close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2519590

код для вставки
Aug- 22; 1950-
` `
D. A. MGCAULAY ETAL
2,519,587
DESULFURIZING HYDROCARBON OILS
Filed June 18, 1947
2 sheets-sheet 1
x
è
if
‘n
A
24‘
STRlP/AG
§34
ZONE
Í
A
5
C`So2m1p/furn“ds
Aug» 22,1950
D. A. MGCAULAY ETAL
2,519,587
DESULFURIZING HYDROCARBON OILS
Filed June 18, ‘1947 '
2 sheets-sheet 2
Patented Aug. 22, 195o
. 2,519,587
UNITED y srA'rEsÍ PATENT OFFICE
l DESULFURIZ’INGv HYDRlOCARBON OILS
Davia A. Macaulay, chicago, 111., and Arthur P.
Lien, Hammond, Ind., assignors to Standard Oil '
Company, Chicagoylll., a corporation of In
diana
ï _ Application June1s,1947,seria1N0.'z55,45'z
10 Claims. (Cl. 196--31)
2
hydrocarbon oils without substantially remov-ing low boiling mononuclear aromatic hydrocar
This invention relates to a process for desul
- furizing hydrocarbon oilsl
More particularly it
bons which possess high octane number.
'
Onel more object of our invention is to provide
relates to a process Vfor the desulfurization ofl
hydrocarbon oils containing hydrocarbon disul
ñdes.
'
a process for removing hydrocarbon disuliides
from a hydrocarbon oil containing substantially
'
In ther petroleum industry a number ofnhydro-`
carbonoils are produced which comprise sulfur
no oleñnic hydrocarbons or containing an ole->
finicïV hydrocarbon in less than an equirnolar
amount based on its content of hydrocarbon di
Particularly, the petroleum industry normally
produces relatively light or low boiling hydro 10 sulñdes; Still another object is to` provide a
method of simultaneously. alkylating aromatic
carbon oils such as gasoline,‘naphtha, kerosene
hydrocarbons contained in a light hydrocarbon
and heater oils which contain hydrocarbon di
oil with olelins and effecting the conversion> of.
sulfides. Thus, for example, mercaptan-contain
hydrocarbon disuliides and other sulfur com
ing (sour) gasoline condensed from natural gas,
distilled from crude petroleum oils orY derived 15 pounds contained therein to compounds which
compounds, l including
hydrocarbon
disulñdes.
ations is ordinarily subjected to so-called sweet
are preferentially soluble in liquid hydrogen ilu'
oride andare extracted from said oils by said
the foul odor of alkyl mercaptans, they markedly
thereof read in conjunction with the accompanyl
from petroleum oil fractions bycracking >oper
liquid >hydrogen fluoride, whereby both the
ening operations in the course of which the mer
clear octane number and lead susceptibility
captans in the gasoline are converted to gaso
line-soluble disulñdes which are retained in the 20 of the light hydrocarbon oil are improved.
These and other objects of our invention will
gasoline.
,
’
become apparent from the ensuing description
Although hydrocarbon disuliides do not possess
ing figures.
reduce the ability of lead alkyls such Aas leadv
We have observed that hydrocarbon disulñdes
tetraethyl to increase the octane‘number of the> 25
are dissolved only to a limited extent by con
gasoline or naphtha in which theyare present,
centrated liquid hydrogen ‘fluoride at normal
i. e., they reduce the Vlead susceptibility of the.
temperatures'. However, we have discovered
that hydrocarbon‘dis’uliides contained in a hy
ñdes appear to exert the greatest depressing eiiîectA 30 drocarbon oil can be reacted with oleñnic hydro-J
carbons in the presence of concentrated liquid
Buell,
on leadNational
susceptibility
Petroleum
(W. News,
A. Schulze
27, No.and
41,_A.
page
hydrogen fluoride to produce reaction products
fuel.r It has been observed that of the various
types of sulfur compounds, hydrocarbon disul
which appear to be almost entirely di-thioethers .
25V (October »9,1 1935.) )_. Hydrocarbon disulñdes
are also undesirable components inhydrocarbon
oils intended for ,use as `fuels 4for the reason @that
in ,the combustion process they are converted to
and which are extremely soluble inr concentrated
35
We have discovered a desuliurization ‘process for'
the removal of hydrocarbon disulñdes from hy
drocarbon oils in which- process concentrated
sulfur vdioxide which, with the water'genera'ted
in the combustionof hydrocarbons, tends 'dto cause
corrosion of metal surfaces with'which it comes
in contact.
