Oc - critical surface tension of packing material [dynes/cm] 16)(1963)Onda, K., E. Sada, C. Kido and A. Tanaka: ibid.

, 27, 140
a = surface tension [dynes/cm] or [kg/hr2]
Subscrip ts 17)(1966)
Onda, K., E. Sada, C. Kido and S. Kawatake: ibid., 30, 226
1, 2 = bottom and top of column, respectively 18) Onda, K., H. Takeuchi and Y. Koyama: ibid., 31, 126(1967)
G, L = gas and liquid phase, respectively
Sawistowski, H. and W. Smith: Ind. Eng. Chem., 51, 915
Literature cited 20) Sherwood, T. K. and F.A.L. Holloway: Trans. Am. Inst.
Chem. Engrs., 36, 21 (1940)
1) Fellinger, L.: Sc. D. thesis, M.L.T., Cambridge (1941) 21) Sherwood, T.K. andC.F.F.A.L. Holloway: ibid., 36, 39 (1940)
2) Fujita, S. and S. Sakuma: Chem. Eng.(Japan), 18, 64 (1954) 22) Shulman, H.L., Ullrich, A.Z. Proulx and J.O. Zim-
3) Fujita, S. and T. Hayakawa: ibid., 20, 113 (1956) merman: A. I. A.E.
Ch. E. Journal, 1, 253Ind.(1955)
4) Furnas, C. C. and M. L. Taylor: Trans. Am. Inst. Chem. 23) Surosky, and B.F. Dodge: Eng. Chem., 42,1112
Engrs., 36, 135 (1940) (1950)
24) Ueyama, K., H. Hikita, S. Nishigami and S. Funahashi:
5) 24,Hikita,
2 (1960)
H., T. Kataoka and K. Nakanishi: Kagaku Kogaku,
Kagaku Kogaku, 18, 68 (1954)
25) Uchida, S., et al.: ibid., ll, 53 (1947)
M.ibid.,Sugata24, and K. Kamo: ibid.,
9 (1960)
18, 454 (1954)
26)44, Van529Krevelen,
D. W. and P. J. Hoftijzer : Chem. Eng. Progrs.,
8) (1950)
Houston, R.W. and C.A. Walker: Ind. Eng. Chem., 42, 1105 27) Vivian, J.E. and C.J. King: A. I. Ch. E.Journal, 10, 221
9) 22,Katayama,
764 (1958)
S., T. Koyanagi and F. Yoshida: Kagaku Kogaku, 28) Yoshida, F. and T. Koyanagi: Ind. Eng. Chem., 50, 365
10) Lynch, E.J. and C.R. Wilke: ibid., 1, 9(1955 (1958)
ll) Engrs.,
Norman,41, W.109 S. (1963)and F. Y. Y. Sammak: Trans. Inst. Chem. 29) Yoshida, F. and T. Koyanagi: ibid., 46, 1756 (1954)
30) (1962)
Yoshida, F. and T. Koyanagi: A. I. Ch. E. Journal, 8, 309
12)235 Onda,
K., E. Sada and Y. Murase: A. I. Ch. E. Journal, 5, 31) Weisman, J. and C.F. Bonilla: Ind. Eng. Chem., 42, 1099
13) Onda, K. and E. Sada: Kagaku Kogaku, 23,220 (1959)
14) Onda, K., T. Okamoto and H. Honda: ibid., 24, 490(1960) 32) Wen, C.Y., H.D. Simons and M. Leva: West Virg. Univ.
15) Onda, K., E. Sada and M. Saito: ibid., 25, 820 (1961) Bull. Eng. Expt. Sta., 26 (1953)


Dept. of Chem. Eng., University of Nagoya, Nagoya

Introduction CO2into aqueous solutions of NaOHin a packed column
is confirmed by using these correlations. Furthermore,
Theoretical analyses for gas absorption with chemical
reaction have been made by many investigators3>4>6'18): the assumption of a-aw is ascertained by comparing with
However, it is difficult to apply these theories to the the data for the gas absorption with pseudo fist-order re-
processes in a packed column, because the individual
mass transfer coefficients and the inter facial area can not I. Experimental Work
be estimated strictly at present.
The assumption that the wetted surface in packings is 1 à"1 Apparatus and procedure
identical with the gas-liquid interface is not only con- The packed column consisted of a 12.0-cm I.D. jacketed
venient for estimation of the area but also reasonable for acryl-resin tube packed to the heights of 0.2m or 0.3m
mass transfer between gas and liquid phases. In our with 15mm ceramic Raschig ring and 1/2- and 1-in.
previous papers11>12\ the correlations for aw, ko and kL ceramic spheres. The liquid distributor was made of
were derived as follows :
acryl-resin and had sixty one 3.5mm I. D. glass nipples
ajat = 1 - exp{- 1.45UWU5aW arranged in a ll.6mm triangular pitch.
