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Патент USA US2406110

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‘Patented Aug.‘ 20,1946?v T a ' ‘1 in‘ in’? Q
'
2,406,110
UNITED STATES PATENT oFnc-E "
MANUFACTURE OF HYDROCARBONS
Louis schmerlingRiverside, 111., assignor to Uni
vversal Oil Products Company, Chicago, 111., a
corporation of Delaware
No Drawing. Application March 31, 1943,
11 Claims.
(Cl. 260-—683.6) '
1
The present invention is concerned with proc
esses for the synthesis of paraf?nic hydrocarbons,
of branched structure which are useful as con:
stituents of high antiknock motor fuel blends. '
Isopara?in hydrocarbons of suitable boiling
point constitute the best type of hydrocarbons
for use in high compression spark type ignition
engines such as aviation engines. These hydro
carbons are de?nitely superior to ‘the ' normal
paraffin hydrocarbons in respect to their relative
antiknock value and they are generally superior
to cyclo‘ paraf?n hydrocarbons of an equal num
ber of carbon atoms per molecule. ' They are bet
ter than corresponding ole?nic hydrocarbons in
their stability during storage and are generally
more desirable than aromatic hydrocarbons on
account of their lower solidi?cation points. Con-‘
sequently, considerable e?ort is being made to
produce the branched chain para?inic hydrocar
bons in increasing quantities for commercial use.
In general the antiknock value of a para?in hy
drocarbon increases with its degree of branching
in the molecule and it is an object of the present
invention to provide a process for the manufac
In the ?rst step of the process as represented
by Equation 1 ‘preceding reaction is brought
about at temperatures of from about 200 to about
ture of highly branched paraf?nic hydrocarbons. 25 250° C. and either ‘according to batch or contin--'
In a broad aspect the invention comprises .a
process for manufacturing branched chain par
a?ln hydrocarbons which consists in'reacting a
mono-ole?nic hydrocarbon with a methyl halide
in the presence of a catalyst to produce a higher so
molecular weight mono-ole?n and‘ hydrogenating
uous procedures. In the batch procedure a slight
excess of the lead oxide over the molecular ‘re
quirement shown in-Ythe equation may be added
to'a pressure vessel, the equivalent amounts of
the ole?n and the methyl halide added, the ves
sel closed and then heated to a temperature
within the range speci?ed. After being held at
this temperature until reaction is complete as
the mono-ole?n to the corresponding para?in. »
In one speci?c embodiment the invention com
prises a process for the manufacture of 2,2,3
indicated by a constant pressure, the vessel ‘is
trimethyl butane which consists in reacting
tetramethyl ethylene with methyl iodide in the
presence of lead oxide to form 2,3,3-trimethyl
butene-l and lead iodide, hydrogenating the bu—'
tene .to'produce 2,2,3-trimethyl butane, reacting
cooled, the pressure released and the hydrocarbon
reaction products and any unreacted methyl
halides separated from the lead compounds and
fractionated to recover the desired heptene and
unreacted charge.‘ The unreacted'portions can
the lead iodide with methyl sulfate to form all)
be combined and reproportioned and subjected to
methyl iodide and lead1sulfate, treating the lead
sulfate with an alkali metal carbonate to reform
lead oxide, and recycling the .methyl .iodide and
lead oxidev to further use.-
-
'
,-_In~a‘ further embodiment the ~2,2,3*trimethyl
butane may be made by starting withan iso
amylene such as, for example; trimethyl ethylene.
further action in the presence'of fresh-for regene
erated lead oxide; Methyl iodide boils at i‘ll-42°
Ci, tetramethyl ethylene at 73° ‘C.', and the 2,2,3
trimethyl ,butene-l at about 78° 0., so that “no
di?iculty will attend the separation of the reac
7 tion products by ordinary fractionation methods.
