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Jan.

19, 1954

2,666,690

|-|_ o. FOLKINS ErAL


PRocEss FOR THE PRODUCTION 0F CARBON DxsuLFIDE

Filed DeCS.y 28, 1951

2 Sheets-Sheet 1

Jan. 19, 1954

H. o. FoLKlNs ETAL

2,666,690

PROCESS FoR THE PRODUCTION oF CARBON DISULFIDE


` Filed nec. 28, 1951

2 sheets-sheet 2

_ ww
| tl

2,666,696

Patented Jan. 19, 1954

f UNITED STATES PATENT] OFFICE .


' ' PnooEssFoR THE PRODUCTION oF

CARBON DISULFIDE

Hillis 0. Folkins and Elmer Miller, Crystal Lake,


and Harvey Hennig, Cary, Ill., assignors to
Food Machinery and Chemical Corporation,
New York, N. Y., a- corporation of Delaware.

ApplicationvDecember 28, 195.1, Serial No. .263,72418 Claims.


1

(Cl. 23-206)

The present invention is directed to a process

for converting hydrocarbons to carbon disulfide


yby reaction with sulfurv wherein a scavenging or
agglomerating material is utilized to nulliiy the

deleterious eiect of side reaction products.


It is known to prepare carbon disulfide by
reaction of sulfur with various hydrocarbons un
der catalytic 'conditions 'at elevated tempera
tures and pressures. It is reported that hydro
carbons having one to three carbon atoms in
the molecule 'are preferred for the reaction for
economic reasons, although certain investigators
show that unsaturated hydrocarbons and higher
molecular weightr hydrocarbons may be satis
factorily used in the process.

n. ,

reaction under conditions that are kinetically


optimum for each hydrocarbon gas. For exam
ple, in some instances the space velocities of the
reactants through the reaction zone must be ad
justed downward from optimum space velocities
suitable for the particular reaction environment
of hydrocarbon gas and operating conditions
used, in order to obtain maximum yields per pass
from the reactants. The alternates to lower
space velocities are to increase temperature and
hence corrosion diiiiculties or to operate' under
high pressures. Generally, the use of higher
space velocities lowers the extent of conversion.
Too low a conversion level will interfere with

Because oi the 15 product separation and recovery. By operating

complexity-of the reaction when using higher


molecular weight hydrocarbon charge gases
wherein there are produced various side reaction
products, it is generally preferable to use meth
Iane or a gas comprising highV percentages of

methane for the reaction. Experiments have in


.dicated that _hydrocarbons containing two to
Iive carbon atoms in the molecule are prone to

yield deleterious side reaction products which


contaminate the carbon disulfide product; cause
severe catalyst decline and consequent vdrop in
conversion, and contaminate the recycle sulfur,
making its recovery for reuse more difiicult. -T-he
ynatural gases containing 4 mole per cent ofrCs
hydrocarbons and 1 mole per cent or more of C4 '

hydrocarbons have been designated as border


line charge gases for the carbon disulfide reac
tion since even these small amounts of- hydro

under conditions of lower space velocities, higher


conversions to carbon disulfide may be main
tained, but the process is more inefficient and
productivity may be lower. Naturally, the use
of excessive amounts of sulfur complicates the

product purification steps and sulfur recovery.


The present process eliminates the above prob
lems without sacrifice of any of thev advantages
gained from the use of theabove mentioned
techniques, and is based on the discovery that

by removing the deleterious side reaction prod


ucts as they are formed by use of an agglomerat

ing materialpresent during the reaction, their


eiiect upon the reaction is minimized and the
sulfur content thereof is made recoverable. Re

moval of the side reaction products allows oper


ation at. all times. under optimum reaction con
ditions for maximum yield per pass without com

carbons of higher molecular weight than methane

plicating product recovery or sulfur recycle.` This

tamination and plugging of the reaction zone

type wherethedeleterious effects of the sulfur

have beenrfound to cause Vsevere catalyst con- .-. - is extremely advantageous in a reaction of this
with tars and polymers.

'

containing sidereaction productsfincrease with

increasing the eiiciency of the reaction and the

time and the presence ,of even a small amount in


the reaction zone is very detrimental.

ease -' of product recovery. These include new


catalysts, use of an excess of _sulfur over the

invention to provide a process for producing

p lNumerousl techniques have been developed for

stoichiometric

requirements,

preheating

the

charge gas and' sulfur to reaction temperature

Accordingly, it is the primary object of this


carbon disulde by reaction of hydrocarbons with
sulfur under conditions of maximum convert

sion, with a minimum of influence from side


orabove, and techniques for separating the car-_
bon disulfide from the` excess sulfur and side 45 reaction products and with little or no diiiiculty
in product recovery or sulfur recycle.
reaction products. These improved techniques
A secondary object of` this invention is to pro
have greatly increased the amount of carbon di
vide a .process for the eiiicient> and economic
sulfide which can bev obtained from a given
production of carbon -disulfide from hydrocar
amount Yof charge gas;UA However, in their prac
tice it is not always i possible to conduct the 5 bons that are prone to form vdeleterious sulfur

2,666,690

containing side reaction products wherein an

agglomerating material, which may be catalytic


or not, acts to remove these deleterious side re

action products from contact with the reactants


before there has been an opportunity for them to
lower the reaction emciency.

