156 Ind. Eng. Chem. Process Des. Dev., Vol. 18, No.

1, 1979

maintains that fact throughout the calculation. Actually,
after each column solution, the distribution of all com-
ponents can be checked by infinite section equations
utilizing the conditions a t the top and bottom of the
calculated column, and the distribution of each component
can be easily found. This serves either to verify that a
component is not distributing or to calculate the amount
in each product if it does distribute.
Also, it is apparent that other specifications of the light
and heavy keys could be used, for example, the concen-
tration of a key in a product, or even a total product
amount or a product boiling point. However, setting the
amounts of the two key components in the products is the
most common way of specifying the separation.
The number of stages to be inserted between the feed
stage and the corresponding infinite section in each ex-
pansion of the column is arbitrary. If the nondistributing
diluents are considerably different from the corresponding
key components, only a few plates are necessary. However,
since many distillation systems are fairly close-boiling,
there are often components which differ in volatility from
a key component by only a small amount, perhaps l o % ,
and which still do not distribute. To reduce the amount
of these components at the ends of the calculated column
to amounts which do not affect the reboiler and condenser
loads usually requires 10 to 15 stages. If the number of
stages added in each column expansion is small, many
columns are calculated unnecessarily. The authors have
found it reasonable to add five stages at a time.
Results
The calculational procedure has been tested on many
examples and has been found to be extremely stable,
yielding a solution to each column in a few iterations. The
method has been used on systems in which the equilibrium
constants were independent of liquid composition, but it
could be readily extended to include such effects. One
interesting result of the test calculations, which were done
on hydrocarbon systems, was the finding that Underwood's
method was usually reasonably correct. If the minimum
sectional flows given by Underwood are assumed to be
flows at the respective pinch points, and energy balances
are used to obtain flows and loads a t the top and bottom
of the column, the error was normally only a few percent.
However, the calculation by Newton-Raphson is suffi-
ciently rapid that there is no reason not to use the correct
calculation. A typical close-boiling four-component system
which required solution of a 14-stage column, a 24-stage
column, and a 34-stage column was solved in 12.5 s on a
CDC 6400 computer. A six-component system which
required a 14-stage calculation and a 24-stage calculation
required 16.9 s. The authors have written a Fortran
program for single-feed two-product columns for systems
up to ten components. The program is available a t no
charge on request.
Literature Cited
Bachelor, J. B., Pet. Refiner, 36 (6), 161 (1957).
Erbar, R. C., Maddox, R. N., Can. J . Chem. Eng., 40, 25 (1962).
Naphtali, L. M., Sandholrn, D. P., AIChE J . , 17, 148 (1971).
Newman, J., Ind. Eng. Chem. Fundam., 7, 514 (1968).
Ricker, N. L., Grens, E. A. 11, AIChE J . , 20, 238 (1974).
Shiras, R. N., Hanson, D. N., Gibson, C. H., Ind. Eng. Chem., 42, 871 (1950).
Underwood, A . J. V., J . Inst. Pet., 32, 614 (1946).
Underwood, A . J. V., Chem. Eng. Prog., 44, 603 (1948).
Received for reuiew February 9, 1978
Accepted August 7 : 1978

Operation of a Tube Wall Methanation Reactor

Henry W. Pennline," Richard R. Schehl, and William P. Haynes

Process Engineering Division, Pittsburgh Energy Technology Center, U.S.Department of Energy, Pittsburgh, Pennsylvania 152 13

The design and operation of a PDU-scale tube wall methanation system are discussed. The tube wall reactor was
constructed from a stainless steel pipe with a surrounding jacket. The inside surface of the tube was flame sprayed
with Raney nickel catalyst for 14 ft of length. The catalyst coating was activated by leaching with a caustic solution.
A liquid coolant in the outer shell of the reactor removed the heat of methanation and maintained the system at
near isothermal conditions. Exposure velocity and recycle ratio were varied during the run. Concentration and
temperature profiles were periodically measured along the length of the catalyst bed. Catalyst performance, methane
production, deactivation, and other results are presented for the test which was terminated after 1179 h on stream.

