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Патент USA US2131806

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2,131,806
Patented Oct. 4, 1938
‘UNITED STATES, PATENT OFFICE
2,131,806
TREATMENT OF HYDROCARBONS
Vladimir Ipatie? and Vaslli Komarewsky, Ohi
cago, 111., assignors to Universal Oil Products
Company, Chicago, 111., a corporation of Dela
ware
No Drawing. Application August 16, 1935,
Serial No. 38,561
'
4 Claims. (Cl. 260-676)
temperature vapor phase and more or less in
The invention relates to the treatment of ole
tensive operations which may produce fairly high
?nic hydrocarbons to produce therefrom satu
rated hydrocarbons of higher molecular weight, yields of high antiknock' materials, there will be
and in a more speci?c sense,'is concerned with relatively more ethylene than its higher homologs
5 treatment of such hydrocarbons by concurrent in the gases, while in liquid-vapor phase opera
tions, which aim at a balance between yield
polymerization and hydrogenation thereof.
The :class of ole?nic hydrocarbons with which and quality of product on an economy basis,
the present invention is concerned is the most there will be relatively higher percentages of
reactive of the various hydrocarbon groups, owing - propylene, the butylenes and the higher molec
10 to‘ the presence of double bonds between carbon ular weight homologs. This last named group, 10
atoms. By virtue of this so-called unsaturation, which is usually designated as the “higher ole?ns”
these hydrocarbons are more or less readily oxi
dized, hydrogenated and polymerized and they
unite directly with practically all inorganic acids
15 and a great many organic acids to form addi
tion compounds, which furnish intermediates
in cracking plant gases is the one which is most
readily polymerized by catalysts under moderate
conditions of temperature and pressure to form
liquids boiling within the approximate range or 18
gasoline.
'
,
The present process is not limited solely to
factured. Thus, any of the ole?nic hydrocar~ the treatment of such gas mixtures but may be
employed for the treatment .of ole?ns which are
bons can serve as a source of an alcohol with a
20 corresponding number of carbon atoms by ?rst . normally liquid. For purposes of reference as 20
making the sulphate and'then hydrolyzing this indicating the character of the compounds treated,
the following table is introduced, which shows the
compound, This reaction is utilized in the manu
from which useful derivatives can be manu
facture of ethyl alcohol from ethylene and in the
manufacture of iso-propyl alcohol from the
>25 propylene present in cracked gas mixtures.
name , formulas, and common characteristics
of some of the lower molecular weight mono-ole
ilns:
25
Ole?n hydrocarbons
The ole?ns are of concern to the petroleum
re?ning industry for several reasons. Those that
are liquid at’ ordinary temperatures and pres
Compound
sures constitute a variable proportion of the
30 cracked gasolines of commerce and contribute
largely to its superior anti-knock value in com-'
,parison with straight run distillates of similar‘
boiling- range. Those ole?ns in such cracked
gasolines which are of the conjugated character,
35 however, are su?iciently reactive with traces of
oxygen, particularly while under the in?uence
of light, to form ?rst compounds of a peroxidic
character, which evidently instigate a series of ‘Z
chain reactions leading ultimately tq'l'the forma
40 tion of gummy and resinous compounds which
may ‘in turn cause a haze or color fin the gaso
lines von storage and leave su?icien't residue on
Formula
30
Ethylene ................. _- cm=cm
Propylene ___________
-1o5°
cmcn=cm
’
‘
-4a°'
'
Ethylethylene ........... -- cnecrncn=cm
Planes'ym. ‘dimethylethyl- omort=cmcm
Axial-sym. one (bntencs).
88560118
-5°
}
+1° 35
2.~5°
Unsym. dimethyi ethylene (CH:)1C=CH:
(iso-butylene).
—6°
_
n-Propyl ethylene, c-amyl- CHsCHzQHaCH=CHz
+39°
Is:n:opylethylene,c-iscam- (CH1)|CH.CH=CH:
+21"
syzm‘inrglolthylethylcthyiene, ornomon=cncm
+36“ 40
ungli’fgihylemylemyi- cnecn,
+31"
ene,7-amylene.
evaporation to effect the normalgfoperation of
feed lines and‘ carburetors in internal combus- g
'
<
C=CH2
.
