2308 INDUSTRIAL AND ENGINEERING CHEMISTRY VOl. 40, No.

12

elastomers is t,he residual double bond. The exothermic art,lvit,y

TABLE
VIII. IGNITION CHSRACTERISTICS O F SMOKE is therefore ascribed primarily to this source.
This int'erpretation is further supported by the work of Midgley
Cup Sample and Henne, which showed t h a t the C--C bond in the 1-3 position t,o
Temp. Temp.
a t Flesh, at Flash, Burning Characteristics the residual double bond in crepe rubber is most readily cleaved.
Sample0 0 c. 0 c. after Flash It is rendered still more probable by the evolution of products
1. Natural rubber 415 270 Continuous a t sample from the gum stocks tested, which require active hydrogen atoms
2. GR-S 437 342 Continuous a t sample for their formation. Very little hydrogen chloride is evolved be-
3. Butadiene-acrylonitrile 430 380 Continuous a t sample
4. Neoprene 410 315 Vapor extinguished pilot fore rapid action begins, and the rat'e of evolution increases
which could not he sharply a t the peak of exothermic act,ion. Similarly, the huh-
relighted diene-acrylonitrile copolymer yields hydrogen cyanide, arid
a Compositions in Table I. natural rubber yields saturated gaseous hydrocarbons.
The evolut'ion of smoke does not necessarily parallel the exo-
thermic action. Smoke densities sufficient t o cause 50% extinc-
tion are always obtained before the beginning of the rapid rise i n
top, and a small pilot flanie was kept burning from the jet during temperature. Complete extinction of the light in the apparatuF:
the rapid heating process. The temperatures mere read a t in- used occurs at a point between the beginning and the peak of the
tervals of one minute, and the temperature a t which the vapor exothermic action. The smoke just above the sample of some
stocks may clear completely during the exothermic action. Stocks
flashed was noted. The samples were of the same size and shape containing zinc and magnesium oxides give colored smokes of a
as those used in the smoke density determinations (Table 3'111). greatly increased order of density during the exothermic action.
I n all cases the initial flash at the pilot occurred exactly at the Phosgene cannot be detected in the smoke from neoprene stocks.
beginning of the rapid rise in temperature of the sample. T h e The outside hcating temperatures at which the smoke and vola-
tile gases flash are very similar for the four elastomers in the gum
flame descended t o the natural rubber, GR-S, and butadiene- stpcks. The initial flash occurs a t the beginning of the exother-
acrylonitrile samples which continued to buiii. With neoprene, mic rise. The smoke from neoprene extinguishes the pilot light
flashes occurred a t the pilot but did not ignite the vapors or the while the other samples are ignited and continue to burn.
sample. The flashes increased in frequency and intensity until
the pilot Iight was extinguished. The interval between the ACKNOWLEDGMEST
flash and the extinction of the pilot light above the neoprene
Grateful acknodcdgment is made to Jackson Laboratory,
stock varied in different trials. A lighted taper n a s now lowered
E. I. d u Pont de Ncmours &z Company, Inc., for aid in this work
into the tube and was extinguished before reaching the pilot.
and for criticisms by members of its staff.
The gas a t the mouth of the chimney burned brieflv and then the
flame went out. The taper was reintroduced as rapidly as
LITERATURE CITED
possible for 7 minutes after the first ignition, but continuous
burning was never attained. (1) Carothers, Williams, Collins, and Kirby, J . Am. Chem. SOC.,53,
4207 (1931).
SUMMARY O F RESULTS
(2) Midgley and Henne, Ibid., 51, 1215 (1929); 53, 203 (1931).
(3) Olsen, Ferguson, Sabett,a, and Scheflan, ISD. ENG.CHEM.,ANAL.
All of the elastomer compositions tested from natural rubber, ED.,3, 189 (1931).
GR-8, butadiene-acrylonitrile copolymer, and neoprene under60 (4) Prentiss, "Chemicals in War," p. 17 (1937).
a n exothermic decomposition when rapidly heated. Increase in (5) Prettyman, IND. ENG.CHEM.,34, 1294 (1943).
the heating rate enhances the abruptness and magnitude of the (6) Rose and Simonsen, J . Chem. Soc., 1944, 101-3.
exothermic rise. Long heating a t 190-200" C. eliminates exo- (7) Yant, Olsen, Storch, LittlefieId, and Rcheflan. ISD. ENG.CBEX.,
thermic action, The rapid action also takes place in a n atmos- ANAL.ED.,8, 20 (1936).
phere of nitrogen. Various compounding agents may modify
this behavior, but they do not eliminate it. The exothermic ac- RECEIVED
September 27, 1947. Presented before the Division of Rubber
tion is therefore characteristic of the elastomers in the stocks. Chemistry a t the 112th Meeting of the . ~ M E R I C A NCHmiIc.41, SOCIITY,New
The only known structural characteristic common to all these York. X. Y.

d
v
d
v
0'

rc
WALTEN A. SCHULZE, J. P. LYON, AND G. H. SHORT
Phillips Petroleum Company, Bartlesville, Okla.