The ?rst step of ‘the process may be conducted
in a continuous manner by passing a‘propor;
The reactions involved in the steps of the
tioned mixture of’ tetramethyl ethylene? and
process arev typi?ed" by those shown in the fol
‘lowing equations which occur in the manufac 50' methyl iodide‘ over granularlead oxide ‘contained
2,406,110
3
4
in a reaction chamber, the stream of reactants
being diverted through a bed of fresh lead oxide
as the initial mass of material becomes con-
'
.
encies to oxidize the hydrocarbons involved in
the reactions, while the suboxide is substantially
unreactive.
v
verted to lead iodide and the reaction stops.
The following example is given to indicate the
In accordance with the next step of the process 5 character, of results obtainable in utilizing the
methyl iodide and lead oxide are regenerated by.
present process for the manufacture of 2,2,3
reacting lead iodide with dimethyl sulfate. Again:
trimethyl butane, which is known as “triptane.”
the reaction may be brought about either by
The data given are merely illustrative, however,
batch or continuous operations. Thus in a batch
and are not introduced with the intention of un
operation an approximately equivalent molecular 10 duly circumscribing the proper scope of ‘the in
mixture of dimethyl sulfate and lead iodide may
vention.
.
be heated to-a' reaction temperature within the
. 18 parts by weight of methyl iodide, 10 parts by
range ofabout 50 to about 180° C., and methyl
weight of tetramethyl ethylene, and :15 parts by
iodide distilled and recovered for further use.
weight of powdered litharge, were placed in a
'As ‘a variation of this procedure continuous;
pressure vessel, the vessel closed and heated at
operations may be conducted by adding the poW- ; , atemperature of 210° C. for a period of four
dered lead iodide to a heated pool of dimethyl. ' hours. After release of pressure the liquid prod
sulfateand methyl iodide distilled and recovered ‘
uct was separated fromthe lead iodide and then
as long as the consistency of the reaction mix
' fractionated to recover unreacted methyl iodide ‘
'ture permits.
'20 from hydrocarbons. It was found that a 90 per
‘
To reform lead oxide from leadsulfate in the,
. cent volume yield of hydrocarbons based on the
third step of the process, it may be either directly ‘
.tetramethyl ethylene charge had been obtained.
produced by heating lead sulfate in admixture‘v This hydrocarbon layer was separated into frac
with ?nely divided carbon at a temperature‘ of»v
tions shown in the following table:
.
from about 550 to about.650° C., or in admixture ‘
3
‘
,
‘
'
‘
f
.
with an alkali metal carbonate at a red heat. . In
this alternative method the principal products
will be lead oxide, sulfur dioxide and carbon
monoxide. In the regeneration by using sodium
carbonate, a mixture of sodium sulfate and lead
carbonate will be formed ?rst, the sodium sul
fate washed out with water and the lead car
bonate converted to lead oxide by. heating to
‘ about 400° C., at which point carbon dioxide is
‘ evolved and lead 'oxide remains as a residue.
As
a further alternative the lead sulfate may be di
, gested with a hot solution of sodium or potas- ‘
-
,
Fraction
B. P.
0 0,’
Volume
percent’
’
7mm
1. 4143
1. 4069
1. 4060
Fraction number 3 boiling at 77° C. contained
at least 85 percent of triptene. Fraction number
1 consisted principally of 2,3-dimethyl butene
and fraction 2 consisted of a mixture of 2;3-di-.
methyl butene-2 and triptene. The triptene was
f
slum bicarbonate.
3
While the process has been described in con-.
identi?ed by preparing the crystalline hydrate of
nection with the use of tetramethylrethylene as 4.0 2,2,3-trimethyl butanol-3 (M. P. 76° C.) by ?rst
1
1
1
i
of 2,3,3-trimethy1 butene-l may.v be
when utilizing such compounds as
ethylene, since in the ?rst reaction of
pound tetramethyl ethylene is formed
a hydrocarbon charging-‘stock, substantial yields
produced
trimethyl
this com
according
§ to the followingiequation andv the tetramethyl
j ethylene then reacts. further ,with the methyl ‘
, halide to form the 2,3,3-trimethyl butene:
dissolving the ole?n in '75 percent sulfuric acid,
and then precipitating the alcohol by adding
water.
