Conclusions y = concentration in vapor, mol %

x = concentration in liquid, mol %

From these studies, it can be concluded that cocurrent O( = relative volatility
contacting of vapor and liquid streams is a very satisfac-
tory method to utilize for the design of a multistage Literature Cited
vapor-liquid equilibrium unit. Fenske, M. R., Znd. Eng. Chem., 24, 482 (1932).
A contactor, six in. in length, with an annular space Gelus, Edward, Marple, Stanley, Miller, M. E . , ibid., 41,
of %- or Y4-in., packed with Metex screen, will be 100% 1757 (1949).
efficient a t throughputs up to 1000 grams per hr per Herring, J. D., MS Thesis, Pennsylvania State University,
cm2, which corresponds, respectively, to 6 and 28 liters University Park, Pa., 1948.
Kirk, Norman, P h D Thesis, Pennsylvania State Uni-
of liquid per hr.
versity, University Park, Pa., 1946.
T o realize this efficiency a t higher throughputs, a longer McCormick, R. H., Barton, P., Fenske, M. R., AZChE
packed contactor can be utilized. J . , 8, 365 (1962).
Nornenclatu re Myers, H. S., Petrol. Refiner, 3, 175 (1957).
Prengle, H. W., Palm, G. F., Znd. Eng. Chem., 49, 1769
a = more volatile component (1957).
b = less volatile component
E.F. = enrichment factor = (yo/yb)(xb/x,) RECEIVED
for review August 14, 1970
n = number of theoretical stages March 15, 1971
ACCEPTED

Selection of Metal Oxides for

Removing SO2 From Flue Gas
Philip S. Lowell', Klaus Schwitzgebel', and Terry B. Parsons'
Tracor, Znc., Austin, Tex. 78721

Karl J. Sladek'
Department of Chemical Engineering, University of Texas at Austin, Austin, Tex. 78712

Oxides of 47 elements were evaluated for use as sorbents for removing SO2 from
flue gas, in processes based upon thermal regeneration of sorbent. Thermodynamic
analysis plus literature data were used to evaluate reaction paths for each oxide.
The most important sorbent requirements involve sulfite and sulfate decomposition behavior.
Sulfites were grouped according to the extent of disproportionation to sulfide and
sulfate during decomposition. Sulfate groups correspond to simple decomposition, decom-
position to oxysulfates, and decomposition with valence change. Examination of all
the relevant data indicated that oxides of AI, Bi, Ce, Co, Cr, Cu, Fe, Hf, Ni, Sn,
Th, Ti, V, U, Zn, and Zr are most promising.

I t is widely recognized that the emission of sulfur oxides This paper covers dry metal oxide processes which pro-
from fossil fuel combustion causes a serious atmospheric duce SO2, SO3, or H2SOa as by-product. I t attacks the
pollution problem. A variety of methods have been pro- problem of selecting from 47 pure metal oxides and an
posed for removing sulfur compounds either from fuels additional group of binary metal oxides those which are
before combustion or from flue gas afterward (7, 36). most promising for a thermally regenerable process. The
Processes for treating flue gas include wet scrubbing, gas- use of thermal, rather than chemical, regeneration should
phase reaction to make a removable solid or liquid product, result in operating cost advantages.
sorption by a nonregenerable solid, and sorption by a A flow diagram illustrating the type of process and
regenerable solid. A process of this last type, described the sorbent requirements is given in Figure 1. Feed flue
recently by Newel1 ( 3 0 ) ,employs sorption of sulfur oxides gas containing SOz, 02,N 2 , H 2 0 , and C 0 2 enters the
on an alkalized alumina, which is an active form of NaAIOr, sorber, which operates a t temperature T s , and is contacted
and regeneration with reducing gas to produce H B . The with regenerated sorbent. For a coal-burning power plant,
cost of producing reducing gas is a major operating cost typical flue gas SO2 content would be 0.05 to 0.3%, and
item in this process. typical O2 would be 2.0 to 3.5%. A lower limit of 100°C
is chosen for T s to minimize corrosion and to prevent
' Present address, Radian Corp., Austin, Tex. 78758 plume droop and resulting localized pollution. The critical
' To whom correspondence should be addressed. sorption requirement is that the exit SO1 content must