ITERATURE references (1, W, 4, 7 ' , 9) t o the synthesis of
mercaptans (thiols) indicate thc use of a rather wide variety
of raw materials and reaction conditions. From the standpoint
of commercial scale process economics, however, b y far the most
attractive synthesis method involves the direct addition of
hydrogen sulfide t o olefinic hydrocarbons. Both patent and
literature references t o the olefin-hydrogen sulfide reaction are
found after about 1925. A number of these (b, 6, 8) pertain t o
the formation of aliphatic mercaptans of low molecular weight
in low concentration through the reaction of a relatively small
portion of the light olefins and hydrogen sulfide over certain solid
contact catalysts. These references, however, do not indicate
process features or economics approaching a commercially fea-
sible synthesis of mercaptans of high molecular weight.
DEVELOPiMENT PROGRAM
Early experimental n-ork in the authors' laboratory had est&
lishcd the activity of certain catalysts for the reaction
C,€L + H2S iCJL,.iSH
Conditions were knovn, for example, under which mercaptans
could be converted t o olefins and hydrogen sulfide, and this
process (5,10, 1 1 ) had been in commercial application for 8
number of years Low pressures, temperatures of 600' t o 800 O F.,
and catalysts with cracking or depolymerizing activity pro-
mote this reaction. It n-as found possible t o employ some of the
same types of catalysts, with suitable modification, under the
reverse conditions to promote the addition of hydrogen sulfide t o
olefins to produce mercaptans. This addition reaction is favored
December 1948 INDUSTRIAL AND ENGINEERING CHEMISTRY 2309

