United States Patent (19) 11) 4,423,271

Obenaus et al. 45 Dec. 27, 1983

(54) PROCESS FOR PRODUCING HIGH PURITY 4,242,530 12/1980 Smith .................................. 585/510
ISOBUTENE BY DEHYDRATING TERTARY 4,313,016 1/1982 Manning ..... 585/510
BUTANOL 4,320,232 3/1982 Volkamer et al . 585/639
4,331,824 5/1982 Ikeda et al. ......................... 585/638
75 Inventors: Fritz Obenaus; Bernd Greving, both
of Marl; Heinrich Balke, Herten; Primary Examiner-Curtis R. Davis
Bernhard Scholz, Marl, all of Fed. Attorney, Agent, or Firm-Wells & Wells
Rep. of Germany 57 ABSTRACT
73) Assignee: Chemische Werke Hills AG, Marl, Tertiary-butanol in an aqueous solution containing from
Fed. Rep. of Germany 40 to 90 percent by weight of tertiary butanol in homo
(21) Appl. No.: 424,576 geneous and liquid phase is dehydrated at a fixed cata
lytic bed consisting of a strongly acidic ion exchange
22 Filed: Sep. 27, 1982 resin at a temperature from 80 to 150° C. and at a pres
30 Foreign Application Priority Data sure from 5 to 25 bars for the purpose of producing
isobutene by dehydrating tertiary butanol.
Dec. 24, 1981 DE Fed. Rep. of Germany ....... 3151446 Thereupon the homogeneous, liquid reaction mixture is
51) Int. Cl. ................................................ C07C 5/22 fractionated in a distillation sector separate from the
52 U.S. Cl. .............. ... 585/639; 585/638 reaction chamber, the isobutene being separated from
58) Field of Search ................................ 585/638, 639 the water and from the unreacted tertiary butanol. The
(56) References Cited unreacted tertiary butanol is returned as an aqueous
solution in a circulating flow rate to the reactor under
U.S. PATENT DOCUMENTS the conditions that the mixture of fresh-fed tertiary
3,510,538 5/1970 Rosenthal ........................... 585/639 butanol and the circulating tertiary-butanol/water mix
3,629,478 12/1971 Haunschild ....... ... 585/638 contains from 40 to 90 percent by weight of tertiary
3,634,535 l/1972 Haunschild ....... ... 585/638 butanol at the reactor inlet.
4,165,343 8/1979 Levine et al. ..... ... 585/638
4,232,177 11/1980 Smith .................................. 585/639 5 Claims, 2 Drawing Figures
U.S. Patent Dec. 27, 1983 4,423,271
 1. 4,423,271 2
creases, such procedures are only suitable for reaction
PROCESS FOR PRODUCING HGH PURITY mixture rich in TBA. Process steps have been described
ISOBUTENE BY DEHYDRATING TERTIARY for TBA solutions which are richer in water, wherein
BUTANOL inert entraining agents are proposed for the water of
CROSS-REFERENCE TO A RELATED
reaction as disclosed in U.S. Pat. Nos. 3,510,538 and
APPLICATION
4,155,945. For instance when adding benzene or xylene
as the entraining agent, there takes place however in the
Applicants claim priority under 35 USC 119 for appli light of the teaching of U.S. Pat. No. 3,510,538 and
cation P 3551 446.4, filed Dec. 24, 1981, in the Patent 10
especially above 100° C. a reinforced oligomerization of
Office of West Germany. isobutene. Moreover, the addition of a third substance
BACKGROUND OF THE INVENTION supporting the reaction, on the other hand, hampers
reprocessing because this accessory substance must be
The field of the invention is isobutene and the present discharged again and be recovered.
