.380 0922098» H3000 soon: .0850: panacea. cones. .3 89892.8 .60 was: 822.808 88qu some 281.88 02. .m passe 57 8 9 10 11 12 13 x 103 u, Wlmz. °c 0 Predicted by equation (44a) A Calculated from the total resistance D Calculated fran energy balance Figure 9. Effect of teuperature difference ratio of the two fluids in the heater, on the over-all heat transfer coefficient . -O.45 8 8.5 9 9.5 10 10.5 x 102 U, w1m2. °c . Predicted by equation (44b) A Calculated from the total resistance [3 Calculated fran energy balance Figure 10. Effect of temperature difference ratio of the fluicb in the cooler on the over—all heat transfer coefficient . temperature of the fluid in the coils determines the nagnitude of the over- all heat transfer coefficient. 'Ihus, large tarperature differences contribute to high U values, while snall talperature differences result in suall U values. C. Performance of the Emerinental Heat Exchanger Figures 11 and 12 illustrate the tenperature distribution of the fluids in the heating and cooling section. The brine inlet and outlet temperature was measured, while the tenperature change with time was predicted by equation (43). The distribution is very similar to that of a double pipe counterflow heat exchanger. Therefore, the mm of the experimental heat exchanger my be calculated in a manner similar to that of a double pipe heat exchanger. Since the IMP!) can be calculated the over-all heat transfer coefficient can be calculated by using equation (44c). The difference between inlet and outlet tenperatures of the hot and cold water is effected by the flow rate of each stream. The larger the flow rate the smaller the tenperature difference. 'Ihe drop in the hot water curve is larger than the rise of the curve of the cold water as shown in Figures 11 and 12. Different flow rates (3.8 Kg/min for the hot water and 5.6 Kg/min for the cold water) accmmt for the variation. Table 6 indicates that the effectiveness of the experimental heat exchanger varied from 73 to 78% for the heating section and 63 to 68% for the cooling sect ion. The lower effectiveness of the cooling section uny'be due to the lower over-all heat transfer coefficients of the cooler. Generally the temperature for both fluids was lower than that in the heater. DISTANCE FROM INLET, m 0 0.43 - #L3A 77.5 7 Hot Water or o Lu. 1 '2 Erin < ' e n: Lu 0. 2 Lu I- 22. 5.8 DISTANCE FROM INLET, m Figure 11. 'Deuperature profiles in the heater of the experinental heat exchanger. 61 DISTANCE FROM INLET , m 9.43 O 81 Brine o0 9 Lu. :2 E < a I.” % Lu 34.4 |- ‘ 11. 1 6 5.13 DISTANCE FROM INfEr, m Figure 12. Termerature profiles in the cooler of the experinmtal heat exchanger. mN.H mo.N mm vb o.Hw mNH Hod .5 E. m6» mm . H 3. H so mm o . mm mm . H mm . H mm mm o . on .HmHooo House: .8300 powwow 0o PE 9... . mmccmSH powwwm chafing wwdoong 68.33%”, wmcoona Hagen as 553— H 90 open 2.on a. we 2am. gnu mfinflnsmpmmm now homage pawn Hanna—nag 23 .3 PE 28 wmmemfi Beam .0 cHnflH. 63 The NI‘U of the heat exchanger is a function of the over-all heat transfer coefficient and the heat transfer area (equation 28) . Higher NTU values also occurred in the heater as shown in Table 6. D. Polygalacturonase Heat Treatment The D values of an organisn increases very rapidly with small increases in temperature. An increase in tenperature also results in a sharp decrease in the velocity constant, k, of a reaction. Therefore, the percentage of inactivation is highly temperature dependent . By increasing the temperature from 70 to 72°C the anmmt of inactivation increases fran 44 to 63%, as shown in Table 7. The effect of teaperature on the degree of inactivation is illustrated in Figure 13. At lower tarperatures the increase is relatively sharp and asynptot ical 1y approaches the value of 100% inactiva- tion. The temperature-time profiles in Figure 