by high pressures and tem- I t was predicted t h a t the

peratures well below those addition reaction would be
a t which mercaptans are de-
A synthesis process is described for the production of promoted by superatmos-
mercaptans (thiols) of high molecular weight. This
composed. pheric pressures at least up t o
process incorporates the direct addition of hydrogen
Preliminary experiments the range required for main-
sulfide to olefin hydrocarbons of petroleum origin in the
had shown the favorable taining the reactants in pre-
presence of catalysts. Research studies i n laboratory and
characteristics of a silica- dominantly liquid phase dur-
bench scale apparatus established engineering design data
alumina gel type catalyst for ing contact with the solid
for the use of solid catalysts-e.g., silica-alumina gel-in
the condensation reaction. catalysts. Accordingly, ex-
the synthesis of mercaptans i n the range of 12 to 16 carbon
This catalyst is prepared by perimental tests were made at
atoms. Supplementary experimental studies were de-
forming silica gel and activat- pressures in the range of 500
voted to a number of process variables, including the type
ing the partially dried gel to 1500 pounds per square
of hydrocarbon feedstoclrs, the effect of impurities in the
with a minor percentage of inch gage. Liquid space ve-
hydrogen sulfide, and the comparative activity of a num-
alumina under closely con- locities in the range of l t o 10
ber of solid and liquid catalysts. Plant construction and
trolled and specific conditions liquid feed volumes per vol-
operating procedures reflect the characteristic properties
(1%). The finished catalyst ume of catalyst per hour were
of hydrogen sulfide and mercaptans. Process design fea-
ordinarily contains about 1 to used.
tures for the dehydration and liquefaction of relatively
5 weight 70of alumina. With these process condi-
pure hydrogen sulfide, and the vacuum fractionation of
Process studies concerning tions selected, the practical
high boiling mercaptans are reviewed and properties of
the commercial synthesis of degree of olefin conversion
some of the products are summarized.
alkyl mercaptans were initi- per pass was primarily de-
ated in March 1943, as a pendent on the nature of the
result of efforts by the Rub- olefin feedstock, although the
ber Reserve Corporation t o heat release accompanying
contract for a supply of the dodecyl mercaptan (dodecancthiol) the exothermic reaction placed a n upper limit on conversion in
utilized in butadiene-styrene copolymerization. The process de- plant scale equipment. Various means for controlling the tem-
velopment program occupied approximately nine months. Com- perature rise in the catalyst bed a t high conversions were in-
mercial plant construction was started in September 1943 and com- vestigated and for plant design purposes experimental d a t a were
mercial mercaptan production began in February 1944, or slightly obtained using a light paraffin hydrocarbon heat carrier and a per-
less than one year after process development work was started. pass conversion of olefin within the range of about 20 to 50%.
Studies of the hydrogen sulfide-olefin reaction were first As the hydrogen sulfide-olefin reaction is capable of producing
carried out in bench scale equipment of relatively simple design. dialkyl sulfides as well as mercaptans, feed compositions were
adjusted t o result in highly selective mercaptan formation.
Feed materials were blended according to the desired molar The adjustment comprised the use of feed mixtures containing
proportions in pressure cylinders and the solution of hydrogen a hydrogen sulfide-olefin molar ratio greater than unity and pref-
sulfide in hydrocarbon liquid was displaced by nitrogen gas t o the
reaction vessel. When solid contact catalysts were employed, the erably at least 1.5 t o 1. The use of a n excess of hydrogen
catalyst case consisted of a short length of high-pressure steel sulfide was found desirable also in providing additional quantities
pipe with caps drilled for inlet and outlet connections. This case of heat carrier material.
was immersed in a n electrically heated oil bath and preheating of Hydrocarbon feed stocks were obtained from plant streams in
the feed was accomplished by a n inlet coil also immersed in the oil
bath. The catalyst case effluent was passed through a pressure- nearly all cases. Pilot plant fractionating columns were used in
reducing valve, condenser, and gas separator and liquid products trimming the plant stream samples t o the boiling range corre-
were recovered.in the separator. sponding t o the desired olefin molecular weight. For the syn-
The conversion was measured by titration of the mercaptan thesis of dodecyl mercaptans, this olefin feedstock boiling range
content of effluent liquid samples and catalyst temperatures were
adjusted t o maintain a desired conversion level. T h e total liquid was approximately 330' to 390" F. The hydrogen sulfide for
products from test runs were fractionated in small packed labora- experimental laboratory tests was purchased in cylinders from the
tory columns t o separate unconverted hydrocarbons from the Barium Reduction Company, Charleston, W. Va. This was a
mercaptan products. high-purity product with minor amounts of impurities such a s
En the course of the bench scale studies a number of process water and traces of carbon dioxide.
variables related t o plant design and feed stock preparation were
studied with silica-alumina gel type catalysts. I n addition, EXPERIMENTAL RESULTS WITH SOLID CONTACT CATALYSTS
studies of other catalysts were made t o the extent permitted b y I n the tables are shown the d a t a from typical bench Beale
the relatively brief over-all time period prior to plant operation. tests which were made t o study reaction variables and to establish
The major portion of the experimental program necessarily per- process conditions for the synthesis of various alkyl mercaptans.
tained t o the selcction of specifications for the plant feed stocks The length of the test period and the conditions employed varied
and catalyst, although much supplementary information was according t o the particular factor being investigated. Because
obtained regarding the synthesis reaction and generalized process the activity of solid catalysts changes with use, the general test
engineering. procedure which was developed involved starting up a t the
minimum temperature a t which the desired conversion could be
REACTION VARIABLES
obtained, and subsequently raising the catalyst temperature t o
The initial bench scale test confirmed the high activity of silica- maintain conversion. The upper temperature limit was reached
alumina gel catalyst in promoting the reaction of hydrogen sulfide when conversion could no longer be maintained or when the
with a Clz olefin fraction at temperatures within the range extent of side reactions indicated t h a t the economic life period of
(roughly from about 100' t o about 500 F.) considered practical the catalyst had been exceeded. Procedures for catalyst regener-
€or theoreticaI reasons. It was expected t h a t temperatures above ation were developed, b u t the initial life of the silica-alumina gel
this range would introduce process complications resulting from type catalyst was too long t o justify the expense of plant regenera-
isomerization, polymerization, and/or depolymerization re- tion facilities.
actions involving the olefinic hydrocarbons and, furthermore, Extensive tests were carried out on the reaction of Clz olefins
