Dec. 30, 1947. C. C.

WATSON 2,433,800
W PRODUCTION OF BUTADIENE
Filed Oct. 29, 1943
16%22zzézze 2-asa Z2-e-

22 esta 2.222 a
222 22e

Jeae.762a1a2z
azzare

as

aza 2%a

17za/2222r.
62%27%2s 6. 02/2asete
222 aet.
Patented Dec. 30, 1947 2433,800

UNITED STATES PATENT OFFICE

2433,800
PRODUCTION OF BUTAOENE
Charles C. Watson, Chicago, Ill., assignor to Uni
versal Oil Products Company, Chicago, I, a
corporation of Delaware
Application October 29, 1943, Seria No. 508,107
5 Claims. (C. 260-680)
2
This invention relates to the catalytic dehy quantities of butadiene and butylene in the first
drogenation of hydrocarbons and is more specif stage, and the butylenes separated from the re
cally concerned with the dehydrogenation of nor action products of the first stage are further con
mal butane to form butadiene. verted to butadene in the Second dehydrogena
Butadiene is extensively employed as the start tion operation. The extent of the improvement
ing material in many organic syntheses and is obtained by the operation of this invention is
of considerable value in the production of high clearly shown in the examples included herein
molecular weight polymers having physical char. after in this specification.
acteristics similar to natural rubber. In one broad embodiment, the present inven
The amount of butadiene used in organic Syn O tion comprises a process for producing butadiene
theses has been limited to a great extent by the which consists of subjecting normal butane to
non-availability of a cheap method for producing. contact with a dehydrogenation catalyst under
it from relatively cheap raw materials. The most conditions such that a substantial quantity of
common method formerly used consisted of start butadiene and butylene, is obtained, separating
ing with acetylene and carrying out various s the butylene from the reaction products and fur
chemical reactions until butylene glycol was ob ther converting the separated butylene substan
tained which was subsequently dehydrated to tially free of other C4 hydrocarbons to an addi
butadiene. More recently butadiene has been tional quantity of butadiene by contact with a
obtained in commercial quantities in an operation dehydrogenation catalyst under dehydrogenation
which is economically feasible by the catalytic conditions. s
dehydrogenation of normal butane. In effect, the present invention consists of
The dehydrogenation of normal butane to buta three units which are cooperatively interrelated
dene involves the following two reactions: to one another, . These units are a first stage de
hydrogenation unit which produces butadiene and
25 butylene from normal butane, a second dehy
drogenation unit wherein the butylene formed in
in view of the equations given above, it would the first stage is dehydrogenated to butadiene
be expected that most efficient operation for the and a separation unit wherein the reaction prod
production of butadiene from butane would be a ucts from both the first and Second dehydrogena
two-stage operation in which butane was first 30 tion units are processed to separate the desired
converted to butylene and the butylene subse butadiene, the normal butane to be recycled to
quently converted to butadiene in a separate re the first dehydrogenation unit, the butylene to be
action zone. The prior art best exemplified by charged to the Second dehydrogenation unit and
Patent #2,209,215 is primarily concerned with this the by-products such as isobutane and lower no
type of operation. lecular weight hydrocarbons such as methane,
It is an object of the present invention to pro 35 ethylene, ethane, propylene and propane, which
vide an improved process for the production of are renoved from the System.
butadiene from butane in which the yield of buta I have also found that the cost of separating
diene and the degree of efficiency of the reaction the butadiene per unit of weight is dependent