Another object of this invention is to take

4
In coil 22 of heater t, the molten sulfur is
heated to a sufficiently high temperature to vap
orize it, as for example, 850 to 12%o F. under
given operating pressures. Preheated charge gas
leaves coil S by line 24, controlled by valve 25, and
passes to line 225 Where it joins and uidizes the

agglomerating or catalytic material before enter


advantage of the unreacted sulfur content and
ing reactor 3E). Sulfur vapors proceed from coil
the combined sulfur content within the effluent
22 via line 32, controlled by valve 34, to join the
products, removed by the agglomerating material,
charge gas before it enters line 28. Simultaneous
to react 'with aprincipal byeproduct, hydrogen
intro'ductionef ythe reactants finto .Contact with
sulfide, .from `the reaction, thus 'reforming in
"each other and "into contact with the agglomer
usable condition sulfur which would .otherwise
ating material bei-ore their entrance into the re
be lost.
-'actor is generally the preferred technique. How
Still another object of this inventionis topro
-even ins-ome cases, especially where higher hy
vide a process for producing carbon `disulfide
-idrocarbons are being used as the charge stock, it
wherein an agglomerating material removes the
maybe preferable to introduce the sulfur vapor
tars, polymers, some of the excesssulfur, anilsul
y'.to'f.theireac'tor separately. In this case, the sulfur
fur-carbon complexes for exidationito substan- `
vapors pass 41Vfrom line 32 to line St, controlled by
tial amounts of sulfur dioxide, Whiehis'utilized" 20 ~valve38,.intoreactor 3&3 where they meet the hy
to react with. the hydrogen suld'e'byeproductito
'drocarbonggas and "fluidized material. Both the
form elemental sulfur for reuserinrthe ...reaction
4icuteheatecl rchar-.ge :gas and the vapor-ized sulfur
Further objects and advantages of the inven
may be subjected to superheating to reaction tem
tion will become apparent as the description
peratures or above prior to their entry into re.
thereof proceeds.
" actor 30.
The term principalproducts fas =used'herein
'Reactor 3B >is providedmvith a bottom conical
appliesto the carbon disuliide andhydrogen sul-'
shaped section it!) yirivvhich the Ya'dmixture.sofipre
fide which are `the normal Yproducts Ao thevco'rr.
heated sulfur vapors vand:chargefgas takes'place.
plete reaction rof sulfur >and -charge gas. "The
A vertical return .sta'ndpipe'iz lprovided with-.valve
term sidereaction.products'wil1lbe usedto refer 30 44 for controlling the flow of iluidized :mixture
to Vthe Aproducts formed from Vthe~'incomplete sul
therein is located vwithin Lthe centralportion of
fur oxidation >of fthe carbon andhydrogen-con
reactor '30. Standpipe i 2 extends `from lower
tent of the charge -gas. These "include carbon
conical section F493 yto upper enlarged conical sec

'hydrogen-sulfur complexes, 'sulfur-carbon com


plexes, tars, and coke 'above referred to.

tion 46.

Make-up agglomerating 'material is

' introducedinto'thesystem iromhopper fgcou

In the accompanyingdrawingsjFigure"l shows


'one'typeofreactor for producing carbon disulde
and a -system for loxidizing' thehydrogen sulii'de
to elemental sulfur. `l'iefure'Zshovvs a'system'for
separating carbon disul?ldefromhydrogen sulfide
and othersid e reaction products.

The present-process lis best described "byrefer


ence vtothe accompanying drawings. In Figure ~1
the charge gas is 'introduced'at vline v,fcontrolled

by valve fdfinto coil S of'heatertavhereiit ispre


heated >to reaction "temperature `or above. Ele
mental suliur is introducedromsulfur hopper I0

into sulfur melter ZWhere itis meltedlby steam


`in coil lll. Heat is appliedto coil ift-so that the

`moltensu'lfur is kept at atemperature between


approximately 250 'fand 300 F. and preferably
about 270
Obviously, those temperatures lare
to be avoided at which~viscoussulfurforms. The
4molten sulfur is pumped from the melter Vi2 by

trolledby valve 5.5,into line T23 whichf'eeds *di


rectly into'lower conical'secti'on 13D >oi reactorll
' via line 52, controlled"by1valve`54~ fUnderfeertain

conditions, itV maybe desirable to vutilize'tlfle latent


heat content of the regenerated agglomerating
material to aid in the lvaporization and 'super
heating ofthe sulfur; "forthis purpose, the'fhvdro
carbon chargegasheated orunhe'ate'd, passes via
lines 24 or 56 into line 28 Where'iluidiza'tion o'f the

agglomerating material-takes place. The iiuid~


ized mixture passes 'from line 28 fv'ia fline "58 'and
valve 60 to `jo'infthesulfur stream at a point in
coil >22 where :the 'temperature 'iis 'about Athe boil

ing point 'of sulfur. The heated lmixture leaves


. Acoil 22 and entersreactor 30 `via lines 32 fand F35.