would be in the region of incipient mercaptan decomposition. with hydrogen sulfide to study the variables of olefin feedstock
2310 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 40, No. 12
FEEDSTOCK 1MPURITIES
TABLE1. REACTIONO F TWELVECARBON OLEFINS WITH HYDROGEr;
SULFIDEOYER SILICA
ALUMINACATALYST I n the course of pilot plant studies it wa? noted
Per Pass Yields that erratic results were sometimes encountered
ClZ Light during initial stages of a test run which indicated
Olefin Average Olefin, hfercaptan, Mercaptans,
Boiling Feed Conversion wt. 70 of wt. 70 of catalyst poisoning. This led to a study of the
Range, Temperature, per Pass, olefin olefin effect of varioua impurities in both hydrocarbon
Olefin Source F. F. wt. 7 0 charge charge
and hydrogen sulfide feedstocks. Various con-
Triisobutylene con- 328-356 220 28.5 17.8 19.0
centrate taminants and impurities were found to suppress
CaH6-CaHs polymer 330-380 230 49 7 61.9 5.9
Propslcne polymer 330-390 230 54.7 55,s 4.5 the activity of silica-alumina catalyst, presum-
Gray towera polymer 330-390 230 18.4 19.3 2.1 ably by adsorption during periods of low tem-
a Liquid polymer from vapor phase clay treatment of gasoline.
perature operation. iZmong the materials a hich
impaired the activity of silica-alumina catalyst
T.4BLE 11. C O K D E X s 4 T I O X O F HYDROGEN S U L F I D E WITH OLEFINS O F at lorn teniperatures n ere water, carbon dioxide.
VARIOUS k1OLECULAR WEIGHTS OVER SILICA-ALU31INh CATALYST oxygenated organic compounds, and arsine. Arsine
-_ Olefin Feedstock Rango of Ultimate was found in commercial tylinder hydrogen
Boiling Conversion Olefin sulfide in trace quantities, but was not a fac-
No. range, Temperature, Conversion, Mercaptan
carbons O F. Source O F. W t . 70 Product tor in the process when using hydrogen sulfide
4 15-25 Isobutylene 80-2;10 100 teri-Butyl t ecovered from hydrocarbon gases. Oxygenated
5 80-120 Refinery amylenes 80-250 90 tetit-Amyl oiganic compounds nere encountered only in
6 148-162 Refinery hexenes 200-300 60 tert-Hexyl
8 205-250 CaHs-C4Hn 160-250 85 tert-Octvl pilot plant and laboratory work and were usual11
polymer
10 290-320 Pentene dimer 200-300 80 tert-Decyl attributable to oxidation of olefins during stor-
14 420-460 Heptene dimer 200-300 80 teit-Tctradecvl
1G 430-500 Octene dimer 200-300 75 tert-Hexadecyl age in small quantities and in frequently opened
containers or to residual traces of solvents used t o
clean and dry apparatus.
Water and carbon dioxide were more effectivt-
source and structure. Some typical experimental results are poisons when present together than when present separately
shown in Table I. The tests listed employed silica-alumina Because it was necessary to eliminate water from the plant
catalyst and hydrogen sulfide-olefin molar ratios of 1.5 t o 1. reaction system to suppress corrosion, it vi as assumed that
Operating pressure was 1000 pounds per square inch gage and dry feedstocks mould be available. I n the absence of uater, it
a liquid space velocity of 2.0 was maintained in the catalyst case. n a s found t h a t hydrogen sulfide containing LID t o about 10
T h e values li,ted in Table I for olefin conversion per pass and mole yo of carbon dioxide could be used without serious poibon-
for yields of the deaired long-chain mercaptans indicate some of ing effects when initial reaction temperatures were in the rangc of
the variations in olefin reactivitj The first stock nas a narron- 130' to 200' F.
cut fraction containing mostly isobutylene (2-methylpropane) Light hydrocarbon impurities in the hydrogen sulfide m r e
trimer. Although the conversion was kept relatively low, the found to be inert as far as the addition reaction was con-
depolymerization was severe, as indicated by the high yield of cerned. K h e n allowance u as made lor the reduced hydi ogen
light mercaptans and the low yield of dodecyl mercaptans. When sulfide purity by adjusting feed compositions, it mas feasible to
the C12 olefin was prepared from propylene-isobutylene polymer, use high percentages of propane diluent as a heat carrier in the
the yield of dodecyl mercaptans wa3 much higher, even at a hydrogen sulfide stream. The presence of methane arid ethane
higher temperature and per-pass convcraion. Results rvith the in the hydrogen sulfide stream, hon ever, was objectionablc h r n
propylene polymer stock appeared very satisfactory. However, the standpoint of hydrogen sulfide losses due to the hsndling of
the C12 olefin fraction from Gray T o ~ ~ polymers er had a low noncondensablc gases in the plant compression system.
reactivity factor under the conditions employed.
Another factor affecting the comparative reactivity of olefin CATALYST STUDIES
stocks from different sources was the variation of reaction rate
with olefin structure. Earlier experimental tests had indicated One phase of bench scale studies concerned the comparative
that in mixtures of various olefin types the tertiary olefins reacted testing of a number of solid catalysts to evaluate their actibitv for
with hydrogen sulfide at a much faster rate. The result of this the hydrogen sulfide-olehn 1eaction. With silica-alulnlna gel
difference in reaction rate was that under conditions for partial established as a standard of comparison, tcst conditions 1%CI'P
olefin conversion a selective conversion of the tertiary olefins approximately the same as those emploj ed 11ith standard silica-
occurred, and the mercaptan products often contained 90% alumina catalyst in the synthesis of Ci, inelcaptans. These
or more of tertiary mercaptans. Inasmuch as prospective plant conditions included the use of temperatures in the range of 150
operation embodied controlled per-pass conversion with recycle to 450" F., pressure of 1000 pounds per square inch gage, liquid
of unconverted olefins, it was apparent that tertiary mercaptans space velocity of 1.O, and hydrogen sulfide-olefin molar ratio o f
would be formed selectively as long as tertiary olefins werr 1.5. The olefin stock for all the comparative tests was a fraction
present in the ole& feedstocks. Changing process conditioiis of propylene-isobutylene polymer with a boiling range of about
to promote the addition of hydrogen sulfide to other types of 300" to 380" F. Each catalyst vas tested b y operation for
olefins was effective only in the substantial absence of tertiary successive 4-hour periods at 50 F. temperaturc intervals over the
olefins. range of 150" to 300" F., inclusive. I n the caw of tho higlili'
T h e hydrogen sulfide-olefin reaction was carried out with active silica-alumina gel, tempcratures were not advanced be-
many other olefinic hydrocarbons of varying source, structure, yond 200 ' F. bemuse of the fact t h a t conversion wa3 in the range
and molecular weight. Most of the test work on other than CIZ of 80 to 90% a t the minimum temperatures.
olefins was done subsequent t o a period of commercial operation The solid catalysts tested and the test results are listed iii
in the production of CU mercaptans and was for the purpose Table 111. Of the catalysts employed the activated alumina,
of evaIuating new raw material sources and producing new bauxite, silica, and silica gel were commercial products of grades
mercaptans for evaluation research. usually specified for catalyst preparatlon. The thoria-alumina
I n Table I1 are listed a number of the olefinic hydrocarbon catalyst was a coprecipitated gel coinposition containing a major
stocks examined. proportion of alumina. The alumina-base catalysts 5%erc prc-
December 1948 INDUSTRIAL AND ENG INEERING CHEMISTRY 231 1

