Journal of Membrane Science, 79 (1993) 123-125

Elsevier Science Publishers B.V., Amsterdam

123
Note
Separation of methanol-hydrogen mixtures using
inorganic membranes
Richard D. Noble, J ohn L. Falconer, Meng-Dong J ia and Tracy W. Perkins
University of Colorado, Chemical Engineering Department, Boulder, CO 80309-0424 (USA)
Abstract
In a previous paper, J. Membrane Sci., 60 (1991) 185-193, large separation factors (as high as 600)
were reported for methanol/hydrogen mixtures. These reported results are not accurate. Repetition of
the experiments gave separation factors between 1.5 and 4 depending on the total pressure at 473 K. The
same experimental apparatus and alumina membranes were used in this study. These results indicate
that capillary condensation in the membrane pores is not the primary separation mechanism as had been
previously reported.
Keywords: ceramic membranes; diffusion; gas and vapor permeation; gas separation; inorganic mem-
branes; separation of hydrogen/methanol; alumina membranes
Previously, large separation factors were re-
ported for methanol/hydrogen mixtures using
small diameter pore (4 nm) alumina mem-
branes [ 11. I t was discovered that this data was
fabricated by one of the authors (D.P. Sperry)
and, thus, the results are not accurate. To cor-
rect this situation, the experiments were re-
peated with the same experimental apparatus
and alumina membranes. The apparatus and
experimental apparatus are described in the
previous paper [ 11.
The experimental conditions are listed on
Fig. 1. Each experimental condition was re-
peated 10 times. This figure shows the experi-
mental results for the permeance of both meth-
anol and hydrogen through the membrane. The
total membrane thickness is also listed so that
a permeability can be computed. The perme-
ante is a better measure in this case since a thin
perm-selective layer dictates the separation and
the rest of the thickness is primarily for me-
chanical support. I t should be noted that these
experiments are difficult to perform mainly due
to the maintenance of a negligible pressure dif-
ference across the membrane. Even a small
pressure difference across the membrane was
very difficult to maintain due to the rapid per-
meation of each solute. This is evident in the
0376-7388/93/$06.00 0 1993 Elsevier Science Publishers B.V. All rights reserved.
124
2
A
I
A A A
8
1
) . A
A A A
@! I ! 5bo1&01doo2ci oo25003ooo35004ooo45005000
1 I
Pressure (kPa)
Mc~banol Vqor Flow Rate: 2.0I IO-6m3(S.T.P.)/s
IMeoHAH2
Iiydrogcn Flow Rate: 3.0 II IO 6mYS.T.P.)/s
TOM Membrane Thickness: 1.25mm
Fig. 1. Permeance vs. total feed pressure ( T= 473 K ) .
scatter in the data with feed pressure in Fig. 1.
sure is shown in Fig. 2. The separation factor
A representative error bar is shown on one data varies from 1.5 to 4. Again, a representative er-
point to indicate the error associated with the ror bar is shown on one data point. These low
average values reported on the Figure. separation factors indicate that capillary con-
A plot of separation factor vs. total feed pres- densation of methanol is not the prima@ sep-
45
8 4
9 3.5.
5
n =_I
m
.
m
m
2
1
.
m
1.5
0 560 1600 1500 2000 2500 3000 3500 4WO 4500 5
Pressure (kPa)
Do
Fig. 2. MeOH/H, separation factor vs. total feed pressure ( T=473 K) I
125
aration mechanism, as previously reported. The
tors, which are 6 to 16 times the Knudsen value.
ideal separation factor-is 0.25, based on Knud-
sen diffusion. Surface flow of methanol proba-
bly contributed to the increased separation fac-
Reference
193.
1 D.P. Sperry, J.L. Falconer and R.D. Noble, Methanol-
hydrogen separation by capillary condensation in in-
organic membranes. J. Membrane Sci.. 60 (1991) 185-
Editors Note
Professor Noble contacted me as soon as he en-
countered difficulty in reproducing the results
cited here. Mr. Sperrys actions were referred
to the University of Colorado Committee on
Research Misconduct. He is no longer a stu-
dent at the University of Colorado.
I t is always unpleasant to confront such mat-
ters, but I believe Professor Nobles and Pro-
fessor Falconers actions in this situation were
exemplary.
W.J. KOROS
Editor-in Chief