384 Ind. Eng. Chem. Process Des. Develop., Vol. 10, No. 3, 1971
 really consisted of rejecting metal oxides exhibiting
unfavorable behavior. The authors suggest that an oxide
which is unsuitable on the basis of its behavior in metal-
oxygen-sulfur reactions should be unsuitable also in the
more complicated case where reactions involving CO, and
H?O occur.
The chemistry of metal-oxygen-sulfur systems is quite
varied. For example, Cu forms compounds in both +1
and +2 valence states; in addition a t least one oxysulfate,
CuS04.Cu0, is known. For sorption on C u 2 0 , one could
envision the following reactions:
3 / 2 C U S O+
~ 1 / 2 CUS

CuzO-2
+1:2 0
2
cuo-
+2 so, f
2 cum3

+SO2

L c u z s of 3l i 2 C U * S O , -cuso4.
+1/202 cuo

For regeneration t o C u 2 0

2 cuso43_
S O [Link] - -so3
2
-112 0
cuo----l
cuzo (3)

2 cum3 -
-2 so, 2 cuo-cuzo
-112 0 2

Besides these bulk reactions, catalytic oxidation of SO,

(4)

to SO,might occur as a side reaction during the sorption

process.
This example illustrates that the chemistry of metal-
oxygen-sulfur systems can involve the following features:
multiple oxidation states, sulfite formation, sulfate formation,
disproportionation of sulfites to sulfates and sulfides, sulfate
decomposition, sometimes via oxysulfates, and catalytic oxida-
tion o f SO?.
To make meaningful predictions of sorption and regen-
eration behavior, it was necessary to determine the nature
of the actual reaction network for each oxide. This was
done by searching the literature on the descriptive chem-
istry of metal-oxygen-sulfur systems and by making pre-
dictions based on thermodynamic evaluation of alternate
reaction paths.
A standard method was adopted for defining equilibrium
constants, K , for the several different types of reactions
involved. The convention was to write gas-solid reactions
t Feed Flue, Gas ( N e , Cop, H20, 0 2 , SOp ) for production of one mole of gas. For example, oxidation
of a 2+ to a 3+ oxide under sorption conditions (Po,
Byproduct SOp. = 0.028 atm) is represented as
Spent
SO3, or H,SO,.
Scrbrnt Psop+ g o 3 ? 001 atm A 2 Me2032 4 M e 0 + 0, (5)
i This equation can represent either the 2+ to 3+ reaction
t Sulfur or the 3+ to 2+ reaction; the 0, is put on the right
Recovery to give a standard definition of K . At equilibrium, K
Regenerator
1 is equal to PO (atm). where the standard state of gases
Purge Gas is 1 atm. I t is assumed that the solids form separate
phases and solid activities are taken to be unity. The
Figure 1. Process flows and requirements 2+ oxide is favored when K 2 0.028 atm, and the 3+

