Thorium oxide: a new catalyst for methanol, isobutanol, and light hydrocarbon production from carbon monoxide and hydrogen

Applied Catalysis, 10 (1984) 313-316 Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

THORIUM OXIDE: A NEW CATALYST PRODUCTION

FOR METHANOL,

FROM CARBON MONOXIDE

Joseph J. MAJ and Carlos University

313

ISOBIJTANOL, AND LIGHT HYDROCARBON

AND HYDROGEN

COLMENARESa

of California,

Lawrence

Livermore

National

Laboratory,

Lawrence

Berkeley

Laboratory,

Livermore,

CA

94550, U.S.A. and G.A. SOMORJAI University

of California,

aWork performed

under the auspices

Livermore

National

Laboratory

(Received

31 October

for the selective

[1,23 or as supported

oxide along with structural as commercial

catalysts

As part of our studies have been investigating

catalysts

found to be active

as completely

derived

for methanol

be copper metal supported that catalysts

of alcohols,

Two thoria catalysts from boiling carbonate Thorias

aqueous

solutions,

prepared

surface areas,

inactive

are now used

of actinide

compounds

thorium followed

nitrate

for the production

"isosynthesis"

of copper-thorium in which

[5,6,7]

alloys

element

of

but

of methanol

[S].

have been

the active phase appears

to

in this communication

components

are active

methanol.

by precipitation solutions

by several

we

gas which occur over thorium catalyst

for the synthesis

transition

principally

were prepared

as mixtures

and chromia

on Th02 [9,10]. We wish to report

based on Th02 without

for the synthesis

properties

the so-called

synthesis,

either

of zinc and copper

[1,43.

of synthesis

from oxidation

from CO and H2-based

elements

[3]. A combination

is the most active

from CO/H2 mixtures,

has also been described Recently,

oxide

of alcohols

such as alumina

of the catalytic

of Energy by the Lawrence

W-7405-Eng-48.

or transition

metals

CA 94720, U.S.A.

1984)

formation

synthesis

the reactions

This refractory

iso-hydrocarbons

promoters

in methanol

number

9 February

gases are based on the d-block

of metal oxides

dioxide.

of the U.S. Department

under contract

1983, accepted

All known catalysts synthesis

Berkeley,

of thorium

using ammonium

aqueous

washes

oxycarbonate

carbonate

or sodium

and calcination

at 520 K.

in this manner

had broad X-ray powder patterns and very high -1 on the order of 120 m2 g , which imply a very small crystallite

size [ll]. The synthesis

experiments

were carried

with 2H2/C0

synthesis

cata1yst.T'

Copper was chosen as the

0166-9834/84/$03.00

gas at a pressure

out in a copper-lined

tubular

reactor

of 5.4 MPa and a flow rate of 1.8 m3 h -' kg

liner

metal for the reactor to prevent

0 1984 Elsevier Science Publishers B.V.

314

FIGURE

1

X-ray photoelectron

spectrum

of used sodium carbonate-precipitated

catalyst.

The copper

FIGURE 2

Mole percent

methanol

catalysts

precipitated

from (A) (NH4)2C03

methane

formation

X-ray

as shown in Figure gas mixture

1. Furthermore,

and time-of-flight

gas from the reactor.

Chromosorb

evaluated

of used catalysts

ied out with a gas chromatograph

alloys.

used copper-lined

temperatures

as high as 873 K.

using an empty reactor

hydrocarbons

Routine analysis

isobutane

in iron-containing

and successfully

mass spectrometry

equipped

for thoria

did not reveal the presence

experiments

102 column. The main products

ethene, methanol,

observed

work which employed

at 600 K did not produce either

chromatography effluent

spectra

vs. temperature

and (B) Na2C03.

is normally

[5,6] thoroughly

in their "isosynthesis"

photoelectron

ethane,

in reactor effluent

from CO+H2 which

Pichler and Ziesecke reactors

2p lines at 932.4 and 952.2 eV are absent.

or alcohols.

and isobutanol.

