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Патент USA US2404661

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July 23, 1946.
Filed Aug. 15, i 1942
Patented July 23, -1946
il 1 ~
`Robert Thomas Sanderson, Beacon, N. Y., assign
or to The Texas Company, New York, N. Y., a
corporation of Delaware
Application August 15, 1942, Serial No. 454,970 i
5 Claims.
(Cl. 260-676)
This invention relates to the manufacture of
motor fuel and particularly to motor fuel rich.
in branched chain hydrocarbons.
The invention has to do With obtaining 2,2,3
trimethylbutane from a mixture comprising the
_ »
2,4-dimethylpentane may be obtained by various
methods of organo metallic synthesis. They may
be obtained in processes of isomerization and
alkylation and by cross polymerization with sub
sequent hydrogenation and synthesis through
trimethylbutane and its isomer 2,4-dimetloyl-` 5 organo metallic compounds.
pentane by a process involving treating the mix-
. One procedure for the catalytic preparation of
ture with sulfuric acid under conditions such
2,2,3-trimethylbutane involves reacting a methyl
that 2,4-dimethylpentane undergoes conversion'
aluminum halide with an alkyl halide as de
into 2,3-dimethy1pentane, and distilling a. frac- 10 scribed in my pending application, Serial No.
tion rich in 2,2,3-trimethylbutane from the
treated hydrocarbon mixture. Advantageously,
the treatment of the hydrocarbon mixture is ef-
452,698, iiled July 29, 1942, for improvements in
Organic synthesis.
As therein disclosed methyl aluminum chlo
fected with concentrated sulfuric acid at a temride or other alkyl aluminum halide is placed
perature in the range about 70 to 125° `F. The 15 or formed in a suitable reaction vessel, and an
acid treated mixture is subsequently treated with
aliphatic halide such as 2-chloro-2,3-dimethylalkali prior to distillation for the purpose _of
butane is introduced slowly, advantageouslyV in
removing traces of acid remaining in the hydrothe form of a solution in 2,3-dimethy1butane.
This solution containing about 12 to 15% of the
. The hydrocarbon 2,2,3-trimethylbutane boils 20 chlorodimethylbutane is added over a period of
at a temperature of about 178° F. while the
isomer 2,4-dimethylpentane boils at a temperature of about 177° F. In the catalytic prepara-
about-,3 hours, while maintaining areaction tem
perature in the range about minus 58° to 32° F.
The total solution added amounts to about 15 to
tion of 2,2,3-trimethylbutane relatively large
2o parts by weight per part of methyl aluminum
amounts of the isomer may be present. The 25 chloride.
isomer 2,4-dimethylpentane has a C. F. R. M.
As previously intimated other methods of pre
octane value of about 82 or thereabouts, whereas
paring branched chain hydrocarbon mixtures
2,2,3-trimethylbutane has a materially higher
containing 2,2,3-trimethylbutane and 2,4-di
methylpentane may be employed.
octane value. For this reason it is frequently
desirable to produce the trimethylbutane in as 30 In any case, the synthetic hydrocarbon mix
concentrated form as possible for the purpose
ture is subsequently treated with concentrated
of making high octane motor fuel. Due to the
acid and thereafter distilled in accordance with
similarity in boiling temperatures, however, this
the method of this invention so as to obtain a`
separation cannot be effected by conventional
hydrocarbon product rich in 2,2,3-trimethyl
35 butane.
fractional distillation methods.
It has been found that concentrated sulfuric
acid at temperatures in the range about 70 to125° F. exerts no substantial effect upon 2,2,3-
Reference will now be made to the accompany
ing drawing illustrating one method of iiow which
may be employed in practicing the invention.
trimethylbutane, but under the same condi- i
In the drawing methyl aluminum chloride from
tions does effect substantial conversion of 2,4- 40 a source not shown is introduced through a pipe
dimethylpentane into 2,3-dimethylpentane which
I to an alkylation unit 2. A solution of 2-chloro
has a materially higher boiling point, namely,
2,3-dimethylbutane is introduced from a source
about 194° F. Consequently, the acid treated
not; shown through a pipe 3 to the unit 2. The
hydrocarbon mixture can be subjected to
charge materials are thus subjected to reaction
fractional distillation and thereby effect re- 45 in the unit 2 so as to produce a hydrocarbon prod-.
moval of the more volatile hydrocarbons from
uct vcontaining 2,2,3-trimethylbutane and 2,4-di
the higher boiling and less valuable hydrocarbon.
For example, by subjecting 2,4-dimethylpentane
to the action of 95% H2504 at a temperature of
The hydrocarbon mixture is accumulated in a
tank 4 from which it may be conducted through
about 120° F. for a period of 2 hours some 15%` 5o a pipe 5 to a mixer B wherein it is brought into
contact with concentrated sulfuric acid intro
or more of the hydrocarbon is converted to 2,3
duced through a pipe 1. This acid may have a
dimethylpentane. The - acid treatment appar
concentration of about 94% to 100% or more `of
ently causes isomerization of the afl-dimethyl
HzSO4, and preferably a concentration'of about
\ Mixtures of the trimethylbutane and its isomer 55 97% H2SO4.