_
hydrofiuoric acid at normal temperatures. Thus,
liquid hydrogen fluoridefunctions both as a cat
40 alyst'and as a solvent for the sulfur-containing
Accordingly, it is an object of our invention
to provide a process for desulfurizing hydrocarbon
reaction products,'i. e. as a desulfurizing agent
oils comprising sulfur `.compounds including hy
appears to take place may be represented“ as
drocarbon disulñdes. Y 'Another object ofv our in
vention is to provide a process for> converting 45
hydrocarbon disyulñdes and oleiins contained in
hydrocarbon oilsinto‘valuable chemical products
which can be recovered ÍOr'empIOyment in in-v
dustry; An additional object is to provide a
for the hydrocarbon oil. 'The reaction which
followsí `
>
`
R1'
R1
Y
i
`
"
Rl
Rl
>
`
R-s--s--R+R'--ë1=è¢af __» R-s-(lJ-¿J-s-R
.
«
A
' l' if
wherein each R >represents a hydrocarbon radical>
process ' for» Vremoving hydrocarbon disulfides and 50 (usually an alkyl radical) and each _R' ‘may be
equimol'ecula'r amounts of oléñnic‘ hydrocarbons
hydrogen or a hydrocarbon radical.
from-hydrocarbon oils containing them“, e. g.,
» Although. our invention may be applied tothe
gasolinev or kerosene.` A further Objectis to pro
vide a method‘ifor removing hydrocarbon disul
fides and otherHsulfur 'corripounds4 from light .
'
‘
desulfurizatìon of any hydrocarbon oil contain
ing disulñdes, it is believed that‘its application
will be of principal interest for the desulfuriaa
2,519,587
3
4
tion of relatively low boiling hydrocarbon oils
acyclic mono-oleñnic hydrocarbons, such as
such as gasoline-s, naphthas, kerosenes.
ethylene, propylene, 1- or 2-butene, isobutylene,
Our in
vention may, however, be applied advantageously
pentenes, hexenes, decenes, dodecenes, cetenes,
to furnace oil and the like.
Light hydrocarbon oils obtained from sour
crudes contain a variety of alkyl mercaptans, in
styrene, vinylacetylene, alpha-alkyl styrenes such
as alpha-methyl styrene, alpha- or beta-vinyl
naphthalenes; polymers of the above and similar
oleñns, for example diisobutylene whichy is a mix
ture of 2,4,`4,-trimethyl-1- and 2-pentenes, pro
pylene or isobutylene trimers and tetramers, and
the like. The oleñnic polymer employed may be
cluding methyl, ethyl', n- and iso-propyl, n- and
iso-butyl, n- and iso-amyl mercaptans and small
er amounts of higher alkyl mercaptans such as
hexyl, heptyl and octyl mercaptans.
In the'
sweetening process these rnercaptans are con
verted to symmetrical and unsymm'etrical alkyl
depolymerizable under the reaction conditions to
yieldi’the monomeric olefin which Will then enter
disulñdes.
In addition to hydrocarbon disulfid‘es the hy-'
drocarbon oil to be treated may c‘ontain‘aromatic
into~ reaction Withî. the' hydrocarbon disulñde.
We) may also employ cyclo-oleflns, e. g., cyclo
hydrocarbons, particularly relatively 10W boiling
methylcyclopentenes, terpenes, 3-vinylcyclohex
mononuclear aromatic hydrocarbfvmsfv such as
ene., cyclohexadiene-1,3-, p-benzoquinone.
hexene,
benzene, toluene, Xylenes, ethylbenzene, ethyl
dimethyl-LIE-butadiene,` cyclopentadiene, dicy
clopentadiene'; l.,4-pen-tadiene-,. Lñ-h‘exadi'ene, di
matics‘are' soluble‘ only to avery; minor extentv irr
- liquid hydrogen;k iiuorid'e.`- at ambient” tempera.
vînylbenzene and the like?
We‘m’ay al'soemploy a. variety of substituted
oleflns in. theî practicevoi'.- this invention, for ex
tures. Thus, gasolinas produced’ by thermal
cracking'î‘of gascoils> or other high'b'oilfing frac-
ample
tions of. crude oil: which. have been sweetened. by
such» as “doctor”
dines'; methyl'vin'yl- ketone', vinyl“ acetate, esters
of vcr'ot’onic,acrylic, metliacrylic‘ or sorbic acids',v
etc;
Thus" in desuliurizing straight: run, sweetened
'
'
The process of the- present invention~ may beI
practiced not- only with ol'eñn'ic compounds but'
also with materials'capable of> yielding these
compounds under certain reaction conditions.
tracts> a'fp'ortiori. of the disulñdes. Gasolines de
rivedfr byY condensation from “sour”y natural- gas
or. by non-cracking; distillation-._url crude petro
leum, followed> byî‘a svveeten-ingi operation, con.