invention is particularly concerned with the production It has been suggested in order to overcome these
of high-purity isobutene by dehydrating tertiary buta 15
nol (TBA) in the presence of a strongly acidic synthetic drawbacks that the aqueous TBA solution be fed to the
resin cation exchanger as the catalyst. rectifier part of a column from which, preferably at 85
The state of the art of processes for producing isobu C. and a maximum pressure of 1.9 bars an aqueous
tene by dehydrating TBA may be ascertained by refer vapor flow rich in TBA is driven through the catalytic
ence to U.S. Pat. Nos. 2,377,026; 3,510,538; 3,665,048; 20 bed mounted in loose bulk above the rectifier section as
4,012,456; 4,036,905; and 4,155,945, and British Pat. No. disclosed in U.S. Pat. No. 4,012,456. Together with the
2,022,129, the disclosures of which are incorporated proportion of TBA and water, the isobutene is with
herein. drawn in gaseous form from the reaction section. This
Ion exchange resins suitable in the present invention method is satisfactory with regard to selectivity, but it
are disclosed in U.S. Pat. Nos. 2,480,940; 2,922,822; and 25 does require a specially formed cation exchange resin
3,256,250, and British Pat. No. 957,000, the disclosures not on the market.
of which are incorporated herein. In addition to the frequently complex reaction proce
TBA dehydration takes place reversibly and endo dure, the prior art methods basically incur a substantial
thermally. The conversion into isobutene and water drawback:
increases with rising temperature in the view of the 30 Isobutene is obtained in gaseous form together with a
chemical equilibrium. partial-pressure determined proportion of TBA and
Accordingly, in industry the TBA dehydration is water at a pressure no longer permitting it to condense
predominantly carried out at high temperatures of using the conventional coolants used in industry.
about 180 to 450° C. in the presence of weakly acidic The extraction of pure isobutene by rectification
catalysts such as silica gel, thorium oxide, titanium(IV)- 35 therefore requires costly compression and condensation
oxide or especially aluminum oxide as disclosed in U.S. stages. To avoid this drawback, the method of British
Pat. Nos. 4,036,905; 3,665,048; and 2,377,026. While a Pat. No. 2,022,129 performs the dehydration of TBA in
high TBA conversion is achieved using high tempera the presence of acid cation ion exchange resins at a
tures, the considerable losses in isobutene by its oligo pressure of at least 5 bars. The temperature is selected
merization on the other hand represent a drawback. In correspondingly to be so high that the produced isobu
addition to isobutene oligomerization there also takes tene can be removed in gaseous form together with the
place an undesired isomerization of the formed isobu proportion of TBA and water from the reaction zone.
tene to n-butenes as disclosed in U.S. Pat. Nos. Depending on the pressure of reaction, temperatures of
3,665,048, and 2,377,026, causing further product losses, about 180° C. or higher are required in this procedure,
more significantly however making the separation and 45 that is, these are temperatures above the limit of applica
extraction of pure isobutene especially disadvanta tion of commercial cation exchange resins and from
geously difficult. which therefore only a restricted catalyst life can be
When the dehydration of TBA is carried out at lower expected under these conditions. Moreover the higher
temperatures (below 180° C) more active and strongly temperatures entail a lesser isobutene selectivity com
acidic catalysts are needed. Due to their inherent draw 50 pared to the previously cited methods. There is a com
backs such as corrosion, waste water problems, costly mon factor in all these procedures reflecting the state of
recovery, etc., the homogeneous acid catalysts such as
mineral acids, organic sulfonic acids and heteropoly the art for TBA dehydration in the presence of acid
acids drop in significance for the dehydration reaction. synthetic resin exchangers, namely that the components
On the other hand, cation exchanger resins assume sig 55 of reaction are present in a mixed phase consisting of a
nificance as catalysts. gaseous and a liquid phase, and that the catalyst is pres
Due to the poorer equilibrium conditions, only partial ent as a third and solid phase. Thereby the mass transfer
TBA conversions remain possible at lower tempera to the catalytically effective centers of the catalyst will
tures. Therefore higher degrees of conversion require be hampered, and as a result, the rate of isobutene for
continuous removal of the reaction products. mation referred to the reactor volume, i.e., the time
This continuous removal is achieved by setting lower space-yield, is unsatisfactory for isobutene.
pressures of reaction below 2 bars, so that the isobutene Accordingly, large amounts of catalyst are required
distills off as a low boiling point component from the to implement the process on an industrial scale. This
reaction mixture in continuous manner together with a causes problems regarding the apparatus to be used and
partial-pressure determined by the proportion of TBA 65 the heat supply to the strongly endothermal splitting
and water as disclosed in U.S. Pat. No. 3,256,250. As the reaction, as heat from only a heat source of compara
rate of formation-which in any event is low-strongly tively low temperature can be fed to the synthetic ex
drops as the water content in the reaction mixture in changers being used on account of the low temperature
 4,423,271
3. 4.