(Vat/pL2g) ~Q^ (L2/pLaaty-2} The aqueous solutions of 0.05, 0.1, 0.25, 0.5 and 1.0iV-
koR T/atDo NaOHwere irrigated over the packings after atheating in
= 5.23 (GWff) °"7 (fiG/PODG)m (atDp) "2-° the thermostat tank which was controlled 30±l°C.
kL {pL/[JtLgy n Air from a blower and carbon dioxide from a cylinder
= 0. 005l (L/aw^Ly/' (fiL/PLDL) -1/2 (atDpy-i (3)
were fed to the bottom of the packed column after the
In this paper, the applicability of the film theory18) of gas gas mixture waswell mixed and saturated with water
absorption with second order reaction to the absorption of vapor. The CO2content in the air was controlled by a
* Received on July 10, 1967
reducing valve at the CO2cylinder. The partial pressure
*å * Dept. of Ind. Chem., Suzuka College of Technology, Suzuka of the solute gas, p, was maintained constant in each run

the aqueous solution is believed to take place in the The diffusivities ratio.14 0. dilution using the liquid jet. under the assumption that the salting effects of these two solutions (that is NaOH expressed by Eq.05m. Kgcl increases with the liquid The rate constants for Reaction (5) have been reported rate and the relationship may be shown by (Kaa)°cLw.05iV-NaOH. For the solution of a given centration.07aim.(3). (8) where the value of factor.lcc. (7).51 0.073 0. The error of analy- sis for lOOcc of sampling gas was about 0. Thus. with solutions of concentration greater than 0. DL and H calculated by the ters y.07 the inlet and outlet of the column. irreversible reactions based on the particular models of The effect of liquid rate on KGa for 15mmRaschig the fluid dynamics of the process.2 and 0. has been taken into account as the salting effect on this The rate of absorption with chemical reaction can be saturated concentration. scales.91 0.5.03~0. which were tabulated in Table 1 for various concentrations of sodium hydroxide. only the initial concentration of NaOH reaction. The dependency of the end effect on liquid rate could not be observed in and Hoftijzer18) and Brian2 3) presented relations between /3 and 7*. Ze. sorption of CO2 in a NaOH solution is regarded as gas Although a part of NaOHwould change into Na2CO3in absorption accompanied by a relatively slow second-order the packed column. depends on the kinetics of the reaction and on the parame. van Krevelen above mentioned methods and liquid properties used in VOL. rings is shown in Fig. DL. r and q for second order or pseudo first-order the range of these runs. NA = pkL{CAi .3m for 15mm Raschig ring and expressed as the equivalent height of packing. Its value. Miwa9) found kro is kr at infinite where n varies within an extent from about 1/3 for the case of high concentration of NaOHto 1/2 for low con. Interpretation for Chemical Absorption the experimental data for the systems of various solute gas and one-valency electrolyte solution containing sodium The reaction between CO2 and sodium hydroxide in ion. Table I End effect of the packed column The gas and liquid samples for analysis were taken at Normality(JV) 0. was used. Estimated values of kr. The reaction factor by Eq. DlVl71 = const.10) and this value was used by assuming HCO3' + OH' > CO3" + H2O (6) that r was independent of temperature in the range of 20~30°C.Y2)P/ZJpim (4) where Apim= [(yi-3^2)/In(3^1/3^2)]P. End effects in the packed column were determined by using two packed heights of 0. the lower the concentration of NaOHbecomes. (9) Miwa9) found that n was 0.Cao) = kL\CAi .05iV solution could not be determined due to the poor Fig. were calculated by the following equation. r# and. the modified Stokes-Einstein's equation more physical the mechanismof gas absorption approaches. at 30°C In ourwhere laboratory.05%. q.062 0.058 0.n whofound the value of n tovary To estimate the diffusivity of the solute in*the electro- from about 0. was estimated as solutions at 3O C 0. bykro=72001/mol-sec many investigators. r=Don'/D.ca*. Kg<z. the ab. however.27 0. Caz. Hence this relation was used for NaOH solution.3 to 0. Koa = GMi(Yi . The material balances of the solute in gas and liquid phases were obtained within the range of 100±10% in all runs except in the case of 0. 