1822 H. E. JONES, E. E.
STAHLY
AND B. B. CORSON
[CONTRIBUTION FROM MULTIPLEFELLOWSHIPS
ON CATALYSIS' AND TAR
Butadiene from Ethanol. Reaction Mechanism
BY H. E. JONES, E. E. STAHLY
AND B. B. CORSON
The manufacture of butadiene from ethanol by
the American two-step process developed by Car-
bide and Carbon Chemicals C o r p ~ r a t i o and
n ~ ~op-
~ aldeh de being continuously regenerated from
erated by that organization and by Koppers Com-
,Inc., comprised (1) dehydrogenation of eth-
an0 to acetaldehyde followed by (2) catalysis of
acetaldehydeethanol to produce butadiene. This
paper discusses the mechanism of the second step,
in which a mixture of approximately 69 wt. % of
ethanol, 24 wt. % of acetaldehyde and 7 wt. % of
water was passed over a 2% TazO&?% Si02 cata-
1 st a t 350' and 0.4 liquid hourly space velocity
ff.h.s.v.), Mechanistic evidence was obtained
from rate measurements and from the behavior of
various feed mixtures.
The importance of crotonaldehyde as interme-
diate4 was confirmed. The primary function of
the silica component of the catalyst was the con-
densation of acetaldeh de to crotonaldehyde,
P
whereas that of the tanta a promoter was the catal-
ysis of the deoxygenation of crotonaldehyde by
the hydrogen donor ethanol. This is a reversal of
the roles assigned by Quattlebaum, Toussaint and
D ~ n n . Crotyl
~ alcohol and acetaldol, perhaps
transitory intermediates, were not rate control-
ling. Both crotonaldehyde and crotyl alcohol were
present in the crude catalyzate, but acetaldol was
not detectable.
The odor of the liquid portion of the catalyzate
furnished qualitative evidence of the presence of
crotonaldehyde. The latter6was separated by dis-
tillation, as well as crotyl alcohol.6 Crotyl alcohol
was subsequently isolated in considerable amount
from plant by-product n-butanol and shown to
constitute about 0.8% of the "by-product oil."
Kinetic study indicated that the rate control-
ling process a t atmospheric pressure was a second
order condensation of acetaldehyde, whereas a t
pressures of 4-30 atmospheres the rate of consump-
tion of acetaldehyde was of first order.
The behavior of various feed mixtures when
passed over the catalyst indicated that diethyl
acetal, vinyl ethyl ether, diethyl ether, n-butanol,
n-butanediols, n-butyraldehyde, ethylene, acety-
lene and tetrahydrofuran were not major interme-
diates. In general, as would be expected, feed mix-
tures capable of producing ethanol and acetalde-
hyde (or crotonaldehyde) in situ, yielded butadi-
ene. Crotyl alcohol mixed with a small amount of
(1) Reconstruction Finance Corporation, Office of Rubber Re-
serve, Washington, D. C.
(2) Koppers Company, Inc., Pittsburgh, Pa.
(3) Toussaint, Dunn and Jackson, Ind. Eng. Chem., 39, 120
(1947).
(4) Quattlebaum, Toussaint and Dunn, THISJOURNAL, 69, 593
(1947).
(5) 2 4-Dinitrophenylhydrazone, m p and mixed m p. 189-191'.
(6) Identified by hydrogenation to n-butanol.
Vol. 71
WELLON INSTITUTE]
croionaldehyde produced a 60% per pass yield of
butadiene when passed over the catalyst, croton-