In applying our invention to hydrocarbon
charging stocks; containing disulfides: but noL ole.
ñnic. hydrocarbons; or less.“ than arr. equimolar'
amount of oleñnic hydrocarbons basedon’the`> di
sulñde'content of: the charging stock, it» will be
necessary> to treat thel charging stockA with: con
centratedffliquid. hydro-gen ñuoride and arri added
oleñn in quantity such that the: total oleñn. avail
able for reactionzwith: thev hydrocarbon disulfide'
is'atwle‘ast e’qu'imolar with; respect to the: disulfide.
trifluoromethylvinyl
vinylthi‘oplienesg. vinylfuranes‘î and vinylp'yri‘
tane-'in'. hydrocarbon cils> to di’sulñdes1 and ex
ñn'icf hydrocarbons..
dichlorostyrenes,
benxzeries;v vinyl heteriocycliccompounds such as
sweetening, or by copper-salts adsorbed on clays,
contain hydrocarbon. dis-ul?ldes, oleñns: and usu-`
allyr-v some aromatic hydrocarbons su‘ch as ben'
zene‘, toluene. andî the'v like: Concentrated. sul’
furi'c acid, e. g. 90' to 98 Weight. per cent sulfuric
acid, in theY absence` of' olefins, converts mercap
tairrhydroca-rbon disulfides" but little? or. no“ ole#
cyclopentene,
venti'on; for example LS-butadiene, isoprene, 2,3
mono-oleñnic hydrocarbons, in addition to the
saturated. hydrocarbons; surprisingly, thesel aro
conventional process
cyclohexenes,
Poly-oleñns may also be employed in this in
toluene, propylbenzene or butylbenzene‘s, and"
some
methyl
Thus, asïhas been pointed out above, depoly
meri‘zable‘ polymers may be- employed asa source
of `oleiinV monomer for the" reaction with a disul
ñd'e:
Examples of such polymers are' di-, tri- or
. tetra-isobutylenes;
In the presencel of acidic
condensation' catalysts’ certainV highly branched
chain paraf'linic hydrocarbons undergo cleavage
tof'yield oleñnichydrocarbons.. and may be em
ployed as a source of oleñns for the 4present in
vention; a suitablel example of‘su‘ch' a highly
branched chain paraffin hydrocarbon is commer
cial isooctane which » comprises predominantly
2,2,4-trimethylpentane. Cycloalkanes of . highly
strained ringstructure- such as cyclopropane and
. substituted cyclopronanes. c.` g.. methyl- or ethyl
' cyclopropane, can function as` a source of pro
pylene or substituted propylenesy in the presence
gasoline or kerosene it is necessary to reactv the'
charging' stockV with addedi olefin. in:Y an amount
equim‘olar with' the amount of hydrocarbondi
sulñde contained in? the. stools».> When the'
of- acidicI condensation- catalysts. ~
Certain derivatives of oleñn- hydrocarbons are
unstable in. the presence of acidic condensation.
catalysts and are capable of yielding oleñns- in
their presence. This is- especially true of de
rivatives`V of tertiaryv oleñns. These derivatives
amount of mono-oleñriichydrocarbons contained
inl the charging stock exceeds thehydrocarbon
disulfide content of the stock, .the treatingcon'
ditions may be- adjusted (by control of ther
comprise mercaptans, alcohols, ethers, halides
amount' of hydrogen iluoride, temperature and 60 and the like. Examples are tert.-butylmercaptan,time) to effect the. disuli'ide-oleñn` reaction~ and
ethanol, isopropanol, tert-butanol, 4di-tertfbutyl
extraction. describedf‘above without causing sub
ether, tertiary octyl chlorides,tert-methylcyclo
stantial polymerization or other react-ion ofthe
pentyl chloride, tertQ-butyl- chloride,` tert-amyl»
olefinic hydrocarbons present in the charging
chloride.
_ stock in. excess of the amount of hydrocarbon di
A` Wide variety of mono-oleñnic’hydrocarbons
may be" added to the disulñde-containing charg
ing~ stocks ltovr adjust the'disuliid'e: olefin mole
65
We prefer to carry out tbe process of our in
vention’` with commercial, liquid, substantially
anhydroushydrogen~ fluoride. However, the in
clusion of» relatively -small amounts of WaterV inV
theî solvent-catalyst may be tolerated; thus the
ratio` to about 1. Either individual. olefins- or 70, liquid hydrogen ñuoridef solvent-catalystV may
mixtures of oleñns‘may bei employed'. Mixtures
contain up to' about l0 Weight per cent of Water.
ofîoleñns with saturated` hydrocarbons, e. g. as
In general, vvaterv tends to reduce theV solvent
found-’in petroleum re‘iìnery fractions,` may like
capacity of hydrogen: fluoride for Sulfur com
wise be employed.