The mixture of acid and hydrocarbons is sub
jected to thorough agitation in the mixer 6 While
maintained at a temperature of about 7_0 to 125°
F. over a period of about 20 minutes to 3 hours.
Th‘e products of reaction are drawn off through
a pipe 8 to a settler 9 wherein separation into
- hydrocarbon and acid phases respectively occurs.
The acid phase; is drawn off fromzthe bottom ofv
the settler through aI pipe I 0 and may be dis
charged all or in part from the system as spent
acid. On the other hand at least a portion of it
may be passed through a pipe l l communicating
with' the previously mentioned pipe 1 whereby it
is recycled to the mixer 6 for use-in. treatingifur
ther'feed hydrocarbon.
The hydrocarbon phase is drawn oiî from the
settler through a pipe I2 to a neutralizing‘vessel;
I3 wherein it may be treatedwith alkali for the>
purpose of removing remaining acid therefrom;
The 'neutralized hydrocarbons are then passed ~
through a pipe' I4 to-afracti’onator l5». The frac,
tionator t5 is“ operated sozaszto separate from. the
hydrocarbon mixture. a> distillatev fraction. con'.
taining.Y 2',2,3-»trimethylbut‘ane and unreactedl 2,4»
This distillate fraction isr dis'.- \
charged from the fractionator. through a, pipe |162.
The., residual fractionY removedl from: the. bottom
on.' theifractiorrat‘or through apipe- l1 comprises.
pentane drawn oir from the fractionator 29
through a pipe 32 may be conducted together y
with th‘e hydrocarbon drawn off through the pipe
l1 to a tank 33.
The liquid fraction comprising 2,3-dimethyl
pentane drawn 01T from .the fractionator 29
through a pipe 32 may be conducted together with
the hydrocarbon drawnoiî throughthe, pipe I1
to a tank 33.
The above described method of flow comprises
a two-stage operation. However, it is contem
platedA that anyÁ number of stages Vmay be used
or instead a single stage may be used as al
ready' intimated.
Moreover, the conditions of
1 acid treatment may'vary from stage to stage with
respect’ to acid" concentration, temperature and
time» of contact.
Obviously many modifications and variations
of the' invention, as hereinbefore set forth, may
be made without departing from the spirit and
scope. thereof', andi therefore only’ such limita
tions shoul‘d: be: imposed: as arezindicatedi
appended claims;
1. 'Iïlrrev method ofev removing. 23s-dimethylpen..-x
` tane from. amixture: comprising 2.4i- dimethylpena
tane: and;r 21,2 ¿3-trimethylbutane»,. which conrprises
subjecting; saidî mixture~ tof the- actionao?' concert..-y
2Q' which'
may b'e'simiiar'
the. pipe.-toi
k6.’ the:
to a1 mixer
second'.AßA andU
hydrocarbons comprising 2,3%-dimethylpentane..-V .
substantiall'yJ similar conditions so: as. to‘ effect
isomer ZA-dimethylpentane, treatingï the: hydro@V
tratedsulfuríc acid ata .temperature in the range:l
The: distillate fraction removed through the; 30. about 'Z0 to 125°: F..for a period; ofy time lessi than.
pipe I6: may“ still contain a relatively larga
about 3; hours,r such" that. 2;,42-dimethylpentanec
amount of 2,4-dimethylpentane. and further; con
undergoessubstantial conversionl into12=,3 edimethzf:
version.` of this' material into the. higl‘i'er` boiling
ylpentane: while 2«,2~,`3;~trim'ethylbutane». remains;
2`,'3r-dîmethy1pentane may; be“ effected by recycling
substantially unchanged. removing; acidv fromatheí
to. the: mixer: lì.4 Insteadi ofîrecyc'lingto thev mixer , treated’ hydrocarbon.- mixture;V and ldistillingK a.
6~itî i'sadvantageousïto pass the hydrocarbon mixe»
fraction enriched ilrl 2»,2-„3"-trimethylbutane- from
ture- toraseparate. stage. Thus; the hydrocarbons
the treated-g hydrocarbon, mixture, the:- remaimng
2. In the manufacture of 2,2,3-trimethylbutane..
wherein». the; hydrocarbons; are; again brought into. 40, t-he steps: comprising.I forming au’ hydrocarbon
contact witlrconcentrated; sulfuric: acid under`
mixture.: containing. 2 ;2;3.-trimethylb11tanel and: its:l
further conversion. of; the, ZA-dimethyipentane;
into; 2,3;-dimethylpentane
The reaction mixture is subsequently passed
through a pipe, 2|v to a: settler 22 wherein the
hydrocarbon' phaseI is separated from the. acid-Y
The acid phasesis‘- drawn-l o?f. through a pipe.- 23'
and; may bel discharged all' or: in part from the
system. Advantageously, however,> this acid is.