14, as predicted by equation (43) , were used for calculating the inactivation at several process tanperatures or constant tarperatures along the holding coil . Because of the exponential nature of the heating and cooling portions, the enzyme was subjected to higher tanperatures for a longer period in the heater than in the cooler for the sane range of tarperature. Thus, the heating section contributed more to the total inactivation than the cooling section, as in Table 8 is shown. The three methods which were used for the inactivation determination, nanely plating, analytical, and general , gave results in close agreement with each other, as shown in Table 7. If it is assured that plating is the more accurate method, the analytical and the general were found to vary fran the plating values from -l.9 to +2.34% (Table 7). Therefore, use of either the general or 7o INACTIVATI ON 70 Figure 13. 75 8) TEMPERATURE °c Effect of tenperature on the degree of enzyne inactivation. 65 .HHoo 3H0: on» wcoHa £3.3ch psmpmcoo .33 as @3395 assuage mars 6338.5 mm .8300 .02 as: 2 m 0.. o2 0.. cap o. 6.2. o. 96 :8 2:28 I000 acumen .2 as a.“ .b 30 ‘3an1vaadwar 66 0200+ 0200+ 2.00.00 000.00 000.00 00.20 002+ 002+ 00.00 20.00 00.00 00.02. 00.2- 002+ 00.00 00.00 8.00 8.00 0.2- 00.0.. 02.00 00.00 00.00 00.00 20.8000 2.8202205 20.20000 282002000 0:2 0.020 00 62.202000 0 722.002.6022 0. .0202. 2202 #03020 9:00.209 20220 0020020 882 008008 2820.22.20 000 20.20000 002 .20 0000002 00.200 002 an 00258.00 82 002 20002 280.200 .0 0200.2. 67 5:00.200 H.003 05 Ho 09322092022 0n» 2200022202 000058.200 222 0.2085: 0202. 2 AwdtdeN. 2333.0 AvaHodH 30380.8 o.Hw 8.0020060 3.88.0 $033.3 8033.8 0.00 20.000000 20.00002 200002.02 202000.00 0.00 23.00:..8 3.820202 Ammvewd 3030060. 0.00 0000.20.22 00092022 2222092022 2:00.209 0.. H28 ozHQHom mag. a 295.2. .252. .228 0020200 03 00020 0.222020202222200 02:30:00 0 0.220: 60508 0002033220 023 3 60003030 .20w220nox0 B002 Hang—92.20920 05 .20 22020000 22000 22 05.2.2380 820.038.0222 000209222ng0me2~2 .m 02020.2. 68 the analytical method for determining the polygalacturonase inactivation in the pasteurization 1mit may give a satisfactory approximation. The analytical may be more advantageous if adequate heat transfer data is available, since it is faster than the general method. It should also be noted, that the variation becomes smaller as the degree of inactivation increases. A temperature of 81°C along the holding eon resulted in a 4.7D process, which may be considered adequate to prevent softening of the cherries. Such an inactivation is difficult to determine by plating if the diameter of the collar is higher than 1 on, because the diameter of the clear zone that the enzyme creates, is less than 1.2 cm. Therefore, collars with a very snall diameter unst be used. In general inactivation in the holding coil is not difficult to predict, because of the isothermal nature of the pm. Application of equation (41) under iSothermal conditions gives the degree of inactivation. The case is unre conplicated where tamerature varies with time. At tenperatures of 76.66 and 81°C the degree of inactivation was as follows: Holding coil: 76.4 and 79.16% Heating and cooling section: 19.89 and 20.16% In the experimental heat exchanger treating cherry brine at a rate of 1 Kg/min, an approxinate degree of inactivation at a teuperature range between 76.66 - 81°C, may be determined by, (a) Calculating the degree of inactivation in the holding section. (b) Adding 20% to the above value. 'lhe total inactivation, calculated in (b) will be :t 0.16% fran the actual inactivation . 69 In order to treat an enzyme, other than polygalacturonase, the rate constants must be known. Suparath (1976) found that pectinase fran Penicillimn janthinellum, which causes softening in brined pickles, is the most heat resistant enzyme in cucumber brine. From Suparath's data the k and Z values of pectinase from P. janthinellun were calculated. 