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Патент USA US2109462

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March 1, 1938.-
R. E, BURK ET AL
_
MANUFACTURE OF ALQOHOLS FROM OLEFINES
2,109,462
Filed Jan. 25, 1936
2l
22'
Hydro/glp?!
jane
I
Patented Mar. 1, 1938
4 2,109,462
_ UNITED STATES
r
_
2,109,462
_
MANUFACTUBÈLÈFFINES
ALconoLs FaoM
Robert E. Burk and Herman P. Lankelma, Cleve
land, Ohio, assignors to The Standard Oil Com
pany, Cleveland, Ohio, a corporation of Ohio
Application January 23, 1936, Serial No. 60,484
12 Claims.
(ol, 26o-15s)
Although the production of alcohols by absorp
tion of oleñnes in sulphuric acid has been known
for sometime, the costs in such procedure have
remained higher than desired and have corre
_5 spondingly restricted the possibilities of produc
tion. This has been due to several factors, in
cluding low eiliciency in absorption, excessive
losses into undesired by-products, and undue cost ,
of concentrating the sulphuric acid> for reuse.
' 10- In accordance with the present invention how
ever, such difficulties may be obviated, and al
cohol products in remarkably advantageous man
ner _may be attained.
To the accomplishment of the foregoing and
15 related ends, the invention, then, comprises the
features hereinafter fully described, and particu
larly pointed out in the claims, the following de
scription and the annexed drawing‘ setting forth
in detail certain illustrative embodiments of the
20 invention, these being indicative however, of but
a few of the various ways in which the principle
of the invention may be employed.
'In said annexed drawingz-The sole figure is
a semi-diagrammatic elevational view of equip
25 ment in accordance with the invention.
Oleilnic gases from any suitable source are
passed into absorption zone A into intimate con
tact with sulphuri'c acid. While absorption may
be carried on in"‘A one absorbing zone, we prefer
30 to pass thev gas through successive absorption
zones, `each of which is adjusted to a condition
selectively effective upon respective oleiines in
succession. Thus, absorption zone A may be oper
ated on a basis to selectively absorb iso-butylene,
35 thence theîgïas is passed through connection 2
to absorption zone A' where operating conditions
are adjusted to selectively absorb propylene and
butylenes, and thence the gas remaining is passed
through a connection 3 to absorption zone A"
40 where conditions are adjusted to selectively ab
sorb the ethylene. Residual gas is vented
through connection 4 to any suitable point for
`other use or disposal. In these respective ab
sorption zones, the acid concentration in zone A
45 may be for instanceabove 60 per cent and the
temperature 60 to 250° F.; in zone A' the acidstrength may be above 80 per cent and the tem
perature 6_0 to 250° F.: and in zone A" the acid
strength may be above 90 per cent and the tem
50 perature 60 to 250° F. Preferably, after each of
the absorbing zones A, etc., polymerized gaseous
components are removed, as by passage through
a scrubbing zone S, S', the gas being flowed
counter-currently therein to scrubbing` liquid
i such as water. In the absorbing zones, the ole
.
fines -may be contacted with the acid in such
manner as >mav be desired, as for instance by a.
spray jet of acid with the feed of gas, but pref
erably we employ an intensified absorption ac
tion by mechanically subdividing and superagi
tating the acid and gas. iiogether, or by employ
ing centrifugal force to produce intimate vand
rapid contact, positive'mechanical agitators be
ing arranged in the absorption zone such `\as to
centrifugally hurl transverse currents of the
vacid through the gas rising through the column
of liquid, and the acid traveling in a general .
downward flow direction, centrifugal elements c
being driven by a suitable source of power, as
a motor m, and the centrifugal units being posi
tioned with respective semi-.partitioning 5 and
counter bailie 6, for further assisting in the in
tensive mixing. At the zone of quiescence at the
bottom of the absorption zone, the acid with ab
sorbed products may be drawn oil’ >to a .vacuum
polymer-stripping zone D, D', D" respectively.
In such zone, which may be in the form of a
plate fractionating column or baille tower, and
which is maintained under partial vacuum by
pump 8, any polymerized products which are ab 25
sorbed in the acid are drawn‘off and cooled in
the condenser coil 9 and caught in receiverl l0.
Desirably, an absorption-promoting catalyst is
present in the absorption zones A, A', A". For
this, we may employ silver sulphate, cuprous sul
phate, mercury sulphate, potassium ferrocyanide,
etc., the catalyst being in small amount; as 0.01
to 7.0 per cent.
'
To arrest reaction by the acid at the stage of
normal ester formation, instead of allowing it
-to go on to loss-occasioning excess, -we mix the
sumciently reacted constituents with a selective
.agent for immediately dissolving the esters out
of the acid.` Such selective solvent may be one
operating upon the acid esters or one operating
yupon the normal esters. Preferably, the latter,
and for this we employ decahydronaphthalene,
or a naphthenic solvent.