-
>
'
'
'
. Hydrogenation'of fraction'numberi3 at 80° C. V
in the presence of a reduced nickel-kieselguhr
catalyst gave ‘a 90 percent yield of‘ 2,2,3-tri
methyl butane, boiling point 80° C. and melting
point.——28° C‘.
'
.
'
-
The lead. iodide recovered fromzthe primary
step was mixed with one-half its weight of methyl
sulfate and the mixture was heated slowly to a
temperature of 150° C. At this temperature
methyl iodide (boiling point 41° to 42° C.) distilled
off and was recovered in an amount correspond
The hydrocarbon charging stocks for the proc
I ess may be made by any available method such
the dehydration of- corresponding alcohols.
‘Tetramethyl ethylene may be conveniently pre
} pared by reacting tertiary butyl chloride and
,3 ethylene‘ to form an alkyl halide which can be
idehydrohalogenated to form5 the substituted
lethylene. Thus the ‘charging stock of the process
lfor the manufacture of, 2,2,3-trimethyl butane
imay be madevfromiole?ns produced incidental to
}the.cracking of hydrocarbon oils-to produce gaso
line since both isobutylene and ethylene occur
. ‘in cracked gas mixtures.
'I'hepreferred'oxide of lead ‘for use in the ?rst
step of the process is the monoxide commonly
v‘known as'lith-arge, whichqis readily available
commercially. The higher oxides of lead, includ
ing the dioxide, ,the sesquioxi-de and the red
rOXide known as Ininium, have too great‘ tend
ing to over 95 percent of that usedrin the ?rst
step.. The reaction mixture was‘ then heated
further to 190° C. in order to distill over the excess
of methyl sulfate. The residue which’ consisted
chie?y of lead sulfate was mixed with one-half
its weight of anhydrous sodium carbonate and
the mixture was heated‘ at a red heat for two
hours. The resulting mass was cooled, leached
with water to remove sodium sulfate and leave
lead oxide in a suinciently pure state for reuse in
the ?rst step of the process.
I claim as my invention:
.
~
1.. A process for the manufacture of 2,2,3-tri
methyl butane which" comprises reacting tetra
methyl ethylene with methyl iodide in the
presence of lead oxide to form lead iodide'and
2',3,3-trimethyl butene-l, hydrogenating said last
.named compound in the presence of a catalyst,
and reacting said lead iodide with methyl sulfate
to form methyl iodideand lead sulfate.
I , >
2. A process for the manufacture of 2,2,3-trie
2,406,110
5.
methyl butane which comprises reacting tetra
methyl ethylene with methyl iodide in the
presence of leadoxide to form 2,3,3-trimethyl
butene-1 and lead iodide, hydrogenating said
2,3,3-trimethyl butene-l in the presence of a
catalyst to produce 2,2,3-trimethyl butane, react
ing said lead iodide with methyl sulfate to form
methyl iodide and lead sulfate, treating said lead
sulfate to produce lead oxide and returning said
methyl iodide and lead oxide to further use.
3. A process for the manufacture of 2,2,3-tri
methyl butane which comprises reacting tri
methyl ethylene with methyl‘ iodide in the
presence of lead oxide to form 2,3,3-trimethyl
butene-1 and lead iodide, hydrogenating said 15
2,3,3-trimethyl butene-l in the presence of a
catalyst to produce 2,2,3-trimethyl butane, react-_
ing said lead iodide with methyl sulfate to form
methyl iodide and lead sulfate, treating said lead
sulfate to produce lead oxide and returning said
methyl iodide and lead oxide to further use.
4. A process for the manufacture of 2,2,3-tri
methyl butane which comprises reacting tetra
methyl ethylene with methyl iodide in the
presence of lead oxide to form 2,3,3-trimethyl
butene-l and lead iodide, hydrogenating said
2,3,3-trimethyl butene-l in the presence of a
catalyst to produce 2,2,3-trimethyl butane, re
acting said lead iodide with methyl sulfate to
form methyl iodide and lead sulfate, treating said -
lead sulfate with carbon to produce lead oxide and
returning said methyl iodide and lead oxide to
further use.