Introduction methanation reactor systems and on the enhancement of

An ever increasing demand for natural gas coupled with
growing supply shortages has renewed interest in pro-
ducing synthetic natural gas from coal. The Pittsburgh
Energy Technology Center of the 17,s.Department of
Energy has developed the SYNTHANE Process. This
process, as well as most gasification schemes, uses a final
methanation step to convert a synthesis gas from the
gasification of coal into a high-Btu pipeline quality gas.
It is the objective of the process development unit (PDU)
methanation program to develop efficient catalytic reactor
systems with emphasis on the development of improved
This article not subject to U.S. Copyright. Published 1978 by the American Chemical Society
catalyst performance.
There are three basic reactor systems currently being
developed at PETC (Haynes et al., 1972,1974,1977; Schehl
et al., 1976). All employ a Raney nickel catalyst because
of its high activity and selectivity toward methane, and
all have very small pressure drops across the catalyst bed.
However, the major difference in the designs is in the novel
method of heat removal. In the tube wall reactor system,
Raney nickel is thermally sprayed on the inside of a pipe.
This reactor is surrounded by a jacket containing a coolant
which removes the exothermic heat of reaction and

condenser
T C wells
- Reactant pas
Dowlhcrm 4 s C h 40 plpe
reservoir dowlherm jacket
cootea internally
with Raney nickel
L
- 7
Product par
Figure 1. Tube wall methanation reactor.
maintains the catalyst a t near isothermal conditions. In
the hot gas recycle system, sufficient quantities of product
gas are recycled over a fixed bed of catalyst-sprayed plates
to remove the heat. In the hybrid reactor, catalyst inserts
are charged into an uncoated tube wall reactor. The heat
of reaction is removed from the bed by both the recycle
of product gas, as in the hot gas recycle system, and by
boiling Dowtherm in the reactor jacket, as in the tube wall
reactor. The purpose of this report is to present the in-
vestigation of one type of process development unit-the
tube wall methanator.
Reactor Description
The reactor, shown in Figure 1, consisted of a 2-in.
schedule 40 pipe flanged on the ends and surrounded by
a 4-in. schedule 40 jacket. All reactor material was 304
stainless steel. Raney nickel catalyst (58% aluminum, 42%
nickel) was flame sprayed onto the inner 2-in. pipe wall
for 14 ft of length. Dowtherm, a liquid coolant with high
boiling points a t low pressures, was added to the annular
shell to remove the exothermic heat of reaction during the
run. A reservoir was adjacent to the vertical reactor and
was used as part of the Dowtherm vapor-liquid recycling
system. The temperature of the saturated coolant was
regulated by controlling the electrical resistance heating
and the pressure of the cooling system. Nucleate boiling
took place on the outer surface of the reactor pipe and
thereby provided a natural convective circulation of
Dowtherm. Both the reactor and reservoir were insulated,
The Dowtherm vapor was condensed by cooling water or
air convection and returned to the reservoir. In a com-
mercial plant the heat removed by the Dowtherm would
be used to produce process steam.
Probes could be inserted into the reactor through the
top and bottom flanged reactor heads. Four thermowells
with thermocouples were inserted to get representative
catalyst temperatures; the sample ports were machined so
that the thermowells were against the catalyst surface.
Thermocouples were positioned to obtain temperatures at
12 different locations along the 14 ft of catalyst length. Gas
concentration profiles were taken by using four stationary
stainless steel tube probes which sampled gases a t the 2,
6,9, and 12 f t levels down from the catalyst top (reactant
gas inlet).
Ind. Eng. Chem. Process Des. Dev., Vol. 18,No. 1, 1979 157
I
Reactor t
Used t u ~ s t i c
tokeoff
I lHeliym
U
LL
Figure 2. Catalyst activation assembly.
The reactor had been used twice before. The inner tube
surface was prepared for catalyst coating by grit-blasting
with compressed air and iron-free virgin aluminum oxide
pellets until any trace of the previous spent catalyst coating