A prolific source of
by-product Waste and loss is thereby obviated,
since the desired esters formed are taken up by 45
_the selective solvent and shielded from further
direct action by the acid. The general mixture'
of acid and ester solvent, settling down into> the
separator zone T, T', T" respectively, separates
into layers of acid and solvent. The solvent and 50
esters carried thereby is drawn oiî from the top
layer by a pump l2, and forwarded to a hydro
lyzing zone H, H', H" respectively, each in asso
ciation with its partof the system operating for
butyl alcohols, isopropyl alcohol and ethyl alco 55
2,109,462
hol respectively. In the hydrolyzing zone, which
desirably is of an elongated or columnar form
and provided with extensive contact-surfacing', as
packing and the like, the solvent-borne ,esters
sure, separating acid in the presence of a selec
tive solvent for normal esters, and returning the
acid for absorption of more oleiines.
2. A process of making alcohols from oletlnes
are subjected to the action _of hydrolyzing water by absorption in sulphuric acid, which comprises
molecules at appropriate temperature, as hot passing the oleiines into absorption contact with
water at approximately'212° F. or exhaust steam. „ vsulphuric acid in the presence> of an absorption
Unlike prior practice involving dilution of esters promoting catalyst, mechanically super-contact
with many times their volume of water, the ing the iluids by centrifugally hurling transverse
10 present process employs a relatively very small currents of the acid through the oleflnes, stopping 10
amount of water. This is introduced at a mid reaction other than ester formation by the mix
point in a relatively small cross section elongated ture with a selective absorbent >taking up normal
hydrolyzing tower. The water molecules as thus esters, removing polymers under sub-atmospheric
introduced are, although in small amount, rela- ' pressure, hydrolyzing at substantially the same
tively concentrated at the point of introduction, temperature as the absorption by subjecting the y15
as related to the cross section of the column.
Thus, a small amount of water localized in its
application effects a thorough-going hydrolysis in
the oncoming stream of ester, and the acid which
20 is formed proceeds on down to the base oi’ the
ester in thepresence of a selective solvent for
normal esters to the action of a small amount
of water molecules at a temperature in the neigh-`
borhood of 212° F. in an elongated hydrolyzing
zone under sub-atmospheric pressure, separating
acid and returning the acid for absorption of
tower becoming more concentrated as it descends
whence it is drawn oil from the quiet zone I5 more oleilnes.
by a connection I6 and pump I1 to re-cycle to
3. A process of making alcohols from ole‘ñnes by
the absorption zone A, A', A", as the case may be absorption vin sulphuric acid, which comprises
in each part of the system for the respective ole
passing the oleñnes into contact with sulphuric
iines being- operated upon. At the same time as acid, mechanically super-contacting the iluids by
the acid is released in the hydrolyzation, the alco
centrifugally hurlingtransverse currents of acid
hol which is formed is at once drawn oil’ from through oleiine, stopping reaction other than ester
the hydrolyzing zone, ythe pressure in the tower formation by mixing a selective absorbent taking
30 being reduced by a suitablereducing means, as
up normal esters, removing polymers under sub,a pump 20, and the alcohol which ordinarily-»con
atmospheric pressure, hydrolyzing the ester solu
tains some water and ether proceeds through ^ tion at substantially the‘same temperature as the
cooling condenser 2| to a receiver 22, With par
absorption by subjecting the ester to the action of
ticular advantage, the hydrolysis and the ab
sorption in each portion of the system may be a small amount of Awater molecules at a tempera
ture in the neighborhood of 212° F. introduced in
carried on at substantiallyl the same tempera
an elongated hydrolyzing zone under sub-atmos
ture. Thereby, heat-waste and linefdciency is
particularly obviated. Thus, the hydrolyzing pheric pressure, separating acid in the presence
zone A for butyl alcohols may be operated at a of a selective solvent for normal esters, and re
turning the acid for absorption of more oleñnes.
40 temperature of 212° F., corresponding to the
4. A process of making alcohols from oleflnes
temperature in absorption zone A; the hydro
by absorption in sulphuric acid, which comprises
lyzing zone H' may be operated at a tempera
passing the olefines into contact with sulphuric
ture of 212° F., corresponding to that of absorp
tion zone A'; and the hydrolyzing zone H" may acid, stopping reaction other than ester formation
by mixing in a selective absorbent taking up nor
be operated at a temperature of 212° F. corre
mal esters, removing polymers under sub-atmos
sponding to the absorption zone A”. The pres
pheric pressure, hydrolyzing at substantially the
ence of the selective solvent in this zone also is
same
temperature as the absorption by subject
particularly eiîective, the acid being excluded and
ing the ester to the action ofïa small amount of
sent down, as rapidly as formed by the hydro
Water molecules at a temperature in the neigh
lytic reaction.