Exploratory bench scale tests were also carried out with a

TABLE111. COMPARISON OF SOLID
OF ACTIVITY number of liquid catalysts including anhydrous hydrogen fluoride,
FOR REACTION
CATALYSTS OF HYDROGEN SULFIDEWITH aqueous hydrofluoric acid, and boron trifluoride and its various
TWELVE-CARBON
OLEFINSTOCK
complexes such as the (IS)hydrate and the phosphoric acid com-
Calculated5 plex. These tests were made in a small turbomixer reactor on
Av. Yield
Wt. % lMeroaptan Sulfur in per paJs feed mixtures comprising olefin, hydrocarbon diluent, and hydro-
Effluent L of c,s gen sulfide. The hydrocarbon diluent employed aided adjusb
150° ZOOo 250° 300' Mercaptan,
Catalyst F. F. F. F. Wt. % ment of the hydrogen sulfide-olefin molar ratio at moderate pres-
Silica-alumina gel 13.9 12.6 ... ... 87.0 sures to values in the range of about 2:l to about 8:1 t o obtain
Activated alumina 0.5 1.1 2.1 3.1 11.1
Bauxite 0.9 1.0 1.4 3.0 10.0 mercaptans in preference to dialkyl sulfides.
Silica gel 0.8 0.8 0.7 0.7 4.9
Diatomaceous earth (silica) 0.7 0.8 0.6 1.4 5.4 The results of a few of the experimental tests, summarized in
Nickel sulfide-alumina 0.7 0.8 1.6 2.9 9.7 Table IV, indicate the extent of the olefin conversion obtainable
Nickel oxide-alumina 1.3 1.2 1.1 1.2 9.1
Thoria-alumina pel 0.6 0.3 0.8 1.8 5.6 with these liquid catalysts. Higher yields of the mercaptans of
0.3 0.4 0.8 1.0 4.1
0.6 0.6 0.9 1.3 5.6 molecular weight corresponding to olefin feed may be obtained
1.1 0.9 0.9 0.9 6.1 by adjustment of reaction conditions and by utilizing olefin stocks
0.3 0.5 1.2 2.4 4.2
0.4 0.6 0.3 0.5 2.8 less susceptible to depolymerization.
0.4 1.6 2.0 2.6 10.0
Assuming no formation of lighter mercaptans.
PLANT DESIGN AND CONSTRUCTION

Process design work for a commercial scale unit to produce

pared by impregnating alumina pellets with about 10 to 20
weight yoof the various metal salts from aqueous solutions. Con-
ventional methods were used t o convert the adsorbed metal salts
to the oxide or sulfide. All the catalysts were dried prior to test-
ing to produce maximum activity.
It will be noted from t h e calculated mercaptan yield values of
Table I11 that only the standard silica-alumina gel catalyst is
outstanding in activity for the reaction. This catalyst produced
initial conversions above 80% per pass (based on weight of
olefins charged) at the minimum test temperatures. The superi-
ority is even greater than indicated by these calculated yields
because substantially all of the mercaptans produced by the
catalysts having very low activity (such as silica gel) were light
mercaptans resulting from depolymerization of the olefin feed-
stock.
The activity of none of the alumina-base catalysts promoted
by metal oxides or sulfides, according to the specific methods em-
ployed, excecded the values obtained with activated alumina
alone as catalyst. I n some instances it appeared t h a t the prin-
cipal effect of the promoter was to suppress the depolymerizing
action of the alumina without greatly affecting the rate of addi-
tion of hydrogen sulfide t o the long-chain olefins. Bauxite was
approximately equivalent to activated alumina.
As it appeared that the optimum temperature range had not
been reached with either bauxite or activated alumina, tests were
continued with these catalysts at 50" F. intervals from 325' t o
425" F. Conversions based on the total mercaptan yields in-
creased uniformly, but maximum yields of dodecyl mercaptans
were noted at about 375" F. with bauxite and at about 325" F.
with activated alumina. Thcse maximum mercaptan yield
values were approximately 25 weight % (based on olefin charged)
for each catalyst. I n the case of the alumina catalyst, increased
mercaptan production above about 325' F. was due almost
entirely to olefin depolymerization and formation of low boiling
mercaptans.
TABLEIV. HYDROGENSULFIDE ADDITIONTO OLEFINS IN
OF HYDROGEN
PRESENCE FLUORIDE AND BORONFLUORIDE
COMPLEXCATALYSTS
tertiary dodecyl mercaptans proceeded concurrently with t h e
latter portion of the pilot plant program. The basic process de-
sign for the catalytic condensation reaction was not greatly dif-
ferent from the pattern defined by early laboratory tests. How-
ever, various other plant operations were studied on a sniall scale
prior to designing the large scale equipment..
The commercial scale plant process flow and operation are
illustrated by the schematic flow diagram of Figure 1.
Fresh hydrogen sulfide gas is taken into the compression system
together with the recycle hydrogen sulfide stream from the high-
pressure stripper. The combined gas streams are passed through
a bauxite dehydrator (not shown) t o the two-stage compression
system. High stage gas passes through a scrubber t o remove en-
trained liquid and then through a condenser and to the liquid hy-
drogen sulfide surge tank.
Feed t o the catalyst case comprises fresh olefin recycle olefin
and hydrogen sulfide. The hydrogen sulfide-olein feed stream
passes through a steam preheater and then through one of t h e
catalyst cases (in alternating service) containing a 4 X 7 foot bed
of granular catalyst. The catalyst case effluent stream passes
through a pressure-reducing valve and a stream heater into the
high-pressure stripper. I n the high-pressure stripper a nearly
complete separation of unreacted hydrogen sulfide is made, and
the overhead vapors from the stripper are recycled t o the com-
pression system. Liquid products from the bottom of the high-
pressure stripper then flow to a lower pressure stripping column
for further removal of low-boiling components. The low-pressure
stripper reboiler serves also as preheater for the liquid feed t o the
subsequent fractionation step.
The first fractionation step effects the separation of unreacted
olefin stock from mercaptan products at a n absolute pressure of
about 5 mm. of mercury. The overhead liquid from this tower re-
turns t o the recycle olefin storage tank. The kettle product from
the recycle olefin tower is ordinarily specification grade mercaptan
when charging a CI?olefin stock. However, a second vacuum
fractionation is carried out in the mercaptan tower at absolute
pressure of about 3 mm. of mercury t o obtain the mercaptan as a n
overhead product. Kettle residues in this second distillation step
are negligible. The overhead product from the mercaptan tower
passes to finished product storage tanks.
The process features, aside from the catalytic reaction step
which received particular attcntion, included:
Dehydration of hydrogen sulfide and compression and liquefac-
tion of this raw material.~