'Contact of the -agglorneratingfmaterial with the


reactants takes place in'reactor Si@ in the same
manner as is employedin'the'moving bed, >pebio'le
and v'llhermofor cracking processes, Standpipe
means of sub-merged centrifugalpump VT5, lsuit- " 42 serves'to vcontrol the'llow of heavier-particles
`able forhandling molten'sulfunthrough'lines f'l'
-through the iiuidized mass. Conical section '46 is
`and 2U into coil 22 Aoi" heater 8. lSufficient pres
designed 'so that the maximumhindered settling
sure must 'be used >to force the Vmolten, sulfur
takes place therein.
'through coil 22. For this Upurpose, pressures "up
Accordingly, reaction vproducts and Athe fine
to 100 pounds per square-inch-ma-y be used. The
portion or smallerparticles of ,agglomeratingfma
ypressures 4under 'which the >molten sulfuris moved
terial rise to the-small upper >section 62Sfor pas
throughout the system will Idepend `upon `'the 'op
sage into .cyclone separator 264.. `Cyclone .separa
eration pressuremaintainedin the reactor, Tur
tor 6.4 .serves to .separate .the line particles -of
naces, and converters.
That portion of the equipment Whichis > in 'con

agglomerating material rom the reactionprod

-tact -With sulfur-bearingvapors at elevatecl"tern-

ucts and return them into zthe denser-phase .of

vperatures >is `cest constructed vof - a >materialwhich

the reaction. Reaction products leave the'top vof

-is 'resistant "to the corrosive -action lof sulfur.


Various stainless 'steel alloys, such as those -ofl

>nde-hydrogen suldefseparation vsystem yto .be kde

reactor 3G vialineii to )pass 4:to the carbon disul

high `chromium content, Vand 4cliromiuzneniclcel 70 scribed in Figure 5.2. The vreaction products may
stainless steels stabilized ywith molybdenum, etc.
contain considerable amounts 4ofinesulfur par
.have proved eiective. Other -materials 'of con
.struction include :aluminum coated steels, ire

.Iractory linings, -and .other .types of :stainless


steels.

ticles -and isome naggloinerating material. This


A-inay be removed .(in apparatus notshown) by

subjecting the product :stream Vto .countercurrent


contact 'with cold :Waterfollowed by 'mechanical

2,666,690
6

erator E3 may be an ordinary furnace type re#


generator for oxidizing theI agglomerating mate

rialtoiree it 'fromocclude'd tars, polymersrand


sulfur-containing productsf The principalfprod
ucts of this oxidation'willb'e sulfur dioxide, car
bon dioxide, carbon monoxide, and water. yRe
generator 68, as shownin Figure l, is a fluid type
' regenerator whereinvthe- oxidizing gas isY intro

a suitable contact area I I0. Within the tower the

duced at line 1d. Burning .of vthe agglomerating


' material takes place throughout the central por
tion of regenerator 68, andthe regenerated ma
terial is caught in the annular space defined >by
inner cylinder I6 and the outer wall of the. re-`A
generator for return via! lines 'I8 and 28 `to the

reactor 30. The cycle of agglomeratingmaterial

tions within converter 84 are from 500 to 750 F.


The reaction may be caused to take place in one
or more stages. For example, the first stage may
be maintained at about 750 F. vand the second
stage at about 500 F. If necessary, heat maybe
applied to the reactor in order to initiate the re
action. The conditions Within converter 84 are
subject to some variation as long as the completeoxidation of the sulfur takes place.
vEffluent gaseous products from the converter
are admitted at the bottom of sulfurv wash tower
|04 by means of line I 05. Sulfur wash tower |04
is provided with a mistseparating section |08 and

separation of the sulfur and agglomerating mai


terial, which is returned to regenerator 68.
Heavier particles of agglomerating material
leave the reactor 30 by line 10, controlled by valve
12, to enter the bottom of regenerator 08. 'Regen

gases are subjected to countercurrent contact


with a stream of molten sulfur conveyed from

sulfur melter I2 vialines I8, H2, and II4 through


spray I I6. Molten sulfur accumulates inthe
bottom of sulfur wash tower and any heat ab
' sorbed from the hot gases or from the con

from- the reactor into the regenerator and back


into the reactor is continuous and conditions are

densation'of the sulfur vapor is removed byj in


direct heat exchange through cooling coil II8.

maintained for complete ~fluidization throughout

t Pump |20 serves to recycle molten sulfur to spray

the system.

'