`
» . '
.
pounds; therefore,v we prefer to employ substan
Thusf the invention may be' practiced-v with
tially anhydrous liquid hydrogen. fluoride or
2,519,687
.
`
s:
and A'charging stock in the liquid phase. 'Ordi
hydrogen fluoride containing ino more than about
5 weight per cent of water.
‘
l.
:
.l
.
The amount of hydrogen fluoride employed will
varyf .somewhat with the particular charging
stock, temperature, other operating. conditions
andthe results sought.` However, we ordinarily
employ atleast sufficient hydrogen fluoride to
i form a distinct acid phase, i. e., a phasein which
liquid hydrogen fluoride is the predominant
component. We may employ 5 to 100 per cent
of commercial liquid hydrogen fluoride or even
more,v based on the volume of the hydrocarbon
charge stock; ordinarily we employ betweenv about
l0 and about 30 volume per cent of liquid hydro
gen fluoride based on the volume of the hydro
carbon charging stock.
‘It 'may sometimes be desirable 'to effectre
action of hydrocarbon disulfldes‘with olefins and
extractionïof'the reaction products, respectively,
narily pressures between about 0y and about 200
p; s. ijg. are suitab1e,ie. g. a pressure of about
25 or 50 pgs. i. g. i
i ’
’
Thecontacting and acid separation equipment
heretofore` employed in I-IF-catalyzed alkylation
of isoparailins with oleñns can be employed in
the-practice of this invention. Thus the charg
ing stock, hydrogen fluoride and added olefin
(if any) can be passed through a coil, which
may be provided with baffles to induce mixing,
and thence into a gravity settler or centrifuge;
the `coil may be immersed in a heat transfer bath
to' provide for removal of the heat generated
in the reaction and to maintain the reaction
temperature within desired limits. In another
mode of operation, the charging stock, hydrogen
fluoride and added olefin may be pumped through
orifice mixers, ‘venturis' 'or' other mixing devices
in twodistinct stages. In` the ¿first stageithe're
andthence into a gravity settler or centrifuge
action between a hydrocarbon disulfide and an
olefln'may‘be effected in the presence of a small,
for effecting separation of desulfurized hydro
carbon and an acidv phase containing extracted
sulfur compounds. Other equipment and process
flows will be specifically described in conjunction
catalytic amount of concentrated vhydrogen
fluoride insufficient to function efficiently as a
solvent for the reaction products;A for example,
the reaction may be effected with between about
116 and about 5 volume per cent of liquid hydrogen
fluoride based on the Volume of the hydrocarbon
charging stock.` When hydrogen fluoride is em
ployed as a catalyst only it is preferred to employ
an'A amount at least equimolar withrespect to
the "amount of hydrocarbon disulfidej contained
in the hydrocarbon charging stock. In the second
with the accompanying figures. `
'
In the specific embodiment of our invention
schematically illustrated in Figure 1, the con'
tactor I0 is provided with a heat transfer jacket
Il through which a cooling fluid is circulated
during the contacting to remove heat generated
bythe reaction, thereby maintaining the contact
ing temperature within the desired limits. In
order to effect intimate mixing, contactor I0 is
liquid hydrogen fluoride is added to the reaction
provided with motor-driven stirring paddles I2.
The hydrocarbon charging stock containing hy
mixture derived from the flrst stage in an amount
drocarbon disulfldes, e. g., a sweetened, straight
(extraction)`
stage,
additional concentrated
suflicient at least to form a distinct ¿acid phase.
The acid‘phase contains the su1fur`"ontaining
reaction products,l predominantly d thioethers.