Yield of Fractional distillation of high boiling mercaptans

- which are in-
Corre- herently unstable at high temperaturei.
HzS/ W t 41 sponding
Olefin Oldfin" Mercaptan, Selection of materials of construction.
Mole Temp., Cop- Wt. % Inspection, analysis, and storage of the finished products.
Catalyst Olefina Ratio O F. version of Olefin
HF (anhydrous) Diisobutylene 3.3 90 100 72
80% H F Triisobutylene 3.5 90 70 37 The plant site was selected in the Borger, Texas, area where
BFa-Hz0 Triisobutylene 2.8 90 41 hydrogen sulfide is available from the desulfurization of gas
BFs-HsP04 Triisobutylene 2.2 90 76
68 61
BFa-H3PO4 Triisobutylene 6.5 40 64 72 streams of high sulfur content.
alO% solution of olefin in n-pentane. I n this particular operation, a crude hydrogen sulfide concen-
trate is obtained from the amine reactifier still of a Girbotol gas
2312 INDUSTRIAL AND ENGINEERING CHEMISTRY Vel. 40, No. 12
c
RECYCLE OLEFIN

3 -STAGE

4-STAGE
STEAM EVACTOR

MERCABTA N

TO
LOADING DOCK
I
c
FINISHED MERCAPTAN
ii
Figure 1. Schematic Flow Sheet of Mercaptan Plant

treat>ingunit as a vapor stream s a h r a t e d with n-ater at atmos-
pheric temperature and a pressure of 5 to 10 pounds per square
inch gage. The crude concentrate is cooled, scrubbed to remove
condensed water, and dehydrated by passage through a bed of
bauxite desiccant to produce a dew point of -30' to -40' F. at
50 pounds per square inch gage. The degree of dehydration is
controlled by regeneration of the bauxite a t suitable intervals.
With dew points in t,Ksrange, corrosion of metal equipment is sup-
pressed and hydrate formation in subsequent compression steps is
eliminated. This Iatter factor is important, since the hydrate
formed at, high pressures is a rather high melting solid capable of
plugging lines and eschangers in the compression system.
Preliminary experimental testing of solid desiccants for hydro-
gen sulfide indicated t,hat bauxite was satisfactory with regard t>o
dew point lowering, water capacity, and service life. However,
it was found necessary to use bauxite of lorn iron content in
order to carry out uncomplicated regeneration of the desiccant.
This was based on the discovery that bauxite of high iron content
tends t o release relatively large amounts of sulfur dioxide and ele-
mental sulfur during regeneration with hot inert g a m at tempera-
tures above about 350" F. This difficult?; has not been encoun-
tered with bauxite of low iron content-Le., belox about' 3 to 5%
I.'ezOa.
The dry hydrogen sulfide gas stream is delivered to the mercap-
tan plant by pipe line a t pressures of 20 to 50 pounds per square
inch gage. Plant compression in t,vm stages effects liquefaction at
pressures in the range of 350 to 400 pounds per square inch gage.
The vapor pressure of the condensed liquid a t ordinary plant cool-
ing water temperatures varies with the purity of the hydrogen sul-
fide. By constantly venting noncondensed gases from the liquid
hydrogen sulfide surge tank the concentrations of carbon dioxide,
methane, and ethane are maintained a t about the values of t,he
incoming fresh hydrogen sulfide gas &ream.
A standard gas engine-driven compressor with two power and
two compression cylinders is used. The cornpression cylinders
have some special fittings such as Ni-Resist liners, stainless st,eel
valve assemblies, and Inconel garter springs for t,he inet'allic
packing. lnterstage cooling and the condensation of hydrogen
sulfide are done in conventional shell-and-tube exchangers fit,t,ed
with steel tubes.
The catalyst cascs are fabricated from alloy steel. Other plant
vessels, piping, and tankage are of common steel with adequate
corrosion allorrance.
I n general, most of the selected materials of construction have
given satisfactory service. Fatigue corrosion due to hydrogen
sulfide has been encountered in some cases. This type of corro-
sion which results in cracking and fracture occurs with metal
parts (including many alloy steel parts) which are subjected to
tension and/or compression and flexing. Examples are pump
plungers, springs of all types, gate valve seats and wedges, ball