that is obtained is decidedly superior to those to primarily on the quantity of butadiene being in
obtained by the processes of the prior art... troduced into the separation unit. Increasing the
It is another object of the invention to provide concentration of butadiene entering said unit pro
a process which has increased flexibility and duces a pronounced decrease in the separation
which can process satisfactorily any type of bu
tane-butylene charging stock.
cost. The operation of the present invention takes
45 ful advantage of this decrease, in separation
I have discovered that contrary to expectations, costs since both dehydrogenation steps are pro
a more efficient operation which produces more ducing substantial quantities of butadiene.
butadiene per unit of butane charged may be ob The catalysts which may be employed in the
tained by employing a two-stage operation in dehydrogenation operations may comprise any
which normal butane is converted to substantial 50 of the well known dehydrogenation catalysts such
 2,488,800
3 4.
as chronium oxide, molybdenum oxide or vanan such as magnesia, iron oxide, copper oxide and
dium oxide supported by alumina in either the potassium oxide or alumina, boria and potassium
powdered, granular or shaped forms such as oxide heretofore mentioned are employed, super
pellets or spheres. It is usually desirable when heated steam is introduced into the reaction zone
employing these catalysts to incorporate a small to give a total pressure of about 3 to 50 pounds
amount of magnesia or zinc oxide in the com per square inch gauge while maintaining the
posite to improve the thermal stability of these partial pressure of the normal butylene at about
catalysts. The same catalysts may be used in 0.05 to about 0.5 atmospheres absolute. The ten
each stage or different catalysts may be em perature utilized in dehydrogenation zone B is
ployed in each stage. Catalysts comprising a O dependent somewhat upon the catalyst but is
composite of a major proportion of alumina and Ordinarily within the range of about 1050 to 1250°
minor proportions of barium oxide and potassium F. at a space velocity measured as volumes of gas
oxide or a composite of a major proportion of per volume of catalyst per hour of about 200 to
magnesia and minor proportions of iron oxide, about 2000. The yield of butadiene per pass is
copper oxide and potassium oxide are particu 5 maintained within the range of about 15 to 30
larly effective for the conversion of butylene to per cent based on the butylenes charged.
butadiene, especially if superheated steam is in During the dehydrogenation reaction in zones
troduced along with the charge to effect a lower 2 and B, some isomerization occurs producing iso
ing of the partial pressure of the butylene in the CA hydrocarbons. Since butadiene cannot be
reaction zone. 20 produced from the iso C4 hydrocarbons because
The invention is explained in more detail in of their molecular structure, it is advantageous
connection with the description of the accom to remove these isomers from the system to pre
panying drawing which illustrates in a conven vent their build-up in the streams being charged
tional diagrammatic flow chart one method of to the dehydrogenation catalyst. These isomeric
conducting the operation. t 92 by-products are removed from the separatioh
Referring to the drawing, normal butane fresh zone through line 8 and are cooled and condensed
feed along with the recycled normal butane ob and recovered as a product of the reaction. The
tained as hereinafter set forth is introduced reaction products from dehydrogenation Zone 6
through line f into dehydrogenation zone 2 are directed through line into separation zone
wherein it is contacted with a dehydrogenation 4 wherein the desired C4 fractions are removed
catalyst comprising alumina and chronia at a therefron.
temperature within the range of about 1050 to In case the original charging Stock contains C.