5. A process for the manufacture of 2,2,3-tri
methyl butane which comprises reacting tri
methyl ethylene with methy1 iodide in the
presence of lead oxide to form 2,3,3-trimethyl
butene-l and lead iodide, hydrogenating said
6
'7. A process for the manufacture of 2,2,3-tri
methyl butane which comprises reacting tri-.
methyl ethylene with methyl iodide in the
presence of lead oxide to form 2,3,3-trimethyl
butene-1 and lead iodide, hydrogenating said
2,3,3-trimethyl butene-l in the presence of a
catalyst to produce 2,2,3-trimethyl butane, re
acting said lead iodide with methyl sulfate to
form methyl iodide and lead sulfate, treating said
lead sulfate with an alkali metal carbonate to
produce lead carbonate, heating said lead carbo~ _
nate to produce lead oxide and returning said
methyl iodide and lead oxide to further use.
8. A process for the manufacture of 2,2,3-tri
methyl butane which comprises reacting tetra
methyl ethylene with methyl iodide in *-the
presence of lead oxide, at a temperature of from
about 200° to about 250° C. to form 2,3,3-tri
methyl butene-l and lead iodide, hydrogenating
said 2,3,3-trime'thy1 butene-l in the presence of a.
catalyst to produce 2,2,3_trimethyl butane, re
‘ acting said lead iodide with methyl sulfate to
form methyl iodide and lead sulfate, treating said
lead sulfate with an alkali metal carbonate to
produce lead carbonate, heating said lead carbo
nate to produce lead oxide and returning said
methyl iodide and lead oxide to further use.
9. A process for the manufacture of 2,2,3-tri
methyl butane which comprises reacting tri
methyl ethylene with methyl iodide in the
presence of lead oxide, at a temperature of from
about 200° to about 250° C...to form 2,3,3-tri
methyl butene-l and lead iodide, hydrogenating
said 2,3,3-trimethyl butene-l in the presence of a
catalyst to product 2,2,3-trimethyl butane, re
acting said lead iodide with methyl sulfate to
form methyl iodide and lead sulfate, treating said
lead sulfate with an alkali metal carbonate to
produce lead carbonate, heating‘said lead carbo
catalyst to produce 2,2,3-trimethyl butane, re 40 nate to produce lead oxide and returning said
methyl iodide and lead oxide to further use.
acting said lead iodide with methyl sulfate to
10. A process for manufacturing branched
form methyl iodide and lead sulfate, treating said
chain paraf?n hydrocarbons which comprises re
lead sulfate with carbon to produce lead oxide
acting a mono-ole?nic hydrocarbon with a methyl
and returning said methyl iodide and lead oxide
2,3,3-trimethyl butene-l in the presence of a
halide in the presence of lead oxide to produce
a higher molecular weight mono-ole?n and hy- '
6. A process for the manufacture of 2,2,3-tri
drogenating said mono-ole?n to the correspond- .
methyl butane which comprises reacting tetra
ing paraf?n.
methyl ethylene with methyl iodide in the
11. A process ‘for manufacturing branched
presence of lead oxide to form 2,3,3-trimethyl
butene-l and lead iodide, hydrogenating said 50 chain paraffin hydrocarbons which comprises re-.
acting a mono-ole?nie hydrocarbon with methyl
2,3,3-trimethyl butene-1 in the presence of a
iodide in the presence of lead oxide to produce a
catalyst to produce 2,2,3-trimethyl butane, re
higher molecular weight mono-ole?n and hydro
acting with lead iodide with methyl sulfate to
to further use.
form methyl iodide and lead sulfate, treating said
lead sulfate with an alkali metal carbonate to
produce lead carbonate, heating said lead carbo
nate to produce lead oxide and returning said
methyl iodide and lead oxide to further use.
genating said mono-ole?n to the corresponding
paraffin.
LOUIS SCHMERLING.
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