stability, as a result of which a large heat transfer area is through 31 that at excessive pressure, that is, in the
required. presence of a homogeneous liquid phase, it is difficult to
To improve the mass transfer conditions for splitting, obtain dehydration. Accordingly, it was surprising that
the methods of the state of the art use a movable cata the process of the present invention allows producing
lytic bed. The synthetic resin structure of commercial isobutene in a homogeneous liquid phase at these tem
cation exchangers when used in polar substances such peratures at heretofore unachieved space-time yields
as TBA and water, experiences marked swelling and and selectivity.
deformation substantially degrading the mechanical The present invention offers another advantage in the
stability of the catalyst. separation between the reaction chamber and the isobu
Therefore, it is impossible to prevent abrasion and 10 tene processing, whereby a free and flexible choice is
fracture of the catalyst particles in a moving catalytic given regarding the optimal conditions for the reaction
bed. and distillation stages and this is a great advantage espe
SUMMARY OF THE INVENTION
cially as regards both the product quality and the cata
lyst stability.
Having in mind the limitations of the prior art it is an 15 In the process of the present invention, the tempera
object of the present invention to provide a process for ture of reaction is between 80' and 150 C. Adiabatic
the large-scale industrial production of high-purity iso operation is advantageous at a raised temperature, for
butene by dehydrating TBA making it possible to dehy instance of 110° C. The preferred temperature is be
drate in a more efficient and more economical process tween 100' and 130° C., because both the catalyst life
using a simpler procedure. 20 and the isobutene space-time-yield are economically
According to the present invention tertiary-butanol optimal in this range.
in an aqueous solution containing from 40 to 90% by The pressure of reaction is between 5 and 25 bars, the
weight of tertiary butanol in homogeneous and liquid pressure being selected at such a level that the isobutene
phase is dehydrated at a fixed catalytic bed consisting of produced in the reactor will remain homogeneously
a strongly acidic ion exchange resin at a temperature 25 dissolved in the reaction mixture without formation of a
from 80' to 150° C. and at a pressure from 5 to 25 bars gas phase. As a rule it is advantageous that the pressure
for the purpose of producing isobutene by dehydrating of reaction exceed the pressure of the column in the
tertiary butanol. reprocessing part, as it is possible in this case to use the
Thereupon the homogeneous, liquid reaction mixture expansion evaporation to support advantageously the
is fractionated in a distillation sector separate from the 30 separation of the isobutene.
reaction chamber and the isobutene is separated from The TBA content in the input mixture prior to the
the water and from the unreacted tertiary butanol. The reactor is between 40 and 90% by weight, preferably
unreacted tertiary butanol is returned as an aqueous between 55 and 85% by weight. The input mixture
solution in a circulating flow rate to the reactor under introduced into the reactor consists of a supply of fresh
the conditions that the mixture of fresh-fed tertiary 35 tertiary butanol, preferably in the form of a TBA/water
butanol and the circulating tertiary-butanol/water mix azeotrope, and of the circulating TBA/water mixture.
ture contains from 40 to 90% by weight of tertiary This mixture is continuously introduced into the reac
butanol at the reactor inlet. tor.
The particular, especially advantageous space veloc
BRIEF DESCRIPTION OF THE DRAWINGS ity (LHSV) depends on the water content of the mix
The drawings appended hereto are flow sheets show ture of reaction and to a high degree on the temperature
1ng: of reaction and the activity of the catalyst used, and
In FIG. 1 a preferred implementation of the process must be determined individually for each catalyst.
of the present invention; and The liquid hour space velocity in liters of input per
FIG. 2 shows another embodiment of the present 45 liter of swelled catalyst per hour at a temperature of
invention which is especially economical. reaction between 80 and 100° C. as a rule is between 50
DESCRIPTION OF THE PREFERRED and 100 liters/liter-hour, between 100 and 130 C. it is
100 to 300 liters/liter-hour and between 130' and 150
EMBODIMENTS C. it is up to 600 liters/liter-hour.
