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Applied Catalysis, 19 (1985) 219-223 219

Elsevier Science Publishers B. V., Amsterdam - Printed in The Netherlands

ETHANOL AND n-PROPANOL FROM SYNGAS

Norman L. HOLy 1 and Thomas F. CAREY, Jr.,


Chem Systems Research Inc., One Evans Street, Fairfield, New Jersey 07006, U.S.A.
lAuthor to whom inquiries should be sent.
Present address: Rohm and Haas Company, 7Z7 Norristown Road, Spring House, PA 19477,
U.S.A.

(Received Z4 October 1984, accepted 20 August 1985)

ABSTRACT
Syngas may be converted to ethanol and n-propanol fairly selectively using tri-
metal catalysts of Fe, Co and Rh on silica. Methane is the major byproduct. These
catalysts demonstrate high activity at Z70C and 900 psi.

INTRODUCTI ON
Higher alcohols from syngas are of interest either as chemicals or as gasoline
additives for octane enhancement. Interest in making higher alchols from syngas
spans 60 years of published literature and hundreds of references [IJ. For higher
alcohol catalysts, two types of product streams are generally seen: catalysts
either produce high percentages of methanol (i.e. the chain growth factor, alpha,
is very low), or high yields of C4-C6 alcohols are formed with isobutyl alcohol
being a major component [ZJ. Apparently, no catalyst has been reported which pro-
duces high yields of ethanol and propanol: we wish to announce the discovery of a
series of related catalysts possessing this characteristic. These are 3-component
catalysts based upon the incipient wetness preparation of CoFeRh/SiO Z formulations.

EXPERIMENTAL
The formulation of the CoFeRh O. 56 illustrates the procedure. To ZO.5 g (50 cc)
of Davison 57 silica (+IZ mesh) was added a 40C solution of Co(N0 3)Z.6HZO
(Z.6Z g 9.01 mmol), Fe(N03)3.9HzO (3.63 g, 8.99 mmol) and RhC1 3.3H ZO (1.33 g,
5.05 mmol). The slurry was stirred for 5 minutes and evaporated under vacuum with
a rotary evaporator at 40C. The partially dried material was heated overnight
(110C) in an oven, calcined at ZOOC for 1 h and 300C for 3 hours. After cooling,
the catalyst was reduced under flowing hydrogen. first at 100C (1 h), ZOOC (I h),
300C (I h), 400C (1 h) and 450C (1 h). The catalyst was cooled under flowing
hydrogen and stored under NZ' For the Rh coated catalyst (column Z) the calcined
but unreduced CoFe/Si02 material was coated with an aqueous solution of RhC1 3.3H20.
recalcined and reduced in flowing hydrogen.

01669834/85/$03.30 1985 Elsevier Science Publishers B.V.


TABLE 1
Summary of syngas experiments with CoFeRh catalysts

Percent loading Co 2.6 2.6 2.6 2.6 2.6 2.6


Fe 2.5 2.5 2.5 2.5 2.5 2.5
Rh 2.6 1.0 3.7 1.0 3.7 2.6
Atomic ratio CoFeRhOe56 CoFeRho,2,a CoFeRho_2, FeRh CoFe
'ORh.56
Test conditionsb
Feed, Hz/CO ratio 1.0 1.0 3.13 1.01 1.16 1.04 1.04 3.10
Feed, CO*,% 0.00 0.00 5.44 0.38 4.11 0.17 0.26 4.96
Average temp./"C 281.0 304.0 272.0 278.0 283.0 278.0 270.0 275.0
Hours on stream 39.5 101.0 134.0 24.0 20.0 14.0 19.0 20.0

Conversion
CO to products, ~01%' 5.81 12.73 19.51 6.15 9.12 5.23 3.24 2.72
co to co2, vol% 1.06 2.97 1.92 1.66 0.16 2.37 0.39 0.03
CO. gm mol/hr/kgm cat. 8.90 24.14 10.75 10.39 12.38 14.54 4.86 1.62
STY of Oxygenatesd 4.27 10.55 5.47 5.33 4.56 7.37 1.62 0.47
Product summary (carbon selectivity)e
CH30H 9.52 30.95 42.29 9.87 17.52 31.41 7.39 4.79
C2-C6 alchols 37.48 12.75 8.62 39.99 18.53 17.84 23.55 24.25
C2-C6 ald. & esters 0.97 0.00 0.00 1.48 0.81 1.45 2.36 0.00
26.43 50.89 46.28 31.73 48.43 45.50 35.97 48.80
CH4
C2-C3 hydrocarbons 11.96 5.40 2.81 12.31 13.89 3.42 25.59 14.97
C + hydrocarbons 13.65 0.00 0.00 4.61 0.81 0.36 5.14 7.19
4
TABLE 1 continued

% Liquid product 61.6 43.7 50.9 56.0 37.7 51.1 38.4 36.2

(Carbon selectivity)

