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Патент USA US2404537

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Patented July 23, l946
' 2,404,537,
, I ‘UNITED
Pars
2,404,537
\
a,
TREATMENT OF HrDI’tooARBoNs
"
Louis ‘Schmerling and Vladimir N. Ipatie?“, Chi- ‘
,cago, IlL, assignors to Universal Oil Products
Company, Chicago,,Ill., a corporation of Dela
I
ware -
v
.
‘ ‘No Drawing. lAp'Dlicatioh July 6; 1942,
Y “Serial No. 449,946
“'16 claims.
v
(01. 260-15834) '
This invention relates to the treatment of iso; V the respective boiling points'which vare listed as"
paraffinic- hydrocarbons to produce‘ therefrom:
'
‘follo'w's:~~*
-
1
:3:
:wi'I
, ' branched chainpara?inic hydrocarbons-oi higher ‘ '
' molecular weight; 1 ‘In a'more'speci?c sense,1th-is
invention'is concerned withsaznovel- proc'esskfor ‘
@ mm?
,pressure»
interacting alkylatable para?inic hydrocarbons,‘
herein termed isopai'af?ni'cuhydrocarbons, with
alkyl esters of chloroformicacidto produce higher
760
760
160
boiling'para?ihic hydrocarbons of gasoline ‘boil
ing range.
,
760v - a
'
, 760
28
15
20
10
In one speci?c embodiment, the present inven
tion relates to a process’v for synthesizing hy
drocarbons which comprises reacting an iso
para?inic hydrocarbon with‘ an alkyl ‘chloro
formate under alkylating conditions in the pres
I5
ence of a Friedel-Crafts type metal halide cata
lyst.
‘
'
Considerable'quantities of butanes, pentanes,
and other parai?nic' hydrocarbons of relatively
low molecular Weights are available in the rela 20
tively light hydrocarbon ‘material condensable
ing head gasoline. These relatively‘light com
ponents of casing head gasoline also includevcer
tain amounts of the corresponding isopara?ins,
namely, visobutane, isopentane, etc. The rela
tively low boiling normal para?ins may also be
isomerized into the corresponding isoparaf?ns by
Friedel-Crafts type; metal halidesv which are; I
utilizable as catalysts for promotingthe alkylaé'"
tion of’ an isoparaf?n with an alkyl chlorofor=?
matein accbrdance with thepresentinvention in-I s
c1ude;suchjsaltfs as ‘aluminum chloride;aluminum
bromide, zi chloride, zirconium chloride, ferric
chloride, ant-i. mom’ chloride». bismuthflphloridé»
and others;v ‘We prefer, however, to employ alu-j .
from natural gas and usually referred to as cas
minum chlorideas the Friedelecraifts type; cata"
lyst in such- alkylation' reactions because ;it
25
usually, higher (in. catalytic “activity than‘; e"
other Friedel-Craits type metal halides in'a given ‘f.
reaction under speci?ed‘ conditions. Aluminum."
chloride may be used as such, maybe ‘supported’, '
by a refractory carrier suchas alumina,‘silica, 1
porcelain,
etc., or it may be used in solution in‘ a;
tanes and pentanes are formed ‘as by-products'in 80 »_ solvent such
as a nitropara?in, particularly nitro
the cracking of petroleum fractions and of ‘other
methane. , Other Friedel-Crafts-type metal hal
hydrocarbon oils to produce‘gasoline.
ides andparticularly chlorides maymbev added ,to
Alkyl esters of chloroformic acidhwhic'h are
the aluminum chloride or to its'solution'ior the
utilizable as alkylating agents in the‘ process of
' suitable treatment.‘ Further quantitiesofjbu
purpose, of modifying the, activity of . the
,
the present invention have the general formula:
num _ chloride.- , ’
ClCOOR, in which R represents'an alkyljgroup.