TABT,E I-. P H Y S I C A L A43D CHEMIC.41, FROPERTIES O F LONG-CHSIN TERTIARY

ALKYLMERCAPTANS
Olefin Feedstock nlercaptan Distillation Range, F. Apparent
Rolling IJ3P-'35VQ Mercaptan Average RIercaptan
range, condensed condensed
*Bp-Q5% Sp. Gravity, Sulfur, Molecular Puilty,
Product Source F. a t 5 mm. Erg a t 760 mm. Hg 60' F./60° F. Wt. yo Weight 7c
tert-Dodecyl 320-380 172-207 420-462 0.8713 15.9 194 97.0
tert-Tetradecyl 400-450 218-252 484-320 0 .a v o 11.9 230 85.0
tert-Hexadocyl 450-500 252-305 520-590 0 5830 10.3 241) 80.0
tert-Tetradecyl 400-450 221-235 488-502 0.8821 14.1 226 99.25
tert-Hexadscyl 450-500 302-327 590-615 0.8890 12.4 2.55 99.1"
tert-Dodecyl Hexene dimer 372-405 196-222 452-485 0.8945 15.6 203 99.3
tert-Tetradecyl Heptane dimer 415-460 240-280 51O-ZG0 0,9046 12.2 234 8'3.3
tert-Hexadecyl Octene dimer 460-5 00 260-310 540-610 0.9121 11,o 2 50 85.1
5 Specially purified for research purposes from a commercial produot.
December 1948 INDUSTRIAL AND ENGINEERING CHEMISTRY
thrust bearings, and the Bourdon tubes of pressure gages and
instruments. Fracture of common steel relief valve springs was
troublesome until aluminum-plated springs were installed.
Inconel springs are apparently resistant to this type of corrosion
and have given good service. The failure of Bourdon tubes is
reduced by the use of molybdenum-stabilized 18-8 stainless steel
tubes. Recording pressure controllers are fitted with tantalum
diaphragms between the transmitting and recording systems.
The vacuum fractionators are of novel design and relatively
high efficiency. The design is based on requirements for (1)
high vacuum operation with minimum internal pressure drop, ( 2 )
minimum residence time for heating the mercaptan-containing
liquids, and (3) heat exchange under positive pressure.
The recycle olefin column, for example, is a 5 X 65 foot tower
containing 30 feet of 1.5-inch Berl saddle packing. The internal
pressure drop in the column is in the range of 5 t o 7 mm. of mer-
cury, and column surveys during operation have indicated a frac-
tionating efficiency of 7 t o 8 theoretical plates when a pressure of
5 mm. of mercury is maintained at the top of the column. Ex-
ternal exchangers are provided for heating the kettle liquid and
cooling the overhead condensate, and are located on the discharge
lines of the respective circulating pumps.
Residence time in the reboiler is very short, and flash vaporiza-
tion of the heated liquid within the column results in a kettle tem-
perature considerably below that a t the reboiler outlet. The
overhead vapors are condensed in an internal condensing section
bv direct exchange with a portion of the cooled overhead con-
densate; the remainder of the cooled condensate 1s withdrawn t o
product storage. Reflux liquid is withdrawn ahead of the cooler
and returned t o the column just below the condmsing section.
MERCAPTAN PRODUCTS
The tertiary dodecyl mercaptan which was the primary objec-
tive of the work was produced from a 330 to 390 O F. fraction of
propylene-isobutylene polymer. This product, as would be
expected from the nature of the feed olefin, is a mixture of mer-
captans having 11 to 13 carbon atoms with a n average molecular
weight corresponding to about 12 carbons. The compounds are
of branched chain structure and the location of the mercaptan
group is not known except in so far as the location of the olefinic
linkage in the polym-er molecule can be deduced. The charac-
teristic reactions of the mercaptan mixture indicate t h a t the
mercaptan groups are almost entirely attached to tertiary car-
bons, indicating t h a t the addition of hydrogen sulfide probably
occurs according to Markovnikov's rule. The high yield of
tertiary mercaptans from a n olefin stock of this nature is also in
agreement with the theoretical considerations regarding the loca-
tion of the double bond in hydrocarbon polymer molecules and
the known tendency of the double bond to migrate toward the
center of the molecule under polymerization conditions. It is
also further confirmation of the more rapid rate of reaction of
hydrogen sulfide with the tertiary olefins under the conditions
employed.
Because the high molecular weight mercaptan products are
mixtures of isomers of a particular narrow molecular weight
range, inspection tests and analyses for mercaptan purity are
based on boiling range, average mean molecular weight, and
mercaptan sulfur content. The latter is the most convenient