1 à"2 Experimental results The overall capacity coefficients. CO2 in a gasphase Equivalent packing å height(w) 0.05iV NaOH solution in which they were fairly beyond the range. Most of the previous data in the literature concentration. is 0. Danckwerts4).Cao) (7) where /3 is the so-called reaction factor and Cao becomes The liquid side mass transfer coefficient was calculated zero for an irreversible reaction.1 NO. q.9 to fit the equation (9) to 2. 1.055 was analyzed by a modified Orsat apparatus which had a lOOcc gas burette with O. by the extrapolation of the end effects for various normalities higher than 0. and Na2CO3 solutions) are the same.875 +?/. The end effect for 0.in the range of 0. since the back pres- sure of CO2over the aqueous solutions of NaOHcan be assumed to be zero. the following relation is found at 30°C on CO2absorption in NaOHsolution have been obtained logfc = 3. It may be expected that the lyte solution. Liquid samples were analyzed for the concentrations of total alkali and hydroxide by the Winkler method. Hatta6). Reaction (5) may be considered to be rate controlling because Reaction (6) is a proton transfer reaction and Saturated concentration of CO2 in an electrolyte solu- about 103 times as rapid as Reaction (5).1 1968 63 . tion was estimated by the van Krevelen's method19).059 0. in potassium or following two steps : sodium hydroxide solution were 1.1339>10).5iV except those of Blumet al.67 at 20°C according CO2 + OH' -> HCO3' (5) to Nijsing et al. I KgOdata for CO2absorption into aqueous NaOH accuracy of data.

it is possible to obtain the inter facial area in packed columns whenthe value of T is greater than 5.27 1. for 0.1/koa + l/HfikLa (ll) of NaOHwas calculated as the arithmetic mean value of inlet and outlet liquid concentrations.037 3.this work are tabulated in Table 2.from(12).15 0. However. because the value of fl is nearly equal toby Ttheand Eq.81 2.the definition of T.14 -1. Cb. Fig.98 71. a is directly determined kL°a kL°a . for each experimental tion. In the calculation of y-^JkrCjiDL /kL.91 2.26 3.identical facial area cal- with aw of Hikita's Fig.Q7 1. 3. it was assumed that aw is identical to a.ON solution.07N. (12) was. The observed values of /3 in the packed column for gas absorption with a chemical reaction can be determined P tanhrVl-E^-D/r?] UW from Eq. /3. 2.93 0. (ll) are compared with /3theo calculated and theoretical by Eq.004 2.9 7. diffusivities.51 1. Henry's law constant of CO2in NaOHaqueous solutions at 3O C OH' Kkg/m3) Mkg/m-hr) (j(dyne/cm) DLx106(m2/hr) Hx102(-g^^) krx10~7f1 ^-r-) \ m à"atm / \kg-moleà"nr/ 0. The evaluated the concentration corresponds to the regemes of the pseudo value of kaa amounted to about 10%of the total resistance for 1.019 3.4 7.97 2. a=lkT=~7m5T _ (12) where Cb is approximately constant and krCB represents the pseudo first-order reaction rate constant. The values of /3ObS obtained by Eq.67 2. (ll) assuming the resistances in each phase are additive .07 71..23 71. >.54 3.93 71.76 0 996 . (l).91 1.49 72. 3. first-order reaction as well as the slow second-order reac- The theoretical reaction factor. condition was calculated by Eq.62 2. Tzgcl and k.3 7.009 3. Yoshida-Miura21) culated reported that the inter by Eq.5 6. 2 Theoretical and observed values of ft for CO2 absorption into aqueous NaOHsolutions equation and this is shown by a dotte_4 line in Fig.6 7. The observed values of (Z are in agreement within an error of ±30%. 3 Inter facial areas for chemical absorption and wetted surface area in packed columns Table 2 Liquid properties of NaOHsolution.La.91Ab solution and 64% for 0. In the case of a pseudo first-order reaction.84 2. The maximum and evaluating each capacity coefficient.57 0.88 71. the concentration 1/Kaa .82 0.59 64 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN . (3) and am by Eq. This range of (2) or kL by Eq. Relationship between Wetted and Inter facial Areas In this study.2 7.71 2. 2.(10) in Fig. the validity of this assumption needs further discussion. (10) of van Krevelen18). for conversion of hydroxide to carbonate amounted to 38% physical absorption from the product of ka given by Eq.49 2. but in the dilute solution it was less than a few per cent.13 2.92 2.001 2.