Alkyl chloroiormates are readily obtainable by
byi‘While
alkyl amyiaudn‘pr
chloroformates
isoparalilil'nici:I
vmayib‘e‘ .e?e'cted ‘in. ‘the. ,1
the treatment of an alcohol with phosgene, Thus,
'
presence,oflaluminumchloridegandother
Fried s,
as indicated in the following equation, reaction of
Crafts type catalysts._ at temperature 011mm
1 molecule of phos‘gefne with 1 ~vmolecul'esofiisoh
about , gzor to. about-1
pro'pyl alcohol results ‘in .the' formation,v oi 11 ,mole- , peraturepf from about-10 1 ,c, ‘neau'selrof Meme. ,
_
to'about ‘7Q?! C, is ,pre- , ,
cule each of isop-ropyl chloroformate andehyd'ro- '
ferred; IPressures‘utilizableyinlthe'process may @_
gen
chloride:
-
H
-
i
03H10H +0001,
Isopropyl
.
gene
‘
'
‘
' varyfrom'substantially atmospheric? to about 50..‘
0100065111, ill am
Phos-
alcohol
v
Isopropyl_‘_
,
; Hydro-
chloroformate , ‘ gen},
.
:
@ > v '
i-'~
ride
‘Some of the alkyl’chloroformates which are ‘
often referred to as alkyl 'chlorocarbonate’s' have
atmospheres or more.‘ Inorder ‘to obtainwhighw,
yields of hydrocarbon products of gasoline boil- _
' ing range with relatively'srnall amounts of jun-l
-
'GhIQ'..~-w
‘
‘
,
desira'ble‘side reactions, such as polymerization,
formation
of
organic
compounds I containing ~ Q
chlorine, etc, it is desirable to maintain a molar »,
~_ excess of isoparailin hydrocarbon-to alkyl chloro
,
V
2,404,537
3
formate throughout the entire reaction period.
organic compounds and catalyst are passed un“
Generally from about 2 to 25 molecular propor
der alkylating conditions and in which sumcient ‘
tions of ,isopara?inic hydrocarbons should be
present per molecular proportion of alkyl chloro
time is given for the completion of the desired
isopara?in alkylation. ~The products from such;
formate introduced to an alkylation reaction mix
ture in order to form a substantially saturated
a reaction zone are then directed to a separating
zone in- which the alkylation‘products are sep-L
hydrocarbon material and to avoid undesirable
polymerization and decomposition reactions.
- aratedfrom. the unconverted iso'parai?nic hydro
’ v
The reactions which occur during the treat;
ment of _an isoparaflinic hydrocarbon with an
alkyl chloroformate in the presence of a Friedel-f
carbon, catalyst, and a‘mixture of hydrogen chlo
10 ride and carbon dioxide. . The recovered uncon
' verted isopara?inic hydrocarbon‘and catalyst are
then recycled to contact vwith'the mixture of 150'- I
' ,para?'lnic hydrocarbon and alkyl chloroformate
Crafts type metal halide, or mi ture of said metal
halides, apparently involve the combination of
being charged to the process. Hydrogen chloride
the isobutane with the ester of chloroformic acid
may also be recycled if desired.
accompanied by splitting out of'carbon; dioxide
and hydrogen chloride as illustrated’ by the fol
’
lowing equation:
-
i—C4Hm + C1C0OQ3H7
Isobu-
Isopropyl
tane
chloroformate
‘ .
e
, ‘ The activity of the Friedel-Crafts type catalyst
employed in the‘ process is dependent upon the
_
—'—->
A101:
C1Hm‘ + 002I» + ' 1101 ‘ '
Hep,
tane
‘
'
Oar- -Hyd.ro- V
.bon
dioxv
'
ide
vlien;
,
ch10:
;
ride '
4 .
'viding a mixing zone through which the reacting
w ' particular metal-"halide ormetal halide mixture
so utilized. The different Friedel-Crafts type
20 metal halide mixtures which may be employed
, to catalyze the alkylation are not necessarily '
g
1' '
'
‘ equivalent in their action particularly when react;
. ing differentisoparaf?ns with various alkylchlo
roformates' having alkyl,1groups of increasing
V ‘ The us'eof chloroformates (or chlorocarbonatese 7'
> _ carbon chain length and'degree of branching. '
' as they are often called) :has the advantage over
v‘The following‘ examples ‘are given to illustrate
i the similar use of other esters in that no :ireeV
the character of'theresults obtained ‘by, theluse l‘ l
organic acid'is produced during such reaction.“ ‘
of the. present process, although, the "data. pre- .