about 1250 F. under an absolute pressure of .05 olefins in any substantial quantity, this charge
to about 0.5 atmospheres. The charge rate may be introduced to line if into line 3 through
through the reaction 20ne will be dependent to which it is directed into the separation zone and
a certain extent upon the temperature and pres the necessary separation of olefins and paraffins
sure chosen but will ordinarily be within the effected, or alternatively, although not shown in
range of space velocities of about 200 to about the drawing, the charging stock may be intro
1000 volumes of gas per volume of catalyst per duced directly into the separation Zone. The re
hour. The actual conditions are selected from 40 action in either dehydrogenation zone may be
these ranges to produce a yield of butadiene of conducted in either the fluid, fixed or moving bed
about 10 to 30 volume per cent of the butane type of operation. When employing a fixed bed
charged. The reaction products comprising un type of operation, the catalyst may be disposed
converted normal butane, butadiene and butyl in externally heated tubular elements connected
ene, hydrogen and a small portion of decomposi 45 in series or parallel. The external heat may be
tion products such as methane, ethane, ethylene, accomplished by indirect heat exchange by hot
propane and propylene leave dehydrogenation combustion gas or other heat-carrying media
zone 2 through line and are directed through such as molten salts, superheated steam, etc.
line 3 into separation zone 4 wherein the light During the dehydrogenation reaction, consid
gases, butadiene and butylenes are separated 50 erable amounts of carbonaceous materials are
from the unconverted normal butane. The un laid down upon the catalyst and after the cat
converted normal butane is recycled through line alyst has been used for some time, it is necessary
into line f as hereinbefore set forth. The bu to remove these carbonaceous deposits to restore
tadiene along with butadiene formed in dehy the catalyst activity. These carbonaceous ma
drogenation zone 6 as hereinafter set forth is 55 terials are ordinarily removed by introducing a
withdrawn from the separation zone through line heated stream of air or air diluted with com
9, cooled and collected in any manner well known bustion gases to burn off the carbonaceous de
to those skilled in the art, posit. Although the description of the drawing
Separation Zone 4 may comprise any of the well has been concerned With Only two dehydrogena
known means for separating C4 hydrocarbon 60 tion zones, it is, of course, obvious that for more
mixtures into the individual C4 hydrocarbons truly continuous operation, it is necessary to em
such as precise fractional distillation, solvent ex ploy at least two reactors for each dehydrogena
traction and azeotropic distillation with azeo tion operation. So that the catalyst in one reactor
trope-forming materials such as furfural, etc. may be regenerated by Oxidation while the other
The separated butylenes are directed from sepa 65 is being processed.
ration zone 4 through line 5 into a second de The following examples give comparative re
hydrogenation zone 6 wherein a substantial por Sults obtained when employing a two-stage oper
tion of the normal butylene is converted into ation wherein butane is partially converted to
butadiene. This dehydrogenation is accompa butylene in the first stage and the reaction prod
nied by the formation of a minor amount of nor 70 ucts from the first stage are charged to the sec
mal butane from normal butylene, Ond stage to produce butadiene and a process
The operating conditions employed in dehy in accordance with the present invention where
drogenation zone 6 are dependent to a consider in butane is converted to butadiene and butylene
able extent upon the type of catalyst being used in the first stage and the butylene thus formed
in said zone. In the case of composite catalysts 75 subsequently converted to butadiene in the sec