carbon. mix-ture'.r with, sulfuric' acid. atv a: tempera.-«
ture.l in the.~ range ab'out;7S0-t'o;125“ for aperio‘d:
of: time. lessi than;`about 3Ã hours. such; that.' 2,45»
dímethylpentane. undergoes substantial. com/.eir-4
sion'. int-o, 2,3.--dimethylpentanez while 2;2,3f.-t1:i:--
methylbutane: remains substantially unchanged..
removing acid from; the vtreated;hydrocarbon miie.v
ture;_ and. distilli'ng4 ai fraction; enriched ini 2,2;35-r
trimethylbutane from: the treated; hydrocarbon.Y
conducted; through a pipe 241 communicating Withî
mixturer the remaining ' hydrocarbons” comprising.'
the.Í previously mentioned pipe.` l; wherein.y itis.Y re
cycled~ tothe mixer Bfor the primary stage;> In
this type of operation fresh acid may be intro 55 the steps comprising: reacting; aemethylï aluminum.y
duced- tothe secondary stage> through the» pipe>~ 25
halide.: Witlr alkyl halide in. solutionV in‘: :an: a/lkane
Whilevused acidi removed from- the secondary~
corresponding to. the`> alkyl radical ofi said. alkyl:
stage» settler 22'A is- used-.solely or largely as, the-re.-`
halide such» that.. a branched` chain hydrocarbon
agent in the prima-ry~ stage mixer 6.. In» th'isëway
comprising 2,2.',3-tri`methylbutane and:
aâcountercurrent treatment betweenA acid and hy-Z-Afdimethylpentane is.t obtained,y treating said-l'
drocarbons> is.- utilized.
Where theV usedV acid is not so recycled; from the
secondary stage or onlyy returned in‘ part,. fresh
producirl with. sulfuric acid at. a temperature»
the: range about 70:: to'. 1525.“ F2. for' aiperi'od’: of. time.l
acidfmay be passedv directly from. a pipe 26 tothe
less than about'l 3b hours; such. that Zyl-dimethylLA
primary stage mixer 6.
2«,3'-dimethylpentane while 2,2,Bî-trimethy-llïJu-tan'eÄ
remains substantially unchanged-f, removing' acidf
The hydrocarbon phase- isf drawn 01T. fromf the
settler 22 through a pipe 21 to a neutralizer'28
wherein the: remaining acid is removed'` from the
The? neutralized hydrocarbons are thennpassedi 1 ‘
to: a. fractionator 29goperatedz irr aA similar? manner
to thezfi‘actionator F55.
Thev distillate fraction ri‘clr in 2;2,3‘-trimethyl;butarre is-y drawnoiî‘ througnapipe 30mg; tank' 3.15..
The liquid fraction comprising ¿lì-dimethyl;
p‘entane> undergoes substantial; conversion: into-A
from the treated? hydrocarbon mixture, and dis-l
tillingi a. traction enriched» in 2=,2\;3f-trimetliylbul--tane> from'. theV treated` hydrocarbon mixture', the
remaining- hydrocarbons; comprising. 2,3i-diimeth‘-~
41:. In; the manu-iî'acture1'y of 2,2,3 -triinet'hylbutane»;
the. steps; comprising reacting a methyl atlumi--`
num halide with alkyl halide in solution iwan-'aale
kan'ef. corresponding. to thek alkyl-radical'. oiî said
alkyl halide at a temperature in the range about
minus 58 to 32° F. such that a branched chain
hydrocarbon product comprising 2,2,3-trimeth
num chloride with 2-chloro-2,3-dimethylbutane
in solution in 2,3-dimethylbutane at a tempera
ture in the range about minus 58 to 32° F. such
ylbutane and 2,4-dimethylpentane is obtained,
that a. branched chain hydrocarbon product com
treating said product with sulfuric acid at a tem
perature in the range about 70 to 125° F. for a
period of time less than about 3 hours, such that
2,4-dimethy1pentane undergoes substantial con
prising 2,2,3-trimethy1butane and 2,4-dimethyl
pentane is obtained, treating said product with
removing acid from the treated hydrocarbon mix
ture, and distilling a fraction enriched in 2,2,3
trimethylbutane from the treated hydrocarbon
while 2,2,3-trimethy1butane remains substantial
ly unchanged, removing acid from the treated
hydrocarbon mixture, and distilling a fraction
enriched in 2,2,3-trim`ethy1butane from the treat
sulfuric acid at a temperature in the range about
'70 to 125° F. for a period of time less than about
3 hours such that 2,4-dimethy1pentane undergoes
version into 2,3-dimethylpentane While 2,2,3-tri
methylbutane remains substantially unchanged, 10 substantial conversion into 2,3-dimethylpentane
mixture, the remaining hydrocarbons comprising
5. In the manufacture of 2,2,3-trimethylbu
tane, the steps comprising reacting methyl alumi
ed hydrocarbon mixture, the remaining hydro
carbons comprising 2,3-dimethy1pentane.
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