' Acco'rdingly,-the aluminum chloride used as 'cata-- ,
senté'd', are ‘not ' introducediwith the‘ intention‘ of i
lyst in the process does not 'form an aluminum
‘chloride-organic acid complex, and hence only .30
unduly limiting
catalytic and not stoichiometric amounts of alu-‘
invention.“ ‘
"
the generally " broad scope "of the E '
'
V
r
.
.
EXAMPLEI
minum chlorideare'necessary for the reaction; _
Although'the mechanismsof the reactionslina '
'Alkylation of isobutane by ethyl chloroformate'
volved are not understood completely and should],
was carried ‘out by charging to a rotatable auto;
not be construed to limit the scope of the 'inyenf -
clave (lined with glass or nickel) a mixture; oi the
tion, the interaction, for example, of'isobutanez, 'is‘obutan'e; ethyl chloroformate, “and catalyst in
with isopropyl chloroformate yields heptanes.‘
the amounts indicated‘i'n Table, I.’ _,
Table I._jAm1/zationlof isobutane with-ethyl
' which, ‘include 2,2,3-trimethylbutane, generally. .
known as triptane. 3Heptanes so formed may re
act rurther with an additional quantity ofthe
<
40
e - . chloroformate 1
alkyl chloroformate such as isopropylg chloro~~
Run number
forrnate to form ‘a para?in hydrocarbon of still
higher molecular weight such as -a decane.v > Dec-I
'
anes'and other hydrocarbons ‘:of relatively high .
1.
-
2
e 3
'
._~ 4
molecular weight may undergo decomposition and
further conversion reactions in the presence of
the catalyst to produce'lowenand higher boiling
hydrocarbons which are generally paraf?nic in
naturelg/
'
'
V’
'
'
’
Reactants, g.:
.
‘
of 'mixing su?icient‘ to“ effect substantially com
110
81
V 172
Aluminum chloride__
_
40_ V. 40
Autoclave lining ___________________ ..' . ‘Nickel
:20
_Glass
agitation islstojpped ‘and the reaction mixture ‘is
separated into}, used catalyst, unconverted iso
paraiiin; alkylation product, and a mixture of
hydrogen chloride an'dacarbon dioxide,’ the latter :
'
Maximum ______ __
»2‘
1 4
30
7
4
1B
,50
25
10
18
43
17
40
1 50
_
7
Duration of run, hours _____________ __ ~
Products, g.:
V
5
.
,
6_
.
'70
. 4
'
7.
‘ :
Gondensible'gas _______ _.
173
Liquid hydrocarbon layer
'
Catalyst layer _________ __
_
70.
152 .
0
27
15
66
43
54
28
45
75
64
Hydrogen chloride, carbon diox-I
ide, and lcss.__._'____; _______ __
Distn.‘ of hydrocarbon layer,. volume‘
‘
percent:
-
.
'
"
a
.
Liquid-fractions:
-
'
‘
'
38
59'
'
'
i
Condensible gas__;______;
‘
plete reactionof the‘alkyl chloroformat'e with so
the ,isopara?imthe isopali‘sl?in being present ;in.
excess :of‘tli'ea1kyl chloroformateat all times‘, the
- \ .401
Nickel
'
-
Temperature, °C_ _ _
hydrocarbon and catalyst at the chosen operat
ing temperature and pressure- and'to introduce
gradually thereto an alkyl chloroformate or a.
mixturev comprising essentially an alkyl chloro-Iv
,
50
168
' Final at 20° O_ ___
procedureis .to, agitate a mixture, of para?inic ~
r
110
172
Initial, nitrogen added-
operation. In batch type operation, the preferred
7
110
_
'
carried 'out either in batch or continuous types of‘
formatsv and . anisopara?inic hydrocarbon or. an
~
_____
Pressure, atm.:
The process of the present invention may be 7
visoparaf?nicjhydrocarbon fraction; After a time ,
Y‘
Ethyl chloroiormate.