Suitable input materials are both industrial TBA con 50 However, less advantageous space velocities are also
taminated with isobutene oligomers, for instance selectable. Control Example 1 of the present invention
diisobutene, and pure TBA. Preferably TBA-water shows the lesser space-time-yield and the clearly de
mixtures are used such as the TBA-water azeotropes graded selectivity for a two-phase, liquid reaction mix
that are obtained in reprocessing by distillation. ture. Control Example 2 shows the increasingly de
Surprisingly the process of the present invention 55 graded isobutene selectivity for a TBA concentration
offers high-purity isobutene with a very high space exceeding 90% by weight in the reaction mixture. Con
time-yield and with an isobutene selectivity of practi trol Examples 3 and 4 show especially the lesser space
cally 100 mole-% provided the splitting or the back time-yield and the poorer selectivity for gaseous-liquid
splitting of TBA into isobutene and water is carried out reaction mixtures from which the isobutene is with
with a strongly acidic organic ion exchanger mounted drawn in gaseous form.
in a fixed bed and that it be performed in a homogene Sulfonated organic resins such as disclosed in U.S.
ous and liquid phase and that the homogeneous liquid Pat. No. 2,480,940, and in particular those sulfonated
discharge of reaction be fed to a distillation section divinylbenzene-cross-linked polystyrene resins dis
where the isobutene and the water are separated from closed in U.S. Pat. No. 2,922,822-which may be gel
the unconverted TBA which is returned as an aqueous 65 like in nature, or which may evince a sponge structure
TBA solution to the dehydration stage. This was unex with macropores as disclosed in British Pat. No. 957,000
pected because West German Published Patent Appli to enlarge the surface, or increase the hydrolysis stabil
cation No. 2,913,976 discloses on page 20, lines 27 ity of their catalytically effective sulfonic acid groups
 5
4,423,271
6
may comprise a halogenated synthetic resin structure as the form of the water azeotrope. The entrained water
disclosed in U.S. Pat. No. 3,256,250 which are suitable separates as a separate phase in the receiver. The TBA
as organic ion exchangers. The commercial organic ion is azeotropically distilled from the draining water in the
exchangers are preferred in hydrogen form. However, separation part of the column, whereby the water rid
commercial, macroporous cation exchangers modified from TBA and isobutene is removed at the sump of the
by partial ion exchange or by thermal desulfonation column K1 through the line 5. A TBA/water mixture
may evince satisfactory activity with simultaneous enriched with TBA is tapped from an intermediate tray
higher hydrolysis stability of the sulfonic acid groups. above the separation part as a side flow through line 4
The pure production of isobutene and the removal of and is mixed as a circulating flow with the fresh flow of
the water takes place in a processing section separate 10 the educt (line 1), whereupon it is made to pass prefera
from the reaction chamber. FIG. 1 shows a preferred bly from top to bottom through line 2 through the reac
implementation of the process of the invention wherein tor. If the reaction mixture contains isobutene oligo
the homogeneous liquid reaction mixture leaving the mers, these can be evacuated by a side tap at the con
reactor is fed through line 5 to a pressurized column centrating part of column K1 through the line 7.
(K1) to produce pure isobutene. 15 This preferred embodiment of FIG. 2 of the process
The head pressure of column K1 as a rule is 3 to 10 is especially economical because the condensation of
bars, preferably 5 to 7 bars, because this range permits the TBA/water azeotrope is eliminated in the separa
especially economical distillation when the distillate is tion of the water in a condenser of its own, for instance
condensed with a coolant. when using column K2, and in lieu thereof the heat of
The isobutene is distilled off through the head with 20 condensation serves to interrupt the energy-consuming
traces of water corresponding to the water/isobutene reaction circulation.
azeotrope as shown by line 6 of the Figures. The water The above described process permits producing in a
deposits in the receiver as a separate phase and can be simple manner high-purity isobutene from TBA with an
removed in problem-free manner. The mixture of TBA isobutene selectivity in excess of 99.9 mole-%. The
and water accumulating at the bottom as a rule contains 25 reaction rate of TBA amounts to practically 100%.
less than 0.5% by weight of isobutene and the main Because the reaction is carried out under mold condi
amount is returned through line 2 ahead of the reactor. tions at a catalytic fixed bed, even commercial organic
The sump temperature can be so selected from the reac cation exchangers offer industrially satisfactory catalyst
tor input temperature that on one hand distillation can lives. The reaction can be performed with continuous
be carried out economically and on the other hand the 30 or batch-wise inputs of fresh TBA into the reaction
temperatures required to maintain catalyst stability are circuit. Preferably the operation will be continuous.