When-reaction and `extraction ar
ffected as
run" gasoline containing substantially no oleflnic
hydrocarbons is passed into the contactor through
valved line I3. A mono-oleñnic hydrocarbon, forV
example a refinery ethylene, propylene or butylene
distinct operations it may be desired'g-ïto conduct
each `operation at a different temperature. Thus
reaction‘may be effected at normalíor elevated
fraction can be charged into the> contactor
-through valved line I4. If desired part or all of the
olefinic material may be premixed with the hydro
temperatures, for example, temperatures from
carbon charging stock so that a blend of olefln and
about 50°’ F. to as high as about 250.*s F. and ex
hydrocarbon charging stock will be charged to the
contactor through line I3. It is preferred to
charge an amount of olefin substantially equi
molar with the amount of hydrocarbon disulfide
contained in the hydrocarbon charging stock in
order to achieve thoroughgoing desulfurization
of said stock. However, it will be appreciated
that less than an equimolar amount of oleñn
may be employed in any one contacting stage
and that a number of contacting stages may be
employedïwith the addition of olefin in `each
stagel ’Ordinarily‘it is undesirable to add more
than an equal amount of oleñn to the charging
traction may be effected at normal- or reduced
temperatures, for example, temperatures from
100°'.F. down to 0° F. or even lower; for example
Where> olefin addition is necessary, the olefin
may be added before, during or afterv the addition
of the hydrogen fluoride to the clïljarging stock.
It is not necessary to employ pure olefins.
`
Ordinarily we may effect the desulfurization
operation at ambienttemperatures', although the
temperature may be varied over r¿ilbroad range,
for example betweenvabout 0° F. and-,about 200°
stock, unless it is desired also to effect oleñn
Usually the process of the invention is con-J
polymerization to increase the yield of hydro
ducted at temperatures between about 50° F. and
about 100° F., for example between 'about 60° F. 60 carbon" product from the desulfurization process.
Also, it may be desirable to add more than an
and about 80“ F.
‘
'
`
equimolar amount of olefin, based upon the
The reaction between a hydrocarbon disulfide
amount of hydrocarbon disulñde, whenit is de
and a mono-olefinic hydrocarbo'nïiis exothermic
sired to effect alkylation of aromatic hydrocar
and ,rapid at about room temperature. Accord
bons or isoparaillnic hydrocarbons which may be
- ingly, dependent upon the particular tempera
ture HFzoil ratio, disulfide concentration in the
oil,fintirnacy of contacting, etc., tlíiëèlìeriod of con
tacting between the hydrogen fluoride, olefin and
disulfide may be varied fromfabout 1 minute
or even less to about 10 minutes‘ ‘1,
.
` ‘
'
Suilicient pressure is maintained in the con
tacting-zone and in the- zoneal‘lwhere the acid
phase is separated from the desulfurized hydro
carbon 'charging Vstock to ‘maintain at least a
substantial proportion of the VVhydrogen fluoride
present inthe hydrocarbon charging stock.
Fresh concentrated liquid hydrogen fluoride is
charged into the contactor from source i5 through
valved line I6, e. g., in anvamount equivalent to
about 20 per cent by volume based on the volume
ofl `hydrocarbon charging stock. It is desirable
to favoid extensive or prolonged contact of the
liquid hydrogen fluoride with the olefin in the
absence lof the charging stock containing hydro
carbon fdisulfldes'since contact may lead to un
astener
1
desirable' rea'ctionsVv such? fas" ’olefin polymerization
accompanied. by hydrogen disproportionation",
whereby the effective concentratioxr'ofoleñn is
appreciably reduced in the contactiri’gpzone". ‘
âß’filito' a;- Z‘orre
Ltlief'hydrogeir fi'uoridezand
sulfur compounds in solution `therein are' s‘epafr
rated-
'f ~
v3;'
`
._:
Í
,
‘
v`i
Whei the recovery of hydrogenffiuorideais'une
'
,.'In' contactorïlûf'the charging stock; vo'lei‘irr1and
important» andthe' ~principal object is' tdsepaìrate
hydrogen fluoride are' agitated at a> rate suñìcient
to' cause intimate admix'ture at a -suitabletenie
perature, for’ example about 60° F..to“a’bout 86°
the' sulfur compounds», the` acid may bel diluted
with water onneutrahZedQwhereupon the-suitor
compounda- notably di-thioethers, separate' asî an
Ff for a" suitable peri'od1,.'.for example' about I
hour, and are theni dischargedv through valved
lin'e l1 into> a» cooler `Iii where the temperature of
the ’mixture 'is adjusted- to a` desirable 'value for.
immi'scible liquid phase which may be washed with
the? subsequent' step of separating the hydroe
carbon and` acid phases.
desired, additional
concentrated liquid' hydrogen.' iiuoride‘ may be'
added-‘to the mixture in- line l1" through' valved
able formz-forireuse irrzthe contacting.; operatioi'ii
It is; therefore', desirable tosubiectthe- acid phase
line
191'“
"
'
Water'and.fractionate-d‘intoclose lboiling fractions
which'fmayîhave industrial value; Ordinarily 'it
is‘d‘esirable- to .separatehydrogen fluoride in suit-I
frottis-’the ,settler .tof aA fractionation- operation.l
This may be effected in` fractionator 3'I Inor'der
to» aidthe vaporization- and withdrawal oi hydro
"
From cooler t8 themixture' passes Vthroug'hilline
zfixinto- a s‘ett1er'2l’ wherein desulfurize'd hydro#
carbons arevsepar'ated from a liqu'idhydrogenl il 0
fluoride
though' the’settler’is
phase- containing
depicted
sulfur
as compounds.