P
croty alcohol by the deoxygenation reaction which
produced butadiene (mechanism E).
Experimental
Materials.-Ethanol, acetaldehyde and crotonaldehy?
were of reagent grade. Crotyl alcohol (b. p. 117-119 ,
%*OD 1.4255, dZo, 0.855, 96% pure by bromine number,
characterized as a-naphthylurethan, m. p. 91-93 ") was
prepared by the reduction of crotonaldehyde by aluminum
isopropoxide. The various other feed materials were
purchased, all samples being analyzed or characterized
before use; if the purity was not 95% or better, the mate-
rial was purified.
Commercial catalyst (2% TazOs-98% SiOn) was ob-
tained from the Rubber Reserve Company. Silica gel
of the type employed in the preparation of the above
catalyst was obtained from the Davison Chemical Com-
pany, its specifications being those of the Rubber Reserve
acceptance test.
Apparatus and Procedure.-Two types of equipment
were employed, the Koppers reactor' charged with 125
cc. of catalyst, and a single tube of the multiple testers
charged with 20 cc. of catalyst.
Catalyzate from the larger reactor was condensed by
Dry Ice and distilled into three fractions: (:) b. p. below
13", (2) b. p. 13-30' and (3) b. p. 30-95 , which frac-
tions were analyzed, respectively, for (1) butadiene and
acetaldehyde, (2) acetaldehyde and (3) acetaldehyde,
acetal and ethanol. Operation a t 850' and 0.4 1. h. s . v.
(6.6 seconds contact time) with commercial feed (2.75
moles of ethanol per mole of acetaldehyde) and commercial
catalyst (2% Taz05-98% Si?,) gave.a 36% per pass yield
of butadiene and a 64% ultimate yield (standard devia-
tions 2.5 and l.6%, respectively). This ultimate yield
duplicated commercial practice.
Catalyzate from the smaller reactor was processed by
extractive distillationg to separate gaseous from liquid
products. The gas was collected over aqueous sodium
sulfate and analyzed for butadiene by the Koppers-
Hinckley methodlo; the liquid catalyzate (bottoms from
extractive distillation-by-products and unreacted feed)
was not analyzed, being too small for significant ultimate
yield data. The per pass butadiene yield averaged 35%
(with commercial feed and commercial catalyst) which Was
in good agreement with the 36% value obtained with the
larger equipment.
Mechanisms
Many of the mechanismsll which have been hy-
pothesized to explain the formation of butadiene
are characterized by lack of evidence. Mecha-
nisms involving the formation and deoxygenation
of crotonaldehyde (mechanisms B, B1 and D) were
indicated by the present study and had been pre-
viously derived by Quattlebaum, Toussaint and
(7) Corson, Stahly, Jones and Bishop, Ind. Eng. Chem., in press.
( 8 ) Whitlock, Haddad and Stahly, I n d . Eng. Chem., Anal. Ed., 19,
767 (1947).
( 0 ) Hinckley and Sheppard, ibid., 19, 771 (1947).
(10) Rubber Reserve method L. M. 2.1.1.7 (or 2.1.1.9.); Shepherd,
Thomas, Schumann and Diebler, J. Research, Nall. But'. Sfandanfs,
39, 435 (1047).
(11) Egloff and Hulla, Chem. Reus., 36, 63 (1945).
May, 1949 FROM ETHANOL
BUTADIENE : THE REACTION
MECHANISM 1823