CH:
45 tion engines. The principal object of the treat- . Trimeghyl ethylene, ?-iso- (cm)lo=on.cm
ments commonly applied to cracked distillates _
of gasoline boiling point range is the removal I
of these more readily activated compounds while ',
pg‘ggé
+ae° 45
8 0.
r3315“: ethylene ____ .- (CHs):C=C(CHa):
+73°
The hydrogenation of ole?ns is a relatively sim
‘ ple process requiring only moderately active cata- 50
ing operations are also relatively high in ole?n . lysts, temperatures of the order of 300 to 500° F.
leaving behind the more stable mono-oleilns.
Fixed gases-produced incidental to oil crack
50
content, though the total concentration of ole
?ns and the distribution of the di?ferent com
pounds vary widely in the gases from different
55 cracking processes. ~In the gases from high
and atmospheric or only. slightly superatmos
pheric pressures. Thus, ethylene is readily hy
drogenated by passing it in a mixture with a
moderate excess of hydrogen or even a hydrogen 66
2
2,181,806
_ such as, for example, hexylene, which occurs to
merizing and a hydrogenating catalyst respec
tively will exert its own peculiar accelerating ac
tion upon the reactions of polymerization and
a considerable percent in cracked gasoline mix
hydrogenation and consequently will speci?cally
tures, hydrogenation is readily e?ected by heat
ing the liquid under pressure in the presence of
in?uence the character of the resultant prod
ucts. Considering the matter in this light will
make it evident tothose familiar with the empiri
cal state of the catalyst art that the various com
binations of catalytic materials which the proc
ess may employ will not necessarily produce iden 10
tically equivalent .results either in degree or in
kind.
The details of procedure in carrying out the
invention will necessarily need to be adapted to
the reactivity and phase of the ole?n or ole?ns 15
containing gas such as water gas over reduced
iron or nickel. When dealing with liquid ole?ns
small quantities of reduced nickel or nickeloxide,
while introducing gaseous hydrogen.
_
.
v
The foregoing brief résumé of the reactions of
10 ole?nic hydrocarbons from the standpoint of the
present process indicates that, in general, the re
actions of polymerization and hydrogenation are
opposite in character, and it was, therefore, not
to be expected on a basis of known chemical
15 laws that the two could be made to proceed con
currently with the production of molecules cor
responding'to multiples of the ole?n hydrocar
bons but of a para?inic character. This result
was‘ still less to be expected from ya consideration
20 of the character of the catalysts used respectively
in polymerization and hydrogenation reactions.
Catalysts e?ective in polymerizing ole?ns com
prise metal halides, such as for example, alumi
undergoing treatment, the relative degrees of
polymerization and hydrogenation required, and
the character and effectiveness of the catalytic
materials chosen to accelerate the reactions of
polymerization and hydrogenation respectively.
A few cases may be chosen which are illustrative
of different procedures and the necesary modi
?cations to take care of cases not covered by the
num chloride, zinc chloride, magnesium chloride, ’
examples will then be more or less obvious to
etc., and also sulphuric acid, phosphoric acid,
perchloric acid, boron ?uoride, etc. Many of
those su?iciently familiar with commercial chem
ical operations.
25
A case may be assumed in which the ole?n to
- these compounds have been found to exert a
poisoning in?uence when present even in small , be treated is normally gaseous and both catalysts
30
traces in ordinary hydrogenation reactions.
The most e?ective hydrogenation catalysts,
are solids. This condition is represented by eth-"
ylene as the ole?n, aluminum chloride as the 80
when considering the incidental poisoning in?u
polymerizing catalyst, and nickel as the hy
drogenating catalyst. In operating with these
materials according to batch procedure, the two
ences to which they may be subjected are the
oxides and sul?des of the metals in the left hand
column of the 6th group of theperiodic table,
85 to wit, chrominum, molybdenum and tungsten,
and the corresponding compounds of the iron
group comprising iron, nickel and cobalt. These
catalysts are suggested ‘as being the most e?i
cient for general purposes but is not intended to
40 infer that the compound catalyst mixtures utiliz
able in the present instance are limited to the
speci?c compounds enumerated. For example, it'
is well known that, in the absence of sulphur,
arsenic and other poisoning in?uences, reduced
45 nickel is a very e?ective hydrogenation catalyst
and that the platinum group comprising plati
num, iridium and osmium are energetic catalyzers
and utilizable when their cost or availability per
It is within the concepts of the present
_ mits.