not exceeded. Obviously lesser or higher pressures also The purity of the isobutene so produced is in excess of
may be applied in this distillation stage, even though 99.9%. As a rule values up to 99.99% are achieved. The
they are less appropriate economically. residue is water. The high-purity isobutene of the inven
To separate the water produced in equivalent 35 tion so obtained is preferably used in preparing
amounts with respect to the isobutene and any water polyisobutene, butyl rubber and in alkylation.
entrained in the fresh TBA, a partial flow of the sump The following examples elucidate the process,
product is fed through line 7 to column K2 where the though they are not to be construed to limit it in any
isobutene dimers contained in the input mixture or pos name,
sibly produced during the reaction in trace amounts are EXAMPLE 1.
distilled off through the head by line 8 as a ternary
mixture with TBA and water. The sump product is fed The catalyst used is a commercial, strongly acidic ion
through line 9 to column K2 from where a TBA/water exchange resin (a macroporous, sulfonated divinylben
mixture of azeotropic composition is removed as the zene-cross-linked polystyrene resin). Further resin char
head product and is fed back through line 3 to a position 45 acteristics are: BET surface of about 40 m2/g of dry
ahead of the reactor. The excess water in the sump of resin, divinylbenzene content about 18%, grain size
column K2 is evacuated through line 10. Columns K2 distribution between 0.5 and 1.3 mm, hydrogen ion
and K2 are operated at normal or higher pressures. capacity about 3.8 mval H/g of dry resin.
The ternary mixture from the head of K2" is appropri As shown in FIG. 1,711 kg/h of fresh educt contain
ately decomposed with water and the aqueous phase 50 ing 623 kg/h of TBA, 85 kg/h of water and 2.84 kg/h
containing TBA is returned to the column. If there are C8 olefins are passed through line (1) into the reactor R
no isobutene dimers in the reaction mixture, column K2 filled with 78 liters of the above-described cation ex
is eliminated. change resin, and into this reactor are fed through line
When a TBA/water azeotrope is used (about 88% by (2) 10,455 kg/h of circulation mixture returned from the
weight of TBA is normal pressure) as the fresh input 55 sump of column K1 and containing 6,480 kg/h of TBA,
mixture (line 1), the ratio of the circulating flow of the 3,938 kg/h of water and 36.9 kg/h of C8 olefins, and
sump of column K1 to the flow from the head of col through line (3), 565 kg/h of circulation mixture from
umn
30:
K2 is preferably 2:1 to 130:1, in particular 5:1 to the head of the column K2, containing 497 kg/h of TBA
and 68 kg/h of water, and a total through line (4) of
The TBA/water mixture preferably is made to pass 60 11,731 kg/h of input mixture containing 64.7% by
from top to bottom through the catalytic fixed bed of weight of TBA.
reactor R. The splitting reaction is carried out at 10 bars and at
Another embodiment of the process of the present an average temperature of 120° C.
invention, which is especially economical, is repro The reaction mixture is made to pass through the line
duced in FIG. 2 for elucidation. 65 5 into the column K1 and is expanded prior to entry to
In FIG. 2, the homogeneous liquid reaction discharge the 6 bar column pressure (-ahead pressure). 470 kg/h
is fed through line 3 into the pressurized column K1 of pure isobutene are evacuated from column K1
where the pure isobutene is distilled through the head in through its head (line 6). The distillate contains water
 4,423, 271 8
7
corresponding to the azeotrope which settles as a sepa the head product receiver and part of the water evacu
rate phase in the receiver and is evacuated. ated from the sump, the TBA/water/Cs olefin mixture
The composition of the sump product of column K1 is decomposed and the aqueous phase containing TBA
is 6,980 kg/h of TBA, 4,242 kg/h of water and 39.75 is fed back. The circulating flow is tapped offsideways
kg/h of C8 olefins. The main amount is returned from the separation part of column K1 through the line
through the line (2). A partial flow of 806 kg/h is fed 4 and is fed back to ahead of the reactor. The isobutene
through the line (7) following expansion to the column selectivity is 99.98%, the reaction rate for TBA is prac
pressure of 1.2 bars (a head pressure) to the column tically 100% and the isobutene purity is 99.99%.