' Isobutane __________ _.
.
___;__ ___-V“
'3 3f;
______ __
.
'4 (52
'
.Below 40° C____'__-__
'
V
____ __
12
Between 40 and 75° 0-.
____ __
30
37
22
Between 75 and 95° 0..
___._
.7
______ __
7
4
Residue__- ________________ ._~______ _.
9
'
9
Analysis ‘of .condensable gas, mole
percent:
>
>
-
'
'
_
r
Ethane _________________________________ ..
Propane_ .
Butane--Ethyl chloride ____ __-___'__.___
-77.5
721.6
'
bons_'_'_;_____~_;:_;__i_;_~ _____ _-
'
'
0.9
1._6
i
I
' ~2.
79.6
. 80;2
16.6 ___.___-_
'
r
.5._8 -_‘__-__.'_
__________ __
Pentane ' and‘ higher ' hydr
8 -
.
79.
_10.
‘
i
3. 8 ' 1 12.74
'
8
two ' materials k resulting from the decomposition
of the alkylfchloroformate. The recovered cata
rutilligedgin?a subseguentalkylation treatment.
lyst andexce'ss of f-unconvertedisopara?in may be _
Sometimes hydrogen chloride is added to the ‘ref’.
7» actionnniggture, said hydrogen chloride either
being introduced from’ an outside source or re
covered ‘from a previous alkylation run.,.
'T-heprocess may be made‘ continuous by pro
1 Vapor pres. of isobutane; no nitrogen added.
.
1 Preceded by 2 hours at room temperature.
"
,
, .
'
’ ‘
I .
.
a Consists of butane, 22.1; ethyl chloride, 18.0; pen ane and higher
hydrocarbons, 59.9%. .
- 4 Consists of butane,
'
‘
44.8; ethyl chloride, 25.4;rpentane and higher '
hydrocarbons, 29.8%.
"The results given in Table i show that alkyla
tion' occurred in good yields atltemperaturevof ,
40° C. or higher. It isi’interesting to‘note that
2.4043537‘
the, liquid‘pro'duct boiled‘ at; a relatively low rem-'7
'we-aaimiajs our?inventionz;
perature and most'of' it boiled between§40°~ and‘
75° C. with very little boilingabove'v 100° C. a ‘ 1 '
EXAMPLE VII
.
.
‘ " ‘
1. A "process for;"s'ynthesi'zirigf hydrocarbons r v ’
which“ comprises 'reacting‘an iso'paia?'lnic'*lji'ydr‘63-‘v
carbo'n‘jwitha-n alkyl cl’iloroforniateiuhder alkyl
'
afti‘ngjconditions in the presence‘ of a lf‘riedelq
A total of' 120 grams'of isopropylchlorofo‘r'mate
‘ CIfaftstype iinetal halide catalyst.
was added slowly toi'a glassareactor"containing a
' “'-‘
I
, 2,: AQ process: fonsynthesizing 7' hydrocarbons
-‘ well stirred mixture of 205 grams of‘ isobuta‘n'e- ‘
which comprises: reacting: an isopara’f?nic hydro_-'
andv v20' grams of aluminum. chloride. ":The reac
. carbon withlan alkyl chloroformate ‘ati'a temper-*
tion temperature was maintained‘até‘aboutfthei
ature of from about —20° to about 100° C. in the‘
presence'fof a _ FriedellCrafts [type metal "halide
boiling point of isobutane"under=lrffatmospheref
pressure by permitting the isobutane Ito-reflux:
under a well cooled ‘condenser while. the isopro~
Catalyst-Y
,
.
-
.
‘
_3. A process for synthesizing hydrocarbons
1 which comprises reacting an iso'paraf?nic' hydro-I
pyl chloroformate was" introduced ."graduall'y't'o.
the reaction mixture 'over a periodof‘3 hours.