i f

' Gaseous oxidation'products' from- regenerator

I I6 when sufiicient sulfur has accumulated in the


bottom of tower I 04. When the process has

reached this point, the recycling of sulfur through


68 pass through line 80', controlled by valve 82, to
line II 2 may be discontinued. Excess sulfur is
catalytic converter 84 for the next step in the
withdrawn through line |22 and passed to >`flash
operation comprising the recovery of sulfur there
~ drum |24. Flash drum |24 eliminates the'occu
from. On 'a molar'basis, for each mole of hy
drocarbon gas reacting with four moles of sulfur, pational hazard in sulfur melter I2 due to ab
sorbed hydrogen sulfide by flashing it off at at
there are produced one mole of carbon disulfide
mospheric pressure. f The sulfur within flash
anl two moles of hydrogen sulfide. One mole of
drum |24 is returned to sulfur melter I2 by line
sulfur dioxide will be required to convert the two
|25.
i
moles of hydrogen sulfide tofree sulfur. Since
Referring now to Figure 2, the carbon di
from the carbon disulfide reaction there will be
sulfide separation system, reaction products
produced in the form of tars and polymers ad
enter through line 280 into the lower portion of
-mixed with unreactedlsulfur, an amount up to
absorber 202. The absorber is fitted with
about 0.5 mole of sulfur, in combined and uncom-l
Raschig rings or other liquid-gas contacting ele
bined form, which will yield an equivalent num
ments. Absorber 282 is preferably maintained
ber of moles of sulfur dioxide in the regenerator,
at a pressure of approximately 20 to 50 pounds
there will ybe an excessof hydrogen sulfide to be
per square inch gauge in orderyto absorb carbon
oxidized by the sulfur dioxide. Consequently, a
disulfide from the reaction product gases. >Lean
portion of the hydrogen sulfide ranging from one
oil is pumped into the top ofV the absorber from
tenth to one-third is oxidized to form addi
accumulator 204 through line 208 by means of
tional sulfur dioxide Vforthe reaction. For. this
pump 2id. As absorber oil, heptane, or petro
purpose, hydrogen sulfide from the separation
leum naphtha having a boiling range of about
system (described in Figure 2) is conducted
250 to 400 F. or other fraction boiling above
through line 88, controlled: by valve. 88, toY fure
the boiling point of carbon disulfide may be used.
nace 90 wherein it is` oxidized to sulfur' diox
ide. The reaction taking place in furnace 90 is i

exothermic, and advantage is taken offthisto


preheat the incoming hydrogen sulde and air
within the furnace itself. Furnace 90 may be
packed with high temperature fire brick. Pre
heating the entire furnace by burning natural
gas therein may be necessary in; order to bring it

to operating temperature before the reactants -are


introduced. By-pass line92 is Vprovided to con-.
duct the balance of hydrogen sulfide .to the cata
` lytic converter 84.

The mixture of sulfur diox -60

ide and water formed in furnace 00 is conveyed by


line 94 to waste heat boiler 85 wherein they are
cooled before passage to catalytic converter 84
by line 98, controlled by valve |08.

Other -solvents or absorbing mediums such as


benzene and o-dichlorobenzene may be used.
It is preferable to choose an absorber oil which

has a boiling point or boiling range not too far


'above the boiling point of carbon disulfide in
order to enable the latter to be readily stripped
therefrom. However, heavier absorption oils
may be used and stripping carried out with the
aid of a stripping medium suchv as- steam,
methane,- or other inert gas. The unabsorbed
gasleaves the top of the absorber through line
2|2 and passes to furnace 98 and catalytic cone
verter 84 of Figure l. This gas is composed of
hydrogen sulfide with a small amount of hydro
carbon gas and about 0.5 per cent'or less of car

bon disulfide. The rich oil is withdrawn from


the bottom of absorber 202 by means of pump
2I4, passed through steam heater 256 where the
from theregenerator 68 and furnace 90A with
rich
oil is preheated to a suitable temperature, as,
the balance of hydrogen sulde to form elemental
for example, 208 to 350 F., and charged to the
sulfur. This is accomplished by means of cata
lytic converter -84 where in the reactant gases Ti) middle section of stripper 2i8. Stripper 2I8 is
provided with Raschig rings 22d or other liquid
pass downward through catalyst bed |02. The
gasV contact elements. Carbon disulfide is
catalystfor this purpose may be coarse Porof4

kThe final step in the sulfur recovery comprises


complete reaction of the sulfur Ydioxide content

cel, a-highfiron activated bauxite which is-sup'.


ported onv a stainless steel screen r'estingon ~al

strippedfrom the absorber oil and passed- from>


the top of the stripper through linef222, water

cast; iron grate..y Normally vthe ,operating condie' '

cooler 'or condenser224, where the temperature

2,363,690

7
is reduced to 31019112- 'or less, to accumulator 22.6.
f'gas and/'or vapor which vremains "uncon

'densed sleeves, the. accumulator '225 through vline

carrying foutfthe invention, attention is now fdi


rected to the reactants, thefgeneral reaction con

ditions, :and .the techniques employed in both the

thermal andcatalytic aspects Yof lthe invention, in


223 yand is returned to the .inlet of the fahsorber
232 'through line v221B. The stripper 2 i3 prefer -5 addition to pointing-out `speoiiic 'examples :of the
ably 'operated at a pressure slightly above the

DIOCBSS.