Dunn4 from their study of the Ostromislensky re- the promoter action of the tantala component of
action.12 the catalyst.
(A) CHICHO +
CzH60H +
CHFCHCH=CHZ
The mechanism of the two-step process-forma-
+
2H20 tion and deoxygenation of crotonaldehyde-is
probably applicable to the one-step process as evi-
(B) 2CHICHO --+- CHaCH=CHCHO + HzO denced by the reported beneficial effect of acetal-
(Bi) 2CH3CHO +
CH3CHOHCHzCHO --f dehyde.l3~l4Minor side reactions of the two-step
CHaCH=CHCHO + Hz0 process become important when the conditions are
(C) CH3CH=CHCHO + C2HjOH ----f intensified to approach those of the one-step proc-
CHaCHO + CHsCH=CHCHzOH + ess. For example, when the second ste was oper-
CHz=CHCH=CHz + Hz0 ated a t 375-400, 0.7 1. h. s. v., with 5 f i ethanol-
(I)) CH:CH=CHCHO + C2HjOH + acetaldehyde feed mole ratio the apparent yield
CHzCHO + CH2=CHCH=CHr + HzO of butadiene based on acetaldehyde16 surpassed
(Dl) CHaCH=CHCHO + RHZ (H donor loo%, which means that the original acetaldehyde
other than ethanol) content of the feed was augmented by additional
CH.=CHCH=CHz f R + H20
acetaldehyde formed in situ, not only by reactions
(E) CHICH=CHCHO + CH3CH=CHCH20H + C, D and F, but probably also by reactions N, 0,
CHZ=CHCH=CHz + CH,CH=CHCHO + H20 P, Q and R ; butyraldehyde, butanol, butane and
CHaCHOHCHyCHO + CzHaOH +
CHvCHO + CH3CHOHCHzCHzOH +
butene were detected in the catalyzate.
CHs=CHCH=CHz + 2H20 (N) CH3CH=CHCHO CZH~OH ++
2CzHeOH +CH3CH2CHtCHiOH + H20
CHaCHzCH2CHO CHaCHO +
(0) CHaCHzCH2CHO f CzHe0H-f
(GI) CH3CHzCHzCHzOH +
H20 + CHaCHzCH=CHn +
CHaCHzCH,CHzOH CHaCHO +
CHz=CHCH=CH2 + H? (PI CHaCHzCHzCHO C2HeOH -----f+
(G2) CHaCHzCHzCHzOH + CHaCH=CHCH3 f Hz0 CHsCHO +
+ CHaCH=CHCH>OH
Hz
CHr=CHCH=CH2 + H 2 0
+
' (Q) CH,=CHCH=CHz 2CzHeOH + +
C H ~ C H ~ C H Z C H2CHaCHO
~ +
(Gs) CHjCH2CH2CH2OH +
Hz + CH3CHzCHzCHO +
(R) C;HjOH + CHjCHO H? +
CHaCH=CHCHO + HZ Kinetic Studies
(G4) CHaCHzCHnCHzOH +
CHz=CHCH=CHz + HZ f Hz0 Effect of Feed Composition.-According to
the data of Table I the general effect of increas-
CHaCHO +
CzHeOH +CH3CHOH(OCzHs) ing the acetaldehyde content of the feed was t o
(Hi) CH3CHOH(OCzHs) +
He0 CHpCH(0CaHJ + TABLE I
(Hy) CHz=CH(OCzHs) CHFCH~ --t
CH?CHCH=CHz CgHsOH
+ + EFFECTOF FEEDCOMPOSITION EXPTS).
(EXPLORATORY
350, 0.4 I. h. s. v., 2% T a ~ O r 9 8 %SiOz, atm. press., 2-hr. runs
(H3) CHaCHOH(0CzHs) + Mole Butadiene yield,
CHaCHOHCHzCHzOH + ratio mole %
' Efficiency, %
CHpCHCH=CH2 2Hz0 + CzHaOH/ Mole fraction"
CHaCHO CnHaOH CHaCHO Passo mated
Per Ulti- CzHa-
OH
CHa-
CHO
5.1 0.70 0.14 23 47 30 110
CHFCH~ + CHGCH 9CH-CHCH=CHt
3.5
3.0
.66
.64
.19
.21 30
28 61
65
92
90
45
51
-CHzCHr +CzHsOH + 2.75 .63 .23 34 66 83 55
-CHzCH (0H)- 2.5 .61 69
.25 35 80 61
=SiOSi= + CzHsOH +=SOH + =SiOC2Hs 2.0 .58 .29 40 59
64 69
1.T5 .56 .32 40 65
64 65
zSiOSi= + CHz=CHCH=CH(OH) + 1.0 .45 .45 3gb 60
65 55
=SOH f =SiOCH=CHCH=CHa 0.5 .20 .40 3Sb 51 69 40
(MI) =SiOCH=CHCH=CHz + .o ..
=SiOCzHI +=SiOSi= + CH2=CHCH=CH2
- 0 0 .83 Ob 0 0
a Water constituted the remainder of the feed. High
The biradical mechanism (K) has little support- acetaldehyde concentration caused rapid carbonization
ing evidence, and i t is not n e ~ e s s a r y ,as
~ origi- of the catalyst. Per pass yield =
nally claimedI3 for an understanding of the by- moles CaHa X 100
products formed. In regard t o the silicon oxide +
(moles C Z H ~ O H moles CH,CHO)/2'
Ultimate yield =
complexes, although the hypothetical formation moles C4He X 100
of catalyst-reactant complexes ranging from ad-
sorption complexes to chemical compounds is a
(moles CPH~OH +
reacted moles CH3CHO reacted)/2'
(14) Lebedev, French Patent 665,917 (1928): British Patent 331,-
well-known concept of catalysis, it is a mechanism 482 (1930); Talalay and Talalay, Rubbev Chem. Tech., 15, 403
which in the present case takes no cognizance of (1942); Talalay and Magat, "Synthetic Rubber from Alcohol,"
(12) Ostromislensky, J. Russ. P h y s -Chem. Soc., 47, 1472 (1915). Interscience Publ., Inc., New York, N.Y., 1945.
(13) Lebedev, et a l . , J. Gen. Chem. ( C S. S. R,),31, 698 (1933); moles CiHs produced X 100.
(15) Acetaldehyde efficiency =
Synlct Kouchuk. 4. 8 (1935). moles CHaCHO consumed
1824 AND B. B. CORSON
H. E. JONES, E. E. STAHLY Vol. 71