Hydrogen chloride was evolved at ‘aimoderate? 15 carbonwithan alkyl‘ ‘chloroiorrnalte' at a tempera;
ture‘ ‘of 'from about ‘>—'20° to-about- 100" C‘. under
rate duringthe time that vthe isopropyl chloro
formate was added but‘ this'e'volution‘ became ' a pressure of, from substantially atmospheric to
more rapid during an additional 3 hour periodlof
stirring which followed vthe intrOduction‘oFall
of ‘the isopropyl chloroformate. The ‘ increased ~20
rate ofreac'tion might have been due to aniin‘»v
crease in reaction temperature 'to‘about--3° C.
which occurred after part of the isobutane had
distilledifrom the reaction mixture during the
last partiof the stifring'treatment. From the
reaction product, Was. obtained 52 grams of col
orless liquid hydrocarbon material and 42 grams -
about 150 atmospheres in‘ the presence of ‘a
FriedeleCraits type metal halide catalyst.
4. A process for synthesizing"hydrocarbons
which comprises reacting an iso'para?lnic‘ hydroé"
ca'rbon' with an alkyl ‘chloroformate under-jalk'yl:
ating'conditions in the 'presencefot'a iFr'iedele
> Crafts '
metal halide catalyst, ’ whilev main-'
' tainingfa molar‘excess of said isopara?lnic hydr
I.
the entire reaction period.
.
carbon'lto said ‘alkyl ‘chloroformate throughout’
.
1
5. A process for synthesizing. hydrocarbons
which comprises reacting an isopara?'inic hydro
dish brown oil. In addition to the liquid hydro
carbons and catalyst, the recovered materials 30 caribon with an alkyl chloroformate at a tempera
ture of from about ~720° C. to about 100° C. un
comprised 148 grams of condensible gases
of used catalyst having the appearance of a red
(chie?y isobutane) and 41 grams of a mixture of
hydrogen chloride and carbon dioxide. The rel
atively large loss of 62 grams was probably due
to a mechanical loss of hydrogen chloride and
carbon dioxide. The condensible gas consisted
of 28.5 mole per cent of propane, 67.2% of bu
tane, and 4.3% of pentanes. The 52 grams of
der a pressure of from substantially atmospheric
to about 50 atmospheres in the presence of a
Friedel-Crafts type ‘metal halide catalyst while
maintaining a molar excess of said isopara?inic
hydrocarbon to said‘ alkyl chloroformate
throughout the entire reaction period.
6. A process‘ for synthesizing hydrocarbons
colorless liquid hydrocarbon material recovered 40 which comprises reacting an isopara?inic hydro
carbon with an alkyl chloroformate under alkyl
in this run represent 125% by weight of the pro
pylene which may be considered available from ' ating conditions in' the presence of an aluminum’
halide catalyst.
the isopropyl chloroformate. Distillation sepa
7. A process for synthesizing hydrocarbons
rated the liquid product into fractions having the
boiling ranges and refractive indexes indicated in 45 which comprises reacting an isopara?inic hydro
carbon with an alkyl chloroformate under alkyl
Table 2.
Table 2.-—-Distillation of normally liquid hydro- '
carbon product formed by reactionnf isobutane '
ating conditions in the presence of an aluminum
chloride catalyst whilemaintaining a molar ex
cess of said isoparaf?nic hydrocarbon to said al
with isopropyl chloroformate in the presence of
kyl
chloroformate throughout the entire reaction
50 period.
aluminum chloride
[Charge: 69 cc. (48.7 g.)]
Fraction No.
Boiling
rgndge,
Vol. of
traction,
cc.
8. A process for synthesizing hydrocarbons
which comprises reacting an isopara?inic hy
drocarbon with an alkyl chloroformate at a tem
Refractive
index @
20° C.
65 perature of from about —20° to about 100° C. in
the presence of an aluminum chloride catalyst
while maintaining a molar excess of said isopar
af?nic hydrocarbon to said alkyl chloroformate
throughout the entire reaction period.