Other modes of applying the principle of the borhood of 212° F. in an elongated hydrolyzing
invention may be employed, change being made zone under sub-atmospheric pressure, separating
as regards the details described, vprovided the acid in the presence of a selective solvent for
features stated in any of the following claims, normal esters, and returning the acid forab
or the equivalent of such, be employed.
_
We therefore particularly point out and dis
tinctly claim as our inventiom-
'
1. A process of making alcohols from olei'lnes
by absorption in sulphuric acid, which comprises
passing the oleflnes into successive absorption
zones in the presence of an absorption-promoting
catalyst at progressively higher concentrations
for selective absorption of butylenes, propylene
and ethylene, mechanically super-contacting the
25
30
35
40
45
sorption of more olei'lnes.
5. A process of making alcohols from oleñnes 55
by absorption in sulphuric acid, which comprises
passing the olefines into contact with sulphuric
acid, stopping reaction other than ester forma
tion by mixing in a’selective absorbent taking up
particularly normal esters, removing polymers
under sub-atmospheric pressure, hydrolyzing the
60
ester by a small amount of water molecules yin>
an elongated hydrolyzing zone under sub-atmos
pheric pressure, separating acid in the presence
of a'selective solvent for normal esters, and re 65
turning the acid for absorption of more oleñnes.
6. A process of making alcohols from oleñnes
tion other than ester-formation by the presence I
of a selective solvent taking up normal esters, by absorption in sulphuric acid, which comprises
removing polymers between absorption zones_ passing the oleilnes into contact with sulphuric
under sub-atmospheric pressure, hydrolyzing by acid, stopping reaction other than ester forma 70
subjecting the esters to the action of a small tion by introducing an absorbent taking up par
amount of water molecules at a temperature in ticularly normal esters, removing polymers under
the neighborhood of 212° F. in an elongated sub-atmospheric pressure, hydrolyzingfthe ester by
hydrolyzing zone under sub-atmospheric pres
a small amount of water molecules at a tempera
a. fluids in each absorption zone by centrifugally
hurling transverse currents of the acids through
oleflnes in each absorption zone, stopping reac
10
15'
3
2,109,462
ture in the 'neighborhood of 212° F. in an elon
gated hydrolyzing zone, separating acid in the
presence _of a selective solvent `for _normal esters,
and returning the acid for absorption o! oleñnes.
'7. A process of making alcohols from oleñnes by
absorption in sulphuric acid, which comprises
passing the olefines into contact with sulphuric
acid, stopping reaction other than ester forma
tion by introducing an absorbent taking up par
10 ticularly normal esters, removing polymers under
sub-atmospheric pressure, hydrolyzing the ester
by a small amount of water molecules at a tem
perature in thevneighborhood of 212° F. _in an
elongated hydrolyzing zone, separating the, acid,
15 and returning the acid for absorption of more ole
ñne.
-
8. A process of making alcohols from oleflnes
by absorption'l in sulphuric acid, which comprises
passing the oleñnes into contact with sulphuric
20 acid, stopping reaction other than ester forma
tion by introducing an absorbent taking up par
ticularly normal esters, removing polymers,
hydrolyzing> the ester by subjecting to the 'action
presence of a solvent selective forA normal ester,
hydrolyzing the ester by water molecules, and re
turing the acid for absorption of more oleñne.
10. A process of making alcohols trom oleiines °
by absorptionv in sulphuric acid, which comprises
passing the oleñnes into contact with sulphuric
acid, separating acid. in the presence of a solvent
selective for normal ester, hydrolyzing the ester
by water molecucs, and returning the acid for `
10
absorption of more oleñne.
11. A process of making alcohols from olei'lnes
by absorption in sulphuric acid, which comprises
passing the oleflnes into contact with sulphuric
acid, removing polymers, separating acid in the
presence of a solvent selective for normal ester, 15
hydrolyzing the ester by water molecules, and
returning the acid for absorption of more olerlne in
the presence of an absorption-promoting catalyst.
12. A process of making alcohols from olefines
by absorption in sulphuric acid. which comprises 20
passing the olefines into contact with sulphuric
acid, separating acid in the presence oi la solvent
selective for normal ester, hydrolyzing’> the ester
of water molecules, separating acid, and returning l by water molecules, and returning the acid for
absorption of more oleñne in the presence of an
25 the acid for absorption of more oleflne.
9. A process of making alcohols from oleñnes absorption-promoting catalyst.
by absorption in sulphuric acid, which comprises
passing the olefines into contact with sulphuric
acid, removing polymers, separating acid in the
ROBERT E. BURK.
>ramRMAN P. LANKELMA.
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