was removed. In a new reactor, a bond coat of nickel
aluminide (80% nickel, 20% aluminum) is first deposited
to about a 6-mil thickness to prevent the catalyst coat from
spalling from the roughened stainless steel surface. Since
this dense bond coat was applied to this particular reactor
before and the grit-blasting did not remove it, there was
no need for reapplication.
The internal flame spraying of the Raney nickel catalyst
was done with a wire-fed metallizing gun using a hydro-
gen-oxygen flame. The Raney nickel wire is specially
made for the gun and is a 1 to 4 mixture of a poly-
propylene/polyethylene binder to a 80-200 mesh size of
powdered catalyst. In the past, the reactor jacket was cut
before the 2-in. pipe was internally flame sprayed because
of expansion stresses. However, for this particular time,
water near its boiling point was circulated through the
jacket while the internal flame spraying was in progress.
No evidence of reactor distortion was detected. Respraying
the tubes in the SYNTHANE prototype plant would also
be a simplified process using the same technique.
For run 16, a reactor length of 14 f t was sprayed to
approximately a 25-mil catalyst thickness which covered
7.4 ft2 of reactor surface area. The spray rate was 1.04
linear feet of reactor per hour. From previous sprayed
pieces of pipe, a laydown figure of 100 g/ft2 pipe area was
found, and the total catalyst weight for this run was 740
g. Battelle Columbus Labs has produced a more efficient
spray gun which can deposit catalyst at a rate of 20 linear
feet of reactor per hour.
After spraying, the reactor was vertically placed in the
carbon steel system and leached in situ, Since catalytic
activity is directly related to surface area, a very porous
layer of nickel is desired. This is accomplished by reacting
the aluminum in the Raney nickel alloy with a 2 wt 5%
solution of ACS-pure sodium hydroxide. The gravity-fed
system is shown in Figure 2. Before the caustic flow was
started, the reactor was filled with deionized water. The
extent of activation was determined by metering the
amount of hydrogen evolved according to three moles of
hydrogen for every two moles of aluminum reacted. The
reaction was stopped after 4.25 h when 70.9% of the
theoretical amount of aluminum in the Raney alloy was
 -
158 Ind. Eng. Chem. Process Des. Dev., Vol. 18, No. 1, 1979
Table I. Catalyst Bed Data for TWR-Run 16
catalyst type flame sprayed Raney nickel
weight percent 42a
percent activated 70.gb
estimated catalyst 0.025
thickness, in,
reactor diameter x 2.067 x 168
length, in.
void reactor volume, 0.311
ft3
weight of unactivated 1.63
catalyst, lb
geometric area of 7.39
catalyst, ft2
effective diameter, ft 0.168
a Before leaching. Theoretical.
GOI
prehealer
Fresh 90s
n and form a metallic coating on the tube.
Reoclor
comprersar Condenser
Woler
Figure 3. Flow scheme of the tube wall reactor system.
reacted. Temperature of the leaching reaction never
exceeded 50 "C. Previous experience indicated that the
unleached Raney nickel substrate acted as an adhering
agent between the leached catalyst and the bond coat.
When leaching was finished, the reactor was drained
under a helium atmosphere, and a continuous stream of
deionized water was flowed over the catalyst. Many times
during the rinsing procedure the catalyst was batch flushed
with this water and always under a helium atmosphere.
No traces of spalled catalyst were found in the effluent
water. Washing was stopped after 93.5 h when the pH of
the rinse water (6.7) was approximately the same as the
demineralized water (6.2). The leaching apparatus was
disassembled and the reactor was incorporated into the
system, all steps performed under a helium flow. The
reactor system was then placed under hydrogen until the
temperature and pressure were brought to methanation
conditions, at which time the synthesis feed gas was
gradually fed into the system to start the run. Pertinent
catalyst bed data are shown in Table I.
Reactor System
The synthesis gas in the experiment was made by steam
reforming natural gas in a Girdler plant. The hydrogen
to carbon monoxide ratio ranged from 3.1:l to 3.3:1, always
with a slight excess of hydrogen to prevent possible carbon
deposition. Two activated carbon traps were located in