K2'. 2.85 kg/h of Cs olefins together with 2.2 kg/h of EXAMPLES 3 THROUGH 8
TBA and 0.65 kg/h of water are removed from the 10
column K2' through its head (line 8) as a ternary mix TBA is dehydrated in a series of further examples by
ture. The sump product is fed through line (9) to the the procedure of Example 1 (see FIG. 1). The commer
column K2 where the azeotropic TBA/water mixture is cial, macroporous, strongly acidic ion exchange resin
evacuated through the head (head pressure is 1.02 bars) (sulfonated, divinylbenzene-cross-linked polystyrene
and is returned through the line (3). The ratio of the 15 resin) used as catalyst has the following characteristics:
circulating flow of column K1 to the flow of column K2 BET surface is about 35 m2/g of dry resin, divinylben
is 18.5:1. 235 kg/h of water accumulate in the sump of zene content is 10%, grain size distribution is between
the column K2 and are evacuated through the line (10). 0.5 and 1.2 mm, the hydrogen ion capacity is about 4.5
The isobutene selectivity practically is 100%. When mval HMg of dry resin. 100 ml of this resin are made to
decomposing the C8/TBA/water mixture from the 20 swell in a TBA/water azeotrope (about 12% by weight
head of column K2' with water and returning the aque of water) and filled into the lower quarter of a tubular
ous phase containing TBA, the reaction rate of TBA reactor 100 cm long (inside diameter=2.29 cm) which
also practically is 100%. The purity of the isobutene is is provided with a heating jacket. The residual volume
99.99%. is filled with V4A packings and acts as the preheating
EXAMPLE 2 25
Zone. A thermocouple is arranged in centrally displace
able manner within the reactor. Viewing windows to
The catalyst used is a commercial, strongly acidic ion monitor the homogeneity of the liquid mixture was
exchange resin (macroporous, sulfonated divinylben provided ahead and behind the reactor. The volume of
zene-cross-linked polystyrene resin) with the following the column sump of columns K1, K2" and K2 is kept
characteristics: BET surface is about 2.5 m2/g of dry 30 constant by an automatic level control. A fresh azeo
resin, the divinylbenzene content is about 8%, the grain tropic mixture of TBA and water that is free of isobu
size distribution is between 0.5 and 1.2 mm, the hydro tene oligomers is supplied through the line 1. Table 1
gen ion capacity is about 4.1 mval H/g of dry resin. below lists the conditions applied and the results ob
According to the flow sheet of FIG. 2, the TBA tained. The space velocity (LHSV) is listed in liters of
splitting is carried out at an average temperature of 120 35 supply per liter of swollen catalyst per hour, the isobu
C. and a pressure of 20 bars as described below. tene space-time-yield is indicated in kg of isobutene per
A reactor R is filled with 42 liters of the above de liter of swollen catalyst per hour. The analysis of mass
scribed catalyst and receives the flow (2) containing flows is performed by gas chromatography. Except for
4,161 kg/h of TBA, 1,040 kg/h of water and 3.4 kg/h of Example 5, column K2 is superfluous. The isobutene
C8 olefins. The flow (2) contains 80% by weight of 40 obtained is 99.99% pure.
TBA and is composed of the fresh input (line 1) of 675 Table 1 follows.
TABLE 1.
flow 4 Space
Fresh TBA 7% by time Isobutene
Tempera- azeotrope LHSV Ratio of mass flows % by weight yield selectivity
Example ture C. kg/h A1. h. 1: 2: 3 weight H2O kg/1.h Mole-2
3 10 0.39 54 1 9.3 1. 70 30 2.6 100
4. 110 0.69 40 1 15.5 1.1 70 30 4.6 100
5 120 0.44 45 1. 6.5 0.9 70 30 2.9 99.9
6 120 1.02 139 8.2 1.3 70 30 6.8 00
7 120 0.48 80 l 12.6 0.6 60 40 3.2 00
8 120 O 206 1 16.0 0.6 60 40 6.5 00

kg/h of TBA, 92 kg/h of water and 2.8 kg/h C8 olefins

and of circulating flow returned from the pressurized
column K1 throughg the line 4 and containingg 3,486
3,480 kg/h
kg 55 EXAMPLE 9
of TBA, 948 kg/h of water and 0.6 kg/h of C8 olefins.