'Ihey were compared with those of polygalacturonase, which were determined by Athanasopoulos (1976). The Z value of the pickle pectinase was found to be 4.592°C. Polygalacturonase has a Z value equal to 8.4°C. Figure 15 illustrates the thermal resistance curves of the two enzymes. Because pectinase from P. Qanthinellun has smaller Z value than polygalacturonase, it is more sensitive to temperature changes, as illustrated in Table 9. At low temperatures the pickle enzyme is Here heat stable than poly- galacturonase. At temperatures higher than 80°C, polygalacturonase is considered more heat resistant. The Arrhenius plots of the two enzymes are presented in Figure 16. In Figure 16 the sharper increase or decrease of the k values of the pickle pectinase can be seen. Suparath's data were inadequate because the D values for the pickle pect inase were detennined for two tameratures only. In the comparison between polygalacturonase and the pickle enzyme, it was assmed that the two D values determined by Suparath are points on the straight line shown in Figure 15. If the assunption is correct, then the experimental heat exchanger used for polygalacturonase inactivation may be used for pickle brine pasteurization since at temperatures above 80°C polygalacturonase has higher D and lower k values (Table 9). 'Ihe carposition of the pickle brine should also be considered. Usually the soluble solids of the pickle brine is aromd 12% which is very close to the cherry brine as indicated in Table A—1. 100 388 D , VALUES , sec 10 O P. Janthinellun I A. nige' rl / Z 8.45 °C / Z 4.592 °C 68 7O 72 74 TEMPERATURE, °c Figure 15. 'Ihemal resistance curves for pectinase fmn "llus' n (PG) at pH 3.0 and for pectinase fmn Penicilliun Janthinellun at pH 3.3 1From Athanasopoulos (1976) 0.10 , 0.05 0 P. lanthinellun . A. niggr1 0.02 2. .80 2.35 2.90 2.95 x 10’3 1 o T 0 Figure 16. Arrhenius plot for polygalacturonase at pH 3.0 and pectinase fran P. lanthinellum at 3.7. K ‘me Athanasopoulos (1976) 883 fig same 883 000832 Ea finds Sn 08.3. 25 8 0033. 86. Show 8.0 we «8.8. mod . Sad 8.8 me @323 «0.3 mama. 8.00 as ohms 8.8 000; 8.02 me name when $0.0 8.8m 2. Venn Ba x a 8a .033, d Teen 62 x a. new .935 .o 00 8283020038 .Sfiefifiaan .c 02E. .asd u we ea 5303550.... .m EH 000230?” was ~06 n mm as 0m§98dww§oa How 38398 0....dm .m 0H3 E. Qxarational Cost of the Pasteurization Process To evaluate the economics of the pasteurization of cherry brine, several factors must be considered including: Labor Fuel Punping and cold water needs. Because the heat exchanger was designed to be in line with the reclamation system, labor cost for the heat treatment itself is difficult to evaluate. Thus, in the following calculations labor will be excluded. The operational cost will be based on the following assumptions: Amount of brine for pasteurization: 1000 gallons Degree of inactivation desired: 99.985% Flow rate of brine: 1 Kg/min Hot water flow rate: 2.7 Kg/min Cold water flow rate: 5.6 Kg/min Temperature drop in the heater: 40°F or 22.2°C Cost of fuel: $2.26 per 1,000,000 B’I‘U1 Cost of the water: $2.50 per 1000 fts‘2 The system includes three pumps with 20 ft or 6 m total length of tubing. Under these conditions, heating of the water requires 14016 BTU/hr which will cost 14016 BTU X 63 hr X $2.26/1,000,000 BTU = $1.99 ‘From Rippen (1977) 2From Rippen (1977) 74 During the process. 