increase the per pass yield of butadiene, but anolacetaldehyde ratio of the feed was decreased.
where the feed was aqueous acetaldehyde alone With an ethanol-acetaldehyde feed mole ratio of
(cu. 92% acetaldehyde, 8% water), the yield of 5.1/1 (expt. 1,Table I) the acetaldehyde efficiency
butadiene was zero, whereas the yields of croton- was 110%. Because of this complication, kinetic
aldehyde and by-products were 18 and 259;b, re- calculations were applied only to feed mole ratios
spectively. The ultimate yield of butadiene in the range 0.5/1 to 3.5/1.
passed through a maximum a t the ethanol-acetal- Rate Data for Atmospheric Operation.-
dehyde ratio of approximately 2.5/1. On the The data in Tables I1 (350') and I11 (232-403')
did not support the assumption of a bimolecular
TABLEI1 reaction between ethanol and acetaldehyde
RATECONSTANTS
AT ATMOSPHERIC
PRESSUREAND 350" (mechanism A) ; they fitted a rate equation
2% TatOi-98% Sios, 8-hr. runs
Mole fraction
CHCHO
Mole fraction
CaHIOH C4H6
+
dx/dt = Kl(a - x ) ~ K2(a - x )
In In mole
In prod- In prod- C. T.0 frac-
feed uct feed uct sec. tion KI Kt
0.214 0.056 0.643 0.384 4.5 0.103 0.319 0.252
.214 .031 ,643 .343 6.7 .113 ,320 .253 where a = initial mole fraction of acetaldehyde,
.223 ,096 .615 .440 2.7 ,085 .332 .262 x = mole fraction of acetaldehyde reacted, K1 =
.223 .082 .615 .417 3.4 ,096 .317 .250 rate constant of acetaldehyde condensation and
.223 .060 .615 .382 4.5 .lo7 .322 .254 Kz = rate constant of side reactions. The expres-
.223* ,036 .615 .298 6.6 .132 .312 .246
.223 ,010 .615 ,280 10.6 .138 .334 .264 sion was solved by simultaneous equations, or by
,247 ,037 ,616 ,310 6.6 ,136 .322 .254 trial and error, depending upon the amount of ex-
.288 .039 .576 .211 6.6 .146 .334 ,264 perimental data. The scattering of the calculated
.317" .IO0 ,554 .320 3.8 .lo7 .313 ,247 K values due to the * 3 O variation of the reaction
.400c .088 .200 ,023 4.9 .lo6 .313 .247
.445 .170 .445 .196 2.8 ,117 .328 .259 temperature was k4y0. This was the principal
Av. ,322 .254 source of error. The scattering due to analytical
C. T. = contact time in seconds, assuming ideal gas uncertainty was * 2%.
laws. Average of 17 expts. O3-h. expts. The apparent activation energies derived from
TABLEI11
RATECONSTANTS
AT ATMOSPHERIC
PRESSURE TEMPERATURES
AXD VARIOUS
2% TazOa-98% SiOt, 8-hr. runs
Mole fraction CHaCHO Mole fraction ClHsOH C. T., C4He mole
T, 'C. In feed In product In feed In product sec. fraction KI K:
232 0.445 0.280 0.445 0.283 8.4 0,089 0.0035 0.054
300 .214 .OB8 .643 .524 5.0 .041 ,057 .170
300 .214 .058 .643 .468 7.5 .056 .056 ,167
300 .223 .063 .615 .396 7.4 .078 .055 .164
300 ,288 .077 ,576 .330 7.4 .090 .056 .169
-
.056 .168 (av.)
325 .214 .070 .643 .422 4.7 .OB9 .141 .219
325 .214 .045 .643 .397 7.0 ,091 .139 .216
325 .223 .050 .615 .352 7.0 .lo2 .129 .200
325 .288 .055 .576 .274 6.9 .122 .142 .220
325 ,469 .160 .435 .192 4.3 ,097 ,136 .211
- -
.137 ,213 (av).
375 .214 .029 (0.041)" .643 .242 6.3 ,126 ,650 ,260
375 ,223 .030( .033)' ,615 .239 6.3 .138 ,648 ,259
.288 .032( .037)" .576 .183 6.2 .155 .697 .279
375
-
.665 .266 (av.)
400 .214 .022( .031)' ,643 .092 6.0 .144 1.20 ,287
403 ,223 .022( .032)" .615 .179 6.0 ,141 1.22 ,292
397 .288 .023( .036)" .576 .133 6.0 ,162 1.28 .306
- -
1.23 .295 (av.)
Final acetaldehyde concentrations were corrected for acetaldehyde resulting from butene formation in excess of that
formed at 350" (uncorrected values in parentheses).
other hand, the ethanol efficiencylBincreased and the plots of In K1and In Kz against reciprocal tem-
the acetaldehyde efficiency16decreased as the eth- perature were 24 kcal. and 8.5 kcal., respectively.
Moles &H6 produced X 100, Both plots deviated from linearity a t the higher
(I6) Moles CnHaOH consumed temperatures, especially that of In Kz. This was
May, 1949 RUTsDIENE FROM ETHANOL
: THE REACTION
MECHANISM 1825