The circulating flow returned through the line 4 con The commercial cation exchange resin of Example 1
tains 78.6% by weight of TBA. The reactor discharge is is used as the catalyst. A steel tubular reactor 80 cm
fed through line 3 into the column K1 and is expanded long and 2.29 cm in inside diameter, provided with a
to the column pressure of 7 bars (ahead pressure). 510 60 casing acting as a thermostat provided with two zones
kg/h of pure isobutene are distilled off in column K1 which can be raised to different temperatures is filled
through the head (line 6). The distillate contains water with 20 ml of TBA/water azeotrope swollen exchange
according to the azeotrope, which is removed as a sepa resin. The resin is located in the lower third of the reac
rate phase in the receiver. 256 kg/h of water arrive in tor. The residual reactor volume is filled with V4A
the sump and are evacuated through line 5. 2.9 kg/h of 65 packings and acts as the preheating zone. A displaceable
Cs olefins together with 2.5 kg/h of TBA and 0.7 kg/h thermocouple is arranged centrally in the reactor. A
of water are evacuated from the concentrating part of viewing window arranged ahead and behind the reactor
the column K1 through a side tap. Using the water from permits monitoring the homogeneity of the liquid mix
 4,423,271
9. 10
ture. The TBA splitting is carried out in a series of tests tene time-space-yield is 1.1 kg/liter-hour, the isobutene
in nearly isothermal manner (the temperature differen- selectivity is 97.8 mole-%.
tial in the catalytic bed is no more than 2 C.) following
the procedure of Example 2, however, at a pressure of CONTROL EXAMPLE 2
11 bars, the temperature and the TBA concentration 5 In accordance with the procedure described in Ex
being varied in the mass flow 2. The fresh TBA is intro- ample 9,-FIG. 2-a TBA/water mixture with 95% by
duced through line 1 as pure (99%) TBA free from weight of TBA and 5% by weight of water is made to
isobutene oligomers. The TBA concentration in the pass in line 2, through the reactor at 150 C., a space
sideways tap of the output section of the column (line 4) velocity of 120 l/1.h and a pressure of reaction of 15
is about 58% by weight for 60% by weight of TBA in 10 bars. The reaction discharge is homogeneous and liquid.
the flow 2, about 68% by weight for 70% by weight of The isobutene time-space-yield is 21.6 kg/h the isobu
TBA, about 78% by weight for 80% by weight of TBA, tene selectivity is 98.6 mole-%.
about 85% by weight for 90% by weight of TBA. The
mass flows are analyzed by gas chromatography. Table CONTROL EXAMPLES 3 AND 4
2 lists the conditions applied and the results obtained. 15 The procedure of Example 2 is followed, except for
The definition in Examples 3 through 8 applies to the the modifications below: 100 ml of cation exchange
space velocity (LHSV) and the time-space-yield. resin from Example 1, swollen in a TBA/water azeo
Table 2 follows. trope, are in loose bulk in an 80 cm long glass reactor
TABLE 2
Isobutene space-time yield Isobutene selectivity
Space (kg/1 h) for TBA 9% by weight (Mole-%) for TBA% by
Temperature velocity in flow 2. weight in flow 2
°C. A. h. 90 80 TO 60 90 80 70 60
90 120 2.0 1.4 1.0 100 100 100
00 2O 4.1 3.0 2.2 100 100 100
116 120 7.3 6.0 4.8 100 100 100
120 120 15.1 2.0 9.8 99.9 100 00
130 300 22.6 19.2 15.3 99.9 99.9 100
140 300 40.5 99.8
Isobutene purity is 99.99%

(4.5 cm inside diameter) with a displaceable thermo

couple at the center and with a heating jacket. The
EXAMPLE 10 pressure of reaction is selected in such a manner that the
A macroporous ion exchange resin with the charac- 35 reaction mixture will boil at the particular reaction
teristics stated in Example 1 is so deactivated using 1 temperature. The fresh TBA/water mixture free of
mmole/g of dry resin Na ions that a residual hydrogen isobutene oligomers and azeotropic in nature is admixed
ion capacity of 2.8 mval H+/g of dry resin remains. with the circulating TBA/water mixtures and made to
30 ml of resin swollen in a TBA/water azeotrope are pass through the reactor from bottom to top. The turbu
filled into the reactor described in Example 9. The de- 40 lence caused thereby and by the evaporation of the
hydration is carried out by the procedure described in formed isobutene keeps the catalyst dispersed. The
Example 9. The conditions and the results obtained are formed isobutene is continuously removed in gaseous
listed in Table 3. form through a bubble tray column (10 trays) located at
TABLE 3 the reactor head. The liquid phase of reaction is evacu
45 ated at the upper reactor end from the reactor volume
timespyrag/l h) (1.2 liters) through a filter cartridge and is treated simi
LHSV at TBA. 26 by weight in flow 2 larly to the procedure described in Example 2. Table 4
Temperature A. h. 90 70 60 shows the conditions applied and the results obtained.