the fresh gas inlet line and one in the product recycle line.
This precaution was taken to eliminate the possibility of
sulfur contamination of the nickel catalyst. Sulfur con-
centrations entering the system were maintained around
66 ppb and were detected by the methylene blue method.
Figure 3 illustrates a simplified flow diagram of the tube
wall methanation system. Fresh synthesis gas enters the
system and mixes with a dry product gas recycle stream
or "cold recycle" stream. In TWR-run 16 this mixed gas
stream was preheated through several heat exchangers and
entered the reactor a t 353 "C. The boiling Dowtherm
coolant system was maintained a t 375 "C and controlled
the maximum temperature variance of the catalyst to
within 20 "C. The product gas exits the reactor and splits;
one stream leaves the system and is flared and the other
is recycled. The recycle stream is cooled and dried by a
double pipe heat exchanger and then compressed. Flow
streams are metered and checked by orifices.
During the test volumetric gas samples which were
representative of a 24-h period were analyzed by both mass
spectrometry and gas chromatography. An on-line gas
chromatograph checked sample results. The gas analyses
along with condensed product water weights and metered
flows were used to calculate the mass balances for each
24-h period.
A sample stream from the mixed gas before the reactor
was sent to an iron deposit unit consisting of a transparent
Vycor tube heated to 300-350 "C in a furnace through
which the sample stream flows. As shown in the past, any
iron or nickel carbonyl in the sample gas will decompose
w
Results and Discussion
TWR-Run 16 was terminated after 1179 h on stream.
The following conditions were investigated during the
experiment: a fresh feed exposure velocity of 10, 20, 30,
and 40 (1 unit exposure velocity = 1 SCFH of fresh
synthesis gas/ft2 of geometric catalyst surface area) and
Product a cold-recycle-to-fresh-gasratio ranging from 3:l to 0. Inlet
gas temperature (av 353 " C ) , Dowtherm coolant tem-
90s
perature (av 375 "C), and system pressure (300 psig) were
held reasonably constant throughout the test. Three brief
unscheduled power outages occurred but did not affect
catalyst life. No shutdowns occurred during the run.
Operating parameters and product gas characteristics are
shown in Figure 4.
The following select representative periods are tabulated
in Table I1 to provide more detailed information in run
16.
Period 3 represents performance of the fresh catalyst
at a 10-exposure velocity and a 3.06:l recycle ratio.
Period 8 indicates the effect of decreasing the recycle
ratio to 1.50:l at a constant exposure velocity of 10.
Periods 11 and 18 show the results of decreasing the
recycle ratio from 1.54:l to 0.50:l at an exposure velocity
of 20. The effect of increasing fresh feed can be compared
between period 8 and period 11.
Periods 21 and 35 provide a comparison of identical flow
conditions a t a 30-exposure velocity and a 0.50:l recycle
ratio but at different times.
Period 26 represents performance a t an exposure ve-
locity of 30 with no recycle.
Periods 41 and 44 represent performance at the highest
exposure velocity attained (40) and the change of recycle
from 0.25:l to 0 a t the end of the run.
Since carbon monoxide was the limiting reactant, a good
indication of the Raney nickel catalyst performance was
the percent carbon monoxide in the product gas. In
general, an increase in exposure velocity a t a constant
recycle ratio brought about an increase in product CO
concentration. At 263 h on stream, the fresh gas was
increased from an exposure velocity of 10 to 20 a t 1.50:l
recycle ratio and the product gas CO concentration in-
creased from 0.13 to 0.52%. At 503 h the exposure velocity
was boosted from 20 to 30 a t 0.50:l recycle ratio with an
increase in product gas CO concentration. At 959 h the
30-exposure velocity condition was raised to 40 and again
the greater the fresh feed the lower the CO conversion.
Although the fresh feed was decreased at 1127 h from a
40-exposure velocity to 30, the percent CO in the product
did not decrease as would be expected. The catalyst was
appreciably deactivated a t this point.
 Ind. Eng. Chem. Process Des. Dev., Vol. 18, No. 1, 1979 159