attributed to the formation of acetaldehyde by re-

actions non-productive of butadiene (e. g., reac-
tions N-R) which decreased the apparent con-
sumption of acetaldehyde.
No satisfactory kinetic equation was derived to
fit the experimental data on the rate of butadiene
production as a function of ethanol consumption.
Rate Data for Operation at 4-30 Atmos-
pheres.-The rate data in Table I V supported
the assumption that the rate of acetaldehyde
consumption was directly proportional to the
acetaldehyde concentration and inversely pro-
portional to that of the ethanol according to the
general theory of Langmuir l7
-dPa=K - Pa
dt Pe
Pa
K , = ' [ ( P a , - Pea) In - Pa, -
t Pa0
+
where t = contact time in seconds and Pa and Pe
= partial pressures of acetaldehyde and ethanol,
respectively, subscript o denoting the initial
state. For convenience in integration it was as-
+
sumed that Pe = Pa - Pao Peo; although in- I
0.0014
I I I I
0.0018
1
correct, the resultant deviation in Kp apparently
was not serious. l/T( OK),
Fig. 1.-Relation between rates of reaction and tempera-
TABLE
IV
ture.
RATE CONSTANTS FOR OPERATION AT 4-30 ATMOSPHERES
AT 325' to be 3.55 X lo5. Using this constant and the ex-
2% TarOr98% SiOr, 3/1 ethanol-acetaldehyde feed ratio, 8-hr. runs perimentally determined K I constant, the equi-
Total librium mole fraction of acetaldehyde was calcu-
pressure, C. T.,
atm. Pao Pco Pa P6 see. Pba Kp lated to be 5 X for 2.75/1 ethanol-acetalde-
1.0 0.214 0.643 0.045 0.397 7.0 0.091 0.120 hyde feed. Extrapolation of rate data showed
4.4) .748 2.39 .a27 1.83 8.4 .264 ,224 that this equilibrium concentration of acetalde-
4.5 .960 2.89 .648 2.47 7.7 .183 ,140
4.6 .985 2.96 .510 2.36 12.7 .276 .141 hyde would be reached in twenty-two seconds con-
7.8 1.67 5.01 1.45 4.71 4.4 .131 .156 tact time (about 10 times the half-reaction time);
7.8 1.67 5.01 1.25 4.40 8.5 .340 .160 a t this equilibrium concentration of acetaldehyde
7.9 1.69 5.08 1.04 4.23 17.0 .385 .133 a 40% per pass yield of butadiene would be ex-
14.2 3.04 9.13 2.47 8.20 10.9 .352 .168
28.2 6.03 18.1 5.30 16.9 16.7 ,474 ,138 pected. Actually, the yield at this prolonged con-
30.0 6.42 19.3 6.97 18.7 8.7 .255 ,161 tact time (eight-hour expt.) was only 30% and
- the catalyst was excessively carbonized.
.150
bv.) Although the per pass yield is presumably not
P b = partial pressure of butadiene. * Expt. made at subject to much further improvement, it is, how-
340". ever, possible to increase the ultimate yield by op-
erating in such manner (by multi-addition of acet-
The physical significance of the above differ- aldehyde) that the optimal high ethanol-acetalde-
ential equation can be visualized in various ways. hyde ratio is approximated throughout the reac-
For example, the slow reaction may be the rate of tion zone.lg
diffusion of acetaldehyde to the chemisorbed
ethanol on the catalyst surface or to the relatively E5ciency of Acetaldehyde, Crotonaldehyde and
small fraction of the catalyst surface which is not Acetaldo112s20
in Ethanol Feed
occupied by ethanol. It is, however, unexpected Ethanol feeds containing acetaldehyde and the
that such a small increase in pressure as three at- two C4-aldehydes (acetaldol and crotonaldehyde)
mospheres should change the order of the reac- were compared on an equivalent basis (3 moles of
tion. ethanol per mole of acetaldehyde or 0.5 mole of
Equilibrium Constants.-From data available G-aldehyde) a t 350' and 0.4 1. h. s. v. The per pass
in 1943 at the beginning of this study, the equi- mole yields of butadiene per G-aldehyde equiva-
librium constant18for the formation of butadiene lent were 1.2, 1.2 and 1.8, respectively; the 1.8
from ethanol-acetaldehyde a t 350' was calculated mole yield corresponded to 90% of the theoretical.
(17) Langmuir, Trans. Farad. Soc., 1'7, 621 (1922). Thus, crotonaldehyde was considerably more ef -
(18) Private communication, A. V. Cowan, Koppers Company, (19) Kampmeyer and Stahly. Ind. Eng. Chcm.. 41, 550 (1949).
Inc. (20) Maximoff, U. S. Patent 1,682,919(1928).
1826 H. E. JONES, E. E. STAHLY
AND B. B. CORSOK Vol. 71

V
TABLE
PERFORMANCE O F ETHANOL-CROTONALDEHYDE AND ETHANOL-ACETALDEHYDE FEEDS
0.4 1. h. s. v., 2% TazOs-98% SiOl, 4-hr. expts., atm. press
Ethanol-crotonaldehyde feed Ethanol-acetaldehyde feed
Temperature, "C. 350 350 350 325 325 325 300 275 350 325 300 230
Feed mole ratio (a1c.l
ald.) 2/1 3/1 6/1 3/1 6/1 8/1 6/1 6/1 3/1 3/1 3/1 1/1
Moles C4He produced
per mole equivalent
Cd-aldehyde 0.7 1.4 1.8 1.0 1.2 1.5 1.0 0.7 1.2 1.0 0.6 0.4
C&, % yield based on
total feed 36" 56" 48" 40" 30" ' 32" 24" 17" 30b 24' 14' 22'
Moles butadiene X 100 Moles butadiene X 100
a (Moles ethanol)/2 +
moles Ca-aldehyde
* t b
(Moles ethanol)/2 +
(moles acetaldehyde)/2 *