734.12 ft of cold water is needed in the cooler. This will cost, 734.12 ft3 x $2.5/1ooo ft3 = $1.83 The pumping requirements were calculated to be $0.10 Therefore, the cost for pasteurizing 1,000 gallons is 1.99 + 1.83 + 0.10 = $3.92 The~above operational cost could be lowered by having a regenerative unit connected after the holding coil where the pasteurized brine would preheat untreated brine. The preheated brine after the regenerative unit would be pumped directly into the heating section. Thus, regeneration ‘would save both fuel and cold water since the untreated brine would.exit the regenerative unit at a temperature higher than that of the roomy while the pasteurized brine would exit the regenerative unit at a temperature lower than that of the holding coil. For example, if the designed percent of regeneration would be 50%, the amount of heat added to the brine in the heater and that removed from the brine in the cooler would be reduced by 50%. This will further reduce the amnunt of fuel and cold water required by 50%. Thus, the operational cost may be reduced approximately 50%. A serious corrosion problem could occur with regeneration because a large surface area is in contact wdth the brine. Cherry brine is considered to be a highly corrosive material. The metals that should be used in the manufacture of a pasteurization unit must be of high quality in order to resist corrosion of the metal surfaces in contact wdth brine. Such a requirement will affect the initial and installation cost of the pasteurization unit . 75 Cucumber brine is probably as corrosive as cherry brine. Using the following information the cost of pasteurizing 1000 gallons is estimated as follows: Labor cost @ $4.00/hr 2.641 Propane 1.29 Pumping 0.79 Chemicals 24.4.1. Total operational cost: $7.05 Pasteurizer 5 yr depreciation $8915/yr: $10.51 The above indicates that the initial cost of the pasteurization unit is higher than the operational cost ($10.51 vs $7.05). Therefore, a less expensive heat exchanger may contribute in cost reduction of the pasteuri- zat ion process. lFrom McFeeters et al. (1977) (IDNCLUS IONS The degree of inactivation of polygalacturonase present in spent cherry brine can be measured by the agar "cup plate" technique after pasteuri- zation of the spent cherry brine in a helically coiled heat exchanger. Application of the general and analytical methods for predicting the degree of polygalacturonase inactivation can give satisfactory results. If adequate heat transfer information is available, the analytical method is more advantageous since the computations are more rapid than the general method. Predicted inactivation and that measured by the agar "cup plate" procedure were found to vary from —l.9 to +2.34%. The variation becomes smaller as the degree of inactivation increases. When the constant temperature along the holding coil is 81°C and the brine is held 9 sec at this temperature, polygalacturonase is inactivated by 99.985%. Shell-side convective heat transfer coefficients in a helical heat exchanger can be calculated by considering coexistence of natural and forced convection. The MD of a helical heat exchanger and further the over-all heat transfer coefficient can be estimated in a manner similar to that of a multiple—pass counterflow heat exchanger. The thermal effectiveness of the heater was 77% and that of the cooler 68%. The pasteurization process under these conditions resulted 76 77 in 99.985% polygalacturonase inactivation. 9. A regeneration unit that would give 50%:regeneration in the heating and cooling sections, may contribute to approximately 50% reduction of the operational cost of the pasteurization unit. BIBLICXERAPHY BIBLICXRAPHY Athanasopoulos, P. E. and Heldman, D. R. 1976. Pilot Plant for Cherry Brine Reclamation. Paper presented in the First International Congress on Engineering and Food. Boston, Mass. Athanasopoulos, P. E. 1976. Kinetics of Thermal Inactivation of Polygalacturonase in Spent Cherry Brine. Ph.D. Thesis, Michigan State University, East Lansing, Mich. Ball, C. O. 1928. Mathematical Solution of Problems on Thermal Processing of Canned Food. Univ. Calif. (Berkeley). Public