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Патент USA US2107794

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2,107,794
ES PATENT. OFFICE
[2,101,194
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'MANUrjAorUaE oF-AwonoLsx
: :Yladimir Ipatieff and’Vasili Komarewsky, cu
assignors to'Univcrsal Oil Product's.
'} a?ompany-gfChicago, 111., a corporation of DeIa-"
- st'rnaeiieaappuaam September 1, 19:3,
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SerialNo. 687,843
Claims.
(0]. 260-156,)
Thisi-inventionr'relates ‘to the manufacture of fins. Among the metals whose salts and oxides
alcohols‘ from oleii'ns,v particularly ole?ns of a
normallyv gaseous character such as are en
countered in. gases from hydrocarbon cracking
-5.
operations.
_
.
'
Y
>
‘ 'In a more specific sense the invention has ref
erence to a process for-the manufacture of rela
tively low boiling‘al'cohols using a particular class
of vacid catalytic reagents.
-
. v
The gases‘from hydrocarbon cracking opera
tions are characterized by a considerable content
oi’ ole?ns and-these ole?ns constitute a primary
source. .of reactive hydrocarbon materials, al
I though this reactivity has been made use‘v of com
meré'ially'only to a limited extent. Ethylene has
15 been used to manufacture ethyl alcohol by selective sulfonation' and hydrolysis and similarly
may be used may be mentioned zinc, manganese,
molybdenum, iron‘, nickel, cobalt, etcetera. As a
rule these metallic promoters are only used in
quantities of 10% and less by weight of the acid 5
and frequently su?lcient promoting action is
obtained when using amounts of the order of 5%.
Various types of salts may be dissolved in or
.mixed with the acid catalyzer, such as nitrates.
chlorides, etcetera and, in the case of some in
metals, goodv results are obtained when oxides
vare dissolved. Owing to the strongly acid char
acter of phosphoric acid some of the salts added
will be decomposed so that the weaker acid is dis
placed and the [resultant ‘?uid mixture contains
, the phosphate of the metal in solution. How
'ever, the extent‘ of‘ this action vwill depend not
H considerable quantities of isopropyl alcohol have 3 only upon thezirelatire strength of the acid radi
. been‘ manufactured. In these processes theusual , cals but upon'the cotn‘e'an‘tration of the phosphoric
method of- operation is to pass the mixture of
gaseous hydrocarbons through a stationary body
- _ of sulfuric acid of regulated strength (or counter
_ current ‘to descending streams of acid in treat
ing- towers) until ‘a sludge containing acid esters
25 is produced, after which alcohols are obtained
bydistilling the sludge after dilution‘ with water,
‘
or bydistilling the sludge with steam.
Inv processes using sulfuric acid to produce al
_~ , cohols from ,olefins di?lculties are encountered
acid, the I temperament-treatment, the amount
of metal
etc; so ‘that, it' is not
intended to
phatesresult.
20v
metalphos
‘
-'
.-
i
It will be-seen from the above-brief. enumera-j
tion of the .various types of fim‘etal ‘compounds
which may be used as promoters thatfa cons'ider- 25'
, able number of alternatives of varying composi
tion comprising phosphoric acid and metal com
pounds are‘ possible.
However, each catalyst
so owing ‘to the tendency of the sulfuric acid tov ‘mixture will exert‘ its vown speci?c action in any
oxidize and polymerize unsaturated hydrocar-'
bons as wellas to form the'desired esters from
_ which ‘the alcohols are obtained by hydrolysis.
Thus, in the case of various vbutylenes the forma
35 tion of polymers may exceed the formation of
given case which will not be exactly equivalent 30
to the action of other catalyst mixtures of the
same general character. When dealing with the ‘’
varying .types of ole?ns which occur in hydro
carbon gas ‘mixtures, acid catalysts of specific 35
the‘ desiredacidesters- and limit the yield of_ composition may be chosen for producing opti
alcohol obtainable. By using the particular acid mum yields of alcohols‘. However, it is not always
catalyst reagents and the method of operation possible to predict the exact action of any given
comprised within the scope of the present inven
reagent but for a given type of cracked gas mix
tion many of the undesirable side reactions are ' ture produced in the normal operation of a
40
, eliminated and the yield of alcohols is increased. cracking plant itis practically always possible to
In one specific embodiment the invention com - select reagents from the present group which will
prises the treatment of ole?nic gases or oleflnic\ produce satisfactory transformation of the ole
,
gas ‘mixtures to obtain alcohols therefrom with ‘w fins into good yields of alcohols.
_
It is preferable in mostcases to: employ the 45
oxides at pressures up to 10 "atmospheres and ' ordinary commercial ortho-phosphoric acid
temperatures up to 120° C.