because the wetted surface measured is the solid-liquid interface and it does not include the et al. The inter facial area for 1. the low partial pressure of CO2. 2. the agreement between Tepe-Dodge17) are in the range of high concentration of a and aw for Raschig rings. cal solution using kr given by Pinsent et al. 6 Effect of alkali concentration on rate of absorption of CO2 V OL.13) All of This agreement between /3theo and /3Obs within a reasonable these data seemto be in the region of the pseudo first-order error substantiates the assumptionthat a=awmaybe ap- reaction because of the high concentration of alkali and plicable for the chemical absorption in packed columns.. /3ot>s calculated by Eq. The inter facial areas from these data are interface. On the other hand. that these gas absorption with a pseudo first-order reaction under matters compensate each other and hence Eq.and l/2-in Berl saddles was calculated from KGa data forKGa and are shown in Fig. 3. 3 with a line of aw from Eq. and from kL°a data assuming a=aw. The rate of absorption of CO2 into an alkali solution NaOH solution in the same apparatus described in the depends not only on the concentration of CO2 at the section 1-1. As shown in Fig. A Inter facial areas for gas absorption with pseudo first. (l) agrees these conditions. Cb. NaOHand shows the maximumpoint of Kgci at about facial area in packed columns. with /3tneo calculated from Eq.and l/2-in: i\. The agreement area on column's wall. 6.5) and Richard et al. (l) for estimation of the inter. Fig.4.. 5 in which the agreement between a and aw is also fairly good. Berl saddles and spheres sub- stantiates the use of Eq. Fig. (l). (ll) coincides of Vassilatos20) on the absorption of CO2 into ammonia. Effect of Alkali Concentration on KGCt spheres were obtained by the absorption of CO2 into 12V. however. (10) as shown in Fig.but also on the concentration on hydroxide ions in liquid. well with the inter facial area. 5 Inter facial areas for gas absorption with pseudo order reaction and wetted surface areas for Berl saddles first-order reaction and wetted surface areas for spheres Fig. for a second order and Leva8) on the absorption of CO2 in NaOH solution reaction has been obtained from the experimental results by neglecting the gas phase resistance. Fig. 6 shows the effect of alkali concentration on Kaa in the literature1>17).1 65 .1 1968 NO. Thus. 4 and 5. /3. the reaction factor. Cai. CO2-NaOHsystem of Leva8) data for 1. shown in Fig.14) These data are shown in Fig. the change between aw and a shows that the gas-liquid interface is of liquid path and the isolated droplets on the packing uniformly effective and essentially identical with aw for pieces make aw larger. the data of As shown in Figs. It seems.a was calculated from Kaa data of Tepe and Dodge17) In this work. The inter facial area in There are obviously somedifferences between aw and a the packed columns has also been reported by Danckwerts in packed columns.

44. 336. (1) for aw. 331 (1963) 22) Weisman.. 869 face area of Eq. Engrs. 1954 (1956) <Xw å . H. C^io . 2 = bottom and top of column. Inst. and shows the maximum point at mole fraction of solute in gas phase [-] 1. Chem.T. andIndustr. Ullrich. Ch.. K.I. 46. [-] into NaOH solution agrees so well with the observed absolute temperature [°K] mole ratio of solute in gas phase [-1 value of Tepe-Dodge. Hurley and E. 7. J. 4) Danckwerts. Am. respectively in the column packed with 15mm Raschig rings and 1/2- in and 1-in Spheres.: Trans. = wetted surface area of packing [m2/m3] 14)Eng..inconcentration of component the bulk of liquid. 