Both gas

products

with a flame ionization detected

and a 2H2/CO

were used to analyze

of the reaction

by the technique C3-hydrocarbons

of copper

the was carr-

detector

and a

were methane, (Q 0.01 ~01%

315

FIGURE 3

Product distribution

catalysts

at 600 K and 5.4 MPa precipitated

detection

limit) and C2+C3

Experimental methanol

results

in reactor with

(% 0.01 ~01% detection

are given in Figures

in the reactor

distribution

(mole percent

effluent

for each catalyst

effluent)

(A) (NH4)2C03

for thoria

and (B) Nap Cog.

limit) alcohols

were not detected.

2 and 3, which show the mole percent

as a function

at the optimum

of temperature, temperature

and the product

for methanol

production,

respectively. Both catalysts

are active for methanol

synthesis,

under optimum

produce

gaseous

contain

Q IO atomic % ionic sodium as determined

copy, which

conditions

The catalyst

hydrocarbons.

is consistent

what higher activity producing

ion of alcohol

mole-'

(560-590

Experimental of active

thoria

[I31 on the thoria

of sodium

efforts

[12]. This catalyst than the sodium-free

which

spectros-

ion exchanger

showed a somethoria, while

is due to inhibit-

is rendered

less acid-

Ea for methanol

synthesis

is 45 kJ

towards

characterization

catalysts.

are now being directed

catalysts

this result

surface,

ions. The measured

K) for both thoria

by X-ray photoelectron

Presumably,

con-

to

using Na2C03 was found to

of Th02 as an inorganic

cations

synthesis

less isobutane.

dehydration

ic by the presence

metal

for isobutanol

comparatively

precipitated

with the behaviour

with a strong affinityforalkali

with the carbon monoxide

being s 3%; both also show little tendency

version

for the determination

surface

of active

site structures.

REFERENCES 1 2 3 4 5 6 7 8 9 IO 11

K. Klier, Advances in Catalysis, 31 (1982) 243-313 and references therein. G. Natta, U. Columbo and I. Pasquon, Catalysis, 3 (1955) 349-411 and references therein. M.L. Poutsma, L. Elek, P.A. Ibarbia, A.P. Risch and J.A. Rabo, J. Catal., 52 (1978) 157-168. S. Strelzoff, Chem. Eng. Progr. Symposium Ser. No. 98, 66 54-68. H. Pichler and K.H.Ziesecke, Brenn. Chem., 30 (1949) 13-22. H. Pichler and K.H.Ziesecke, Brenn. Chem., 30 (1949) 60-68. H. Pichler, K.H.Ziesecke and B. Traeger, Brenn. Chem., 30 (1950) 361-374. E. Audibert and A. Raineau, Ind. Eng. Chem., 20 (1928) 1105-1112. E.G. Baglin, G.B. Atkinson and L.J. Nicks, Ind. Eng. Chem. Prod. Res. Dev., 20 (1981) 87-90. G.B. Atkinson, L.J. Nicks, E.G. Baglin, and D.J. Bauer, United States Bureau of Mines, Report of Investigations, 8631. A crystallite size f 3nm may be estimated from the formula SD = 360 (where S = surface area in m s /g and D is the crystallite size in nm), which was derived

316 for thorias produced by calcination of thorium oxalatea and thorium hydroxideb. a) V.D. Allred, S.R. Buxton and J.P. McBride, J. Phys. Chem., 61 (1957) 117-120. b) W.S. Brey and B.H. Davis, J. Colloid Interface Sci., 70 (1979) 10-17. 12 a) C.B. Amphlett, L.A. McDonald and M.J. Redman, J. Inorg. Nucl. Chem., 6 (1958) 236-245. b) B. Venkataramani and K.S. Venkateswarlu, J. Inorg. Nucl. Chem., 43 (1981) 2549-2552. 13 B.H. Davis and W.S. Brey, J. Catal., 25 (1972) 81-92.