4 (HaPOO rather than any of ‘the other acids of
7 According to the present process various ‘metal phosphorus although the invention is not limited
‘ 45 phosphoric acid containing metallic salts and/or . ‘
' compounds are used to, promote the action of
50 phosphoric acid in producing alcohols from'ole
to the use of the ortho acid.. In general also the -
acid of approximately, 90% concentration prod 50v
2
2,107,794
duces good results in practice although this con
centration may also be varied as desired, ‘both
as a means of controlling the solubility of‘ the
added promoters-and the rate and character-of
the hydrolysis which results in alcohol formation.
The following equations indicate the probable
course of the main reactions leading to the pro
duction of alcohols by the present process:
CaHs
10' (1) Propylene
plus
Phosphoric acid
=CaH'IH2PO4
lsdpropyl phosphate
(2) C3H7H2PO4 plus H2O==C3H7OH plus HaP04
Isopropyl alcohol
The exact mechanism 'of the action of the dif
15 ferent'promoters is di?lcult to follow and, there
fore, it is only possible to suggest what their ac
tion is. It may be that there is some intermedi
ate formation of metal salt addition compounds
from which the alcohols later result,'or it may be
20 that the action of the metal salt promoters is
more de?nitely catalytic and that such addition
compounds if formed are very transient in char
acter and notcapable of separation and identi?
cation.
25
‘
The details of process operation may be varied
considerably and both batch and continuous types
in the distillate fractions may be puri?ed and
separated from hydrocarbon material by solution
in water and a secondary distillation of the aque
ous ‘extract.
_
The following examples are characteristic of
results obtainable by the use of the process and
are introduced as illustrations but it is to be un‘
derstood that many others are available.
Example. 1
10
52 parts by weight of commercial 90%‘ortho
phosphoricacid and 5 parts by weight of black
nickel oxide were added to a'pressure vessel. 50
parts by weight of propylene were added under a
pressure of 120 pounds per square inch after
which the temperature was raised to 120° C. and
held there until constant pressure conditions ob
tained.
‘
.
'
There‘ was produced byv this operation 25 parts
by weight of liquid products comprising 60% 20
isopropyl alcohol and 40% propylene polymers,
principally dimers and trimers, which were of a
character suitable for use as high anti-knock
blending ?uid in. gasoline.
Example 2 _
may be employed. In batch operation phospheric
acid ' and a small amount of a selectedv metal
50 parts by weight of 90% orthophosphoric
compound promoter may be added to a pressure
vessel lined with some corrosion-resistant mate
acid and 5 parts by weight of ‘commercial zinc
‘g rial and a pure ole?n or an ole?n-containing gas
chloride were added to a pressure treater. 50
parts by weight of propylene was added under a , 30
may be pumped into the bomb until a certain pressure of 8 atmospheres and the temperature
pressure is reached, after which the bomb is heat-v again raised to 120° C. and maintained at that
ed and the contents agitated either by rotating point until constant conditions were observed.
In this case 22 parts by weight of liquid prod
the bomb or by mechanical stirring-devices. The
process is interrupted when the rate of absorp ‘ucts were obtained, 62% of which consisted of 35
tion becomes too low as indicated'by a stationary isopropyl alcohol extractable by water and 38
pressure. and the liquid products comprising al
.cohols and some polymerized ole?ns are removed,
after which the cycle is repeated using the same
40
catalyst mixture until its e?lciency is lost due
to the gradual accumulation of heavy polymers
and high molecular weight acid esters. It is
characteristic of the present invention that the
.45 deterioration of the catalyst is much slower than
that of other acid catalysts, particularly sulfuric
acid. so that larger yields of alcohols are obtain
able for a given amount of catalyst.
In continuous operations an acid catalyst mix
ture, water or steam and gaseous ole?ns ‘may be
50 injected simultaneously in regulated proportions
into tubular heaters through which- the reacting
parts of propylene polymers which as before were
utilizable as high anti-knock blending constitu
ents for admixture with gasoline.
The foregoing speci?cation and examples, while
40
disclosing the character of the invention and giv
ing selected results showing its practical value,
are not to be considered as imposing’ undue lim->
itation thereon.
We claim as our invention:
45
1. In the production of alcohol from ole?n
hydrocarbons, the step which comprises treating
the ole?n with a phosphoric acid solution to
which nickel oxide has been added.
"
.
2. In the production of alcohol from ole?n 50
hydrocarbons. the step which comprises treating
the ole?n with a phosphoric acid solution to
components pass and from which they are dis
charged into a separator or a ?ash distilling. which‘ has been added from about 5% to 10%
by weight of a metal oxide.
‘
55 unit. The acid catalyst is then withdrawn frjom
v 3. In the production of alcohol from ole?n by? 55
the bottom of the distilling chamber-and re
turned to the entrance _of the heating. element drocarbons,. the stepv which comprises treating I
for further usewhile the vaporous- products‘ of the olefin with phosphoric acid in the presence
the reaction; both hydrocarbons and alcohols,
to are passed through a‘ fractionating column to ob
tain desired cuts containing different alcohols in
case a mixture of ole?ns was used. The alcohols
of ‘nickel oxide.
_ '
VLADHHIR IPATIEFF.
VASILI ROW.
60
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