Health 1 (2): 15. Ball, C. 0., Olson, F. C. W. 1957. Sterilization in Food Technology. McGraw Hill Co., N. Y. Beavers, D. L., Payne, C. H., Soderquist, M. R., Hildrun, K. L. and Cain, R. F. 1970. Reclaiming used Cherry Brine. A.E.S. Oregon State University. T. B. III. Berg, R. R. and Bonilla, C. F. 1950. Heating of Fluids in Coils. Trans. N. Y. Acad. Sci., 13, 12. Brekke, J. E., Watters, G. 6., Jackson, H., and Powers, M. J. 1960. Texture of Brined Cherries. U. S. Department of Agr. Res. Serv. 74-34. Bigelow, B. W., Bohart, G. S., Richardson, A. L., and Ball, C. 0. 1920. Heat Penetration in Processing Canned Foods. NCA, Bull. 16—L. Dean, w. R. 1927. Note on Motion of Fluid in a Curved pipe. Phill. Mag., 4,208. Deindoerfer, F. H. 1957. Calculation of Heat Sterilization Times for Fermentation Media. Appl. Microbiol. , 5, 221-228. Deindoerfer, F. H. and Hmphrey, A. E. 1959. Analytical Method for Calculating Heat Sterilization Times. Appl. Microbiol., 7, 256-264. Deincberfer, F. H. and Hurphrey, A. E. 1959. Principles in the Design of Continuous Sterilizers. Appl. Microbiol . , 7, 264—270. Dingle, J. and Raid, W. W., and Solomons, G. L. 1953. The Enzymatic Degradation of Pectin and other Polysuccharites II. Application of the "Cup-Plate" Assay to the Estimation of Enzymes. J. Sci. Agri. a, March, 149. 79 80 Edney, H. G. S., Edwards, M. F., and Marshall, V. C. 1973. Heat Transfer to a Cooling Coil in an Agitated Vessel. Trans. Instn. men. Engrs. , 51, 4-9. Gillespy, T. C. 1962. The Principles of Heat Sterilization. ”Recent Advances in Food Science". Butter work. Iondon. Hankin, L., and Anagnostakis, S. L. 1975. The Use of Solid Media for Detection of Enzyme Production by Fangi. Mycologia, Vol. LXVII, N0. 3, 597. Hicks, E. W. 1951. (h the ENaluation of Canning Processes. Food Technology. 5, 134. Iblman, J. P. 1976. Heat transfer. 4th Ed. McGraw Hill 00., New York, N. Y. Ito, H. 1959. Memoirs of the Institute of High Speed Mechanics. Tonoku Univ. (Japan)., 14, 137. Ito, H. 1959. Friction Factors for Turbulent Flow in Curved Pipes. Trans. ASME, J. Basic Engrs., D81, 123. Kays, W. M. and London, A. L. 1955. Compact Heat Exchangers. The National Press, Palo Alto, CA. Kern, D. Q. 1950. Process Heat Transfer. McGraw Hill 00., New York, N. Y. Kertesz, Z. I. 1951. The Pectic Substances. International Publiéaers, New York, N. Y. Kreith, F. 1961. Principles of Heat Transfer. International Textbook Co. , Scranton, PA. Kubair, V. and Kuloor, N. R. 1966. Heat Transfer to Newtonian Fluids in Coiled Pipes in laminar Flow. Int. J. Heat Mass Transfer. g. 63. McAdams, W. H. 1942. Heat Transmission. 2nd Ed. McGraw Hill 00., New York, N. Y. McAdams, W. H. 1954. Heat Transmission. 3rd Ed. McGraw Hill 00., New York, N. Y. McCready, R. M. and Mchb, 0. A. 1954. Texture Changes in Brined Cherries. Western-Packer, 46, 17. McFeeters, R. F., Palnitkar, M. R., Velting, M., Fehringer, N., and Coon, W. 1977. Reuse of Brines in Camercial Cuculber Fermentation. Unpublished. Michigan State University, East Lansing, MI. Messa, C. J., Foust, A. L. and Phoehlein, G. W. 1970. Slell-Side Heat Transfer Coefficients in Helical Coil Heat Exchanger. I.E.C. (Proc. Des. Dev.), 8, 344-347. 81 Mari, Y. and Nakayama, W. 1965. Study on Forced Convection Heat Transfer in Curved Pipes. (lst report, laminar region). Int. J. Heat Mass Transfer. 8, 67. Mori, Y. and Nakayama, W. 1967. Study on Forced Convection in Curved Pipes. (2nd report, turbulent region). Int. J. Heat Mass Transfer. 10, 37-59. Panasiuk, 0., Sapers, G. M. and Ros, L. R. 1975. Recycling Bisulfite Brines in Sweet Cherry Processing. Unpublished. E.R.S.C. Philadelphia, PA. Richards, J. W. 1965. Br. Chem. Eng. 10, 116. Rippen, A. L. 1977. Survey of Energy Utilization in Dairy Plants in Michigan. Unpublished. Michigan State University, East Iansing, MI. Rippen, A. L. 1977. Methods, Concerns and Plants for Handling Dairy Plant Wastes in Michigan, Unpublished, Michigan State University, East Iansing, MI. Rogers, G. F. C. and Mayhew, Y. R. 1964. Heat Transfer and Pressure Drop in Helically Coiled Tubes with Turbulent Flow. Int. J. Heat Mass Transfer. 