ond stage. It is obvious from a study of the data locity of from about 200 to about 1000, and the
given below that the process as practiced in ac
cordance with the present invention is consider
ably improved over that of the prior art as to
the actual yield of butadiene per pound of bu is about 0.05 atmospheres to about 0.5 atmospheres,
tane charged,
Tole
Example I,
Ordinary
Operation
Stage--------------------------------
Absolute Pressure, inn. Eig.--------- Atmos.
Catalyst Temp., F---------------. 1,100
Conversion, Mol per cent per pass... 34
E. Velocity ...-------...------. 250
age, Mol per cent:
'H----------------------------- 2.0
C4H10---------------------------- 98.0
Product,
Stage: C's Mols/100 Mol Feed to
CH----------------------------- 0.0
C4Hs---------- 33.0
C.H.O.--------------------------- 33.0
Overall Efficiency-----...--...--------------
Defined here as nols C4H--C4H10 decomposed per 100 mols 25
Cis-CH10 feed to each stage.
Defined as volunes of feed at standard pressure and temperature
conditions per volume of catalyst space per hour.
It is to be noted that the actual yield of buta
diene in the improved operation is about 18.8%
greater. The per cent increase in the yield is
about 41.8%.
I claim as my invention:
1. Thie process which comprises contacting
normal butane in a confined reaction zone with
an alumina-chromia dehydrogenation catalyst
and therein dehydrogenating only a portion of
said normal butane to normal butylene and bu
tadiene, the yield of butadiene being from about
10 to about 30 volume percent of the normal
butane charged, separating the normal butylene
from the butadiene and unconverted normal bu
tane, contacting the thus separated normal
butylene in admixture with superheated steam
with a dehydrogenation catalyst comprising a
composite of a major proportion of magnesia
and minor proportions of iron oxide, copper ox
ide, and potassium oxide, in a separate confined
reaction zone and therein dehydrogenating nor
mal butylene to butadiene, and recovering buta
diene formed in said zones.
2. A process which comprises introducing nor
mal butane into a first dehydrogenation zone and
therein catalytically dehydrogenating only a por
tion of said normal butane to normal butylene
and butadiene, the yield of butadiene being from 55 Number
about 10 to about 30 volume percent of the nor
mal butane charged, separating the normal bu
tylene from the resultant products, introducing
the thus separated normal butylene into a second
dehydrogenation zone and thern catalytically
dehydrogenating normal otylene to butadiene,
and recovering butadiene formed in said first
and second zones.
3. The process of claim 2 further character
ized in that the dehydrogenation in said first
reaction zhe is effected at a temperature of from
about 1050' F. to about 1250° F., an absolute
pressure of from about 0.05 atmospheres to about
05 atmospheres, and a gaseous hourly space ve
6
dehydrogenation in said second reaction zone is
effected at a temperature of from about 1050 F.
to about 1250 F., an absolute pressure of from
and a gaseous hourly space velocity of from about
200 to about 2000,
4. A process which comprises introducing nor
mal butane into a first dehydrogenation Zone and
Example II, O therein catalytically dehydrogenating only a por
Improved
Operation tion of said normal butane to normal butylene
and butadiene, the yield of butadiene being from
about 10 to about 30 volume percent of the nor
mal butane charged, introducing the resultant
5 reaction products comprising normal butylene,
butadiene, and unconverted normal butane into
a separation ZOne and therein Separating a bu
tadiene fraction, a normal butane fraction, and
a normal butylene fraction, introducing said nor
20 mal butylene fraction into a second dehydro
genation zone and therein catalytically dehydro
genating normal butylene to butadiene, introduc
ing reaction products from said second zone con
prising butadiene, a minor amount of normal bu
tane formed in the second dehydrogenation step,
and unconverted normal butylene into said sepa
ration Zone, recycling said normal butane frac
tion from said separation zone to said first de
hydrogenation zone, and recovering said buta
3) dene fraction.
5. A process which comprises introducing a
butane-butylene charging stock and reaction
products formed as hereinafter described into a
Separation Zone and therein separating a normal
butane fraction and a normal butylene fraction,
catalytically dehydrogenating said normal bu
tane fraction to normal butylene and butadiene
in a first dehydrogenation zone, the yield of bu
tadiene being from about 10 to about 30 volume
40 percent of the normal butane charged, catalyti
cally dehydrogenating said normal butylene frac
tion to butadiene in a second dehydrogenation
Zone, introducing the reaction products from said
first and second dehydrogenation zones into said
45 separation Zone, and recovering from said sepa
ration zone the butadiene formed in said dehy
drogenation 2Ones.
CHARLES C. WATSON,
REFERENCES CITED
50
The following references are of record in the
file of this patent:
UNITED STATES PATENTS
Name Date
2,209,215 Wiezevich et al. ----- July 23, 1940
2,265,641. Grosskinsky et al. ---- Dec. 9, 1941
2,271,670 Thomas ----------- Feb. 3, 1942
2,307,240 Ruthruff------------ Jan. 5, 1943
60 2,313,107 Chickinoff et al. --- Mar. 30, 1943
2,367,622 Schulze et al. ------- Jan. 16, 1945
2,172,534 Grosse ------------ Sept. 12, 1939
2,370,797 Kearby ------------- Mar. 6, 1945
2,386,355 Schulze et al. -------- Oct. 9, 1945
35 FOREIGN PATENTS
Number Country Date
Great Britain -------. July 5, 1939
508,764