2 51 I I I I 1 nrl
Exp TWR-16
1
400 .-
Maximum catalvst 1

350

c
300 t 05

1000
W Product qos heating value
U

1
vi 800
a
W

1 t I Cold recycle ratio

iI
I LCL1-
o 200 400 600 eo0 io00 1200 0 200 400 600 800 IO00 I200
TIME ON STREAM h o u r s TIME ON STRELM.hours

Figure 4. Reactor conditions and product gas characteristics.

It should also be mentioned that, at a constant fresh feed
rate and cold recycle ratio, the percent CO in the product
gas gradually increased with time. An example of this
observation can be seen at the exposure velocity of 30 and
0.51 recycle ratio in the period from 697 to 963 h when
the percent CO increased from 0.66 to 0.84. Results in-
dicate a time-dependent poisoning which deactivates the
catalyst throughout the run.
The recycle ratio also directly affected the catalytic
reactor performance. When the recycle ratio was initially
increased from 1-51to 3:l a t an exposure velocity of 10,
ol--L--- IO 2 0 30

the CO percent in the product increased. Later the CO
concentration decreased when the recycle was brought
back to 1.5:l. A t a 30-exposure velocity the recycle ratio
was changed from 0.51 to 0 back to 0.51. Here the best
reactor performance was at the no recycle level. A decrease
in recycle at an exposure velocity of 20 or 40 also brought
l/"t
Figure 5. Least-squares fit through plotted representative data.
by dimensionlesss group analogies between heat and mass
transfer. Specifically, the following correlation of Sieder
and Tate for laminar flow was used (Bennett and Myers,
1962).