Liquid summaryf
Methanol 23.4 77.6 87.4 25.3 57.1 69.9 27.6 20.5
Ethanol 26.1 18.7 10.8 30.3 19.2 20.7 29.9 11.2
Propanol 21.1 3.7 1.8 24.9 16.7 5.7 15.7 48.0
Butanol 7.3 0.0 0.0 6.6 2.8 0.0 6.7 3.9
Pentanol 5.4 0.0 0.0 4.7 1.2 0.3 5.4 2.5
Hexanol 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Other oxygenates 1.5 0.0 0.0 2.7 1.8 2.2 6.0 0.0
C4-C9 hydrocarbons 15.2 0.0 0.0 5.5 1.2 0.3 8.7 13.9

aRhodium coated onto CoFe/Si02.


b
Other conditions: 900 psig; VHSV = 3,000 l/hr/kgm cat.
'Includes conversion to CO.
dSpace time yield (STY) = VHSV/22.4 x %CO in feed/100 x %CO conv./lOO x Se.

eMole % of CO converted to a product.

fPercent (w/w, H20-free).


222

The synthesis data were obtained using a Berty reactor equipped with a fixed
catalyst basket (2 inch 1.0. x 1.88 inch high) and an impeller mounted at the
bottom. The catalyst is retained in the baskets by screens secured at both ends.
The reaction temperature was measured by two thermocouples positioned at the top
and bottom of the catalyst basket. A thin layer of Pyrex glass wool was placed on
the bottom retaining screen with 25 cc of catalyst distributed evenly in the cata-
lyst basket. Another thin layer of Pyrex glass wool was placed on top of the cata-
lyst followed by the top retaining screen. Due to the high recirculation rate,
the use of a diluted bed of catalyst and inerts was not necessary. All experiments
were conducted at 900 psig and VHSV of 3,000 1 h-' kg catalyst-'. In some experi-
ments CO2 was included in the feed.

RESULTS
Results obtained under syngas are summarized in the table. Noteworthy features
include the following:
1. The presence of rhodium demonstrably increases activity and enhances the pro-
duction of alcohol compared to the CoFe/Si02 base case [3]. For the CoFe/Si02
catalyst, it was noted [3] that the methanol yield at 1 atm was enhanced over
that observed at atmospheric pressure. (Our space time yields (STY) are cal-

culated on the basis of moles of CO converted to a product h -' kg cat-'). The

trend isscontinued in our data: ethanol and propanol are selectively formed
at 60 atm (column 8), though the STY is quite low. However, high STY's and ex-
cellent ethanol and n-propanol yields are demonstrated by results summarized
in columns 1, 4 and 5, and by other CoWFeXRhYMZ catalysts which will be reported
later.
2. Methanol yields are modest. Most higher alcohols catalysts produce large
quantities of the C, alcohol.

3. The trimetal catalysts produce far less acetaldehyde and acetic acid than most
rhodium-based catalysts [4].

4. The space time yield of oxygenates are comparable to those of the best reported
higher alcohols catalysts.
5. While chain growth is enhanced by low H2/C0 ratios, the product stream is not
as sensitive to this ratio as copper-based catalysts.

6. The mild conditions for synthesis mean that these catalysts could be used as
a retrofit for ICI-type reactors.

7. Low shift activity is seen.

8. A Schultz-Flory distribution is obtained. For the CoFeRhO 56 formulation, CI =


0.28 with r = 0.97.

9. Whereas the principal C, product leaving the catalytic surface is methane, the
principal C2 and C3 products are oxygenates.

The hydrocarbon yields (based on carbon selectivity) range between 40% (carbon
selectivity) for the highest rhodium containino trimetal catalyst (column 4) to 62%
for the catalyst with the least rhodium (column 5). Methane yields and reaction rates

are highest when rhodium is coated onto FeCo/SiO2 (columns 2 and 3).
223

The catalysts have not received thorough investigation below 27O"C, but they
retain modest activity even at 220C. Increasing the temperature has little effect
on the product distribution until about 3OO"C, where methane yields increase
dramatically.

REFERENCES
For review of early work see: R.B. Anderson, J. Feldman and H.H. Starch,
Ind. Eng. Chem, 44 (1952) 2418-2424; G. Natta, U. Columbo and I. Pasquon, in
"Catalysis", P.H. Emmett (Ed.,), Reinhold, New York, 1957, ~01.5, 131-174.
For a recent summary see: K.J. Smith and R.B. Anderson, Canad. J. Chem. Eng.,
61 (1983) 40.
K.B. Arcuri, L.H. Schwartz, R.D. Piotrowshi and J.B. Butt, J. Catalysis, 85
(1984) 349-361.
P.C. Ellgen and M.M. Bhasin, U.S. Patent,4,096,164 (June 20, 1978 to Union
Carbide); P.C. Ellgen and M.M. Bhasin, U.S. Patent, 4,162,262 (July 24, 1979
to Union Carbide).