Ind. Eng. Chem. Process Des. Develop., Vol. 10, No. 3, 1971 385
is favored when K 5 0.028 atm. For a 3+ sulfite reaction Results, given in Table 11, indicate that sulfite formation
?4 Me*(S03)32 M Me203+ SOz (6) is favorable over the entire temperature range for the
alkali metals and some of the alkaline earths. Materials
To satisfy the sorption requirement, K must be ~ 0 . 0 0 0 1 5 such as MnS03 become unstable a t temperatures between
atm, or log K must be 513.82. The regeneration require- 100" and 4OO0C, while some sulfites, such as Fe2(S03)3,
ment is, K 2 0.01 atm, or log K ? -2.00. are thermodynamically unstable in the entire temperature
To find equilibrium constants as a function of tem- range considered.
perature required data on standard entropies and heats With these results on sulfite stability, the problem of
of formation as well as heat capacities and phase-transition sulfite disproportionation was considered.
data. Compounds of interest were metal oxides, sulfites, Sulfite Disproportionation. Results of calculations of AGO
sulfates, and sulfides, plus a large group of stoichiometric for disproportionation to sulfate and sulfide are given in
binary metal oxides, such as P b W 0 4 and NaAlOz. After the last column of Table 11. I n every case, the calculated
obtaining all available information from the literature, AGO was either positive or negative over the entire range
estimation procedures were developed to fill in the gaps. of 25" to 800°C; in no case did the sign of AGO change
The most important of these was an extension of Erdos' in this interval.
method ( 8 ) , which correlates heats of formation using These predictions can be broadened by including the
numerical coefficients for cations and anions in the solid. experimental results of Castellani-Bisi and co-workers (2,
Unknown standard entropies were estimated by Latimer's 3, 4 , 5, IO), and others (9, 19, 34, 3 8 ) , in which sulfites
method (21j, and heat capacities were predicted from were heated in an inert atmosphere. Using both
group contributions. The resulting thermodynamic data experimental and theoretical results, sulfite behavior can
base has been reported elsewhere (23). Some results of be classified in the following groups.
equilibrium constant calculations will be presented in the Group A . Sulfites of the alkali metals plus Ca, Sr,
next section. and Ba disproportionate with little or no SO2 evolution
Reaction Networks when heated in an inert atmosphere. This result is in
accord with thermodynamic predictions since dispropor-
The complexities of the expected reaction networks were tionation is favorable while decomposition to oxide is not
described above. Having results of an extensive literature favorable over the whole temperature range.
survey and the thermodynamic data base, the features Group B . Sulfites of Mg, Zn, Cd, Pb, Mn, La, Sc,
of each reaction network were found as follows. Sm, and Y both disproportionate and decompose to the
Oxides. For metals having multiple oxidation states, oxide when heated in an inert atmosphere. Dispropor-
the equilibrium constants for conversions of one oxide tionation is favored over the whole temperature range,
into another under a flue gas atmosphere were calculated. but decomposition to oxide begins below 800" C; the course
Results indicated the temperature ranges in which each of the decomposition is controlled by the rates of the
oxide was stable. Table I shows the results of all these two competing processes. Because of their chemical simi-
calculations. larity to La and Sm, it would be expected that Ce and
Sulfite Formation. Formation and decomposition of the other lanthanides belong in this group.
sulfites involves several competing reactions. Formation Group C. Sulfites of Be, T h , and U show no thermo-
of sulfites under flue gas ponditions occurs in competition dynamic tendency to disproportionate over the entire tem-
with sulfate formation. Once formed, a sulfite can de- perature range considered. This conclusion is based on
compose by a solid-state disproportionation to sulfate estimated thermodynamic properties; no experimental
and sulfide, or it can dissociate to give oxide and SOe. work on sulfites of these metals could be found.
To determine the actual reaction path, both qualitative I n summary, only the oxides of Be, T h , and U are
information from the literature and quantitative thermo- expected to be capable of performing as reversible sulfite
dynamic calculations were used. formers. The other sulfites are either too stable, too unsta-
As a starting point, equilibrium constants were cal- ble, or exhibit disproportionation. However, these three
culated for sulfite formdtion under flue gas conditions. oxides can also form sulfates during sorption, since flue
gas contains oxygen. Sulfate reactions are considered next.
Sulfate Decomposition. Formation and decomposition of
Table I. Stable Oxidation States at Po = 0.028 atm sulfate appears to be the most likely reaction occurring
Temperature
in an SO2 sorption process. Thermodynamic calculations
Stable oxide Other oxides considered range, O C' indicated that nearly all the oxides of interest satisfy
the sorption requirement. The critical requirement is then
CenOs CeO? 25-750"
c0304 coo 25-739" the sulfate decomposition temperature.
coo Co304 739-750' Since the literature on sulfates is so extensive, ex-
cuo CUZO 25-750" perimental values, rather than results of thermodynamic
FeZOs FeO, Fe304 25-750" calculations, were used in evaluating sulfate decomposition.
Mn02 MnO, Mn20s, MnaO, 25-390"
Mn203 MnO, MnaOa, MnO, 390-750" Literature values are collected in Table 111. I n cases
PbOl PbO 25-268' where duplicate studies have been reported, the authors
PbO Pb02 268-750' have chosen a preferred value; sources of additional values
SnO, SnO 25-760" are also listed. Some of the data have been taken from
uo3 U308, uo2 25-544" a recent review (37).
us08 UOZ, UOa 544-750"
VZO, V o , v201, V204 25-750' I t should be emphasized that the studies referred to
wos won 25-750G in Table I11 cover a variety of techniques. The most
Calculations were performed for the range, 25" to 750" C
common technique is thermogravimetric analysis (tga),
in which the sample is heated in a gas stream and the

