Documenti di Didattica
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27, 1931
rivatives can easily be separated from those tion, there is recovered 1.1 gallons of hydro
of the amylenes by fractional distillation. carbons boiling up to 60 ? which are now
Addition of sulphuric acid of a concent treated with 77%, HSO in two portions,
stration of 77% more or less to this refined each of .55 gallons or 7.65 lbs. In this stage 9.
amylene causes absorption with concurrent the temperature is allowed to rise to 35° C.
formation of the corresponding intermedi and maintained at under 40° C. preferably,
ates of the alcohols from which the corre and agitation is continued over a total pe
sponding alcohols may be recovered by di riod of six hours. The mixture is then al
30 lution and distillation. lowed to settle and the lower or acid layer 95
To further illustrate the advantage of is drawn off, diluted with water to bring the
this invention we have treated the rich gas concentration of acid below 20%, and then
from vapor phase cracking as described, distilled until practically all of the alcohol
without first removing the amylene fraction, is carried over. The distillate consists of two
with 95% acid. The result was an evolu layers, a lower or water layer and an upper
tion of excessive heat, rendering control dif.
ficult, if not impossible, and the recovery or alcohol layer. From the 26 gallons of
amylene fraction at the start of this process
of small amounts only of secondary al ing, there is recovered under the above spe
cohols, and no tertiary alcohols. There cific conditions.56 gallons of crude secondary
were also formed large quantities of alcohols. 05
heavy tar-like polymers. By first removing . Secondary and tertiary butyl alcohols are
the olefines higher than propylene we have successfully recovered from the butylene
successfully used fuming sulphuric acid as fraction by first scrubbing with 65% more
an absorbent for the remainder, obtained or less sulphuric acid, and then with 77%
5 an alcohol yield of 40% of the weight of more or less sulphuric acid, as above de O
acid used, and minimized the polymer for scribed.
mation to under 50% of the alcohol pro- i Eavample II
duced.
For specific examples of treatment of the Concurrently with the production of 2.6
amylene fraction 3, (b) We have obtained gallons of amylene fraction there is recov
the following results:
5
ered 102 cu. ft. of butylene fraction as set
Eacample I forth in the example above of a typical vapor
From the processing of 32° Bé. gas oil fractioncracking
phase ???????????” As stated, this
can be absorbed under pressure or
under the conditions mentioned for example cooling or both in the amylene fraction;
above, there is obtained 2.6 gallons of amy by
or it can be treated separately to produce
lene fraction (condensables recovered by tertiary and secondary butyl alcohols. The
fractionation to 60° C.) per barrel passed. following is an example of separate treat
The preferred treatment of this fraction ment : -
c and its results are as follows: The butylene fraction, is first scrubbed or
To the 2.6 gallons of amylene fraction we treated with a relatively dilute sulphuric
first add 12.2 lbs. of sulphuric acid (65%) acid, followed by more concentrated acid.
under conditions of horough agitation keep We have obtained satisfactory results by
ing the mixture preferably below 20° C., and using in the first absorption stage 65% acid
s continue this treatment over a period of 6 and in the second 77% acid. The amount of 3)
1,790,528 9
acid required depends upon the physical effi
ciency of the absorption apparatus employed moving tertiary olefines from said fraction,
in large measure; using even comparatively fines contained sulphating
and thereafter
in said
the secondary ole
fraction by admixing
inefficient apparatus, an acid efficiency can said fraction with aqueous sulphuric acid
be realized wherein three pounds of acid (cal while maintaining an acid concentration and 70
culated as 93%) produces one pound of alco a temperature at which sulphation of said
hol. From the treatment of 100 cu. ft. of secondary olefines takes place.
the butylene fraction herein described, we 2. Process according to claim 1, in which
have produced .28 gallons of tertiary and 46 the selective removal of tertiary olefines from
O gallons of secondary alcohols.
During the absorption of the butylene in said fraction is accomplished by admixing
said fraction with aqueous sulphuric acid of
the treatment for tertiary alcohol with the from 60 to 65%, HSO, content, while main
particular reagents mentioned above we taining a temperature below that at which
prefer to keep the temperature below 20°C., substantial amounts of said secondary ole
15 and during the secondary stage at about 35 fines are sulphated. 80
C. As in the case of the tertiary amyl 3. Process according to claim 1, in which
alcohol, it is necessary to distill the tertiary
butyl alcohol from a neutral or slightly alka the selective removal of tertiary olefines from
said fraction is accomplished by admixing
line solution to secure the highest yields, said fraction with aqueous sulphuric acid of
though tertiary butyl is not subject to de from 60 tonot65%, HSO,20°content, at tem 85
composition in acid distillation in the same peratures exceeding C.
degree as tertiary amyl alcohol. 4. In the process of generating secondary
Wherever in this specification particular amyl alcohol from a mixture of hydrocarbons
concentrations of acid reagent substances produced by cracking petroleum oil and con
2 5 adapted to olefine absorption are alluded to, taining not less than 30% of olefines, the 90
it will be understood according to the com steps of separating from said mixture by
mon knowledge of the numerous chemists distillation a fraction, the olefine content
familiar with the behavior of acids toward of which consists predominantly of second
olefines for nearly a century, that the acid ary and tertiary olefines of 5 carbon atoms
30 concentration is relative to the respectively to the molecule, selectively removing tertiary 95
mentioned or to normal temperatures, and olefines from said fraction, and thereafter
that at different temperatures another con sulphating the secondary olefines contained
centration of acid is equivalent, within those in said fraction by admixing said fraction
limits at which the action of the acid reagent with aqueous sulphuric acid while maintain
35 ceases to become an absorption, and enters ing an acid concentration and a temperature 00
upon the destructive formation of the com at which sulphation of said secondary olefines
pounds herein alluded to as polymers. takes place.
For the operations of fractional treatment 5. Process according to claim 4, in which
with HSO, e.g. of the amylene fraction (b), the selective removal of tertiary olefines from
40 we recommend the use of apparatus com said fraction is accomplished by admixing 105
prising a chamber adapted to be heated or said fraction with aqueous sulphuric acid of
cooled, and equipped for mechanical agita from 60 to 65%, HSO, content, while main
tion of its contents; adapted for the slow taining a temperature below that at which
feed of acid of the appropriate concentra substantial amounts of said secondary olefines
tion; suitable settling vessels for decanting are sulphated.
off the unchanged residue of the materials of 6. Process according to claim 4, in which 110
lesser reactivity; and appropriate vessels for the selective removal of tertiary olefines from
acid reaction upon the decanted residue. said fraction is accomplished by admixing
IDistillation of the olefine-acid liquors may said fraction with aqueous sulphuric acid of
proceed in appropriate steam stills. In es from 60 to 65%, HSO, content, at tempera 5
sentials, the units of apparatus required are tures not exceeding 20°C.
familiar in the practice of the chemical in HAROLDS. DAVIS.
dustries, and one of the advantages of this WALLACE J. MURRAY.
invention resides in the relatively simple
nature of the instruments and operations re 120
quired.
We claim:
1. In the process of generating secondary
amyl alcohol from a mixture of hyrocarbons
produced by cracking petroleum oil and con 125
taining olefines, the steps of separating from
said mixture by distillation a fraction, the
olefine content of which consists predomina
tion of secondary and tertiary olefines of 5
carbon atoms to the molecule, selectively re 30