a gravity settler,
it-:will be» appreciated that a` centrifuge couldbe
employed instead. If desired,- thesettler‘ may be
provided with packing to serve- as an aid to'strati-~
gen. fluoride-zr,"> a; stripping gas," whiclfr> mayy form
a/minimum-yboiling` azeotrope withchydro-gen flu--r
oridev mayfbe :introduced intol the.“ lowerî portion
ofithe- iractionatorthrouglr Valved line .32; Suit»a
abile"-stripping` gases include' methaner-ethane‘-,
propane, butanestandf pentanesi` If desired» frac'a
tionator 3! may be operated at a subatmospheric
. pressure-_V Hydrogenrluoride is vaporizedfin: the
iäcation'.: . Suitable packing materials comprise
tractionator and. passes i overhead through v-valved
shaped- fragments of carbon, coppen'Mon‘el'» metal,
line-33> for condensation ¿and reuse-in contacter l0.
carbon steel and certainl magnesium alloys con--->
tain-ing'minor‘ amounts of aluminum and still
smaller amounts of otheralloyingelements such
as zincfor manganese'. (Dowmetals). The-settler'
is‘equippe'd with an overhead‘valved Vent line‘ 22
through which 'light gases maybe released to> ad
The higher boiling- sulfur compounds are with
drawir from the fractionator through-valved line
tdi» _'Iv-‘hey may _be freed lfromv traces oi acid-«by`
washing withalkaliesf-and- water or by passage
over materials capable ofadsorbing orcombi-ning
chemically with: hydrogen fluoride»
just the pressure to a desired value. Suitable
Figure-f2 illustrates another embodimentzoi our
operatingl conditions for the settler‘compris‘e" a n - invention wherein counterñow contacting of. the"
temperature-between about~60° F. arid. about 120°
andzpressures between about Ofand about-«10'
hydrocarbon charging stock with liquid hydrogen
pls. i». g; ‘ InY the'settler ar‘erormedalower'phase
fluoride and separation of »a desulfurized hydro
carbon phase and an; acid phase enriched in sul
in’ which liquid hydrogen' fluoride is the~`~ pre~
furzc'ompoun'dsware effected in one tower. » Desuldr
dominant component and'ariupper hydrocarbonA
furizatioir tower _HI8 is provided with contacting
phase'of diminished sulfur c'ontent. ~ The hydro#
means» iol', for example shaped-:packing vmaterials
such as fragments of carbon, copper, -Monel metal,
carbon" phase’is ‘withdrawn through; valved line
23A through a hydrogen» fluoride-f stripping-zond 2'4»
wherein dissolved or Ydispersed hydrogonïfluoride»
is vaporized, optionally at pressures below atrnfos» ‘
phericand/or
asßmethaneg. eth‘ane-,fwith thepropane;
aid- o‘t’ stripping
bu-tane,gases’
permane,-V
etcî: From theY stripping ‘zone- the hydrocarbon
passes throughl valved line 275y tot storage or. tot such
ulterior treatment,- e. g.r, neutralizationfvas.may
be desired.
-
'
`
' Residual hydrogen' fluoridernay be .removed
from> the hydrocarbon oil by washing-with alka-f
carbon steel, - magnesium alloys, etc.A
Heat" ex
change coils m2 -are provided in the» contacting
section ofthe tower to aid in' controlling the tem
perature.; Hydrogen ñuori'de is admitted into the
tower from Ya source'such as storage tan-ky H13;
valvedline l Slt and line |05, passing into the upper
portion of the contacting zone in- the tower,
whence it passes-.downwardly'to-«the lower end. of
the-tower. The-‘hydrocarbon- charging stock con
tainingV hydrocarbon Adisuliides- is passed into the
lower portion toi the contacting zone inthe tower
throughvalvedli-ne' I o5 »and rises thro-ugh the con
tactingr zone `against the -counterflow oi' liquid
hydrogen ñuor-ide. The desired amount 'oi olefin
line»materia-ls,` e.v g; caustic'soda; by ypass‘ag‘e‘ over
metal ñuori'des, e. g., sodium'or potassium ñuo~
rid-es or hydroíiuorides; by passage o‘ver'adsorp'a
tive‘materials such as-»a’ctivated alumina, chrom;
is
iuin»r 0Xicle‘ï---alur‘nina,v silica gel;~ activated-„carbon
throughpva-lved line i?'l, The upper end oi the'
and the like.
tower, above the contacting zone~„serves1asaset~
tling'zone- for. the“ d‘esuliurized or partly' desul»
furized hydrocarbon charging stock'which-is'withA
drawn .therefrom through' valv'ed line- mit; whence
it may 'be withdrawn through l'iydrogen~ fluoride
stripping zone tti-Siandidischarged from ther system
.