fective than acetaldol, the latter being merely longer than one hour the catalyst was excessively
equivalent t o acetaldehyde. Evidently, acetaldol carbonized, and when the temperature was raised
was reversed to acetaldehyde and not dehydrated t o 400, the production of by-product gas in-
to crotonaldehyde. Table V presents additional creased a t the expense of butadiene.
data supporting the hypothesis that the formation
of crotonaldehyde is a rate determining reaction; TABLE \'I
i. e., the yield of butadiene from ethanol-croton- BUTADIENE
PRODUCTION OVER Si02 AND 2% Ta205-98%
aldehyde was considerably greater than that from Si02AT 350' (one-hour runs)
Mole % '
ethanol-acetaldehyde. Incidentally, the forma- C4Hi
tion of butadiene from ethanol-acetaldehyde was based on
Feed Catalyst 1. h. s. v. total feed
appreciable a t 230, i. e., 120" lower than the Ethanol-croton-
commercially employed temperature. aldehyde (6/1) SiOz 1 8
Functions of Silica and Tantala Components of Ethanol-croton-
Catalyst aldehyde (6/1) 2% TasO6-98% Si02 1 48'
E thanol-acet-
Condensation of Acetaldehyde.-Unpromoted aldehyde (3/1) Si02 1 3
silica was more effective than tantala-promoted Ethanol-acet-
silica for the above condensation. Silica gel a t aldehyde (3/1) 2% Ta205-98% SiOz 1 20
280' and 0.4 1.h.s.v. converted 22 mole % of Crotyl alcohol Si02 1 41
the acetaldehyde to crotonaldehyde and 13 mole Crotyl alcohol 2% Ta2O5--98% Si02 1 32
% to by-products, whereas 2% Ta205-98% Si02 Crotyl alcohol Si02 0.4 75
under the same conditions converted 12 mole % Crotyl alcohol 2% Ta205-98% Si02 0 . 4 50
to crotonaldehyde and 15 mole 70to by-products. a Forty-eight mole 7 0 yield corresponds to the forma-
Silica gel a t 350' and 0.4 1.h.s.v. converted 26 mole tion of 1.92 moles of butadiene per mole of crotonaldehyde
yo of the acetaldehyde to crotonaldehyde and 16 fed (96% of the theoretical yield).
mole yo to by-products, whereas 2% Ta205-98Y0
Si02 under the same conditions converted 18 mole Catalysis by Si02 Admixed with 2% Ta20b-
% to crotonaldehyde and 25 mole yo to by-prod- 98y0 SiOz.-Since unpromoted silica gel was more
ucts. effective than tantala-promoted silica for the
Catalysis of Ethanol Mixtures of Acetalde- dehydration of crotyl alcohol, i t follows that,
hyde, Crotonaldehyde and Crotyl Alcohol over if the dehydration of crotyl alcohol be a rate
Unpromoted S O z and 2y0 Ta2O5-98yO SO2.- determining step, a mixture of unpromoted and
Unpromoted silica was more effective for the promoted catalysts should be more effective than
dehydration of crotyl alcohol t o butadiene, but either alone. Two tests were made in which
promoted silica was more effective for feeds re- 2.75/1 ethanol-acetaldehyde feed was passed a t
quiring deoxygenation, e. g., ethanol-acetalde- 350' over equal volumes of (1) promoted catalyst,
hyde, ethanol-crotonaldehyde and crotonalde- and (2) a 50150 mixture of unpromoted and pro-
hyde-crotyl alcohol feeds (Table VI). The dif- moted catalysts. The per pass yields of butadiene
ferent conclusion of Toussaint, Dunn and Jack- over the promoted catalyst and over the unpro-
son3 was possibly due to the use of a different type moted-promoted mixture at 0.4 1.h.s.v. were 35
of silica gel. Crotyl alcohol has been proposed21 and 25%, respectively; a t 0.8 1.h.s.v. over the pro-
as source material for butadiene and as an inter- moted catalyst, which was the space velocity with
mediate in the ethanol process for butadiene.22 respect t o the promoted component of the mix-
When crotyl alcohol was processed a t 350' in runs ture of catalysts, the yield of butadiene was 25%.
Therefore the dehydration of crotyl alcohol was
(21) Kyriakides, THISJOURNAL, 86, 986 (1914); Prevost, Ann. not a rate determining step.
Chim., [lo] 10, 152, 407 (1928).
(22) Rigamonti and Cardillo, Ann. chim. applicala, 37, 347 Deoxygenation of Crotonaldehyde by Ethanol,
(1947); Natta and Rigamonti, Chemica e Industria, 29, 195 (1947). Isopropyl Alcohol and Crotyl Alcohol over Si02
May, 1949 FROM ETHANOL
BUTADIENE : THE REACTION
MECHANISM 1827

