HYDROCHLORINATION OF METHANOL T O

METHYL CHLORIDE IN FIXED CATALYST BEDS

M. S. T H Y A G A R A J A N , R A J I N D E R K U M A R , A N D N. R. K U L O O R
Department of Chemical Engineering, Indian Institute of Science, Bangalore, India

The vapor phase hydrochlorination of methanol to methyl chloride in fixed beds with silica gel-alumina
(88 to 12) and y-alumina catalysts was studied in a glass tubular reactor in the temperature range of 300"
to 390" C. Of the two catalysts studied, y-alumina gave nearly equilibrium conversions under the experi-
mental conditions. The data are expressed in the form of second-order irreversible rate equations for both
the catalysts studied.

METHYL CHLORIDE is an important starting material in the
manufacture of silicone high polymers. Apart from
this, it finds applications in the low temperature polymerization
of butyl rubbers and as intermediate in the manufacture of
methylene chloride, which is extensively used in industry. The
methods used for the production of methyl chloride are chlo-
rination of methane and hydrochlorination of methanol ( 3 ) .
The first method suffers from the disadvantage that it results in
the formation of a group of compounds which have to be
fractionated in order to obtain pure methyl chloride. Very
little information is available on the hydrochlorination of
methanol. The present investigation was undertaken to study
the reaction in fixed beds of silica gel-alumina (88 to 12) and
y-alumina catalysts.
Thermodynamic Considerations
The stoichiometric equation for the preparation of methyl
chloride from methanol and hydrogen chloride is given as
CH3.OH + HC1 --t CH3.Cl + H20
The equilibrium constants a t various temperatures were eval-
uated from the available thermodynamic data (4). The

1
equilibrium conversions were then evaluated from the equation

0 ~ 8 1 - 11 I I 1 I 1
s ZOO 400 600 e00 1000
TBHPERATURE, *K and are shown in Figure 1. The equilibrium conversion de-
Figure 1. Effect of t'emperature on equilibrium conversion creases from 99% a t 300' K. to 85% a t 1000" K. T o produce

WATER

Figure 2. Experimental setup

1. Constant overhead tank 6. Reactor
2. Aspirator bottle 7. Thermocouple
3. Hg manometer 8. Condensers
4. Methanol storage 9. N a O H bubbler
40. HCI generator 10. Mariotte system
5. Mixer

VOL. 5 NO. 3 JULY 1966 209

methyl chloride in high conversions and in reasonably high
rates the temperature range of 600’ to 700’ K. is explored for
kinetic studies.