386 Ind. Eng. Chem. Process Des. Develop., Vol. 10, No. 3, 1971
 Table II. Behavior of Sulfites, Based Table Ill. Decomposition of Sulfates
on Thermodynamic Calculations"
Sulfates which Decompose Directly to Oxide
Sulfite
Sulfite formation decomposition Disproportionation
temperature, ' C temperature, I^ C, fovoroble, Decomposition
Oxideb log K = -3.82' log K = -2.00' 25-800"C temperature Meth-
Compound" range, ' C od* References'
Ag2O 315" 420" Yes
Be0 30° 75" No
Bi,Oi 150; 2203 Yes 650-950" F 37,l
CaO 590' 75P Yes 690-760" F, V 2 0
CdO 240" 325" Yes 650-950" A 26,40
coo 255. 340" Yes 781-810' F 35, 16,22
FeO 190= 265' Yes 560-700' s 37
MgO 160" 2302 Yes 550-650" s 11
MnO 25P 325' Yes 730-890' S 15,22
MnlOi 25. 75" 300-587" V 37
NiO 185" 270" Yes 550-650" s 11
PbO 345' 445. Yes
Tho? 200" 275. No Sulfates which Decompose via Oxysulfates
uo, 140" 210' No
ZnO 120" 190" Yes
ZrOL 335" 440" Decomposition
temperature Meth-
'Temperature range of calculations was 2 2 to 800" C . Compound Solid product range, ' C od* References'
bInsufficient data available for reactions of Ce203, CeO?, Cr203,
CsLO,Ga20g, GeO?, HfO?, I r 0 2 , La?O.],MoO.3, Nb?Os, PdO, R e o ? , F 24
425O
R h 2 0 1 ,SciOi, T a r o j , TiO,, WOi, Y,Oi. KO sulfites or sulfates
are known for As201, B,O,, Si02. ' Sulfite formation temperature
is <25"C for A120i, Fe,Oi, Sb20,, SnO,. dSulfite formation and
5550 F 24
decomposition temperatures are >800c C for BaO, K O . LilO,
6203 24
Na,O, SrO. 'Reaction 2 AgrSO, + 2 Ag + SOr + Ag2SOI occurs
a t 1000C. 24
860"
Biz(SO,)
cdso, 853-870" 31, 23, 25
> 1065" 31, 23, 25
400-860' 22
weight change is measured. Another technique is the static > 860" 22
method, in which the partial pressure and composition 460-640° 22
of gas above the sample are measured in a closed system. 700-840" 22, 14, 25,
These methods can produce quite different results, since 33
840-935" A 22, 14, 25,
in the former method the partial pressure of gaseous prod- 33
ucts above the sample approaches zero, while in the La2O2SO, 890-1096' A 26
latter method, it approaches the equilibrium value. Other h203 1300-1400° A 26
methods use still different conditions; for example, in some PbO .PbSO, 860-960" A 25, 18
cases, samples have been heated in air. While the informa- PbO > 9600 A 25, 18
TiOS0, 150= F 37
tion in the tables comes from a variety of sources, some TiO? 430-600' F 37
comparisons and conclusions are still possible. The most v,oj 100-200" 37
important of these is the fact that sulfates can be Y,O,SO? 920-1124' A 26
categorized as to the path of the decomposition reaction. Y?OJ 1124-1248" A 26
The parts of Table I11 refer to the following groups. ZnO. 2 ZnSO, 610" A 25, 17, 33
ZnO 740; A 25, 17, 33
Group A . Sulfates of the alkali metals, alkaline earths,
plus A13-, Ce3-, Fe3-, Ga3-, Hf", ScJ-, Sn'-, Th", and Sulfates which Decompose with Oxidation
Zr' exhibit simple decomposition directly to the corre-
sponding metal oxide. Nine of these show some decomposi- cos04 c o o , co301 680-9303 s 12,22
tion below 8OOOC. FeS04 Fe,Oj 603-810" F 35, 1 , 22,
Group B . Sulfates in this group decompose ultimately 32, 38, 39
MnJO, 880-11000 A 22, 6, 13
to the corresponding oxide, but with intermediate forma- SnO? 320-597" v !37
tion of oxysulfates. This group includes sulfates of Bi3-, UO?SO, 30O-50Oa s 37
Cd", Ce'-, Cr'-, Cu2-, La1+, P b L - , Ti4-, V'-, Y3-, and uo,, u305, 500-700" s 37
Zn'-. While complete decomposition may require very uo3
high temperatures, partial decomposition to oxysulfate v20,, v2os 38O-40an v 37
may occur at much lower temperatures, as for example
v205 431-553" s '37
with Bi2(S04)3.
"Other sulfates in this class are BaSO,, CaSO,, C s S 0 4 , K2S04,
Group C. This group decomposes with oxidation and Li2S04, MgS04, Na2S04, RbSO,, Sc~(S04)3,SrS04, Th(SO&;
includes sulfates of Co2-, Fe", Mn'-, Sn2-, U", V3-, decomposition temperatures of these are > 800° C. F , sample under
and V02-. The only sulfate in this group which decomposes flowing inert gas, V , sample under vacuum, A , sample decomposed
via an oxysulfate is U(SO4)?.The placement of sulfates in air, S, static experiment. 'First reference listed is source of
in this group is rather arbitrary, since the formation of data given here; others give additional data. Further references
on some of these are given by Stern and Weise (37). d n = 2,
a higher oxide depends strongly on the temperature and 3, or 4.
atmosphere.