When unsaturated hydrocarbon charging stocks
are employed, alkyl ñ'uorides- are-usually formed
added i to v the hydrocarbon charging stock
therein. The alkyl ñuoridesf have detrimentalE ef.-`
tects- oni the octane number of hydrocarbon fuels
and should bel'removed therefrom.
number. of
methods are amai-labile> iorde?luorination, includ;
" through.lineflfMl’.:> It is‘usually desirable to 'neue
ing high temperature treatmentwith bauxite and
tralize traces ot, hydrogen ñuoride which I‘iiay` be
thelike..
-
‘
.f . "Eher 'acid :phase `isf discharged from' the ‘ settler
through .valved line 28, whence partV or all ‘thereof
may be recycled> to 'contactor 'Id through- Valved
liner` 2l, heat exchangerv 28% inl which> its tempera?
ture 'is brought tothe desired value> for the con:
tac'ting operation', and valve‘d linelt'.î It is de‘
sirable to pa'ss`> atleast a partr of the‘ acid: phase
fromêthe settlerrthrough Vals/,fed line; 29' and heaterY
contained- irr the?y oilfleaving the - system through
[email protected]
,',
Y
«`
Y
Partf of the 'partly' desulfurized‘ hydrocarbon
stock may be recycled tothe vcontacting zone in
tower I?ß through-valved line i i I, Vheat exchanger
I IEfand‘ valved- lined-llt.AA TheV acid containing' dis#
solveds'ulfur compounds’settles into' the lower
most portion of tower ißt whence: it iswi-thdrawn
through .valvedline H3; and may: be recycled to
¿diaria?
10
ation .might be ,used instead. Although we have
the contacting zone through'pum'p'fl I4, valved line
|,I 5, cooler IIB and line |05. ,_ It is, however, desir
emphasized the reactions of ,hydrocarbon disul
fides with oleñns in the presence of liquid hydro
gen fluoride as. a ïcatalyst and solvent for the
tower |00 through valved line II1 and heater II'8
into a fractionator': I I9." lIn the fractionator, hy 5 product, it is appreciated thatïthe liquid hydro
gen-»fluoride may exert more or less solvent` ca
drogen fluoride is vaporized and passed overhead
pacityl for other sulfur compounds which may b_e
through Valved line |20, whence at least a .por
able to pass part or all of the-acidy phaseI from
presentiin thechydrocarbon chargingstock, .for
tion of the hydrogen iluoride vapors may~ be re
moved from> the 'system' through valved line- I2| ;
‘ exampleî thiophenes, Athiophanes or, thioethers.
preferably part ' or " all of l; the `hydrogen c ñuoride
vapors are >passed through valved line"V |22r and
condenser |23 -foi1 recycle'throughlline A,|05 tothe
Mercaptans react with olefins in the presence of
liquid hydrogen ñuoride as a catalyst-solvent to
form thioethers which are extracted by the hy
desulfurization tower |00. Toaid in the -v'aporiáa
drogen fluoride from the hydrocarbon charging
tion of hydrogen fluoride in the fractionator, a
stock.l Thioethers are far more soluble in liquid
hydrogen fluoride than the correspondingmer
stripping gas is passed through valved line |24
Captaris...`
ï „ i
->
and/or the fractionator may be operated at a
The general reaction of : organic disuliìdes
subatmospheric pressure. Sulfurcompounds are
with-:_oleñnic hydrocarbons in the presence
withdrawn from fractionator ||9 through valved
of chemical -compounds'which are acidic chemi
line |25. Gases which may accumulate in the
system may be removed from the desulfuri'zation 20 ical condensation catalysts to effect the prep
aration of dithioethers is claimed in applicants’
Vtower |00 through a valved vent line |26.
copending application for U. S. Letters Patent,
The following examples are introduced in order
Serial No. 755,456, filed of even date herewith.
to illustrate but not unduly to limit the scope oí
Having thus described our invention, what we
the process of this invention.