Experimental
Equipment a n d Operation. A flow diagram of the appara-
tus is shown in Figure 2 . The reactor is a borosilicate glass
tube of 15-mm. i.d. and 700 mm. long. A thermowell is
provided for inserting the calibrated iron-constantan thermo-
couple. Care is taken to keep the tip of the thermowell at the
center of the catalyst bed when the catalyst is packed inside
the reactor tube. The reactor is also packed with porcelain
beads which serve as the preheater for the reactant gases and
as a distributor. The reactor is provided with a radiation
heater and the energy input to the heater is controlled by a
Dimmerstat. Arrangements are made for the admission of the
reactants a t the bottom of the reactor and for withdrawal of the
products through a side tube a t the top.
Reactants. METHANOL, analytical reagent grade, is metered
through a calibrated all-glass rotameter and fed into the
preheater. A steady feed rate is obtained by the pressure of
air displaced by water from a constant-level tank.
HYDROGEN CHLORIDE.An all-glass apparatus for the
preparation of hydrogen chloride is a modified form of the
apparatus developed by Bhatnagar and Kuloor ( Z ) , so that
dry hydrogen chloride could be produced a t pressures slightly
higher than atmospheric. The gas is dried by passing it
through a calcium chloride tube and is metered using a cali-
brated glass capillary flowmeter. The manometric liquid
used in this flowmeter is concentrated sulfuric acid.
Preparation of Catalysts. SILICAGEL-ALUMINA (88 to 12)
CATALYST.Aluminum foil is dissolved in potassium hy-
droxide solution to yield potassium aluminate solution. Silica
gel (obtained from water glass) is then dispersed in potassium
aluminate solution. Carbon dioxide is passed into the solu-
tion until all the alumina is precipitated. Then a 15Oj, solu-
tion of ammonium chloride is added to maintain the required
pH. After some time the precipitate is washed free of chloride,
filtered, and then dried.
7-ALUMINACATALYST.y-Alumina is prepared by dis-
solving aluminum foil in a solution of potassium hydroxide
solution and bubbling carbon dioxide into the resulting potas-
sium aluminate solution until all the alumina is precipitated.
T h e precipitate is washed and then dried. The alumina thus
obtained is then activated a t 400’ C. for about 16 hours and
then used as such.
Characteristics of Catalysts. SILICAGEL-ALUMINA. Par-
ticle size, -28+ 48 Tyler mesh. Surface area, 775.0 sq. meters
per gram.
?-ALUMINA.Particle size, cylinders of 2.1 -mm. length,
1.0-mm. diameter. Surface area, 169.0 sq. meters per gram.
Experimental Procedure. The preheaters, mixer, and
reactor are heated to the desired temperature. Methanol
and hydrogen chloride in predetermined proportions are then
fed into the reactor through the mixer by applying the constant
pressure device. When steady state of temperatures and feed
rates is reached, the product coming out of the reactor is con-
densed, scrubbed through sodium hydroxide solution, and
finally collected over brine solution in a Mariotte system.
Each run is conducted for 10 minutes and a sample of product
is analyzed immediately.
Analysis. The methyl chloride content in the product gas
is determined by absorption in glacial acetic acid (7).
Results and Discussion
Influence of Variables on Conversion. The pressure of
operation was considered to be of negligible effect because the
number of moles of the reactants is equal to that of products.
Hence, all of the experiments during the present investigation
were conducted at nearly atmospheric pressure. Separate
design equations are developed for each of the two catalysts
studied-silica gel-alumina and y-alumina. The composition
of the feed was not very important and only a few experiments
were conducted by changing the composition of the feed.
/ A I
/m I
Catalyst: r-Alumlna
Ratio of rcrctants=l:l (HCI:CHaOH)
I 1 I I I I I 1 I
0.1 0.3 0.5 0.7 0.9 11 1.3 1.5
W/F, gm of crtalyrt/gm mole of fccdlhr
Figure 3. Conversion vs. time factor at various tem-
peratures
Catalyst. y-Alumina
Ratio of reactants 1:l
The effect of the other variables- WJF and temperature-is
dependent on the levels of each. To take these interactions
into account, a complete factorial design approach was resorted
to. Thus, for each level of temperature, four levels of space
velocity were studied. The amount of catalyst was mqintained
the same throughout the investigation, but was changed for a
few runs in order to ascertain whether diffusion or chemical
reaction rate constitutes the rate-controlling mechanism.
EFFECTOF TIMEFACTOR. The time factor ( W J F ) in the
present case was varied by changing the feed rate while main-
taining the weight of the catalyst constant. The data obtained
by varying the time factor on both the catalysts a t temperatures
of 300°, 330°, 360°, and 390’ C. are shown in Figures 3 to 6.
The fact that the curves do not register fall or sudden rise in-
dicates that the rates of side reaction are negligible.
EFFECTOF TEMPERATURE. The manner in which the tem-
perature increases the conversion is shown in Figure 7, where
the conversion has been plotted against temperature for various
WJFvalues as parameters. This increase is expected from the
Arrhenius equation, which gives the effect of temperature on
homogeneous reactions. For catalytic reactions, the final
apparent effect of temperature is due to both the effect on
adsorption constants and specific reaction rate constants. I n
the present case, as the change in conversion with temperature
is high for both the catalysts, the effect of adsorption constants
appears to be less.
No fall in the activity of the catalyst was observed with rise in
temperature within the range of temperatures studied. Higher
temperatures, however, could not be employed because of the
lowering of the equilibrium conversion and the higher prob-
ability of formation of side products like ether.
E ~ F E COF
T COMPOSITION OF REACTANTS.I t is seen (from
Figures 4 and 5) that a t lower temperatures the effect of change

210 l&EC PROCESS DESIGN A N D DEVELOPMENT

E
30.3
U
-
-
a?
U

-u
I

Catalyst: r-Alumina
Ratio of reactantr=l:2 (HCI:CH3OH)

I I
0 0.5 1.0 1.5
WIF, gm o f c a l s l y r l / g m mole of.feed/hr

Figure 4. Conversiori vs. time factor at various tem-

peratures
Catalyst. y-Alumina
Ratio of reactants 1 :2 I I I
1 2 3
W/F, grn of catalyrt/gm mole of fced/hr
Figure 6. Conversion vs. time factor at various tem-
peratures
Catalyst. Silica gel-alumina
Ratio of reactants 1 :1