(;y3(
about a lowered product CO percent and thus a better CO
conversion.
From the previous tlndings a simple plug flow model can Nu = 1.86Re1/3Sc1/3 $14 (2)
be developed. For a catalyst sprayed tubular reactor, mass
transfer of reactants and products to and from the tube Finding the mass transfer coefficient and substituting
wall becomes an important factor. In the reactor the bulk
gas diffusion resistance is assumed much greater than that
of the surface reaction, and thus the global rate of reaction
is limited by the rate of flow of reactant to the surface.
SD0.667
2*37D2.333L0.333
(:)"'I
into the design equation yields
- 1-
u0.667
-

Since bulk mass transfer is limiting in this laminar flow

region, the reactant concentration at the catalyst surface
will be negligible, and the global reaction rate for the
disappearance of CO is directly proportional to the bulk
CO concentration. For this isothermal isobaric system the
fractional change in volume of the system can be con-
sidered by making the restriction that the volume of the
reacting system varies linearly with conversion. This
contraction factor, e , accounts for both the reaction
stoichiometry and the presence of recycled inerts. Solving
the design equation for a plug flow reactor in terms of CO
conversion yields
An equation for the mass transfer coefficient can be found
If the model represents the reactor, a plot of the right side
of eq 3 vs. l/v0.667 should yield a straight line. In Figure
5 data from selected periods were plotted as indicated
above. A linear least-squares fit through the points has
a slope of 1.63 ( f t / ~ ) O . ~If~ the
. bracketed theoretical slope
of eq 3 is calculated, a value of 2.43 ( f t / ~ ) Ois. ~found.
~~
Agreement between the slopes is good considering the
various assumptions and approximations in the calculation.
The design equation does not take into consideration
catalyst deactivation and, as previously noted, deactivation
did occur throughtout the run. At the end of the test
extensive deactivation had occurred and a point plotted
a t that time does not fall near the straight line in Figure
5.
160 Ind. Eng. Chern. Process Des. Dev., Vol. 18, No. 1, 1979
0 - 5
2 4 6 8 IO 12
,TIPI
REACTOR LENGTH, f e e t
Figure 6. Actual gas concentration profiles for two different times
on stream but same exposure velocity and recycle ratio.
The design equation can further be simplified in terms
of the fresh synthesis gas rate and the recycle flow. It can
be seen that the reactor CO conversion decreases with an
increase in fresh feed or an increase in cold recycle. These
results have been verified as shown before in the data.
Besides the predominant methanation reaction a sec-
ondary reaction is noticeable due to the CO, concentration
in the product gas. The "water gas shift" reaction com-
bines CO and HzO to form COPand Hz
CO + HzO + COZ + Hz (4)
Apparent equilibrium constants were calculated for the
water gas shift reaction and methanation reaction and are
tabulated for select periods in Table 11. True equilibrium
values for the reactions at 380 "C are 14.4 and 19600 atm-*,
respectively. The small values of the apparent equilibrium
constant for the water gas shift reaction indicate that the
reaction does not proceed to any appreciable extent, unlike
the results in methanation bench-scale testing units
(Savinell et al., 1976). The magnitudes of the methanation
reaction constants are much greater and indicate that the
reaction is dominant over the Raney nickel catalyst. At
the end of the test the methanation constant decreases
considerably due to catalyst deactivation.
The stationary gas probes were used to take samples
along the catalyst length at various steady-state conditions
a t a specific time. However, the CO in the product gas
increased with time a t constant flows and thus the CO in
the mixed gas to the reactor increased, which made profile
comparisons difficult. The concentration profiles at 625
and 1177 h can be compared at a 30-exposure velocity due
to the no recycle situation. Figure 6 shows the CO con-
centration profiles along the catalyst length. In the earlier
profile most of the reaction took place along the top 2-6
ft of bed. In the later profile extensive deactivation had
occurred and the 9-14 ft of catalyst length was more re-
active. Deactivation of the inlet portion of the bed was
so extensive that the exit percent CO never went below
3.3 a t the 14-ft level. The above findings would suggest
a deactivation which proceeds zonally rather than uni-
formly along the catalyst length.
Catalyst temperature profile data indicate temperature
fluctuations along the catalyst length. Figure 7 represents
the temperature profiles a t several different conditions.
The maximum temperature or "hot spot" is the position
along the reactor length a t which a major portion of the
exothermic methanation reaction takes place. As catalyst
performance decreases, the hot spot moves down the length
of the reactor as seen in Figure 8, again suggesting zonal
deactivation. Similar results are found in the bench-scale
methanation studies of Savinell et al. (1976). The hot spot
location is affected only by the fresh feed rate and time
and not by recycle, for although a decrease in recycle will
increase CO conversion, the hot spot does not move up the
e1;4
Figure 7. Actual temperature profiles for various times on stream.
0 240 480 720 960 I200
7 ME ON STWEAM hour5
Figure 8. Hot spot location at various exposure velocities.
reactor length. If a particular concentration profile is
compared with the temperature profile, it is found that
the hot spot falls within the catalyst length where most
of the conversion takes place. The movement of the hot
spot along the catalyst length combined with the con-
centration profile findings strengthens the theory of a zonal
deactivation.
Spent Catalyst Analysis
At 1179 h the synthesis gas feed to the reactor was
halted. The electrical resistance heaters and the com-
pressor were turned off, and the system was bled, pressure
purged with hydrogen, and left under a hydrogen at-
mosphere until cool. Later the reactor was removed from
the system and scrapings of the brittle spent catalyst were
obtained from the top 2 ft of catalyst (reactor inlet), middle
2 ft, and bottom 2 ft (product exit). Bulk samples were
subjected to chemical analysis, X-ray diffraction analysis,
and BET surface and pore size distribution measurements.
Results of the chemical analysis and X-ray diffraction
are shown in Table 111. The sulfur concentrations found
by wet chemical analyses are roughly the same in all three
spent catalyst samples. These are within the limits of
0.2-0.3% sulfur in unactivated Raney nickel. Gas samples
were analyzed for sulfur by the methylene blue method
both before and after the final carbon trap in the fresh gas
system. The average sulfur concentration entering the
reactor was 66 ppb.
The iron concentrations were greater than the 0.1-0.3%
found in unactivated Raney nickel. The mixed gas into
the reactor was sampled for iron carbonyl by using the iron
deposit units as previously described, Two trials, one a t
the beginning and one at the end of the run, yielded after
453 and 573 h 15.5 ppb and 4.2 ppb, repectively. The iron
carbonyl concentration is probably greater than above
because the units are not 100% efficient. Since most of
the reactor system was carbon steel and under high partial
pressures of carbon monoxide a t room temperature, it is
conceivable that Fe(C0)5 was formed, entered the hot
reactor in the feed stream, decomposed, and then de-
posited iron on the Raney nickel catalyst (Schehl et al.,
1977).
 Ind. Eng. Chem. Process Des. Dev., Vol. 18, No. 1, 1979 161