- -- The space velocity and the time-space-yield always
110 120 5.2 4.1 50 refer to the swollen catalyst volume. The mass flows
120 130 10.5 9.2 were analyzed by gas chromatography.
40 300 28.3 TABLE 4
% by weight
CONTROL EXAMPLE 1 5s fi
tfrol Tem- Reac-
tion inisobutene
the flow space
This example shows the activity and the selectivity of Ex- pera- pres- ahead of the time selec
the catalyst resin in a two-phase liquid reaction mixture. a tire sure Hsy reactor yield tivity
The catalyst and the test procedure correspond to the Ple bar Ash PA 29 K9/h - Mole
data in Examples 3 through 8. For an average reaction 3 80 105 90 80 20 0.32 99.7
temperature of 130 C., a reaction pressure of 15 bars 60 - B -- B-B-B-B-
and a space velocity of 120 liters/liter-hour, 0.16 kg/h
of fresh azeotrope are made to pass in the line 1, to- What we claim is:
gether with the circulating flows from lines 2 and 3, 1. A process for producing high-purity isobutene by
through the reactor from top to bottom. The ratio of the dehydrating tertiary butanol in the presence of an acid
mass flows from lines 1, 2 and 3 is 1:64.5:0.12. The 65 catalyst, comprising:
TBA/water mixture at the reactor intake contains 25% (a) continuously feeding an aqueous solution contain
by weight of TBA and 75% by weight of water. The ing from about 40 to 90 percent by weight of ter
reactor discharge is two-phase and liquid. The isobu- tiary butanol into a reactor and dehydrating in a
 4,423,271 12
11
homogeneous and liquid phase at a fixed catalyst 3. The process of claim 1, wherein the tertiary buta
bed consisting of a strongly acidic ion exchange nol of step (a) is dehydrated at a temperature from about
resin at a temperature from about 80 to 150° C. 100' to 30° C.
and a pressure of about 5 to 25 bars; 4. The process of claim 3, wherein the entire mixture
(b) fractionating the homogeneous, liquid reaction of tertiary butanol and water at the reactor intake of
mixture in a distillation part separate from the reac step (a) contains from 55 to 85% by weight of tertiary
tion chamber and separating isobutene from the butanol.
water and from the unreacted tertiary butanol; and 5. The process of claim 2, wherein said isobutene of
(c) concentrating the unreacted tertiary butanol by step (b) is separated from the water/tertiary butanol
distillation and feeding back a first portion of the 10 mixture through the head of a distillation column, step
mixture of water and unreacted tertiary butanol (c) is executed from an intermediate tray below the feed
from step (b) to step (a), and discharging a second flange of said column, said first portion of the mixture of
portion of said mixture at a rate sufficient to re water and the unreacted tertiary butanol being fed back
move exceSS Water. to step (a) and said second portion of this mixture con
2. The process of claim 1, wherein said second por 15 taining excess water flowing down to a separation sec
tion of said mixture of water and unreacted tertiary tion of the same column located between the bottom,
butanol discharged by step (c) is distilled to concentrate where the excess water is discharged, and said interme
the unreacted tertiary butanol, and said concentrated diate tray, to which the unreacted tertiary butanol is
unreacted tertiary butanol is recycled to step (a), and distilled azeotropically for recycle to step (a).
:k k k k :
excess water is discharged as a bottom product. 20

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