50 invention to employ any catalyst or catalyst mix
ture to effect the reactions of hydrogenation
which may have been found'suitable for use in
processes involving substantially only hydrogen
ation reactions.
55
.
In one speci?c embodiment the present inven
tion. comprises the manufacture of para?in hy
catalysts may be placed in a rotatable pressure
bomb and a mixture of ethylene and hydrogen 35
pumped in until a given pressure is reached,
after which the bomb is heated and rotated until
the reactions have taken place with the forma
tion of such compounds as butanes, hexanes, oc
'tanes, etc. The step of introducing the mixture 40
of ethylene and hydrogen may be repeated inter
mittently after the pressure has ceased to drop
under the given temperature conditions and may
be repeated until the catalysts indicatedhave lost
their activity or the presence of too great quan
titles of accumulated liquids renders their re
45,.
moval imperative. The reaction between ethylene
and hydrogen may be brought about in a con
tinuous manner by passing the gas. mixture un
der pressure and at a suitably elevated tempera
60
ture over a solid composite mass comprising nickel
or other hydrogenating catalyst while injecting
controlled quantities of aluminum chloride.
When operating with an ole?n which is nor
mally liquid, such as for example amylene, this 55
material is charged to a pressure apparatus in -
drocarbons from ole?n hydrocarbons by concur
contact with the polymerizing and hydrogenating
rently catalyzed polymerization and hydrogena Jcatalyst and reaction is induced by heating to a
tion reactions.
suitable temperature and simultaneously intro
60
From a consideration of the numerous olefin
ducing hydrogen under pressure, preferably 60
hydrocarbons, which include both mono-ole?ns, through a perforated distributing device which
di-ole?ns and still more highly unsaturated com
pounds, and also the large number of possible
polymerizing as’well as hydrogenating catalysts,
maintains the catalysts in suspension and causes
su?icient intimacy of contact to insure the com
pletion of the desired reactions with a minimum
it is evident that a large number of combinations
'of different hydrocarbons with the diiferent mem
bers of the two groups of the catalysts exist to
‘give the present invention a broad scope on a
basis of the number of speci?c reactions which
70 it may bring about. The scope-is further widened
in that groups or mixtures of ole?ns may be
treated and that catalyst combinations may be
employed which are found by trial to be most
?ow of hydrogen. The steps of removing the 85
hydrogenated polymers intermittently will be fol
useful in promoting a given reaction.
75
Each catalyst combination comprising a poly
hydrogenation catalysts, the amount of hydrogen ,
lowed in'this case as before in the preceding
example.
The relative degree of polymerization and by,
drogenation may be more or less separately con
trolled by varying the quantity of different poly
merizing catalysts of varying activity among
themselves while at the same time varying the
and the conditions of hydrogenation in respect to’
70
3
aiaaaos
temperature and pressure. Thus, taking ethylene
ditions of Example 1, utilizing the same weight
as an example again, its reactions may be varied
of aluminum chloride in place of the zinc chlo
ride. In this case the boiling range of the liquid
between two extremes of complete polymerization
without hydrogenation and complete hydrogena
tion of _ polymers.
The ultimate polymerization
of this gas and generally of other ole?ns leads to
the production of high molecular weight com
pounds of a viscous character which are partic-'
ularly suitable as lubricants since they have in
products was somewhat higher, 50% oi‘ the prod
ucts being iso-para?insboiling at temperatures
from .130 to 325° C.
Example 3
A run was made on iso-butylene using as a poly-,
addition to a high viscosity and low sludging
merizing catalyst a solid composite comprising a 10
characteristics, a viscosity index usually equal to
siliceous carrier and phosphoric acid, and as the
hydrogenating catalyst nickel oxide. The pro
portions, temperatures, pressure and time were
or better than the standards from para?ln crudes.