Table 11. Selected Test Data TWR-Run 16

period number
3 8 11 18 21 26 35 41 45
hours o n stream
119 239 311 479 551 67 1 887 1031 1127
fresh gas:
rate, scfh 75.8 73.9 148.0 147.3 223.8 225.2 223.6 291.5 299.7
H, , vol % 75.5 75.8 75.2 7 5.4 75.2 74.3 75.7 74.1 76.1
co, vol % 23.6 23.7 24.2 23.6 24.3 24.3 23.8 24.0 23.1
co,, vol % 0.1 0.1 0.2 0.1 0.1 0.2 0.2 0.2 0.3
N,, vol % 0.7 0.3 0.2 0.8 0.3 1.2 0.3 1.6 0.5
CH,, vol % 0.1 0.1 0.2 0.1 0.1 0 0 0.1 0
H,O, vol % 0 0 0 0 0 0 0 0 0
H,/CO 3.20 3.20 3.11 3.20 3.10 3.06 3.18 3.09 3.29
exposure velocity, scfhlft' 10.26 10.00 20.03 19.93 30.28 30.47 30.26 40.26 40.56
space velocity, h" 244 237 476 414 720 724 719 957 964
mixed feed gas (wet):
rate, scfh 308.0 183.5 375.0 220.4 336.1 223.5 331.0 371.0 298.0
H,, vol % 21.53 33.92 33.20 52.47 52.64 74.30 54.10 62.41 76.10
co, vol % 6.06 9.57 10.01 15.78 16.36 24.30 16.25 19.47 23.10
co,, vol % 0.33 0.20 0.37 0.24 0.38 0.20 0.49 0.46 0.30
N,, vol % 0.97 0.99 0.65 0.91 0.52 1.20 0.69 1.48 0.50
CH,, vol % 70.99 55.22 55.67 30.56 30.04 0 28.42 16.11 0
H,O, vol % 0.12 0.10 0.10 0.05 0.06 0 .06 0.04 0
H,/CO 3.55 3.54 3.32 3.33 3.22 3.06 3.33 3.21 3.29
inlet superficial velocity, f/s 0.43 0.25 0.52 0.31 0.46 0.31 0.44 0.50 0.39
inlet Reynolds no., 1702 876 1797 802 1248 557 1221 1159 7 54
exposure velocity, scfh/ft2 41.68 24.83 50.75 29.82 45.48 30.24 44.79 50.20 40.33
space velocity, h-l 990 590 1206 709 1081 719 1064 1193 958
vol. cold recycle/vol. fresh gas 3.06 1.50 1.54 0.50 0.51 0 0.49 0.25 0
temperatures:
gas inlet, " C 366 359 373 371 361 373 341 350 335
maximum catalyst, " C 392 394 396 395 396 392 395 397 396
average catalyst, C 385 386 386 388 389 383 385 385 383
pressure, psig 300 300 300 300 300 300 300 300 300
product gas (wet):
H,, vol % 3.76 5.31 4.97 5.23 6.14 5.08 7.45 11.44 14.42
c o , vol % 0.33 0.12 0.67 0.16 0.50 0.11 0.58 1.10 1.45
co,,vol % 0.38 0.24 0.40 0.39 0.70 1.04 0.81 1.06 1.60
N,, vol % 1.02 1.30 0.79 0.86 0.73 0.53 1.13 0.71 0.60
CH,, vol % 90.45 82.45 76.67 69.99 68.13 46.62 65.97 56.21 42.01
H,O, vol % 4.06 10.58 16.50 23.37 23.79 46.57 24.06 29.37 39.76
H,KO 11.39 44.25 7.42 32.69 12.28 46.18 12.84 10.40 9.94
conversion:
H,, % mixed feed 85.25 87.92 87.51 93.56 92.30 96.66 90.98 89.00 90.58
CO, % mixed feed 95.46 99.06 94.43 99.34 97.97 99.78 97.67 96.60 96.89
(H, + CO), % mixed feed 87.50 90.37 89.11 94.89 93.65 97.43 92.53 90.80 92.05
usage ratio 3.17 3.15 3.07 3.13 3.03 2.96 3.10 2.95 3.08
heating value, Btu/scf 967.9 952.9 951.1 947.1 933.0 916.5 913.4 865.8 796.3
system carbon recovery, % 93.04 88.44 88.25 93.69 92.88 95.44 93.66 95.22 96.51
scf CH,/lb of catalyst 10.94 10.96 21.79 21.16 33.10 32.70 32.09 42.17 39.57
K,, apparent:
methanation, atm-l 457 1059 336 1559 306 3285 144 21.9 8.38
water gas shift 1.07 1.00 0.18 0.55 0.36 1.03 0.43 0.38 0.40
Table 111. Properties of Spent Raney Nickel Catalyst (1) the decomposition of iron carbonyl, (2) the decom-
reactor position of carbon monoxide, and (3) the formation of
reactor t o p reactor bottom nickel carbide. As shown, there is evidence of iron being
(gas inlet) middle (gas exit) carried into the reactor and some carbon associated with
chemical analysis, carbonyl deposition is possible. The iron probably further
% promotes carbon deposition through the decomposition of
Ni 38.7 39.2 51.7 carbon monoxide. Furthermore, X-ray diffraction studies
A1 31.3 32.9 28.3 have verified the presence of a nickel carbide a t the reactor
C 1.3 0.8 0.6 inlet.
Fe 0.47 0.38 0.44 As shown in the chemical analyses, the nickel concen-
Na 0.14 0.14 0.12
S 0.19 0.3 0.34 tration a t the reactor exit is greater than a t the reactor
entrance. Two possibilities can be speculated: first,
X-ray diffraction Ni,C, Ni,Al, Ni,C, Ni,AI, Ni provided no catalyst eroded during the run and the spent
NiAI, NiAl,
catalyst samples were scraped to the same depth, then
unequal leaching along the 14 f t of catalyst occurred. In
Carbon content was determined by the standard ASTM the leaching diagram, Figure 2 , the gravity-fed caustic
combustion technique. The concentration is greater at the solution enters the reactor bottom first. Since the acti-
entrance and all samples were greater than the 0.1-0.270 vation time was short (4.25 h) and a forced circulation of
inherently in unactivated Raney nickel. Carbon may be the caustic solution was not used, the bottom leached the
present on the catalyst as the result of several reactions: most as seen by the highest Ni content (51.7%) and the
162 Ind. Eng. Chem. Process Des. Dev., Vol. 18, No. 1, 1979