7, 1207-1216. Runkhlyadeva, M. R., and Korchagina, G. I. 1975. Interferometric Determination of the Activity of Pectinoloytic Enzymes of Fungal Origin. Applied Bioch. and Microbiol. June, p. 782. (Translated from Russian: original Nov-Dec., 1973). Seban, R. A. and McLaughlin, E. A. 1963. Heat Transfer in Tube Coils with laminar and Turbulent Flow. Int. J. Heat Mass Transfer. 6, 378. Soderquist, M. R. 1971. Activated Carbon Renovation of Spent Cherry Brine. J. WPCF. 43:1600. Stumbo, C. R. 1948. Bacteriological Considerations Relating to Process Evaluation. Food Technol. 2, 115. Stumbo, C. R. 1949. Further Considerations Relating to Evaluation of Thermal Processes for Foods. Food Technol. 3, 126. Sturbo, C. R. 1953. New Procedures for Evaluating Thermal Processes for Foods in Cylindrical Containers. Food Technol. 7, 309. ‘ Srinivasan, P. S., Nandapurkan, S. S., and Holland, F. A. 1968. Pressure Drop and Heat Transfer in Coils. Trans. Chem. Engrs., 46, CE113. Suparath, C. 1976. Thermal Inactivation of Pectinase in Cucurber Brine. M.S. Thesis, Michigan State University, East Iansing, MI. 82 Watters, G. G., Brekke, J. E., Powers, M. J., and Yang, H. Y. 1961. Brined Cherries Analytical and Qiality Control Methods. ARS Bull. 74—23. White, C. M. 1929. Steamline Flow through Curved Pipes. Proc. R. Soc. A128, 243. White, C. M. 1932. Fluid Friction and its Relation to Heat Transfer. Trans. Inst. (hem. Engrs., London. 10, 66—80. Wiegand, E. H. 1955. Brine Cherry Breakdown. In. Proc. Oregon Hort. Soc. APPENDICES Table A—1. Brine composition for certain cherry varieties in Michigan.1 Cherry variety pH SCz Ca Soluble (%) (%) Solids (76) Schmid 3.1 0.345 0.312 10.5 Windsor 3.4 0.355 0.374 11.1 Bing 3.5 0.414 0.414 10.1 Napoleon 3.1 0.330 0.286 10.5 lFran Panasiuk et al. (1975). Length Area Volume velocity Density Force Mass Pressure Energy, heat Heat flow Heat flux per unit area Energy per unit mass Specific heat Thermal conductivity Convective heat transfer coefficient Dynamdc viscosity (v) Kinematic Viscosity (v) Volumetric flow Power Thermal diffusivity Thnmeuature 85 APPENDIX B Units Conversions 1 Kg/mesec 1.mF/sec l.mfi/sec l.mF/sec 1°K = °C + 273.15 °R = °F + 459.67 ENGLISH 3.2808 ft 10. 35 [000 00000000 0. .2248 lb 7639 ft2 .3134 ft3 .2808 ft/sec .06243 lbw/ft3 f .2046 10m .45 x 10'“psi .9478 Btu .4121 Btu/hr .317 Btu/hr—ft2 .4299 Btu/lbm .2388 Btu/lbmr°F .5778.Btu/hrbft-°F .1761 Btu/hrbft2—°F 672 Ibm/ft-sec 10.764 ftZ/sec 35.3134 ft3/sec 1. 34 hp 10.764 ftz/sec 5 /9( °r+32> 5/9(°R) 86 APPENDIX C Recorded temperatures at various posit ions within the pasteurization 1mit for four different trials (°C). TRIAL PCBITION OF THE 1 2 3 4 THERMXIJUPIE Temperature along the holding coil 70 72 76.7 81 Brine inlet (Heater) 23.3 22.2 22.2 22.2 Brine outlet (Heater) 70.3 72.2 77.2 81.7 Brine inlet (Cooler) 69.7 71.7 76.1 80.5 Brine outlet (Cooler) 33.3 32.2 34.0 34.4 Hot water inlet 87.8 86.1 93.9 98.9 Hot water outlet 72.2 74.4 77.5 76.6 Hot water stream 81.5 79.4 84.4 87.5 Cold water inlet 11.7 13.0 13.0 11.1 Cold water outlet 25.6 19.5 22.0 19.2 Cold water stream 18.0 16.5 18.0 15.0 Upper wall (Heater) 73.3 74.4 78.8 84.4 Middle wall (Heater) 66.6 68.3 72.8 77.0 Lower wall (Heater) 37.2 38.9 40.0 40.5 Upper W311 (Cooler) 53.3 54.4 57.2 58.6 Middle wall (Cooler) 32.2 34.0 36.5 37.2 Lower wall (Cooler) 24.1 23.3 25.0 25.8 Upper wall surface (Heater) 72.2 75.0 80.5 85.8 lower wall surface (Heater) 37.0 37.7 40.5 42.5 Upper wall surface (Cooler) 48.8 42.0 45.0 47.0 Icwer wall surface (Cooler) 25.5 19.5 22.0 20.0