9. A process for synthesizing hydrocarbons
which comprises reacting an isoparaf?nic hydro
carbon with an alkyl chloroformate at a tem
perature of from about --20° to about 100° C.
under a pressure of from substantially atmos
From the above table it is to be noted that the
pheric to about 50 atmospheres in the presence
product obtained by reacting isobutane with iso 65 "of an aluminum chloride catalyst while mainpropyl chloroformate contained relatively large
taining a molar excess of said isopara?inic hy
amounts of hydrocarbons boiling in the range of
drocarbon to said alkyl chloroformate through
the pentanes, hexanes, heptanes, octanes, and
out the entire reaction period.
a,
higher molecular weight paraf?nic hydrocarbons
10. The process of claim 9 further character
of gasoline boiling range.
70 ized in that said isopara?inic hydrocarbon com
The foregoing speci?cation and examples in
prises isobutane. '
'
'
dicate the character and practical value of the
11. The process of claim 9 further character-,
present invention, although it is not intended
ized in that said isoparaf?nic hydrocarbon com-'
that either section should impose undue limita
prises isopentane.
76 12. A process for synthesizing hydrocarbons
tions thereon.
}
‘2,404,582
,
7?:
from substantially atmospheric-to'about50 at:
I
which comprises reacting ; an - isopara?inic hydro
carbon vwith an alkyl ohloroformatew at a tem
mospheres in the presence-of an aluminum "chlo
ride catalyst. while maintaining, a molar excess; '
perature‘ of from about —20‘j.toabout‘10p“-,C.
under'a pressure of from substantially atmos-v
pheric to about 50 atmospheres in the presence)
of said isobutane to said ethyl 'chloroforrnate
throughout the entire reaction period.
of aluminum chloride and'another Frieydel-tCrafts '
portion of ethyl‘ chloroformate and from about 2', '
chloroformate throughout .thee'entire reaction
'
,
.7
1
13, A process for synthesizing hydrocarbons
which comprises reacting an isoparaf?nic hydro:
carbonrwith an» alkyl chloroformate ata ,tem
'
gasoline boiling range and-high ‘antiknockrvalue
which‘comprises contacting one moleculanpro
type catalyst while maintaining a, molar excess
of-said isopara?inic hydrocarbon to said alkyl
peri'od.~v
]
15.-A process forsynthesizing hydrocarbons of
to ‘about 25 molecular proportions of isobutane‘.
with an aluminum chloride catalyst at a ‘semi-1 .
perature of» fromryabout 40° toabout 100°‘ C. _
under --a pressure of *from ‘substantially atmos- '
pheric . to' about :50: atmospheres.= 1
perature‘ of from’ about 720° to about ‘100910.
. '16." A process for synthesizing hydrocarbons ‘of
under- a»; pressure , of: _from substantially atmlo'se.‘ 115' vgasoline boiling range and highrantiknock value
pheric to about 50 atmospheres in the presence
which comprises contacting one molecular pro-'
ofa composite comprisingvessentially, aluminum,
of a propyl chloroformate ~and from'about:
chloride Vanda refractory carrier ‘while maintain-. ' ' 2portion
to about 26 molecular proportions of isobutane
ing a molar excess of- said isopara?inichydroe,
with'an aluminum chloride catalyst at a tem
carbon torsaid alkyl ' chloroformate I throughout 20~
"perature of from about —20"»-to ‘about 100°C.
the entire ‘reaction ‘period, »
under a pressure of from substantiallyatmosw
‘_‘;14;;A<_ process for'synthesizing hydrocarbons
‘ of gasoline boiling range and high antiknock
value which
comprises
reacting isobutane V with ,
I
_
ethyltchloroformate at a temperature of, from 25;
"about'lio‘ito about (51009» C. under a pressureof
pheric‘ to about 50'atmospheres.
>
LOUIS SCHMERLING;
:
;
-,_>VLADIMIR N. IPA'I‘IEER,"
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