and '2% Ta205-98yo SiOz.-The function of TABLE

VI11
ethanol was t o deoxygenate crotonaldehyde, but PRODUCTION
BUTADIENE FROM VARIOUSFEEDS
other alcohols could also serve. For example, as 350, 0.4 1. h. s v., 2% TazOa-98% Si02
shown in Table VII, crotonaldehyde-isopropanol Per, C4
equiva-
produced butadiene although with considerable lent
other Per total
Cg- and Ca-by-products. A 60% yield of buta- than Cd-equiva-
diene per pass was produced by crotonaldehyde- Feed ethanol lent
crotyl alcohol over TazOb-SiOz, but the yield was Ethanol 0.0 0.02
considerably less over unpromoted silica, which is Ethanol-acetaldehyde 1.20 .30
confirmatory evidence for the deoxygenating func- Ethanol-acetal 1.12 .28
tion of the tantala promoter. Ethanol-paraldehyde 1.12 .28
Ethanol-ethylene oxide 0.80 .20
TABLE VI1 Ethanol-ethylene glycol 0.08 .02
DEOXYGENATION OF CROTONALDEHYDE BY ETHANOL,Ethanol-crotonaldehyde 1.80 .46
ISOPROPYL ALCOHOL,AND CROTYL ALCOHOL OVER Si02 AND Ethanol-acetaldol 1.20 -30
2% T a ~ o & 3 %si02 Ethanol-methyl vinyl
350'. 0.6 1. h. s. v., 1-hr. expts. ketone 0.60 .24
Moles of C4Hs produced
per mole of Ethanol-diacetyl 0.51 .17
Croton- Crotyl Ceequiva-
2% Taz06-98% Si- aldehyde alcohol lent Ethanol-butyraldehyde 0.22 .09
Ethanol-crotonaldehyde (6/1) .
1.6 . 0.40 Ethanol-acetone
Isopropyl alcohol-acetal-
1.00 .25
Isopropyl alcohol-crotonalde-
hyde 0.6 .. -15 dehyde 0.60 * 12

Crotyl alcohol-crotonaldehyde 1,3-Butanediol 0.12 .12

3.6 0.60 .51 E thanol-butadiene
(611
')
Crotyl alcohol * * . 0.43" * 43
monoxide 0.52 .26
SiOa
Ethanol-butadiene
Ethanol-crotonaldehyde (6/1) 0.6.. .15
monoxide
Ethanol-dioxolane
1.48
0.84
I37
.12
Isopropyl alcohol-crotonalde-
Methyl dioxolane 0.10 .10
hyde 0.2 .. -05
Ethyl acetate-water-
Crotyl alcohol-crotonaldehyde
acetaldehyde 0.80 .20
2 . 1 0.35* .30
Crotyl alcohol ... 0.65" .65
from acetaldehyde formed in the reduction of
Catalyst was rapidly carbonized; molal yields in 4-
hour runs over promoted and unpromoted catalysts, re- butyraldehyde by ethanol; by-products were n-
spectively, were 0.40 and 0.25. * The predicted yield on butanol and butanes (mole ratio 5/1). 1,3-Bu-
the basis of the performance of crotyl alcohol alone was tanediol, proposed by Ostromislensky12 as inter-
about 0.55 mole. mediate, gave a 12% per pass yield of butadiene,
Generation in Situ of Ethanol and Acetalde- whereas ethanol-acetaldehyde gave a 30% yield ;
hyde (or Crotonaldehyde) .-It was not surprising 1,2: and 2,3- butanediols gave no more than traces
that various systems (Table VIII) capable of of butadiene.
generating the above reactants produced buta- Vinyl Ether-Ethylene, Acetaldehyde-Ethyl-
diene a t rates roughly inversely proportional to ene and Acetaldehyde-Acetylene.-These feed
the number and difficulty of the generative mixtures (mechanisms H2 and I)24were processed
steps. For example, in unit time, acetal gave less over a variety of catalysts, including aluminum
butadiene than acetaldehyde, ethylene oxide less and 2% Ta20~-98% Si02, under the conditions of
than acetal, and ethylene glycol less than ethylene the ethanol-butadiene process. The yield of
oxide. Butadiene production from ethyl acetate- butadiene was negligible in all cases. The addi-
water-acetaldehyde has commercial significance tion of 4% of acetylene to the commercial feed
because ethyl acetate is a by-product of the com- (ethanol-acetaldehyde) showed no benefit; the
mercial process.23 acetylene was recovered unchanged.
Additional Non-operative Feeds.-Table IX
Miscellaneous Mechanisms lists 28 feeds from which only traces of butadiene
Butanol, Butyraldehyde and Butanediols as were obtained upon processing over 2% Ta205-
Intermediates.-n-Butanol (mechanism G) did 98% Si02 under the commercial conditions of the
not produce butadiene under the conditions of American ethanol-butadiene process. The ma-
the present process, which eliminated the possi- jority of these feeds contained intermediates of
bility of n-butyraldehyde as intermediate mechanisms proposed by various investigators" ;
(mechanism G3). Ethanol-butyraldehyde gave a others were mixtures of acetaldehyde (or ethylene
970 per pass yield (Table VIII), but this butadiene oxide) with possible hydrogen donors. Doubtless
probably did not come from butyraldehyde but certain of these feeds would produce butadiene
(23) Stahly, U. S. Patent 2,439,587 (1948); Stahly, Jones and
with the proper catalysts and conditions, but the
Corson, I n d . Eng. Chcm., 40, 2301 (1948). (24) Miller, U. S. Patent 2,377,025 (1945).
1828 H. CASE
FRANCIS Vol. 71