25 claim is:
Example 1
1. A process which comprises sweetening a mer
captan-containing hydrocarbon oil to produce
A solution of n-octyl disulñde and n-heptane
a, hydrocarbon oil containing disulñdes, adding
was prepared containing 1.50 weight per cent of
an oleñnic hydrocarbon to the sweetened oil in
sulfur. This solution was agitated for 1 hour at
room temperature’ with 200 cc. of commercial 30 an amount sufficient to increase the molar ratio
liquid, substantially anhydrous hydrogen fluoride
per liter of the solution, ,after which agitation y
was discontinued and the contacting mixture was
allowed to separate by gravity into an upper hy
drocarbon phase and a lower acid phase. Sulfur
analyses of the phases indicated that only 9
v weight per cent desulfurization of the n-heptane
had occurred. Under otherwise identical operat
ing conditions but with the addition of 1 mol of
diisobutylene per mol of disulñde contained in
the n-heptane, 95 per cent desulfurization of the
of oleñnic hydrocarbons to disulñdes to at least
one, contacting the sweetened hydrocarbon oil
in the presence of said oleflnic hydrocarbon with
liquid hydrogen fluoride in quantity suñìcient at
least to form a Àdistinct liquid phase at a tern
perature between about 0° F. and Vabout 200° F.
under a pressure sufficient to maintain the liquid
phase, thereby effecting chemical reaction be
tween said disulñdes and said oleñnic hydrocar
bon to produce a hydrogen fluoride-soluble sul
fur-containing reaction prod'uct, and thereafter
» n-heptane occurred. Since diisobutylene depoly
merizes readily, one mol thereof can be considered
as the substantial equivalent of two mols of iso
separating a hydrocarbon oil of reduced sulfur
content and a liquid hydrogen fluoride solution
of said sulfur-containing reaction product from
butylene. It is apparent that the disulfide reacts 45 the mixture produced in the contacting opera
with the olefin to produce a sulfur compound
tion.
which is far more soluble in liquid hydrogen
2. A process which comprises sweetening a
fluoride than n-octyl disulfide, which under the
cracked sour hydrocarbon oil, adjusting the ole
conditions lof this experiment was relatively in
finzdisulfide molar ratio of said oil to about one
soluble in liquid hydrogen fluoride. It appears 50 and contacting said oil with liquid hydrogen
that the HF-soluble sulfur compound which is
ñuoride in quantity sufficient at least to form a
produced when an olefin is added is a di-thioether.
distinct liquid phase, thereby effecting chemical
reaction between said disulfide and said olefin to
Example 2
form a hydrogen ñuoride-soluble sulfur-contain
A solution of ethyl disuliide in n-heptane was
ing reaction product, and thereafter separating
55
prepared containing 5.6 weight per vcent of sul
a hydrocarbon oil of reduced sulfur and olefin
fur. The solution was agitated for 1 hour at room
content and a liquid hydrogen fluoride solution
temperature with 200 cc. of commercial, sub
stantially anhydrous hydrogen ñuoride per liter
under ethylene pressure, after which the pres
60
sure on Ythe contacting mixture was reduced to at
mospheric by bleeding ofi excess ethylene gas
and the mixture was allowed to separate by gravity
of said sulfur-containing reaction product from
the mixture produced in the contacting operation.
3. In a multi-stage process of removing a hy
drocarbon disulfide contained in a hydrocarbon
oil, the steps of contacting said hydrocarbon
oil in a plurality of stages with concentrated
hydrogen
ñuoride in quantity sufficient at least
acid phase. Sulfur analyses of the two phases
65 to form a distinct liquid phase with an added
, indicated that 99 weight per cent desulfuriza
olefinic hydrocarbon in an amount such that the
tion of the n-heptane had occurred. In the ab
olefinic hydroearbonsdisulñde molar ratio is less
sence of an added olefin desulfurization to the
than one in any stage but the total olefinic hy
extent of only about 60 weight per cent could be
drocarbomdisulñde molar ratio in all the stages
expected.
Although we have speciiically described the de 70 is atleast one, effecting chemical reaction between
said disulfide and said olefinic hydrocarbon in
sulflurization of hydrocarbon oils containing hy
each stage to form a hydrogen fluoride-solu
drocarbon disulñ-des by reaction and extraction
ble sulfur-containing reaction product, and with
with liquid hydrogen iluoride and a, mono-ole
drawing from the process a hydrocarbon oil sub
ñnic hydrocarbon, it will beappreciated that other
into an upper hydrocarbon phase and a lower
organic compounds containing olefìnic unsatur
stantially free of said hydrocarbon disulfide and
Документ
Категория
Без категории
Просмотров
0
Размер файла
1 111 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа