PETROLEUM AND GAS PROCESSING

LOW-TEMPERATURE I8OMERIZATION OF n - B U T A N E
TO ISOBUTANE

N. R. B u r s i a n , N. K Volnukhina, UDC 542. 952.1 : 447.214

G. V. S t a v r o v a , and E. I. Z h e m c h u g o v a

Considerable importance is attached to the production of polymers and the manufacture of polymer-based syn-
thetic rubbers.

Soviet plants are now synthesizing isoprene rubber from isobutylene and formaldehyde.

Our reserves of natural isobutylene and isobutane do not ensure the required development of isoprene manu-
facture, so that we must concentrate on the isomerization of n-butane to isobutane.

The United States now has several industrial processes for effecting such isomerization [1-4].

The USSR has developed a process for h i g h - t e m p e r a t u r e isomerization of n-butane to isobutane, effected on
tungsten sulfide [5].

This paper gives data on l o w - t e m p e r a t u r e isomerization of n-butane to isobutane. The process is effected at
150-200~ which ensures a favorable state of c h e m i c a l equilibrium and thus gives high yields of isobutane for a
single pass across the catalyst.

The catalyst was platinized aluminum oxide, promoted by chlorine (NIP-66 catalyst).

We used c o m m e r c i a l n-butane, of which the characteristics are given below.

Hydrocarbon composition, wt. ~ :

isobutane . . . . . . . . . . . . . . . . . . . . . 0.8
n-butane . . . . . . . . . . . . . . . . . . . . . 99.0
above C4 . . . . . . . . . . . . . . . . . . . . . 0.2
Content of sulfur compounds, m g / m a . . . . . 18
Moisture content, m g / m a . . . . . . . . . . . . 200

TABLE 1. Isobutane Content of Equilibrium Mixture

(vapor phase) Versus Temperature
Isobutane content (mole %) from
Temp.,
exptl. exptl. calculated
~
data [7] data [8] data [9]

25 85,5 72
50 81,3
70 79 77,9
100 72 72,9
125 68 69 56*
150 64 65
183 58
227 46

* At 127 ~ C.

All-Union Scientific-Research Institute of Petrochemical Processes (VNllneftekhim). Translated from Khimiya

i Tekhnologiya Topliv i Masel, No. ii, pp. 4-8, November, 1969.

@1970 Consultants Bureau, a division of Plenum Publishing Corporation, 227 West 17th Street, New
York, N. Y. 10011. All rights reserved. This articie cannot be reproduced for any purpose whatsoever
] without pcr,~isaion of t,~c pub!iaher. ,4 cop)" ef this artic!e is availab!e from the publisher for $!5.00.

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Fig. 1. Scheme of pilot plant for low-temperature isomerization of n-butane: 1) feedstock buret; 2) buret
for discharge of isomerizate; 3, 4) feedstock driers; 5) dropper; 6) reactor; 7, 18) coolers; 8) gas separa-
tor; 9) condenser; 10) circulation pump; 11) oil separator; 12) dry filter; 13) differential manometer;
14) preliminary catalytic purifier; 16, 17) circulating gas driers; I) hydrogen; II) buffer Hz; III) n-butane;
IV) calibration for gas meter; V) hydrogen from buffer for calibration; VI) emergency device; VII) sampling.

3 Study of low-temperature isomerization of n-butane to isobu-

,.2' O tane and the determination of the technological indices of the proc-
ess were performed in an apparatus under pressure and with recycling
9 of hydrogen-containing gas.
(0
:~.//"
O The scheme of the apparatus is shown in Fig. 1.
O
O
Measuring burets operating under pressure were used for intro-
ducing the feedstock and discharging the product.
3" L_o'~Y~2l_2_a_ . . . . . !. . . . . . . ~ _ _ _ ~
~Y 0 :0 20 2a 4,9 :r
The feedstock and the circulating gas were dried over aluminum
oxide and NaA molecular sieves, which were regenerated when re-
L~ !sobutane content, %
quired, The moisture content of n-butane after drying was 15 m g / m ~,
Fig. 2. Catalyst selectivity versus degree and that of the circulating gas 20 m g / m 3.
of conversion of n-butane: 1) specimen
The feedstock and reaction products were analyzed by gas-
A; 2) specimen B.
liquid chromatography [6]. The moisture content of the circulating
gas was determined by a KIVGI instrument connected to the system
of the apparatus.
The catalyst was synthesized directly in the reactor. A specimen of platinized aluminum oxide was placed
in the reactor and subjected to calcination, chlorination, and activation; isomerization of n-butane was thenbegun.

Since the selectivity of the catalyst was fairly high, its performance under differing test conditions was
assessed from data on the composition of the liquid reaction products. The catalyst activity was assessed from the
isobutane content of the liquid product, the catalyst selectivity from the content of decomposition products (C~-C 3
hydrocarbons).
 TABLE 2. Effect of Temperature and Volumetric Feed
Rate of n-Butane on the Activity of NIP-66 Catalyst
Catalyst ]
Catalyst Test conditions selectivity-t Catalyst
speci- ] . . . . . . . . . C2-C3hy- [ activity-
men [temper- feed of n- drocarbon :] isobutane
[ ature, C butane,h "l content, I content,wt.%
wt.qo I
I 150 1,0 0,1 6,5
t 160 1,0 0,3 11,8
160 2,0 0,2 7,1
180 0,5 0,5 23.2
180 1,0 0,5 25,5
183 2,0 0,4 15,0
200 0,5 2,7 35,2
200 1,0 2,2 40,1
200 2,0 1,3 34,7
160 0,5 0,7 33,0
160 1,0 0,4 23,9
160 3,0 0,2 12,3
160 1,0 0,3 25,1
180 1,0 1,0 34,9
193 0,5 2,4 4-I ,0
19:3 1,0 1,8 44,2
190 1,0 2,0 43,5

TABLE 3. Effect of Working Pressure on Catalyst Activi-

ty (specimen A).Test Conditions: Temperature 180~
Feed of n-Butane 1.0 h -I MH2: Mb = 1 : 1

Pressure, Content in catalyst, wt. %

atm c2--c3 iso- c4 H-C4 >C4

20 0,7 26,7 72,6 Traces

30 1,0 25,4 73.6 Traces
40 0,9 27,2 71,9 Traces

TABLE 4. Prolonged Testing of NIP-66 Catalyst (speci-

men A) during Isomerization of n-Butane
Time from Content in catalyst, wt. %
Expt. tern- ----
beginning
of work, h perature, C c2-c3 iso- c4

66 200 2,3 39,2

400 200 1,6 37,7
700 200 1,9 3,1,3
1826 200 I, 1 35,9
2000 215 1,6 38,6

The activity, selectivity, and stability of the catalyst during the process depend on correct selection of the
process parameters.
Table 1 gives data on chemical equilibrium (experimental and calculated) for isomerization of n-butane to
isobutane at differing temperatures.
It will be seen from Table 1 that a discrepancy is observed between the experimental and calculated isobu-
tane contents of the equilibrium mixtures. With a fall in temperature from 227 to 25 ~ the isobutane content of the
equilibrium mixture increases by 20-25%,

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 TABLE 5

Electrolytic Hydrogen-containing gas from

Indices
hydrogen cat al y t i c reforming plant

Gas composition, vol. %

hydrogen . . . . . . . . . . . . . . . . . . . . . 99.3 85.6
methane . . . . . . . . . . . . . . . . . . . . . 6.4
ethane . . . . . . . . . . . . . . . . . . . . . . 3.5
propane . . . . . . . . . . . . . . . . . . . . . . 2.0
isobutane . . . . . . . . . . . . . . . . . . . . . 1.4
n-butane . . . . . . . . . . . . . . . . . . . . . I.I

Feedstock
Hydrocarbon composition, wt. %:
isobutane . . . . . . . . . . . . . . . . . . . . . 0.8 0.8
n-butane . . . . . . . . . . . . . . . . . . . . . 99.0 99.0
above C4 . . . . . . . . . . . . . . . . . . . . . 0.2 0.2
Process conditions
temperature, ~ . . . . . . . . . . . . . . . . 200
pressure a i m . . . . . . . . . . . . . . . . . . . 20
n-butane feed, h -1. . . . . . . . . . . . . . . 1.0
molar ratio of hydrogen to n-butane . . . I:I
Yield of components, wt. %
methane . . . . . . . . . . . . . . . . . . . . . 0.27 0.40
ethane . . . . . . . . . . . . . . . . . . . . . . 1.03 I. 70
propane . . . . . . . . . . . . . . . . . . . . . . 1.60 2.20
total C c C a . . . . . . . . . . . . . . . . . . . 2.90 4.30
isobutane . . . . . . . . . . . . . . . . . . . . . 44. 78 45. i0
n-butane . . . . . . . . . . . . . . . . . . . . . 51.80 49.84
hydrocarbons above C 4 . . . . . . . . . . . . 0.52 0.76

soV The use of an NIP-66 catalyst enables us to effect i s o m e r i z a -

tion at 150-200~ Under these conditions the mixture may contain
isobutane: 55-65% from e x p e r i m e n t a l data [8, 9] and 50-55% from
COW"~ev'i c a l c u l a t e d data.
oa I_ We used two catalyst specimens (A and B) with differing
activities.
1 • I I
O I 2 3 4" 5 To study the effect of the v o l u m e t r i c feed rate of n-butane
Molar ratio of hydrogen we recorded the kinetic curves at 160, 180, 190, and 200~ The
to butane experiments were performed under a pressure of 20 atm at a molar
Fig. 3. Molar ratio of hydrogen to n - b u - ratio of hydrogen to n-butane equal to 1. The rate of feed on n - b u -
tane versus catalyst activity (specimen A). tane was 0.5-3.0 v o l / v o l of catalyst per hour (Table 2).

It will be seen from Table 2 that an increase in temperature

from 150 to 200~ heightened the isomerization of n-butane on both
specimens: other conditions being equal, the isobutane content increased from 6.5 to 40.1~ on specimen A and
from 23.9 to 44.2 wt. % on specimen B.

It was shown that a decrease of the volumetric rate below 1.0 h -I did not increase the activity, but merely
i m p a i r e d the catalyst selectivity.

Figure 2 plots the yield of decomposition products versus the process depth for the catalysts (specimens
A and B).

The data show that the more a c t i v e catalyst (specimen B) was also more selective; with 40% isomerization
of n-butane the yield of Ca-C a hydrocarbons was 2.2% for specimen A and 1.4 wt. % for specimen 13. Furthermore,
we can infer that even for the most active catalyst (specimenB) an increase of isomerization beyond 45 wt. % is
undesirable because it reduces the selectivity of the process.

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 From the viewpoint of catalyst activity and stability during the process, the principal role is played by the
working pressure and the molar ratio of hydrogen to n-butane. We therefore performed experiments on the effects
on these parameters on catalyst activity, The work was effected at a temperature enabling us to operate well away
from equilibrium.

As we see from Table 3, other conditions being equal a change in the working pressure in the range 20-40
aim had no effect on catalyst activity. An increase of the molar ratio of hydrogen to n-butane from 1 to 5 reduces
the activity: the isobutane content fell from 26.7 to 11,7 wt. % (Fig. 3).

From the results of these investigations we selected the following conditions for isometization of n-butane:
temperature 200-205~ pressure 20 atm; feed of n-butane 1.0 h-i; and molar ratio of hydrogen to n-butane 1 : 1.

Tests on the catalyst were performed under these conditions for 2000 h (Table 4). It was found that the cata-
lyst has a perfectly satisfactory stability; the loss of catalyst activity was 3.3 abs, % and was compensated by ele-
vating the process temperature by 15~

In this connection the catalyst selectivity remained virtually unchanged.

Technological Indices of Isomerization of n-Butane

Some industrial units may find it necessary to use hydrogen-containing gas from catalytic reforming instal-
lations as the feed source of hydrogen for their isomerization plants.

We therefore determined the technological indices of isomerization of n-butane to isobutane on electroiytic

hydrogen and on hydrogen-containing gas from a 35-5 installation.

Table 5 gives data on the process conditions and yield of the reaction products.

It will be seen from Table 5 that good results were obtained when hydrogen-containing gas from reforming
plants was used for isomerization of n-butane. In this case the yields of the decomposition products were increased
by the presence of C~-C 3 hydrocarbons in the initial hydrogen-containing gas,

Since low-temperature isomerization is performed at relatively low temperatures (~200~ and a pressure of
20 aim, the plant can be made of carbon steel. Since the catalyst contains chlorine, we determined the HC1 con-
tent of the circulating gas at different moisture contents of the latter: at a moisture content of 20 m g / m 3 the HC1
content was 5 9 10 -6 mg/ma; and at a moisture content of 375 m g / m 3 , a . 3 9 10 -3 m g / m 3 HC1.

It will be seen that under conditions ensuring a moisture content of the circulating gas below a limit of 20
m g / m ~ the HC1 content cannot cause marked corrosion of the apparatus.

CONCLUSIONS

1. A process has been developed for low-temperature isomerization of n-butane on an NIP-66 catalyst.

2. The process parameters have been studied and the conditions for effecting isomerization of n-butane
selected.

3. The catalyst has been subjected to prolonged tests under the selected conditions; it exhibited satisfactory
stability over a period of 2000 h,
4. The technological indices of the process based on electrolytic hydrogen and on hydrogen-containing re-
forming gas have been determined, At 200~ 20 aim, an n-butane feed rate of 1.0 h -1, and a 1 : 1 molar ratio of
hydrogen to n-butane,the isobutane yield was about 45 wt. %, which is about 80~ of the equilibrium value. The
yield of the decomposition products was 2.9 wt. % for electrolytic hydrogen and 4.3 wt. % for reforming gas,

LITERATURE CITED

1. S. K.Lalabekan, Isomerization of hydrocarbons in the Petroleum Industry [in Russian], BTEK. TsNMT Nefti
(1948).
2. P. Refiner, 43, No. 9 (1964).
3. Petroleum, 22, No. 12 (1959).
4. Oil and Gas, 59, No. 27 (1961).
5. G. M. Maslyanskii and V. A. Kobelev, Chemical Processing of Petroleum Hydrocarbons [in Russian], Izd. AN
SSSR (1956), p. 499.

774
6. M. I. Dement'eva, Methods of Studying the Products of Petroleum Refining and Petrochemical Synthesis [in
Russian], Gostoptekhizdat (1962).
7, B. L. Moldavskii and T. V. Nizovldna, Zh. Obshch. Khim., 9, No. 18, 1682 (1939).
8. H. Pines, Catalysis in Organic Chemistry [Russian translation], IL (1953), p. 17.
9. A. A, Vvedenskii, Thermodynamic Calculations of Petrochemical Processes [in Russian], Oostoptekhizdat
(1960).

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