present interest was the mechanism of the spe- Summary

cific ethanol-butadiene process as operated. 1. The rate controlling process in the second
TABLE IX step of the ethanol-butadiene process a t atmos-
NON-OPERATIVE FEEDS pheric pressure is a second order condensation of
acetaldehyde to crotonaldehyde, whereas a t pres-
1,4-Dioxane E thanol-water-p yrrole
sures of 4-30 atmospheres the rate of consumption
Ethanol-l,4-dioxane Ethylene-ethyl vinyl ether
of acetaldehyde is of first order.
Butadiene monoxide Ethylene-acetal 2. The final reaction which produces butadiene
Tetrahydrofuran Ethanol-water-diethyl ether
is the deoxygenation of crotonaldehyde by ethanol.
Thiophene Ethanol-water-ethyl acetate 3. A mixture of crotyl alcohol with a minor
Ethanol-thiophene Ethanol-water-ethylene amount of crotonaldehyde is ideal for the produc-
Dioxolane Acetaldehyde tion of butadiene under the conditions of the eth-
2-Methyl-1,3-dioxolane Acetaldehyde-water-diethyl anol-butadiene process (60 mole % yield per pass).
Ethanol-2-methyl-l,3- ether 4. Feed mixtures capable of producing acetal-
dioxolane Cyclohexanol-acetaldehyde dehyde (or crotonaldehyde) in situ produce buta-
Ethanol-glyoxal hydrate Cyclohexene diene when processed over TazO&iOz catalyst.
Ethanol-ethyl vinyl ether Cyclohexene-acetaldehyde
5. The primary function of the silica compo-
Pyrrole Ethyltetralin-acetaldehyde nent of the commercial catalyst is to catalyze the
1,2-Butanediol Ethyltetralin-ethylene oxide condensation of acetaldehyde, whereas the func-
2,3-Butanediol (levo and meso with and without ethanol) tion of the tantala promoter is to catalyze the de-
Acknowledgment.-Thanks are expressed t o oxygenation of crotonaldehyde by ethanol.
J. Cohen and B. J. Steenbergen for assistance in 6. Numerous mechanisms proposed by various
the experimental work; to G. C. Akerlof, J. R. investigators were demonstrated to be inoperative
Bowman and P. H . Emmett for valuable com- under the conditions of the second step of the
ments; and to L. H. Cretcher and E. R. Weid- American ethanol-butadiene process.
lein for friendly encouragement. PA.
PITTSBURGH, RECEIVEDJUNE 30, 1948

[CONTRIBUTION FROM THE O F TEMPLE

CHEMISTRY DEPARTMENT UNIVERSITY]

Substituted 1,lO-Phenanthrolines. 111.'~~ Polymethyl Phenanthrolines Related

to 3,4-Dimethyl-1,lo-phenanthroline
BY FRANCIS
H. CASE
The use of l-hydroxy-2-methyl-3-butanone, The action of 2-nitro-4-methylaniline and 1-
CH&OCH(CHs)CHsOH, as a reactant in the hydroxy-2-methyl-3-butanone yielded 3,4,6-tri-
Skraup synthesis has been l i ~ n i t e dto ~ synthe- methyl-8-nitroquinoline VII. The corresponding
~ .the
sis of 3,4-dimethylquinoline. In this Laboratory amine VI11 yielded on reaction with glycerol,
a series of polymethyl- 1,lO-phenanthrolines has 3,4,6-trimethyl-l,lO-phenanthrolineI X ; with
been prepared by the use of the above keto alcohol methylacrolein diacetate, 3,4,6,8-tetramethyl-
with the object of furnishing derivatives which in 1,lO-phenanthroline X ; and with methyl vinyl
the form of their ferrous complexes would be likely
CHI CHs

- -
to have a low oxidation potential. I I
The action of o-nitroaniline and l-hydroxy-2-
methyl-3-butanone under Skraup conditions
yielded 3,4-dimethyl-8-nitroquinoline I (see dia-
gram). The corresponding aminoquinoline I1
under Skraup conditions yielded 3,4-dimethyl-
I c3cHa
1,lO-phenanthroline I11 (with glycerol) ; 3,4,7,8-
tetramethyl-1,lO-phenanthroline IV (with 1-
hydroxy-2-methyl-3-butanone) ; 3,4,8-trimethyl-
1,lO-phenanthroline V (with methylacrolein diace-
tate (2-methy1-2-propene-1,l-dioldiacetate) ;
and 3,4,7-trimethyl-l, 10-phenanthroline VI (with
methyl vinyl ketone).
(1) For other papers in this series see Case, THISJOURNAL, 70,
3994 (1948),and 71, 821 (1949).
k'
(2) This work was supported by a Grant from the Committee on I1 + G ----t I11 R a n d R' = H
Research and Publications of Temple University. I1 + MB +IV R and R' = CHs
(3) Prill and Walter, United States Patent, 1,806,563(1931). I1 + MAD +V R = CHs, R' = H
(4) Manske, Marion and Leger, Can. J . Rqs., 2OB, 133 (1942). 51 + MVK --f VI R = H, R' = CHj