:pressure in 4the yabsorber .262, as, for example, 25


-to 55 pounds per square inch gauge', .in order to

The chargegas of theipresent process will `com


prise .anymixture- of hydrocarbons which vcon

avoid the necessity :of compressing the Y.gas re

tain :small amounts, that is, borderline amounts,

turned ythrough -line 228.

of constituents

which fare _prone

to .form

.'Ifhe vabsorber -oil is Withdrawn .from `the >plate


deleterious side reaction products, to larger
230 in 4.the bottomrportion of stripper 2i 8 through
amountsV of these. constituents. A typical hydro
carbon comprises ya lnatural gas containing in
line i232 vand lcharged Ato reboiler v234 and thence
returned throughline 235 to the section of the
excess of -one mo1e,;per cent of C4 and higher '
stripper below the plate 230. Plate 239 .is pro 15 molecular weight 4hydrocarbons or jmore than
vided with V.vapor uptakes 238. Lean absorber
four mole viper cent :of :C3 and higher molecular
oil is withdrawn from the bottom of stripper 2:28
Weight hydrocarbons. AHeavier gases including
through line
`cooled in Watercooler 242 to :a
propane, -butana :and :even unsaturated .higher
temperature below 106 F., and returned `to ac
molecular weight `hydrocarbons may be used.
cumulator 2534. it will he apparent that the rich ~> The agglomerati-ng material, as has been stated,
oil from absorber i2-ii?. can be used to ,partially
may be >either'catalytic or Vnon-catalytic. If the
cool the lean oil from stripper' il?, .by providing
material is non-catalytic, the >reaction is con
a suitableheat exchanger. Fresh absorber -liquid.
ducted kunder substantially Ythermal conditions
is I'added to :accumulator 294 -as required .through
and the agglomerating material used may'com
line 2.44.

prise -sintered alumina, silica, fdiatomaceou-s earth,

'

Liquid carbon .disulfide is Withdrawn from ac


of .the'carbon disulde may be pumped >through ,

and pumice. >Suchxnaterialsshould have :a par


ticlesizesuicientto pass through -a 100 `to .200
mesh 'screen in order that -they vmay -be vproperly
?luidized. If `a moving >bed process is used, -the

line .252 -to the upper portion of stripper 2i8 as


redux. The stabilizer :25d is operated at pres

pellets may measure from 1/8 inch to %;inch. `In


conducting the thermal reaction, the zpurpose of

cumulator i226 through line 2th and charged lby


means of pump 248 to stabilizer 25d. Aportion

sures of 20 pounds per square inch gauge or

the inert ` agglomeratingmaterial` is `to "fscavenge

above,1and,preferably inthe ranges of 5) to -150


pounds. The temperature in the bottom of the
stabilizer is that needed to eiiectivel-y boil the
>carbon disulfide Iand >free it of >hydrogen .sulfide
and hydrocarbon gas under the conditions of
operation. The stabilizer 25B is equipped with
contact surfaces 254, such as Raschig rings, with
apla'te 253 having vapor uptakes 25B and a re
.boiler 25S.
In the stabilizer 25d, any hydrogen

the tarry rand <.polymer--containing by-produc'ts,

sulfide or hydrocarbon gas absorbed in the car

bon disulde is boiled off and passes overhead


through line 2&2 through Water cooler 254. A
small amount of carbon disulfide passes over

head, is condensed in part in cooler 24,~and


collected in accumulator 266. The condensate
from accumulator kit@ is returned to the top oi

the stabilizer through line 268 by meanssof pump


210.

The uncondensed _gases and vapors are

withdrawn from the accumulator 266 through


line 212 and recycled to the inlet `oi .absorber
>2il2 .through linell. The bottoms from the sta
bilizer 25.0 are withdrawn through a pressure con

trol valve 214 .and charged through line 216 with


the necessaryheating or cooling, `to the middle

portion >of fractionating column l2.78 from which


the carbon disulhde is .taken overhead through
line 28B, condensed _in water cooler 282 and col
lected in accumulator k28A as ,iinished product.
Any bottoms, such as absorption oil, which may
have passed overhead with thefcarbon disulfide
'from stripper 228 are withdrawn from the bot
tom o'f the fractionator 2i'8 through line 236.
Fractionator 2li? is equipped with contact surn
lfaces 238, such as Raschig rings, a separator

and 'vfor this purpose only a relatively small


' amount of inert material in relation' to'theamount

of :Charge reactants Ais znecessary. Generally, the


amount .of fagglomerating material will need vto
be suicient tozocclude 'all of .the tarry `products
inherently :present in -the hydrocarbon charge
under the'operating conditions employed. Gen
erally, this :amount 'will -vary -from about dive `.to

fifty weightfper cent lbasedfon :the Vtotal yWeight


of charge reactants.
`The thermal'freactiontmay be :conductedat from
about 842 .to l650 F., lAlthough hydrocarbons
higher Yin molecular Weight than .fmethane will
react thermally with -sulfur vapor :fat'compara

tively moderate temperatures, this technique


requires long contact tim'esand, asia-consequence,
dehydrogenation and :tar'iormation reactions Vare
increased relative to that 'of carbon disulhde
formation. .Atmore elevated temperatures vWhere
the lfrate of .carbon disulfide 'reaction "is rapid,
these side'reactions'will 'be minimized `-and any

previously .dehydrogenate'd products -that may


have 4`formed `.Willareaot with sulfur to form ad
ditional "amounts .of carbon disulde. For these

reasons, .the preferred thermal 'reaction'tempera


turerangesfromlQSZ" .F.lto '1500" 1F. with adequate
residence time within .the reaction .zone for car
bon 4disulfide formation. These >reaction or
residencetimes -will vary .according to the tem

perature .employedand .according to the type of


hydrocarbon charge gas used. The preferred
reaction times "are in .the order of 0.5 to '25 sec

onds `under .atmospheric pressure conditions.