Table IV. BET Surface Areas, Pore Volumes, and Pore advantage in future scale-up work. Even without the use
Radii of Spent Raney Nickel Catalyst of a recycle flow, catalyst temperatures can be controlled
reactor reactor with relative ease. The reactor is capable of converting
top bottom fresh feeds with a CO concentration as high as 25%. With
2 ft middle 2 ft different flows there is negligible pressure drop across the
(inlet) 2 ft (outlet) reactor. Recent improvements in the catalyst flame
surface area. m2/e 43.17 39.40 28.80 spraying techniques and equipment have decreased
pore volume, cA'/g 0.118 0.121 0.132 spraying laydown time by 20-fold. Although this particular
average pore radius, 54.88 61.22 91.87 run lasted only 1179 h with a wide range of fresh feed and
A recycle flows, the catalytic reactor did show relative
percent pore volume stability during the test with little difficulty in operation.
with the following
radii: Since run 16, the process development system has been
<30 A 12.69 6.04 0 modified. Vessels and piping of carbon steel have been
30-40 A 14.14 13.74 0 replaced with stainless steel to retard or eliminate the
40-50 A 11.45 12.14 4.09 formation of the iron carbonyl poison. A future test will
50-60 A 9.91 10.69 11.69 utilize this new system.
>60 A 51.81 57.39 84.22
percent total surface Nomenclature
area with the
following radii: D, inside diameter of reactor, ft
<30 A 26.12 13.46 0 D, diffusivity, ft2/s
30-40 A 22.46 24.20 0 e, contraction factor
40-50 A 14.04 16.59 8.25 h , mass transfer coefficient, ft/s
50-60 A 9.93 11.95 19.55 L , catalyst length, ft
>60 A 27.45 33.80 72.20 Nu, Nusselt number
Sc, Schmidt number
lowest A1 content (28.5%). Also, X-ray diffraction results Re, Reynold number
indicate A1-Ni compounds, which are found in unleached Q, reactor inlet volumetric flow, ft3/s
Raney nickel, in the top section of the catalyst. S, geometric catalyst surface area, ft2
The other possibility is replacement of the active nickel wo, catalyst surface gas viscosity, lb/ft-s
W , bulk gas viscosity, lb/ft-s
a t the reactor inlet by migration of the aluminum from u , reactor inlet gas velocity, ft/s
pockets of unleached catalyst or from aluminum complexes Xco, CO conversion
formed by leaching. Most of the reaction took place along
the catalyst top length during the experiment and the local L i t e r a t u r e Cited
heat of reaction could provide a driving force for the Bennett, C. O., Myers, J. E., "Momentum, Heat, and Mass Transfer", Mc(3awHIl1,
New York, N.Y.. 1962.
migration. Haynes, W. P., Elliott, J. J., Forney, A. J., Am. Cbem. Soc. Div. FuelChem.
Although metal surface area measurements were not Prepr., 16 (2),47 (1972).
Haynes, W. P., Forney, A . J. Elliott, J. J.. Pennline, H. W., Am. Chern. Soc.
performed on the spent catalyst samples, BET surface Div. Fuel Chern. Prepr.. 19(3), 10 (1974).
measurements were obtained and shown in Table IV. The Haynes, W. P., Schehl, R. R., Weber, J. K.,Forney, A. J., Ind. Eng. Chem.
surface areas of the samples are not as great as freshly Process Des. Dev., 16, 113 (1977).
Savinell, R. F., Youngblood, A. J.. Haynes, W. P., ERDA PERU RI-7614,(1976).
leached Raney nickel (64 m2/g). However, there is a Schehl, R. R., Pennllne, H. W., Strakey, J. P., Haynes, W. P., Am. Chern. Soc.
decreasing trend from reactor inlet to outlet. The high Div. Fuel Cbem. Prepr., 21 (4),2 (1976).
Schehl, R. R., Pennline, H. W., Youngblood, A. J., Baird, M. J., Strakey, J. P.,
amount of carbon at the inlet would account for the large Haynes, W. P., ERDA PERC/RI-77/10, (1977).
surface area. Amorphous carbon would also indicate the
smaller pore radii associated with carbon a t the reactor Received f o r review April 7, 1978
inlet as compared to the outlet. Accepted July 20, 1978
Summary Presented at the Division of Colloid and Surface Chemistry, 2nd
The tube wall methanator provides an efficient method Joint Conference Chemical Institute of Canada/American
of heat removal and a relative simple design which is an Chemical Society, Montreal, Canada, May 1977.