Ind. Eng. Chem. Process Des. Develop., Vol. 10, No. 3, 1971 387
 Group D . Sulfates of Pd, Ag, and the noble metals Evidently, the sulfate decomposition temperature was
decompose to give the free metal; these are not included below the operating temperature for the more active
in Table 111. oxides, and was above the operating temperature for the
Decomposition temperatures of sulfates cover a wide less active oxides.
range, as shown in Table 111. Metals having sulfates The reactions of a sorbent going through the process
which show some decomposition with SO, or SO3 evolution shown in Figure 1 can now be summarized as follows.
below 800°C are Ag, Al, Be, Bi, Ce, Co, Cr, Cu, Fe, The sorbent recycled from the regenerator is an oxide
Ga, Hf, Ni, Sn, Ti, V, U, Zn, and Zr. (or oxysulfate). Flue gas feed to the sorber contains oxygen
Results of this sulfate decomposition survey are useful and this may cause a change in oxidation state; favored
in selecting materials which can undergo regeneration oxidation states have been listed in Table I.
within the specified range of temperature. As mentioned Sorbent can then react with SO, to form sulfite (Table
earlier, sulfate will probably be formed with all oxides, 11). However, sorbent can also react with SO, and oxygen
either directly during sorption, or by way of sulfite oxida- to form sulfate. This may occur as a bulk reaction in
tion or disproportionation during sorption, or as one of which all or most of the sorbent is converted to sulfate,
the regeneration reactions. Some insight into direct sulfate or it may be confined to a thin surface layer because
formation or sulfite oxidation during sorption can be gained of simultaneous SOs desorption. A few results have been
by examining the catalytic properties of metal oxides in presented in Table IV.
SO, oxidation. Spent sorbent enters the regenerator and is contacted
Catalytic Oxidation. Adsorption and oxidation of SO:! with purge gas. At regeneration temperature, which is
on an oxide surface can be regarded as a precursor to higher than that of the sorber, equilibrium is shifted
bulk sulfate formation. These surface processes have been toward complete dissociation to an oxide or oxysulfate.
widely studied in investigations of catalysts for SO, oxida- However, if the spent sorbent contains sulfite, dispropor-
tion. The catalytic process on oxides should involve the tionation to sulfide and sulfate may occur (Table 11).
following steps: sorption of SO, to form a sulfite, oxidation Most likely, spent sorbent will be sulfate or oxysulfate;
of sulfite to sulfate, and sulfate decomposition with evolution decomposition of these has been summarized in Table
of sos. 111.
Requirements for a good catalyst can be compared to
Selection of Potential Sorbents
those for a good SO2 sorbent. For the catalyst, all three
steps are surface reactions and occur at the same tem- The purpose of selecting oxides as potential sorbents
perature. For the SO, sorbent, the first two steps should at this point was to provide a rational basis for the future
occur as bulk reactions converting much of the sorbent development of processes of the type shown in Figure
to sulfate during sorption a t Ts. The last step should 1. Considerable future sorbent development will be
occur during regeneration to oxide a t a higher temperature. required, involving many factors not discussed here, such
With this in mind, the literature on SO, oxidation as sorption rate and sorbent stability during long term
catalysts was surveyed; results are summarized in Table sorption-regeneration cycling. As the development work
IV. Since Pso, was so high in these experiments, it is will be quite expensive, it appeared most economical to
difficult t o compare these results with those in Table proceed as far as possible using thermodynamic analyses
111. At least some sulfate was formed in most cases. plus literature data, as has been done here.
At the outset, oxides of 47 elements were considered.
While this list is rather extensive, the authors believed
Table IV. Behavior of Oxides in 502 Oxidation" that consideration of a complete list was the best way
Catalytic Temperature toward unambiguous solution of the present selection prob-
activity range lem.
relative investigated, Transformation of The elements considered and those having oxides
Oxide to Pt "C catalyst t o sulfate
selected as potential sorbents are presented in Figure 2.
BL03 None 500-700" Sulfate formed below The general philosophy of selection was to eliminate only
600" C, evolved SO3 above those materials for which some definite unfavorable be-
600° C
CeOp Slight 600-700" Some sulfate formed havior could be cited. Initially, oxides of Ba, Ca, Cd,
CUO Moderate 450-750° Much CuSO, formed Cs, K , La, Li, Mg, Mn, Na, Rb, Sc, Sr, and Y, were
below 650" C and eliminated mainly because of unfavorable sulfate decom-
deactivated catalyst position temperatures. T h o , was retained because of possi-
Fez03 High 500-700" Not reported, ble favorable sulfite behavior. Oxides of Ag, As, B, and
probably none
Mn02 Slight 450-70OG Much MnSO, formed Si were eliminated because of unfavorable chemistry (see
PbOs None 500-700" Catalyst completely Table I1 and discussion of Group D sulfates). Be was
converted to PbS0, eliminated mainly because of the toxicity of its compounds,
Sn02 Slight 400-750" Small amounts of and Ga, Ge, Ir, Pd, Re, and Rh, because of high cost.
SnSO,, Sn(SOa),formed
TiO, Moderate 500-750° Small amount of Since Moos has a relatively high vapor pressure a t elevated
TiOSO, formed temperatures, it was eliminated. Experimental data
UO, None 500-750' Sulfate formed showing reasonable sulfate decomposition temperatures for
below 700" C, evolved oxides of 15 of the remaining 20 elements have been
SO, above 700° C, U02S0, given in Table 111, and these 15 plus Th are the ones
found after test
v205 High 425-700' Not reported, which were selected. No decision was possible for oxides
Drobablv none of Nb, Sb, Ta, and W.
'Results of Neumann (27, 28, 29). Feed was 7% SO, in air. In summary, the 16 potential sorbents represent the
authors' best judgment based on all the available informa-