plate 2.3i) having vapor uptakes 2&2 and a re
When higher pressures yare used, vthe reaction
boiler 2M. Fractionator 218 is preferably oper
times `Will fbe v'relatively increased. Since unsat
ated at atmospheric pressure. The finished >car
urated hydrocarbons react'more readily than sat
bon disulfide is Withdrawn from the accumulator 70 urated hydrocarbons, with other factors being284 by means of pump 28E through line 298 to
equal, .the reaction time for the former will be

storage. .A portion of the carbon disulfide may


he .recirculated through line .3M as .reflux >to y.the

lessened.

topof the fractionation-278.

lwill serve .to both vpromote `the lreaction and,

4Semeral catalyticmaterialsare available which

-Having thusdescribed `the apparatus useful in .175 when used according to the methods outlined

2,666,690

10

tion products. These materials include synthetic


silica-alumina, silica gel, fullers earth, bauxite,

mass. The temperature of the regeneration may


be controlled by recycling into the regeneration
zone a portion of the regenerated agglomerating

activated alumina, and in general .thosetypes of


clays Ywhich are effective in theiremoval of color
bodies and gum-forming bodies from petroleum
oils. These catalysts may be used alone- or in

of cooled recycled agglomerating material is de

here, will serve to remove deleterious side reac

material after this portion has been cooled toa


suitable temperature in aV cooling zone extra
neous of the regeneration zone. The quantity

pendent upon its temperature, and decreases with


decrease in temperature of the cooled recycled
material stream. Common practice is to with
draw the cooling material stream from the dense
conium on silica gel or activated carbon are es
phase of the mass Within the regeneration zone,
pecially eiective catalysts. Oxides of titanium
cool it to the desired cooling temperature and
and thorium may likewise be used. In addition,
recycle it -to the regeneration zone.
the oxides and sulfides of iron, vanadium, chro
It is apparent from the description thus ffar
mium, molybdenum, and manganese may be used 15
that the method of operation of this invention
as` >promoters in combinationv with silica gel,
permits the >continuous ecient conversion of
fullers earth, or activated alumina catalysts.
higher molecular Weight hydrocarbons into car
When conducting these reactions catalytically,
bon disulfide. By operating in accordance with
lower temperatures maybe employed, the pre
ferred range> being from 842. F. to 1300YF. For 20 the invention, these higher hydrocarbons are
reacted almost quantitatively _to carbon disul
both Athe catalytic and thermal reactions, it is
fide with continued high catalyst activity
preferred to use about the stoichiometric amount
throughout the reaction. This isV inherent in the
of sulfur needed to react'with `all of the carbon
process since the reactants are'- continually be
and hydrogen ofthe hydrocarbon to form car
ing contacted with fresh or regenerated agglom
bon disulide andk hydrogen sulfide. Theratio
erating material under either thermal or cata
of lsulfur to hydrocarbon charge gas may, how
lytic conditions andthe agglomerating material
ever,vary considerably and it is preferred to op
is continuously removing the deleterious side re-.
erate with an amount of sulfur between 10 per
action products from contact with the reactants>
cent in excess Aof stoichiometric requirements and
110 per cent below stoichiometric requirements. 3 0 during their combination to .form carbon disul
de and from the atmosphere of thexreaction.
Within this range, reactions leading to the forma
The sensible heat carried by the regenerated ag
tion of low boiling sulfur compounds such as mer
glcinerating material, when recycled back into
captans and alkylsuldes are minimized and at
the liquid sulfur stream, will aid in the Vapori
the'same time the amountof recycle sulfur that
zation of the sulfur 'and its subsequent super
would have to be regenerated with the tarry
heating. The present method also provides an
products is limited to avreasonable amount. Al
efficient means for the reclamation of the sulfur
though the-reaction has been described through
content of they tar or free sulfur admixed or in
the use of the iluidized technique, other methods
solution with the tar for recycling in the'proc'
may be used tov circulate the catalyst or ag
glomerating material through the system.- VThese 40 ess. Lastly, sensibleheat is provided >for the
reaction itself under endothermic conditions of
include movingbed methods such as those em
combination with one oivmore; compounds of
metals of groups IV, V, VI, VII, and VIII of the
periodic table -as promoters. The oxides of zir

operation.

_ ployedin pebble heaters and in Thermofor crack

ing processes.