The end product of ‘hydrogenation of ethylene is,
of course, ethane.
The present process is particularly well adapted
to the production of iso-parailins boiling within
the range of commercial motor fuel from the -
mono-ole?ns normally present in the cracked gas
mixtures produced incidental to oil cracking oper
ations. The mechanism of the joint reactions is
apparently such that there is a decided prepon
derance of iso-paraillns in these liquid products.
which hydrocarbons are known to be of consider- 7
ably higher antiknock value than their normal
counterparts. Thus, for example, from the ole?ns
in the stabilizer re?ux of plants operating in con
the same as in Example 1. In this case, however,
‘a yield of 50% by weight of also-octane was ob-.
tained.
V
The solid phosphoric acid catalyst composite
used in this example was manufactured by add
ing 70 parts by weight of pyro-phosphorlc acid to
30 parts by weight of lrieselguhr at a temperature 20
of 150° C.,‘mixing to a uniform pasty consistency
and calcining for 20 hours at 275° 0.. The solid
cake thus produced was ground and sized out of
contact ‘with moist air and particles were saved
which were smaller than 4 mesh and larger than
10 mesh:
'
junction with craclnng plants andcomprising
The novel and useful character of the invention
percentages of propylene and butylenes of the
order of 30 to 50%, high yields" of iso-hexanes,
heptanes and octanes are produced which have
great value as blending components in gasoline
mixtures. Such compounds have complete sta
bility lmder ordinary conditions of storage and
is evident from the descriptive matter of the pre- __
ceding speci?cation and the: numerical datasub
mitted, although neither section is‘ intended to 30
unduly limit the invention’s generally broad
scope.v
'
We claim as our invention:
_
water white color and require no other treatment ‘
1. A process for producing hyrocarbon liquid
than a light caustic wash tov renderv them lit for
blending purposes
boiling within the motor fuel range and contain 35
ing iso-,'which comprises subjecting ole
The temperatures necessary for eifeeting the ?nie gas to concurrent polymerization and hydro
present type of concurrent polymerization and genation by treatment thereof with hydrogen in
hydrogenation reactions do not as a rule ‘exceed the presence of a solid compo?te of a siliceous
300° C., and the pressure of hydrogen under the carrier, phosphoric acid and a hydrogenating 40
.
operating conditions is practically always below’ catalyst.
2. A process for producing hydrocarbon liquid
100 atmospheres. The exact conditions of tem
perature and pressure,v rate of ?ow in continuous
operations, etc., will in a majority of instances
be determined best by small scale operations be
fore transferring the process to commercial
setups.
'
'
‘ The following examples are given to illustrate
the general character of. the results obtainable
by the use of the process, although not with the
intent of unduly restricting its scope as an inven
on.
'
boiling within the motor fuel range and contain
ing iso-para?ins, which comprises subjecting ole
?nic gas to concurrent polymerization and hydro
genation by treatment thereof with hydrogen in
the presence of a'solid composite of a siliceous
carrier, phosphoric acid and nickel oxide.
3. A process for producing iso-octane from
butylene which comprises subjecting the butylene
to concurrent polymerization and hydrogenation
by treatment thereof' with hydrogen in the pres
Example 1
ence of a solid composite of a siliceouscarrier.
100 parts of iso-butylene was heated in a closed
pressure vessel in the presence of 2.5 parts by
butylene which comprises subjecting the butylene
weight of nickel oxide and a corresponding weight .
of zinc chlorider'for 12 hours at a temperature of
275° C. and a maximum pressure of 100 atmos
pheres oi’ hydrogen. Fractionation of the prod
ucts of reaction shows a yield of' 35% of pure iso~
octane (2,2,4-trhnethylpentane) .
Example 2
Iso-butylene was treated again under the con
50
phosphoric acid and a hydrogenatlng catalyst.
4. A process for producing‘ iso-octane from 55
to concurrent polymerization and hydrogenation
by treatment thereof with hydrogen in the pres
ence of a solid composite of- a siliceous carrier,
phosphoric acid and nickel oxide.
vmnmm IPA'I‘IEFF.
VASILI xomaawsxr.
60
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