388 Ind. Eng. Chem. Process Des. Develop., Vol. 10, No. 3, 1971
 I SERIES I 1 I [ I I I I I I I 1
Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm yb L u

ACTINIDE Np Pu Am Cm Bk Cf Es Fm Md Lw
SERl ES
Figure 2 . Selection of oxides
Horizontal and vertical cross-hatched, oxides considered; vertical cross-
hatched oxides selected

tion. The information developed here should provide a These calculations indicate that the addition of a second
useful framework for design of future experimental oxide may affect quite substantially the equilibrium con-
development. Some study of sorption kinetics on these stant of a given sulfate decomposition. I t should be
materials has been carried out and will be reported else- emphasized, however, that calculations were based upon
where. the assumption of separate phases and upon estimates
of thermodynamic properties, in most instances. The next
Binary Metal Oxides step would appear to be to test the predicted effect in
Many well-defined stoichiometric oxides such as CaCr204 an experimental study of the decomposition of sulfate-
are known. The existence of these compounds indicates oxide mixtures. Until experimental work has been per-
that a negative standard free energy change occurs upon formed, it will not be possible to reach a general conclusion
reaction of the constituent oxides-e.g., CaO + Cr203. on the applicability of binary oxides.
Because of this AGO, one would expect a binary metal Conclusions
oxide to exhibit different behavior towards sulfur oxides
than either of its single constituent oxides. The objective of this work was to identify potential
The reaction of CaCrn04with SO3 can be represented sorbents for removal of sulfur oxides from flue gas. To
by do this, it has been necessary to establish as well as
possible the chemistry of metal-oxygen-sulfur systems.
CaS04 + Cr203 2 CaCr204 + SOs (7) Published data furnished the basic facts and thermo-
where the so3 is written on the right-hand side in dynamic correlations extended these to previously un-
accordance with the convention described previously. This known cases. Judicious combinations of reported data and
is only one possible representation of the sorption process thermodynamic calculations made it possible to predict
and assumes that the sorption product exists as two dis- reaction paths for many cases. Examination and compari-
tinct phases, rather than as a solution or a compound son of compound behavior have led to useful chemical
(Cr203.CaS04). Unfortunately experimental information generalizations. Results have been used to select 16 poten-
on mixed sulfate-oxide pairs is not available. tially useful single oxide sorbents. Binary oxides constitute
This equation represents the process as an oxide dis- an additional class of possible sorbents; selection of poten-
placement. Going toward the right, C r 2 0 3displaces SO3, tially useful binaries will require experimental work.
while the opposite occurs in the reverse direction. Literature Cited
Assuming that this representation is correct, AGO for the
above process can be predicted from a knowledge of AGO Clark, E. L., Belgian Patent 638,611 (February 3,
1964).
for the reaction of C r z 0 3with CaO, plus free energy data Clerici, A., Castellani-Bisi, C., Gazz. Chim. Ital.,
on the individual oxides. As mentioned earlier, AGO for 93, 1444-54 (1963).
formation of binary metal oxides was included in the Cola, M., Castellani-Bisi, C., ibid., 91, 173-86 (1961).
thermodynamic data base developed for this work. Cola, M., Castellani-Bisi, C., ibid., 92,447-53 (1962).
Using these data, several sets of calculations were per- Cola, M., Castellani-Bisi, C., Tarantino, S., ibid.,
formed. For Equation 7, log K a t 750°C was predicted 91, 105 (1961).
to be +4.3, compared with -10.5 predicted for decomposi- Dollimore, D., Tonge, K. H., in “Fifth Int. Symp.
tion of CaS04 alone. As another example, log K a t 750” C on Reactivity of Solids,” G-M. Schwab, Ed.,
for decomposition of NiS04 + V 2 0 5 to SO, and NiV206 Elsevier, New York, N. Y . , 1965, pp 497-507.
Enuiron. Sci. Technol., 4, 474-5 (1970).
was predicted to be +0.5, as compared with -2.8 for Erdos, E., Collect. Czech. Chem. Cornmun., 27, 1428-
NiS04 alone. Finally, for decomposition of Na2S04+ Al2O3 37 (1962).
to 2 NaA102 and SO,, log K a t 750°C was predicted Foerster, F., Kubel, K., 2. Anorg. Chem., 139, 261-
to be -11.1, compared with -20.3 for Na2S04 alone. 92 (1924).

I n d . Eng. Chem. Process Des. Develop., Vol. 10, No. 3, 1971 389
 Garrini, E. R., Castellani-Bisi, C., Gazz. Chim. Ital., Neumann, B., ibid., 38, 304-11 (1932).
93, 1252-8 (1963). Neumann, B., Goebel, E., ibid., 34, 734-40 (1928).
Hevesy, G. V., Cremer, E., 2. Anorg. Allg. Chem., Newell, J. E., Chem. Eng. Progr., 65 (8),62-6 (1969).
195, 339-44 (1931). Pannetier, G., Bregeault, J. M., Guenot, J., Bull.
Ingraham, T. R., Can. Met. Quart., 3 (3), 221- [Link]. Fr., 1962, 2158-63.
34 (1964). Pechkovskii, V. V., Amirova, S. A., Vorob’ev, N.
Ingraham, T. R., ibid., 5 (2), 109-122 (1966). I., Izu. Vyssh. Ucheb. Zavend., Khim. Khim.
Ingraham, T. R., Trans. A I M E . , 233,359-67 (1965). Tekhnol., 6 (2), 268-73 (1963); CA, 59, 96148 (1963).
Ingraham, T. R., ibid., 236, 1064-67 (1966). Pechkovskii, V. V., Gaisinovich, M. S., Zh. Neorg.
Ingraham, T. R., in “Proc. First Int. Meeting on Khim., 9 ( l o ) , 2299-302 (1964); C A , 62, 1205a
Applications of Fundamental Thermodynamics to (1964).
Metallurgical Processes,” G. Fitterer, Ed., Gordon Pechkovskii, V. V., Ketov, A. N., J . Appl. Chem.
and Breach, New York, N.Y., 1967, pp 179-96. USSR, 33 (8), 1706-10 (1960); Zh. Prikl. Khim.
Ingraham, T. R., H. H. Kellogg, Trans. A I M E . , (Leningrad), 33 (8),1724-9 (1960).
227, 1419-26 (1963). Pechkovskii, V. V., Ketov, A. N., Uch. Zap. Perm.
Kellogg, H. H., Basu, S.K., ibid., 218, 70-81 (1960). Gos. Uniu., 17 ( l ) ,15-34 (1960); CA, 57, 4287c
Ketov, A. N., Pechkovskii, V. V., Russ. J . Inorg. (1962).
Chem., 4, 118-20 (1959); Zh. Neorg. Khim., 4, 272- Sherwood, T. K., Technol. Reu., 72 (3), 24-31 (1970).
6 (1969). Stern, K. H., Weise, E. L., National Bureau of
Langer, H. G., Gohlke, R . S.,Anal. Chem., 35 (9), Standards, NSRDS-NBS 7, Washington, D. C.,
1301-2 (1963). 1966.
Latimer, W. M., J . Amer. Chem. SOC.,73, 1480- Trautz, M., Pakschwer, S., J . Prakt. Chem., 122,
5 (1951). 147-81 (1929).
Lorant, B., Z . Anal. Chem., 219 ( 3 ) ,256-271 (1966). Trojan, S.,Nemecek, J., Czechoslovakian Patent
Lowell, P. S.,Schwitzgebel, K., Parsons, T. B., 115,167 (June 15, 1965); C A , 64, P15431d (1966).
65th National Meeting, AIChE, Cleveland, Ohio, Wendlandt, W. W., J . Inorg. Nucl. Chem., 7, 51-4
May 1969. (1958).
Margulis, E. V., Grishankina, N . S., Kopylov, N.
L., Russ. J . Inorg. Chem., 10 ( l o ) , 1253-6 (1965); RECEIVED
for review September 9, 1970
Zh. Neorg. Khim., 10 ( l o ) , 2304-9 (1965). ACCEPTED March 4. 1971
Margulis, E. V., Remizov, Yu. S.,Sb. Nauch. Tr.,
Vses. Nauch.-Issled. Gornomet, Inst. Tsuet. Metal.,
The work upon which this article is based was performed pursuant
1960 (6), 171-82, CA, 56, 3109a (1962). to contract PH-86-68-68 with the National Air Pollution Control
Nathans, M. W., Wendlandt, W. W., J . Inorg. Nucl. Administration, Environmental Health Service, Public Health Ser-
Chem., 24,869-79 (1962). vice, Department of Health, Education, and Welfare, Leon Stankus,
Neumann, B., 2. Electrochem., 34, 696-734 (1928). Project Officer.

Continuous Precipitate Flotation

of Chromium( Ill) Hydroxide
Robert B. Grieves’ and Richard W. lee
Department o f Chemical Engineering, University of Kentucky, Lexington, Ky. 40506

T h e separation of ions from aqueous solution by precipita- Cr(II1) with NaOH, followed by batch flotation with an
tion followed by flotation of the precipitate was shown anionic surfactant (sodium dodecylsulfate), provided 97%
to be a feasible process by several investigators, including removal of chromium from aqueous suspensions 0.93 m M
Baarson and Ray (1964), Grieves and Bhattacharyya in Cr (Bhattacharyya et al., 1971). The process was
(1969), Mahne and Pinfold (1969), Rubin (1968), and strongly pH-dependent: below p H 6.3, soluble chromium
Skrylev and Mokrushin (1961). Precipitate flotation of species became appreciable, and the flotation results
the first kind involves collection of charged precipitate tended to parallel the decrease in the fraction of Cr present
particles by a surface-active agent of opposite charge. as precipitate; above pH 9.7, the charge of the precipitate
Precipitate flotation of the second kind (Mahne and Pin- was reversed, as indicated by surface potential measure-
fold, 1968) eliminates the use of a surfactant; instead ments. The optimum pH range for flotation was 7.0 to
it relies on the interaction between a hydrophilic, cyclic 8.8. For suspensions with a doubled Cr concentration
organic reagent and a metal ion to form a hydrophobic (1.86 m M ) , the optimum p H range was lowered and nar-
precipitate which is floatable. rowed to 6.3 to 6.5, indicating modifications in particle
A three-stage process of reduction of acid chromate surface characteristics. In a batch process, 87% flotation
(HCrO;) with NaHSOI, followed by precipitation of was achieved a t a 0.093-mol dodecylsulfate per mol Cr
ratio.
To whom correspondence should be addressed. Virtually any precipitate flotation process of commercial

390 Ind. Eng. Chem. Process Des. Develop., Vol. 10, No. 3, 1971