'

` kThe following examples are given to illustrate

Another procedure 'consists in

the invention:

mixing the agglomerating material to~~form ar

'

_Example 1.-Substantially pure ethane- gas wasL

slurrywithfthe liquidsulfur to be charged to

reactedv with, a stoichiometric amount of sulfur

the reactor.- An alternateprocedure comprises

vapors at 1112c F. in a fixed bed reactor. Ini


fluidizing the agglomerating material with the
tiaily only a small amount oftar formation was
sulfur vapors at apointafter vaporization and
experienced. However. after a few hours, con~
before orduring the super-heating of thesulfur.
A preferred feature of> the thermal technique 50 4.version to carbondisulfide had declined from its
initial level- of .90 per cent to a value in the order>
is to- separately preheatthe sulfuryapors and
of 20 per cent, and it was necessary to reactivate
hydrocarbon charge gas up toreaction tempera
tures and then combine these preheated streams
immediatelyV prior to their entrance into `thefre
action zone, This procedure overcomes thel de'
hydrogenating effect of hot sulfur yvon the hy
drocarbons with subsequent coke formation. Whether ` thermal or catalytic; the rreaction

the catalyst.

t of pentanes and >0.5 percent hexanes and heavier

hydrocarbons was passed at substantially at-_


mospheric pressure intoa reaction zone Jmain

conditionsand proportions of reactants may vary

somewhat~depending~onthe type `of charge gas


employed. Based on reaction conditions of about
1112" F. and atmospheric pressures the weight

ratio of agglomerating material to charge-gas

_,

Example AfA natural gas containing 91 per


centmethane, v5 per cent ethane, 2 per cent pro
pane,l 14 per cent of C4 hydrocarbons, 0.5 per cent

60

ktained at a temperature of 1112 F. and fitted.

with a static bed of silicagel catalyst. Employ


ing a stoichiometric ratio of gasand sulfur at a
total space velocity of 450 (gas and sulfur (S2)

may vary-from.- 1:1 -tof20:1 with thepreferred

volume calculated at 0

range -being 2:1to 10:1 and thermedian about

niercurw , a conversion _of 58 per cent ofthe hy

5:1. ' yThis may be based on either a 10 per cent

deficiencyor 10 percent excess of sulfur based


on stoichiometricity.Y

IIYhe regeneration-of used agglomerating ma-_ vterial is' eifected by suspension ofthe particles.
in an oxygen-containing gas and passage,V of the
suspension> through a regeneration zone under
conditions adapted to cause combustion of the

and 760 millimeters of

drocarbon gas to carbon disulfide was obtained.


It was found Aunder these. Iconditions that com
peting side reactions occurred to such an extent Y
that aboutA 2 per cent of the charged gas 're--y

acted with the sulfur to yield a viscous tarry


polymeric material .and some coke, With the re- '

sult that a material decrease in over-all >eiiiciency


and catalytic activity followed. Recovered Vsul

_fur .was around 40`per cent'of that charged.' An


facethereof. during >contact .Withthe reaction 75: initial high conversion-'of around 76 per cent

occluded tars andpolymers .1 collected on the sur.- .

acca-,69o

l2

ll

of. stoichiometric requirements. for the reaction;`

was attained fora period of about one hour after

which conversion dropped gradually and after.


about six hours operation, conversion leveled off

7. The method in accordance with claim, 1> in

at about 58 per cent.


Example 3.-A natural gasv containing around
3.0 per cent of C4 hydrocarbons and heavier is
passed through a uid reactor using the iluid
technique in the presence of the. saine agglom
erating material or catalyst as used in Example
2. The reactor. is maintained at 1112o F. under il

substantially atmospheric pressure conditions.


rIvhe sulfur to gas ratio is controlled to approx

imately stoichiometric requirements. The Weight


ratio of catalyst. to natural gas is maintained at
about 6:1, and the. contact. time is about ten
seconds. The over-all conversion of the hydro

which the oxidation of occluded sulfur-contain


ing by-products on said agglomeratirig material
Vis conducted at temperatures in the order. of 800
F. to 1500L7 F.
8. The method in accordance'with claim 1. in
which the reactants and agglomerating material
aremaintained in a I'luldized state Within the re

action zoneat about 1112 F; under s'ubstantlally;

atmospheric pressure with the ratio or' agglom


erating material to hydrocarbon being mains>
tained at about 6:1 with a contact time of about
10 seconds.
9. ille method inv accordance with claim l in
Whiclithe sulrur dioxide and hydrogen sulfide. are
reacted at temperatures Irom 500 F. to 150 F.
in the presence or a catalyst capable oi' promot

carbon. gas over. a period of 12 hours will bev


about. 90 per cent. of .which 88 per cent appears.
ing the ioi'mation oi' elemental suliur;
as carbon disulde, and 2 per cent as tar. Ten
10. The method or continuously producing car
per cent. of the natural gas remains. unreacted 20
bon disulfide by reaction or hydrocarbons and
and 'substantially 10 per cent of the. sulfur is un
sul'iur, said hydrocarbons containing substan
reacted.

From the. above examples, it isseen by em


ployingA the technique ofthe present _invention
the. .deleterious eiect of side reaction products .

eliminated andtheoverali reaction efficiency is

tial amounts 0I constituents tending to iorm dele-

terious tarry suliur-containing by-products comm


pi'isillg, contacting preheated nydl'ocarbonsv and
preheated suliur vapors with an agglomerating.

maintained. atv a high level. Although the inven

material in_a reaction zone under conditions ca

tion has been described by specic embodiments,

pable ol tlieiormation oi- carbon usuliide and hy

these. are only illustrative and the only limita


tions. to be placed. on the. invention are found in
the. appended claims.