analytical method, as other sulfur compounds are absent and the
mercaptan sulfur determination is a rapid and accurate volu-
metric or amperometric analysis. The boiling range of the high
boiling mercaptans is determined in a standardized distillation
apparatus a t a constant pressure of 5 mm. of mercury. Average
molecular weight is determined by the cryoscopic method in which
the freezing point depression of benzene is measured.
Impurities present in the mercaptan products are hydrocarbons
which have been incompletely separated in the distillation steps
or which, in some cases, occur in the mercaptan boiling range as a
2313
result of further polymerization reactions undergone by t h e
original olefin feed stock. I n general, separation of hydrocarbon
impurities can be relatively complete within the limitations of t h e
plant fractionation equipment since the boiling point increment
due to the introduction of the mercaptan group is of the order of
60 O t o 80' F.
The tertiary alkyl mercaptans are stable at temperatures below
about 300" F. Oxidation is relatively slow, and metals are not
appreciably attacked under usual storage conditions by the com-
pounds of higher molecular weight. Product storage tanks of
mild steel are used and are closed to the atmosphere and blan-
keted with a n inert gas. Retain samples have been observed over
a period of 3 years without indications of deterioration, as the
mercaptan sulfur content, distillation range, and color have re-
mained constant.
Commercial scale production of the high molecular weight
tertiary mercaptans has yielded a number of products identified
as tertiary dodecyl, tetradecyl, and hexadecyl mercaptans.
Typical properties of these products are listed in Table V.
The properties listed in Table V indicate the gradation of phys-
ical characteristics and purity between the commerical CIZ,C I ~ ,
and Cre products. The plant distillation equipment permits both
light and heavy end separations on the CIS and C14 carbon mer-
captans, and these products can be produced in very high purity.
The hexadecyl mercaptan product, however, is obtained in the
plant as a n undistilled kettle product, so t h a t commercial puri-
ties are somewhat lower. Two of the products listed were ob-
tained by chemical purification of commercial tetradecyl and
hexadecyl mercaptan mixtures t o separate associated hydrocar-
bons.
These long-chain mercaptans are mobile liquids of moderate
viscosities a t ordinary temperatures, and colors ranging from
water white t o light straw, depending on the extent of purifica-
tion to remove hydrocarbon impurities. They have distinctive
and persistent odors which, however, are not objectionable like
the odors of the lower molecular weight mercaptans. Higher pu-
rity and higher molecular weight are accompanied by a decrease in
odor intensity. They are soluble in hydrocarbon solvents, the
lower alcohols, and many common organic solvents, and are sub-
stantially insoluble in water.
-4number of typical reactions have been studied. These ter-
tiary mercaptans as a class undergo metal salt formation, oxida-
tion t o disulfides, and other known reactions of the sulfhydryl
group but with gradations of reactivity attributable t o the
molecular weight and the tertiary mercaptan characteristics.
LITERATURE CITED
(1) Arndt, F , Milde, E., and Eckert, G., Ber., 44, 2236 (1911).
(2) Braun, J. von, N d . , 42, 4568 (1909).
(3) Buell, A. E., and Schulze, W. A. (to Phillips Petroleum Co.),
U. S.Patent 2,016,271 (Oct. 8, 1935).
(4) Claus, A., Ber., 5, 659 (1872).
( 5 ) Duffey, M. R., Snow, R. D., andKeyes, D. B., IND.ENG.
CHEM.,
2 6 . 9 1 (1934).
(6) Johansen: E.-'M. (to Gray Processes Corp.), U. S. Patents
1,836,170 and 1,836,171 (Dee. 15, 1931).
(7) Kramer, R. L., and Reid, E. E.. J. -4m. Chem. SOC.,43, 881
(1921).
(8) Nisson, P. S.,and Mandelbaum, M. It. (to Gray Processes
Corp.), U. S. Patent 1,836,183 (Dec. 15, 1931).
(9) Roemer, H., Rer., 6 , 7 8 4 (1873).
'%1 A. (to Phillips Petroleum e o . ) , U S. Patent 2,151,-
(10) Schulze, .
721 (March 28, 1939).
(11) I b i d . , 2,162,319 (June 13, 1939).
(12) Ibid., 2,392.554 (Jan. 8, 1946), 2,392,555 (Jan. 8, 1946), and 2,-
426,646 (Sept. 2, 1847).
(13) Schulze, 1%A., '. and Crouch W. W.( t o Phillips Petroleum Co.),
I b i d . , 2,426,647 and 2,426,648 (Sept. 2 1947).
RECEIVEDSeptember 23, 1947. Presented before the Division of IndustrisI
and Engineering Chemistry a t the 112th Meeting of the AMERICANCHEMI-
CAL SOCIETY, New York, N. Y .