0.5-
>
U
m
r
U
I 0.4-
0

-
u

: - 0.3

.-$- 0.2-
E Catalyst : r-Alumina
W/F, gm of catalyst/gm mole of feed/hr >
C

Figure 5. Conversion vs. time factor at various tem- 8 0.1 - Ratio of reactants=l:l (HCi: CH30t

peratures
Catalyst. y-Alumina 0,0
Ratio of reactants 1 :3 300 330 360 390 410
TemperatUrQ *C
Figure 7. Effect of temperature on conversion
in molal ratio is not considerable but a t higher temperatures it Catalyst. y-Alumina
is more significant. Thus, conversion can be increased mainly Ratio of reactants 1:l
by increasing the temperature.
Comparison of Catalysts. Comparison of Figure 4 with
Figure 7 shows that y-al.umina catalyst gives higher conversions higher surface area for the reaction, thereby making it possible
throughout the range of temperatures and time factors consid- to achieve higher conversions even if its activity is slightly less
ered. However, it s e e m unreasonable to compare the catalysts than the other. In the present case, the density of y-alumina
in the above fashion because their densities are not the same. is very low compared with that of silica gel-alumina, so much
As a result, the volume of the catalyst possessing a lower density so that the volume of 1.O gram of silica gel-alumina catalyst is
will be much greater than that of the other and the number of smaller than 0.5 gram of y-alumina. The bulk densities of
particles of this catalyst is greater than that of the other. Thus, silica gel-alumina and y-alumina are, respectively, 0.6302 and
for the same weight, the catalyst having lower density offers 0.2857 gram per cc.

VOL. 5 NO. 3 JULY 1966 211

Rate Equation
The method employed for expressing the results quantita-
tively is based on the order of reaction approach.
The design equation for a catalytic flow reactor can be put
in the form
Arrhenius plots were made for both y-alumina and silica
gel-alumina catalysts. The plot for y-alumina is presented in
Figure 8, and that for silica gel-alumina is presented in Figure
9. The values of k employed in these graphs are averaged
values which are considered to be more representative than
any arbitrary chosen value.

W/F' = [ dXA/T (2)

From the slopes and intercepts the values of E and A are cal-
culated for both the catalysts and are given below:
I n Equation 2 r is a function of x A because the concentrations y-Alumina
of unreacted materials vary with conversion. The second- E = 19,178 cal./gram mole
A = 1.816 X lo7
order rate equation for the reaction can be expressed as
Silica Gel-Alumina
r = k CA C B (3)
E = 18,860 cal./gram mole
By substituting this in Equation 2 and making substitution and A = 2.615 X l o 3
integration, the final equation obtained is Employing these values of E and A , the final integrated rate
equation is written by expressing k of Equations 4 and G in
W/F' = n$/k - 1
---
nAo - nBo
In 0
nAo
n.4

- XA
+ terms of E and A . Thus for 7-alumina, the final rate equations
are :
1 nBo Where the feed does not contain equimolal quantities of
In - (4)
nAo - nBo nBo - XA methanol and hydrogen chloride :
This equation applies only when the initial moles of the
reactants are not equal. For the special case when nAo = n B o ,
Equation 3 becomes
r = k CAz (5)
Substituting Equation 5 in Equation 2 and integrating we When feed contains equimolal quantities of methanol and
obtain hydrogen chloride:
pV/F' = D
k.nAo
n 2 ( ~

nAu - xA ) (6)

The known values of %A, nAo, n B o ) no, and p!'/F' are substituted Similarly for silica gel-alumina catalyst the final integrated
and the values of k calculated a t various conversion values.
rate equation is
T h e resulting values of k are given for y-alumina and silica
gel-alumina catalysts in Table I.
Table I shows that a t 300' C. the values of k are nearly equal
for feeds of various molal ratios. Similar is the case with
values of k a t 330" and 360' C. These observations confirm
that the reaction is definitely of first order with respect to each
of the reactants, methanol and hydrogen chloride.
Reaction velocity constants for silica gel-alumina catalyst
a t various temperatures are also presented in Table I.
Effect of Temperature on Reaction Velocity Constants. 1.0 -
The reaction velocity constant is related to the reaction tem-
perature, in accordance with the Arrhenius equation, as 0.8 -
follows :
k =A ,--E/RT
(7) -
0.6
or .x
In k = In A - E/RT (8) 01
0 0.4-