6 and Greek letters the maximumpoint is found at about 4.W. H. Trass and A. A. 587 (1948) D. 253A. 2969 (1952) 0.Koyama: Kagaku Kogaku. M.y G superficial of gas 255 (1943) GMi superficial molar velocity of inert gas 18)67.F.K. The relation is seemed to be originated in the kr = reaction rate constant for second-order reaction changes of the diffusivity and solubility of solute gas in [mVkg-mole . Kaa = total pressure [atm] =å partial pressure [atm] for alkali solution can be calculated by Eq. 20.. sorption with second-order reaction derived by Krevelen.W. Nagoya University. Kogaku.F. J.A.. 3) Brian. Nagoya (1964) clarified and this tendency coincided quite well with the 10)Eng. Literature cited Kaa for the chemical absorption is proportional to the 1/3~1/2 power of the liquid rate in the range of 1. p. Hendriksz andH. E. Kgcl values calculated by height of packings [ml Eqs. and T.S. and R. at = total surface area of packing [m2/m3] Faraday Soc.. (ll) and (12). I. == parameter defined by {Cbq/vCai) gas constant [-] [m3-atm/kg-mole. becomes smaller.Kramer: Chem..atm] [m/hr2 ] 19)XXIeme Van Krevelen. 226 (1961) with Eq.: J. 6 (1968) a = inter facial area in packing [m2/m3] 13) Pinsent. Danckwerts: Chem.R. Ch. 528(1956) inter facial area. Eq. 325M. (l) may be approximately equal to the (1928) 7) Hikita.T. M. 126 (1967) Nomenclature 12) Onda. Eng. For KOH solutions. D. 1. P. E. P = reaction coefficient defined by kiP/kz [-1 ference of Cb between NaOHand KOHsolution comes 7 = parameter defined by {\lkrCsDL /kz) [-1 from the fact that the variation of the viscosity of KOH P . 224(1955) The dependencies of Kaa on NaOHconcentration was 9) Miwa.1.. Faraday Soc. the more viscous NA = rate of absorption [kg-mole/m2 -hr] the solution is and hence Dl.. respectively into aqueous sodium hydroxide solutions were carried out G.: Sc. Hoftijzer: 168 (1948) Chim.A. experimental data. R. Tepe.Takeuchi and Y. M. R. This dif.V. Onda. Pig ford: "Absorption and Ex- concentration of the reactant in the bulk of liquid traction" 2 nd. O. Chim. 63 (1963) reactions. McGraw-Hill. K. Takeuchi and Y. E.H. M. thesis.hr] g H gravitational constant Henry's law constant [kg-moles/m3 . D. G.5AT.8AT. 42. (3) for kL.. Van563. I.75AT.05iV-NaOH. Don'/Deo. ll) 31. Chem. Ind. The higher Cb is. Ch.(Japan). Danckwerts. 18.. P. H. Kennedy and D. Cambridge (1956) using the reaction factor of the film theory for gas ab. Dodds. S.L.H.I. Johnson: Can. and C. B.. Set. Stutzman and W.Nijsing.F. E. kG Eng. Japan. L. Kataoka: Kagaku1. KGa calculated for CO2-absorption ratio of liquid diffusivities. Proulx and J. Chem. absorbed respectively at interface [kg-moles/m3] and 15) Sherwood.viscosity [kg/m-hr] P = density [kg/m3] solution with Cb is smaller than that of the viscosity of NaOHsolutions. I.. 19. J. (ll) and (12) is shown by a curve 5 in Fig. Okumoto: J.: Sc. P. L = gas and liquid phase.Journal.J.T. V. 6.y 52. 7 (1963) gas-phase mass transfer coefficient [kg-moles/m2 à"hr à"atm] 21) Yoshida. and B. KG overall coefficient [kg-moles/m2 . Zimmer- cB D diffusivitymass velocity [ [kg/m2-hr] m2/hr] 17)39. H.V. Chem.. Chem. P Assuming the reaction to be a pseudo first-order. Ratcliff and P. P. Dodge: Trans. H. Eng. Person and F.. J.°K] As shown in Fig. New York (1952) average concentration [kg-moles/m3 of the reactant [kg-moles/m3] ] 16)man: Shulman. Sci. Ch. Congr. J. Hoftijzer: Rec. 1389(1932).Z. 6) Hatta.hr] L = superficial mass velocity of liquid [kg/m2 -hr] electrolyte solution. 1099 liquid-phase mass transfer coefficient [m/hr] liquid-phase coefficient for chemical absorption (1950) [m/hr] 66 JOURNAL OF CHEMICAL ENGINEERING-OF JAPAN .F.hr . C. 300 (1950) 5) Eng. 8) Leva.I. 31. Richards. Y.Miura: A. 35. B. Int.F. O. (1964) G. a = surface tension [dynes/cm] or [kg/hr2] Oc = critical surface tension of packing material [ dynes/cm] Conclusion v = stoichiometric factor [-] Subscripts The experiments of the absorption of carbon dioxide 1. (1955) A.. Soc.W. L. Roughton: Trans. L. Hasseltine: A. These values of Kgcl can be evaluated by 2) Brian. [kg-moles/m2 ..J. and P. (2) for kG and Eq. 9. G.atm] 20) Vassilatos.L. 10.. and Y. Journal. Krevelen. Journal. Roberts: Chem. it has been substantiated that the wetted sur. T. Cai. A. By means of the gas absorption with pseudo first-order Sci. L. 88 (1959)O. Industr. Bonilla: Ind.: Ind. P.Journal...: A. thesis.1. Chim. 41.å W.0~ 1) Blum. Chem. Trav.T. Eng.F.