drogen sulfide;4 said agglomerating material being,

. What is claimed

1. The method of converting hydrocarbons to


carbon disuliide by reaction Withzsuli'ur, said hy
drocarbons.. `containing constituents tending to
form tarry sulfur-containing. by-products, com
prising passing preheated hydrocarbons and pre
heated suliur vaporsv into contact With an ag
glomerating material in a reaction zone, said ag

capable 0Iv occludlngv said, Sulrurf-containing by


products, sepa-rating carbon-_ disul1ide hydrogen
sulfide, and said agglomerating material iroin.
eacii other, subgecting saidagglomeratlng, ma.
terial to an oxidizing atmosphere capable 01 pro-_
ducing sullur dioxide _ :rom said occluded by-4

products, reacting. said suliur dioxide and said


Spaiated hydrogen sliliide under conditions ca.

pable or forming elemental sulfur.


il. 'The method in accordance with vclaim 10

glomerating. material being capable of occluding 40 in which the agglom'erating matei'ialisv selected
saidisulurecontaining by-products and-said reac
tion zone being maintained under conditions to
promote. the formation of , carbon disulfide and

hydrogen sulde, separating said agglomerating


material and. the` carbon disuliide and hydrogen
sulfide so.` formed, subjecting' said agglomerating
material to. an oxidizing atmosphere capable of
oxidizing the sulfur contenter said occluded by
products to. sulfur dioxide, and reacting said sul
fur dioxide so. produced With- the hydrogen sul
fide under conditionsV to produce elemental sul~ur for reusein the reaction.
2. rihe method in accordance withy cla-im 1 inl
which the aggl'omerating` material is selected
fromy the. group consisting of sintered alumina,Y

silica, diatomaceousr earth, silica gel, activated


alumina, vactivated clays,- andsilica-alum-ina coin'
positionsi.

3. _The. method in. accordance with claim 1- inf


whichl the hydrocarbon isselected from- the group
consisting of natural. gas, propane, butane, and
their existing olenie homologues and mixtures
thereof.

'

Which the. carbonv disulfide forming reaction isv .

conducted ata temperature between about 842


Rand 1500 F., and the ratio of agglomeratingy
material: to hydrocarbons. is in the range'of 2:1
`

Y'

_5. `'Ihe method in accordance with claim 1 in


Which the hydrocarbons. andsulfur are preheated`

to reaction temperature._

silica,y diatoiiiaceousv eartn,_,sillca gel; activated.


alumina', activated clays, and silica-alumina coin
positions.

iz. 'i ne-method,in_accordance with claim 10 in


which the hydrocarbonisselectedrroin _the group
consisting 0I' natural gas, propane, butane,` and
their existing olennic homologues. and mixtures
thereof.

13.. ',Lhemethod in accordancerwith claim 10 in


which the carbon. disulfide vIorining reaction is.

conducted ata temperature betweenwabout 842


l?. and 1500u Fi, and the ratio of agglomerating,
material 11o-hydrocarbons is in the. range of 2:1.
to` 10:1..

i4. 'lhemethod in accordance with claim 10


in which the hydrocarbonsand suli'ur are pre
heated _to reaction. temperature.
_

15. 'I'he method in> accordance With` claim 10


in which the sulfur. is present in 4an amount be
" tween av lo. per cent ld_.en'ciencyand a ll) per cent

excess of stolchiometric requirements for the re


action

`4. rThe method in> -accordance with' claim 1 in

to10:1.A

rrom tile group consisting o1 sintered alumina,_

__

lo. VThe method of converting hydrocarbons to


carbon disulfide-by reaction with sulfur, said h_y
drocarbons containing' constituents tending to
formtarry suliur-containlng by-pioducts,l y coin

piising passing preheated hydrocarbons and pre


heated sulfur vapors into contact Withan ag
glolneratlng; materialin areaction zone, said ag
gloinei'ating material being capable of occluding
saidsuliurscontaining by.-products and saidreac

6. _The method in accordance With claim 1v in.


tion zone being maintained. `under conditions to.
Which the sulfur is present in an amount betweenA
promote the iormation` of carbon disulfide and
a4 I0 per cent deficiency anda 10 per cent excess 75 hydrogen suliide,A separating said. agglomeratingY

2,666,696
13

14

material and the carbon disulde and hydrogen


sulfide so formed, subjecting said agglomerating

`References Cited in the le of this patent


UNITED STATES PATENTS

material to regeneration in an oxidizing atmos

phere.
17. The method in accordance with claim 16 in 5

Number

Name

Date

2,187,393
which the oxidizing atmosphere is an'oxygen
2,330,934
containing gas.
Y
2,389,810
18. The method in accordance kwith claim 16
2,480,639
in which said agglomerating material is a cat
alyst capable of promoting the formation of car- l0 2,487,039
2,530,243

De Simo>______ _'_____ Jan. 16, 1940

2,556,177

Gamson _________ __ June 12, 1951

bon disulde from said hydrocarbons and sulfur.


HILLIS O. FOLKINS.
ELMER MILLER.

HARVEY HENNIG.

'

Thacker __________ __ Oct. 5, 1943


Odell et al. ______ __ Nov. 27, 1945
Ferguson ______ __ Aug. 30, 1949
Belchetz ________ __ Nov. 8, 1949

Holder __________ __ Nov, 14, 1950