Table 1. Reaction Velocity Constants at Various Ternpera- 0.2 -

tures
Mole
Ratio of 0.0 -
Reactants
Aaerage Value of k
NO.
( HCl :
CHaOH) 300'C. 33'0'C. 36OOC. 390'C. 7,s -
?-Alumina Catalyst 1 1
0.15
1
0-16 0-17
I 1
0.18
1 1:l 1.034 2.202 3.404 7.714
2 1:2 1.032 2.198 3.403 ... +*lo2
3 1:3 1.036 2.206 *.. ... Figure 8. Effect of temperature on reaction velocity con-
Silica Gel-Alumina Catalyst stants
1 1:l 0,2573 0,6415 1.4010 2.8180 Catalyst. y-Alumina
Ratio of reactants 1 :1

212 I&EC PROCESS D E S I G N A N D DEVELOPMENT

 Table II. Validity of Rate Equations
Catalyst. ?-Alumina
Ratio of reactants. 1 : 1 (CHaOH:HC1)
Conversion Temlberature 300" C. Temperature 330" C. Temperature 360' C. Temperature 390" C.
X W/F' calcd. W/F' exptl. W/F' calcd. W/F' exptl. W/F' calcd. W/F' exptl. W/F' calcd. W/F' exptl.
0.05 0.2546 0.2220 0.1101 0.1170 0.5160 0.7600 0.0260 0.0280
0.075 0.4044 0.3510
0.10 0.5729 0.5000 0.2477 0.2520 0 .'1.162 0 .'l620 0 0582 0,0660
0.15 0.9820 0.9050 0.4245 0.4120 0.1988 0.2660 0.0997 0.1330
0.20 ... ... 0.6603 0.6270 0.3092 0.3950 0.1551 0.1780
0.30 ... ... 1.4853 1.2740 0.6956 0.8250 0.3488 0,3900
0.35 ... ... ... ... 1.0816 1.1600 0.5425 0.5950
0.40 ... I . . ... ... *.. ... 0.9293 0.9230

silica gel-alumina catalyst showed that Equation 11 expresses

the data well.

Acknowledgment

0.50- The authors thank the authorities of the Council of Scientific

and Industrial Research, New Delhi, for the award of a Junior
Research Fellowship to one of them (M.S.T.).
0.30 -
Nomenclature

JL
0.10 - A = frequency factor, gram moles/hr. (atm.*) (gram
cn
0
cat.)
CB = concentration of species A and B
?so - CA,
E = activation energy, cal./gram mole
F = feed rate, gram moles/hr.
F' = feed rate, gram/hr.
7-70 - k = reaction velocity constant, gram moles/(hr.)
(atrn.2) (gram cat.)
K = equilibrium constant
T.50 - nAo, nBo = number of moles of species A and B initially
present, gram moles per unit mass of feed
-1.30 - 2
=
=
total moles of feed per unit mass of feed
universal gas cmstant
r = rate of reaction, gram moles/(hr.) (gram cat.)
T = absolute temperature, O K.
w = weight of catalyst, grams
XA = moles of hydrogen chloride converted per unit
Figure 9. Effect of temperature on reaction velocity mass of feed
constants X = moles of methyl chloride formed per mole of total
Catalyst. Silica gel-alumina
feed
Ratio of reactants 1:l
literature Cited
(I) Allison, V.C., Meighan, M. H., J. Znd. Eng. Chem. 7, 943
Reliability of Equsrtion. T o verify that the equations (1919).
derived represent the data adequately, calculations were (2) Bhatnagar, R. K., Kuloor, N. R., J . Sci. Znd. Res. (India)
12A, No. 11, 520 (1953).
made for W/F' values Iby putting various values of conversions (3) Kirk, E. R., Othmer, D. F., "Encyclopedia of Chemical
x A in the equations. A. set of values calculated through Equa- Technology," Vol. 3, p. 741, Interscience Encyclopedia Inc.,
New York, 1949.
tion 10 as well as experimentally determined values is given in (4) Kobe, K. A,, Crawford, H. R., Petrol. Rejner 37 (7), 125
Table I1 for y-alumina catalyst. (1958).
Table I1 shows that the calculated values agree well with RECEIVED
for review January 18, 1965
the experimental ones. Similar calculations conducted for ACCEPTEDJanuary 24, 1966

VOL. 5 NO. 3 JULY 1966 213